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PERSPECTIVE

Energy & Environmental Science Accepted Manuscript


Catalysis for CO2 conversion: a key technology for rapid introduction of
renewable energy in the value chain of chemical industries
Gabriele Centi,a Elsje Alessandra Quadrelli,b and Siglinda Perathonera
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5 DOI: 10.1039/b000000x
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Replacement of part of the fossil fuel consumption by renewable energy, in particular in the chemical industry, is a central strategy for
resource and energy efficiency. This perspective will show that CO2 is the key molecule to proceed effectively in this direction. The
routes, opportunities and barriers in increasing the share of renewable energy by using CO2 reaction and their impact on the chemical
and energy value chains are discussed after introducing the general aspects of this topic evidencing the tight integration between the CO2
10 use and renewable energy insertion in the value chain of process industry. The focus of this perspective article is on the catalytic aspects
of the chemistries involved, with an analysis of the state-of-the-art, perspectives and targets to develop. The reactions discussed are the
production of short-chain olefins (ethylene, propylene) from CO2, and the conversion of carbon dioxide to syngas, formic acid, methanol
and dimethylether, hydrocarbons via Fisher-Tropsch and methane. The relevance of availability, cost and environmental footprint of H2
production routes using renewable energies is addressed. The final part discusses the possible scenario for CO2 as an intermediary for the
15 incorporation of renewable energy in the process industry, with a concise roadmap for catalysis needs and barriers to reach this goal.

throughout the value chain (e.g. increase of bio-based feedstock


Introduction share, production of more performing products, end-of-life feed-
35 streams management, recycling within and between value-chains
Chemical industry is an energy-intensive industry: it the second-
towards zero-waste processes, etc.).3
largest industrial energy consumer since it uses fossils fuels both
While progresses in chemical production are continuously
as raw materials and as power and fuel, accounting for about 14%
lowering its impact, the challenge of sustainability requires a
20 of total industrial energy consumption. In US the chemical step-forward in addressing the use of fossil fuels as both raw
industry is even the largest energy-intensive branch, with 25% of 40 material and energy source. It is necessary to increase the share of
industrial consumption in 2009, and the highest energy use of renewable energy (RE) and valorise alternative raw
consumption per unit of value added.1 Moreover, its energy
materials. In other words, it is necessary to develop processes and
intensity has increased by 0.8% year-1 since 1990, whereas it has
technologies for a resource- and energy- efficient process
decreased in the case of almost all other main producers. China’s
industry.2,3
25

energy intensity is also high. The cost of energy represents from 45 It will be shown here how the conversion of CO2 into
8% up to 50% in cost structure of materials produced from feedstock for the chemical/process industry is an efficient — and
chemical industry. It is therefore evident that chemical industry in some cases, already close to market — way to introduce RE in
has a key role in creating a resource-efficient, low-carbon
this value chain. Some of the possible routes involved in this
30 economy and society.2 Chemical industry is also a pillar for
approach will be discussed here, with a special focus on the
essentially all manufacture sectors, and it provides enabling
50 catalytic aspects underpinning them.
technologies and materials to improve resource efficiency

Broader context
The chemical industry has a key role in creating a sustainable, resource-efficient, low-carbon economy and society. A strategic
element to seize such opportunity consists in effectively introducing renewable energy in the chemical production chain. Presently,
over 95% of the industrial processes still use thermal energy. Electrical energy use in the chemical industry is still quite low although
electrical energy is the main output of the actual renewable energy sources (with the exception of biomass conversion). This
perspective article shows how the conversion of CO2 into feedstock for the chemical/process industry is the most efficient way to
rapidly introduce renewable energy in this value chain and discusses the various options possible to proceed in this direction, in
particular from the perspective of the state of the art of catalysis. While these two issues — CO2 management and the use of
renewable energy (RE) — have been usually considered as separate aspects, we will show here how they are tightly interconnected.
The paper defines also the needs and possible roadmap for catalysis in order to enable the chemical conversion of CO 2 to become the
key component towards a resource and energy efficient future for the chemical industry.

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Many reviews have discussed the conversion of CO2,4-14 mostly is used in some thermochemical cycles to produce solar fuels. For
from the perspective of using a waste and/or a cheap readily 60 example, CeO2- or ferrite-based ceramics reduce spontaneously at
available raw material, and not necessarily from that of the high temperature, and can be reoxidized (at a lower temperatures)
relevance of this reaction for the introduction of RE in the by H2O or CO2 producing H2 and CO, respectively.21 However,
5 chemical industry, with the notable exception of the Olah and co- problems of stability, productivity, scalability etc. indicate that
workers15 which discussed in their book and articles how the this also is a long-term solution.
conversion of CO2 to methanol can be the basis for a new 65 The 2-step RE  chemical routes, that is the ones, for
economy. example, based on the intermediate production of electrical

Energy & Environmental Science Accepted Manuscript


energy as output, can rely on renewable energies other than solar
The issue of introducing renewable energy in the chemical
10 production chain power. Hydropower, geothermal energy, wind and solar energy
(photovoltaic cells, PV) are producing electrical energy.
The various approaches ultimately leading to production of 70 Conversion of electrical energy to other forms to be used in
chemicals powered by renewable energy can broadly be chemical industry is then needed, because electrical energy does
subdivided in three families:
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

not integrate well into chemical production, except as utility.


- direct RE  chemical routes; Nearly all the industrial chemical processes are based on the use
15 - 2-step RE  chemical routes - that is, for example, routes of heat as the source of energy for the chemical reaction,22 apart
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going through the intermediate production of electricity; 75 from very few processes using electrical energy (chlorine and
- 3-step RE  chemical routes, where a further intermediate soda production, for example). In the chemical sector, on the
step consists on the production of a ‘sacrificial’ energy average only 20% of the input energy is used as electrical energy
vector (such as typically H2 production from electricity) and (including that generated on-site) to power the various process
20 subsequent use of this energy vector to yield the desired units and for other services.23a This value nearly halves if we
chemical (for example, by using H2 to produce methanol). 80 include that the feedstocks for the chemical sector are also
The direct RE  chemical routes are essentially limited to solar: derived mostly from fossil fuels. In the petroleum refining sector
(i) biological or (ii) abiological catalytic pathways, and (iii) solar only about 5% of the of the input energy is used as electrical
thermal conversions. Nature has indeed chosen CO2 as its vector energy,23b and this value becomes few percentage if we consider
25 molecule to inject solar energy in the plant growing processes. the raw materials. A further compounding difficulty for the use of
Several strategies are being pursued to expand these metabolic 85 RE in the chemical production is the discontinuity of electrical
cycles to the tailored production of fuels and other chemicals. energy production from wind, PV solar cells, etc. since chemical
For example, genetically modified cyanobacteria have been production typically requires constant power supply.
recently reported to consume carbon dioxide in a set of steps to Furthermore, the amount of RE produced by PV, wind and other
30 produce a mixture of isobutyraldehyde (primarily) and RE sources amounts to around few percentages of the total
isobutanol.16,17 Artificial metabolic pathways involving enzymes 90 energy consumption, and yet, in some cases (typically in off-peak
or cyanobacteria have been proposed to use NADPH and ATP times), the modest quantity of electrical energy thus produced
from photosynthesis for the synthesis of n-butanol (UCLA) or already exceeds the grid capacity. By increasing the total
isobutene (Global Bioenergies) directly from carbon dioxide and production of renewable electrical energy the need of storage the
35 water.4 However, the data available on these biocatalytic routes excess of electrical energy will become a more relevant issue. 24-26
are still preliminary and productivities low. Their relevance in the 95 Conversion of renewable to chemical energy can help
context of introducing massive quantities of RE in large-scale integration of RE in the chemical production chain; it can be
chemical production chain are thus long-term. We do not achieved by RE-powered synthesis of molecules which can be
consider here the routes using biomass to produce chemicals and easily stored and transported, as well as used as raw materials in
40 fuels. Although some of them are already close to the chemical industry. Some base chemicals can be directly
commercialization, and in the short-medium term they will play a 100 obtained from CO2 by electrolysis, as will be discussed hereafter.
role to introduce RE in the chemical production chain, many It was shown, for example, that it is possible to reduce
steps are necessary and life-cycle assessments indicate the high electrocatalytically CO2 to formic acid or to long-chain alcohols
environmental footprint.18 (isobutanol and butanol) both in gas phase27 and liquid phase.28
45 A long-term approach is also the abiological production of Issues related to productivity, overpotential and electrode
solar fuel, e.g. related to the vision of developing artificial leaves. 105 stability, inter alia, need to be addressed before such strategy
Such vision is inspired from the highly complex machinery of becomes industrialized.
natural leaf in using solar light and water to convert CO2, but in Finally, the most established technology for storage of
an intensified process and with the ability to tailor the type of electrical energy as chemical energy is H2 electrochemical
50 products obtained. The conversion of CO2 to hydrocarbons and production (see dedicated paragraph below). H2 is ill-adapted to
alcohols using radiations alone or in combination with electrons 110 serve as the ultimate fuel given its unfavourable volumetric
(photo- and photoelectro-catalytic methods) is indeed actively density, compressibility, flammability, overall lack of
investigated worldwide.19,20 The results are at the level of proof- compatibility with the current energy infrastructure and other
of-the-concept with productivities still quite low indicating that issues. A further reaction consuming H2 to yield a chemical which
55 the applicability of these discoveries will occur eventually only in can be (more) easily stored, transported and used is desirable.
a long-term perspective. 115 Typically, a liquid fuel with adequate gravimetric and volumetric
The other possible direct RE  chemical approach is based on energy density can meet such requirements, albeit systems related
high-temperature solar heat (concentred solar panel – CSP) which

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Energy & Environmental Science Accepted Manuscript


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Fig. 1 (a) Schematic overview of the CO2 conversion routes to incorporate renewable energy in the chemical and energy chains. The renewable
energy is used either directly (in the solar thermal production of syngas) or indirectly, according to two main possibilities: (i) production of renewable
H2 or (ii) production of electron, or electron/protons (by water photo-oxidation), used in the electrochemical routes.
(b) Detail of the different possible routes to synthetize light olefins (as raw material to incorporate RE in the chemical production chain) from CO2 and
renewable H2.

on gaseous fuels, such as syngas, are also within the scope of this switching to alternative raw materials such as biomass. Carbon
chemical-based strategy. Such 3-step (RE  electricity  H2  15 dioxide has been identified as one such potential vector molecule
chemical) conversion of RE in chemical energy are the one (through reduction to syngas, methanol, methane, formic acid,
closest to industrial deployment. DME, etc. as will be reviewed hereafter) with the added benefit
with respect to other possible energy vectors (H2, ammonia, etc.)
5 Goal, scope and limits
of directly contributing to inject RE in the energy chain while
The goal of this perspective article is to show that the use of 20 contributing to closing the carbon cycle connected to CO2
RE to convert CO2 to some valuable base materials for chemical emissions (under the hypothesis that such CO2 comes from
industry, is an effective — and, when 3-step (RE  electricity captured CO2 emissions).29 In addition, the products of CO2
 H2  chemical) strategies are taken into account, also short- conversion can be easily inserted in the chemical production
10 term — way to smoothly integrate RE into the chemical chain. The specific focus of this contribution is on the catalytic
production chain. Such approach also preserves the actual 25 aspects of CO2 conversion with RE, since catalysis is the
infrastructure and thus limits the massive costs related to a enabling technology to achieve the efficient chemical conversion
change in the process and raw materials often necessary when

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of CO2. The goal is to outline the state of the art and define the DME, methane, formic acid, short-chain olefins, etc.) can be
needs and possible roadmap for catalysis to enable the chemical produced from CO2 and H2. When hydrogen is originated directly
recycles of CO2 as a key component towards substantially 60 from renewable energy, r-H2, hydrogen becomes the key for
increasing the RE vs fossil fuel usage. connecting renewable energy and basic chemicals production, i.e.
5 We focus the discussion on the abiological pathways of CO2 novel 2-step routes for RE injection in the chemical industry
conversion incorporating RE in the final molecule. Attention is (RE r-H2  chemical), in complement of the 3-step RE-to-
especially dedicated to base chemicals, because they are large chemical strategy outlined in the introduction (RE  electricity
volume products and thus with a higher effective (fossil) fuel  r-H2  chemical), based on hydrogen production through RE

Energy & Environmental Science Accepted Manuscript


65

consumption. We will hence not discuss the use of CO2 in fine electrolyzers and PEM cells,34 or solid-state high-temperature
10 chemical production, because in general they do not incorporate electrolyzers.35,36 Recent reviews have examined approaches to
RE, or when this happens it is through the intermediate formation produce r-H2 by other approaches than electrolysis: i) producing
of chemicals such as methanol, which is discussed as base H2 through the use of cyanobacteria37 and other bacteria38 (bio-
chemical. In addition, fine chemical production is rather limited 70 H2), ii) use of photocatalysis,39,40 iii) H2 from biomass41 and
microbial electrolysis,42 iv) use of wind power43 for H2
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

in term of volume of products, and will thus have a minor impact


15 in terms of introduction of RE. We still distinguish between the production, and v) of solar energy (low and high temperatures
production of fuels (also often indicated as solar fuels), 20,29-31 approaches).44 All these routes are attractive and under active
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which can be used in the chemical industry for the production of research. The maturity of r-H2 production routes, their respective
the heat necessary in the processes and the production of base 75 GHC impact and their costs therefore all become relevant in the
raw materials for the chemical production chain (such as short- context of assessing RE injection in the energy or in the
20 chain olefins). Methanol is classified in the 1st class, although it is production chains through CO2 recycling. A brief overview of
also a raw material widely used in the chemical industry, and is a these aspects will therefore be included hereafter.
possible intermediate to produce olefins, as discussed later. Given
GHG impact of H2 production routes from RE
the originality of using CO2 for synthesis of intermediates (such
as short-chain olefins) this part will be discussed in more details. 80 A sustainable route for the introduction of RE through reduction
25 An overview of the different possibilities and routes is presented of CO2 requires that the whole process is sustainable also in terms
in Figure 1a, while Figure 1b reports a more detailed view of the of GHG emission impact.45 r-H2 may be produced from biomass-
different possible routes to synthetize short-chain olefins (as raw derived products through different methods,46 either via aqueous
material to incorporate RE in the chemical production chain) phase catalytic reforming47 or through thermocatalytic
from CO2 and renewable H2. 85 methods,48,49 but due to both the impact of biomass cultivation on
30 Finally, since the main gap in the catalytic routes of CO2 GHG emissions and the significant energy consumption in the
conversion is still economic, with the cost of production of harvesting, transport and processing biomass, the net impact on
renewable H2 as the key factor for the rapid short-term 3-step GHG emission per mole of H2 is significant, although lower than
routes, we start discussion with an analysis of cost and from fossil fuels. Methane steam reforming is the main current
perspectives in producing renewable H2. 90 commercial method to produce H2.50 Four moles of H2 are
35 The origin of CO2 (and purity, as well as how to recover in a produced per mole of CO2, i.e. 5.5 kg CO2 per kg H2, but
cost-efficient way) is certain a critical aspect of the possible considering the life-cycle of production this value rises to about
large-volume use of CO2, because determines costs and type of 8.9 kg CO2/kg H2.51 We feel more appropriate to only consider
technologies to be used. However, we believe that this will be a hydrogen producing methods using directly RE sources. Fully
later issue, when the use of CO2 will be above some significant 95 reliable estimations do not exist or are highly depending on the
40 threshold, because there are many large-volume sources of rather specific case. On the average, the estimated values is about 5-6
pure CO2 in refinery and chemical processes (ammonia kg CO2/kg H2.52,53 For the production of H2 using direct RE
production, ethylene oxide production, gas processing, H2 sources, the current most consolidated methodology is to produce
production, liquefied natural gas, Fischer-Tropsch -synthesis electrical energy using photovoltaic panels, wind turbines or
coal)32 as well as from biorefineries (ethanol production).33 At 100 other similar options (geothermy, waves, etc.), and then use an
45 least in an initial phase of these technologies for the introduction electrolyzer. LCA data are not reliable, because all technologies
of RE in the value chain of chemical industries it is not necessary are still at the stage of development. For wind/electrolysis, a
to recover CO2 from the flue gases of combustion processes, with value below 1 kg CO2/kg H2 was estimated.54 Utgikar and
the related problems of purification from contaminants. Thiesen55 reported life-cycle CO2 emissions for various hydrogen
We will also not discussed here the problem of CO2 activation, 105 production methods and indicated values for H2 from
50 because this aspect is relevant in the production of fine hydroelectric/electrolysis or solar thermal around 2 kg CO2/kg
chemicals, and particularly in relation to improving mechanisms H2. Higher values (around 6 CO2/kg H2) were reported for the
of homogeneous catalysts, but it is not typically an issue in most photovoltaic (PV)/electrolysis combination, but this estimation
established heterogeneous catalysis processes discussed in this was based on an old PV technology. Taking into consideration
contribution for large-scale introduction of RE in the chemical 110 the fast progresses in the field, a more reasonable estimate is 1-2
55 production chain. kg CO2/kg H2.
Therefore, although the lack of detailed comparisons and
H2 production using renewable energy analyses do not allow to make conclusive estimations, it may be
indicated that direct routes of producing r-H2 have an impact on
As outlined in Figure 1a, various products (syngas, methanol and 115 CO2 emissions tallying to about one third of that of producing r-

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H2 from biomass conversion routes and about one fifth that of in the electrolyte and lower polarisation losses from the electrode
current methods to produce H2. Since this step of producing r-H2 60 reactions, being the kinetics of the electrolysis reactions faster. H2
is the most relevant in terms of energy accounting for the entire costs from high-temperature electrolysis have been estimated in
process of conversion of CO2 to chemicals by hydrogenation, it is the 1.5-2.6$/kg H2 range,57 although it appear an optimistic
5 evident that direct methodologies using RE to produce H2 are estimation.
preferable to those relying on the use of biomass in order to
Economic perspective of CO2 conversion processes with r-H2
introduce RE in the chemical production chain.
65 H2 production from renewable sources may be estimated to have

Energy & Environmental Science Accepted Manuscript


Cost of production of r-H2
a cost in the 2-10 US$/kg H2 range. H2 using PEM electrolyzers
The economic perspectives of converting CO2 are largely can be already produced on a small-medium scale. There are
10 depending on the cost of producing r-H2. We limit discussion relevant possibilities for a further decrease in the cost,
here to the production of electrical energy using RE sources, and particularly in terms of optimization of the electrocatalysts (the
the production of H2 using these energy sources, that is the 3-step 70 key issue), electrodes and device configuration. H2 production
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strategy, which are the most mature currently. Cost is clearly the from biomass transformation products (bio-oil, byproducts, etc.)
critical factor to enable the possibility to use RE to produce H2. is also falling in the same range, but as discussed before, the
The production of H2 by electrolysis with the electrical energy impact on GHG emissions is significantly higher. BioH2 using
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15

deriving from photovoltaic (PV) cells, wind turbines etc., may be cyanobacteria or green algae, and photo(electro)chemical water
considered as an established technology, even if further 75 splitting or photoelectrolysis have a larger potential for the future
improvements are possible. Efficiencies up to about 12% could large-scale production of renewable H2 at competitive costs, but
be obtained on optimized PV-electrolysis system.56 Modern intense R&D effort is necessary to realize this potential.
20 electrolyzers produce H2 under pressure, differently from other Available (low-cost) sources of r-H2 already exist which make
routes, and this is a relevant cost-advantage. PEM water some production of fuels from CO2 already viable. Mitsui
electrolysis technology is considered today the safer and 80 Chemicals and Carbon Recycling International are two
preferable way to produce renewable H2. Stack efficiencies close companies which are running pilot plant projects to exploit the
to 80% have been obtained operating at high (1 A·cm-2) current conversion of CO2 to methanol (see above), while Mantra
25 densities using low-cost electrodes and high operating pressures Venture Group and DNV are exploring at pilot plant scale the
(up to 130 bar).34 The absence of corrosive electrolytes, and the electroreduction of CO2 to formic acid.4 A recent techno-
better integration with solar and wind power can be cited mong 85 economic assessment58 has evidenced that it is possible to
the advantages of PEM electrolyzers over the well-established produce methanol from CO2 at a competitive cost with respect to
alkaline technology. Recent developments in terms of catalyst the market (about 300-350 €/ton) when the cost of H2 production
30 optimization, optimized design of electrolyzer cell and cost by electrolysis is as low as 0.140 € per Nm3H2, a value possible
reduction of the membrane-electrode assembling have already by producing electrical energy using hydropower in some remote
lead to a significant stack capital cost reductions. Reduction of 90 areas. CO2 may be shipped to these areas, and methanol can be
the overpotential in H2 production remains a still relevant send back using the same ships, realizing thus an interesting and
problem to solve, but this will require a better understanding of economic alternative to CCS.
35 the fundamental aspects of the reaction mechanism.
A hydrogen cost ranging from 2 to 4 $/kg H2 was considered CO2 as raw material to introduce renewable
competitive by DoE (US Department of Energy) for distributed energy in the chemical production chain
water electrolysis, although this cost does not take into account
the carbon taxes for producing H2 using fossil fuels present in 95 Syngas and short-chain olefins (C2-C3), together with aromatics,
40 some countries (Europe). Considering the incidence of electricity are the main raw materials for petrochemistry and thus of the
on H2 production cost and that off-peak electrical energy at entire value chain of chemical industry.22 As remarked in the
competitive costs is available, it is possible to estimate a future introduction, the objective of resource and energy efficiency in
renewable H2 at around 8-10$/kg H2 decreasing to 5-6$/kg H2 in chemical industry2-3 or a low-carbon footprint production, is not
year 2020 and possibly below.29 Currently, as discussed in the 100 only a defined political objective in Europe which agreed to reach
45 previous section, methanol can be produced commercially from an 80% reduction in CO2 emissions by year 2050,59 but also a key
CO2 using H2 deriving from the use of geothermal electrical element for the innovation strategy of the chemical industry.3 To
energy in Iceland, with an estimated H2 cost in the 2 to 4 $/kg H2 meet this objective, the use of CO2 together with biomass (and
range. waste) is necessary. We will discuss here the production of
Together with the improvements in technology of production 105 syngas and short-chain olefins from CO2 using RE sources,
50 of RE and of electrolyzers, it is likely to produce H2 at a cost mainly used to produce r-H2. Today this is the only feasible
below about 4-5 $/kg H2 in a near future. Using a combination of solution, but alternatives will be possible in future. The other
solid oxide electrolysis cells (SOEC) and thermal solar products indicated in Figure 1a (CH4, HCOOH, hydrocarbons,
technologies it is also possible to produce renewable H2 at etc.) are not suited as raw materials for the chemical production
competitive costs. For low temperature electrolysis a larger 110 chain: methane, for its difficult activation, HCOOH, being
55 quantity of electrical energy is necessary to overcome the limited the type of products which can be obtained, etc.
endothermic heat of reaction, while at high temperatures the Production of syngas using renewable energy (RE)
primary electric energy demand is considerably reduced and the
There are different possible routes to syngas (Figure 1a), the main
electrical losses in the cell decrease due to lower ohmic resistance

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two involving (i) RWGS reaction (using r-H2; eq. 1), and (ii) dry while then a graphitization process occurs with formation of
reforming with hydrocarbons (DR, eq. 2 for reaction with carbon nanotubes. The support and doping, for example with
methane). Other possibilities, include bioroute (for example, 60 gold, inhibits this graphitization process.
using (1) a hybrid enzyme-TiO2 system for CO2 reduction to CO
CO2 + H2O  CO + 3 H2 (5)
5 using visible light)60, (2) concentred (high-temperature) solar
CH4 + ½ O2  CO + 2 H2 (6a)
energy,21 (3) photo- and electro-catalytic reduction of CO2.61-63
CH4 + 2 O2  CO2 + 2 H2O (6b)
However, these routes are still far in terms of performances for
possible large-scale applications. In terms of introduction of RE energy in the chemical process

Energy & Environmental Science Accepted Manuscript


65 chain, the net energy balance of using methane oxidation
CO2 + r-H2  CO + H2O (1)
reactions (eq.s 6) to produce the energy necessary for the
10 CO2 + CH4  2 CO + 2 H2 (2)
endothermic reactions of dry (eq. 2) and wet (eq. 5) reforming is
CO2 reforming not favourable. Conversely, when the heat of reaction for the
endothermic process is provided from thermal solar radiation
The potential advantage of DR route is that it can be applied
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70 (Concentrated Solar Power, CSP), DR is preferable to tri-


directly to flue gases11 (even if technical problems exist), while
reforming for higher productivity.74 Halmann and Steinfeld66
all the other routes require a first step of separation of CO2 from
estimated that combining tri-reforming with the use CaO (to
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15 the flue gases. However, DR is an endothermic reaction occurring


adsorb and transfer CO2 from the flue gas) CO2 emission
at high temperature (about 900-1000°C) and in equilibrium with
avoidance of up to ∼59% and fossil fuel savings of up to ∼75%
side reactions of methane cracking (eq. 3) and the Boudouard
75 may be attained when concentred solar energy is supplied as
reaction (CO disproportionation, eq. 4).
high-temperature process heat for the calcination step, all relative
CH4  C + 2 H2 (3)
to conventional H2 production by coal gasification.
20 2 CO  C + CO2 (4)
These estimations do not consider the major issue of scaling-
Eq. 3 and Eq. 4 both lead to carbon formation and are hence
up a catalytic reaction coupled to CSP: i) large fluctuations in
responsible for coke formation, which causes catalyst
80 temperature with inhomogeneous distribution of the temperature,
deactivation, reactor pressure build up and decrease of heat
related to the difficulty of irradiating in an homogeneous way (in
transfer. A second challenge of the DR approach is due to the
space and time) the whole catalyst, ii) continuous severe cycling
25 current high temperature of operation involved, due to the
in temperature leading to easy sintering and catalyst deactivation,
unfavourable thermodynamic (G>0 Kcal/mol) at temperatures
iii) large area of CSP panels required per catalyst volume to heat
below 600°C and the related mediocre overall efficiency of the
85 to the necessary temperature to drive the reforming reaction.
processes. Achieving systems capable of operating at lower
The International Energy Agency75 in its roadmap on CSP
temperature – and hence with lower energy consumption – could
concluded that today this technology is not competitive and
30 also allow heat integration with the highly exothermic FT
requires high capital investments, but may become attractive in
reaction, typically operating at much lower temperature.
the future is some areas to generate electricity. CSP also allows
Therefore a current research direction is to develop low-
90 the production of hydrogen with a future costs (for year 2025)
temperature dry reforming technologies for the recycling of waste
competitive with the combination of photovoltaic + electrolysis,
carbon (CO2 and CH4 in the FT tailgas) to be integrated into FT
even though estimations appear optimistic. Solar-assisted steam
35 fuel production plants. Given the unfavourable thermodynamics,
or wet reforming of natural gas would become competitive with
the required catalytic development has to be coupled to further
natural gas (as an energy source) at prices of about US$11/MBtu
technology development such as membrane reactors for
95 and thus with limited possibilities to be implemented.
continuous H2 removal to achieve higher conversions.64,65 The
A better application with respect to the use in producing
cost of membranes, their limited range of pressure and thermal
syngas by conversion of CO2 in flue gases through tri-reforming
40 stability (typically about 550°C) are some of the current
of methane (eventually assisted by CSP) would be the application
challenges of membrane technology in this context.
of this concept to the production of syngas from biogases
A different approach to limit the external energy consumption
100 (produced by the anaerobic digestion of biomass), which already
necessary to power the DR reaction can be the combination with
contain methane and CO2. Fierro and coworkers76 reviewed
the wet reforming of methane (with H2O, eq. 5) and its oxidation
recently the dry reforming of biogas showing, in particular, how
45 (eq 6), leading overall to the so-called tri-reforming.11,66,67 It was
Ni-based catalysts (the most used reforming catalysts) are prone
shown by Minutillo and Perna68 that the tri-reforming process
to carbon deposition and how their stability can be improved by
utilizing flue gases to generate a synthesis gas suitable in
105 incorporation of a second metal, for example trace of noble
chemical industries for production of chemicals (methanol, in
metals.77 It was shown recently, however, that for the effective
particular) is an attractive solution to introduce near zero-
utilization of biogas (in terms of carbon present in the final
50 emission technologies in vehicular applications. An integrated tri-
syngas mixture) DR is even slightly worse with respect to the
reforming power plant for co-generation of electrical power and
alternative of removing CO2 from the biogas, and then use
synthesis gas shows advantages in terms of energy and
110 methane for steam reforming or partial oxidation reactions.33
environmental sustainability, but only when the exhausts contain
Both these works have not considered the integration of CSP in
low oxygen concentrations (i.e. flue gases from steam cycle
the biogas reforming process which can be well integrated with
55 power plant). Doped metal catalysts supported on rare-earths
CSP technology given their usual small scale. Although solar-
have helped develop high resistance to carbon formation.69-72
heated fermenters for biogas production is an established
Guczi et al.73 showed that carbide-type species are first formed,

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increased productivity. Further decrease of CO2 concentration in


syngas can also reduce the rate, showing a complex mechanistic
profile, since CO2 can also be formed by steam addition to syngas
45 stream. Water, in fact, can be an inhibitor. A partial solution
resides in continuous water removal through distillation or
membranes, such as hydrophilic nano-pore zeolites (NaA).89 In
the CAMERE process for CO2 hydrogenation to methanol via a
RWGS reaction90 it was shown that the two-step process (with

Energy & Environmental Science Accepted Manuscript


50 intermediate water removal) allows a three times higher
productivity than the single-stage process, due to the removal of
the inhibition by water and the shift of the equilibrium.
Fig. 2 Simplified process flow diagram for the RWGS reactor and The alternative solution is the design of new type of catalysts,
methanol synthesis system. specific for methanol synthesis from CO2, not sensitive to water
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

55 inhibition and possibly involving a different type of mechanism


technology,78 the use of solar energy to drive the production of not passing through the first stage of RWGS reaction, e.g. syngas
syngas from biogas has been not analysed in terms of techno- formation. For this reason, there is an increased interest on the
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economic and environmental feasibility. There are, however, reaction mechanism of this (old) reaction.91-94 In parallel to these
various recent technical papers on the development of catalysts mechanistic studies, other recent advances regard the nature of
5 for biogas reforming.79-82 60 the active sites and the in situ dynamic behavior of the catalyst.
RWGS Worth to note are the results of Schlögl et al. 95 showing the
presence of lattice strain in the copper particles as the result of an
The catalysts active in methanol synthesis or FT reaction are advanced Cu-ZnO interface. Complementarily, a highly defect
active also in RWGS.83,84 Therefore this step is integrated in these rich nature of both Cu and ZnO has been found in the short-range
processes and will be discussed in the related sections, although 65 order structure. The twinning, fault defects, and strain in the Cu
10 in terms of process, it may be preferable to separate the reactors lattice were related to increased activity in methanol synthesis via
of RWGS from those of methanol synthesis, or FT reaction. In WGS reaction of CO, CO2, and H. Lattice strain in the copper
fact, the water formed in RWGS (eq. 1) decreases the reaction nanoparticles were an index for a homogeneous microstructure of
rates of these reactions and it is thus convenient to have a process superior Cu/ZnO/Al2O3 catalyst for methanol synthesis.
scheme based on two staged reactors with an intermediate water 70 These studies give a new perspective to the issue of the direct
15 separation stage (Figure 2, for methanol synthesis). Short-chain methanol synthesis from CO2, but still very limited novel and
olefins can be then produced from methanol in a separate stage, conceptually different catalytic systems have been developed. A
as discussed below in alternative to the direct synthesis from recent DFT study on methanol synthesis from H2 and CO2 on a
syngas using modified FT process. Methanol is also feedstock for Mo6S8 cluster (the structural building block of the Chevrel phase
various chemicals such as formaldehyde and acetic acid, and 75 of molybdenum sulfide) suggests that alternative materials could
20 from there into products as diverse as plastics, plywood, paints, be developed.96 Pd-ZnO on carbon nanotube can be also
explosives, and permanent press textiles. considered as a new type of catalyst.97 The peculiarity of carbon
Conversion of CO2 to methanol nanotube is the ability to reversibly adsorb a greater amount of
hydrogen.
The possible pivotal role of methanol and dimethyl ether (DME) 80 An alternative approach to the use of solid catalysts and a gas
in the energy scenario has been extensively discussed under the phase process is the use of the so-called low-temperature
25 “methanol economy” concept.15 Methanol synthesis from syngas methanol synthesis (LTMS).98,99 LTMS is based on the catalytic
is a well-known commercial process occurring on Cu-Zn-oxide hydrogenation of methanol to HCOOH with subsequent
based catalysts.85 The same catalysts may be applied also starting etherification to methanol formate (alternative to methyl formate
from CO2.83,86 The traditional approach consists in a two-catalyst 85 from syngas) and the subsequent hydrogenation of formate to two
systems such as Cu/oxides to catalyze the RWGS (eq. 1) methanol molecules using pincer-type ruthenium(II) catalyst.99-102
30 followed by a CO reduction to methanol catalyst (eq. 7) These homogeneous catalysts are able to hydrogenate efficiently
CO + 2 r-H2  CH3OH (7) organic carbonates, carbamates and formates in mild conditions,
offering thus new routes to produce methanol by hydrogenation
A typical catalytic system is Cu/ZnO/Al2O3, possibly with 90 of these compounds which can be produced from CO2 and CO.
additives such as ZrO2, Ga2O3, SiO2.87,88 A multicomponent Huff and Sanfort101 have demonstrate recently the homogeneous
system such as Cu/ZnO/ZrO2/Al2O3/SiO2 displays high hydrogenation of CO2 to CH3OH via cascade catalysis using
35 productivity (600 gCH3OH/lcat∙h at 250°C) and stability. three different homogeneous catalysts: (PMe3)4Ru(Cl)(OAc),
Nevertheless, the complex equilibria involving CO, CO2, H2O, Sc(OTf)3, and (PNN)Ru(CO)(H), which operate in sequence to
CH3OH make catalysts comparison difficult, since the 95 promote this transformation (Figure 3). Hydrogen should be
performances are critically dependent on feed composition. This produced using RE sources also in this case.
said, Ga2O3 appears to favor specific activity, while alumina,
40 zirconia or silica appear to improve Cu dispersion.83 While direct
H2:CO2=3:1 is a slow reaction, higher CO/CO2 ratio leads to

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worldwide in an amount of about 200 Mt·y-1 and their synthesis


is the single most energy-consuming process in the chemical
20 industry.105 They can be produced from different sources, the
main process being the steam cracking of oil or of natural gas
fractions. Steam cracking accounts for about 3·1018 J of primary
energy use, not counting the energy content of the products. 106
Due to their high energy of formation, C2-C3 olefins represent an
excellent opportunity to store solar energy and incorporate it in

Energy & Environmental Science Accepted Manuscript


25

the value chain for chemical production.107


There are different possible routes to produce short-chain
Fig. 3 Cascade reactions in the catalytic hydrogenation of CO2 to CH3OH olefins from CO2 and renewable H2 (Figure 1b). The reverse
in a homogeneous phase via three different catalysts. (Adapted from Huff water gas shift (RWGS) is typically present, being often
and Sanford.101)
30 promoted from the same catalysts for the consecutive steps.
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

These atom-efficient reactions proceed under neutral, However, it would be preferable to develop direct routes
homogeneous conditions, at mild temperatures and under mild converting CO2 (e.g. not involving the RWGS reversible
reaction), to overcome thermodynamic constrains related to
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hydrogen pressures, and can operate in the absence of solvent


with no generation of waste, representing the ultimate green' RWGS equilibrium reaction. Short-chain olefins could be directly
5 reactions. However, from the practical perspective, the effective 35 produced from syngas (CO + H2) using modified Fischer–
catalyst productivities per unit volume of reactor are still too far Tropsch (FT) catalysts or indirectly, via the formation of
from those which can be obtained using the conventional gas- methanol (using conventional commercial methanol catalysts)
phase methanol catalysts. Catalyst recovery and product and then converting methanol to short-chain olefins using the
separation are also more costly making the process for the methanol-to-olefin (MTO) process based on small-pore zeolites.
10 synthesis of methanol from either CO or CO2 still un-economic. 40 In the presence of an acid catalyst, two methanol molecules could
Interestingly, copper-zinc-oxide catalysts active in the gas-phase be dehydrated to dimethylether (DME), which can be also
conversion of syngas to methanol are also active in liquid phase converted to short-chain olefins (it is an intermediate in the
methyl formate synthesis.95,96 Ma and coworkers10b have recently process).
discussed in more detail these aspects in a review on the catalytic It is also possible to combine the catalysts for methanol to the
15 hydrogenation of carbon dioxide. 45 zeolite for MTO to have the direct one-step formation of short-
chain olefins from CO2 and H2. Up to now, all catalysts tested are
Conversion of CO2 to short-chain olefins
based on catalysts for syngas (CO/H2) adapted to operate with
Short-chain olefins (ethylene and propylene) are produced CO2 and H2, but not specifically developed to work with carbon

Table 1 Selection of relevant recent results in syngas to light olefins FT conversion.

Optimal reaction conditions CO Selectivity, % Yield, % C2-C4


Catalyst H2/ Temp., GHSV, P, con C2-C4 C2-C4 Alkene/ Ref.
CH4 C2H4 C3H6 C4H8
CO °C h-1 atm v, % olefin olefin alkane
Co40Zn6/TiO2 2 240 1100 1 65,2 9,3 46,5 30,3 2,7 120a
nanosized Co3Fe1-K2% 2 260 2200 1 63,8 10,2 54,4 18,6 16 19,8 34,7 3,2 120b
(1)
Fe20/SiO2 2 380 1 41 22,6 20,2 5,2 12 3 8,3 1,7 122
Core (Fe/SiO2)- (1)
2 380 1 21,2 20,6 30 11,8 14,9 3,3 6,4 1,5 122
Shell (Silicalite-1)
Fe50Mn50 -K6% 2 280 1400 3 64,4 6,1 48,9 21,1 14,1 13,7 31,5 2,6 120c
Fe/SBA-15 (reduc. H2) 2 430 1176 1 20,1 18,4 16,9 3,4 123
Fe40Ni60 (6%)/Al2O3 2 260 2600 3 64,1 20,2 40,1 19,2 15,3 5,6 25,7 1,9 120e
Fe40Ni60 (40%)/Al2O3 2 360 3600 7 78 14,1 73,9 37,8 19,6 16,5 57,6 14,2 120d
Fe–Cu–K/ZSM-5 (Si/Al = (2)
2 300 1 80,7 18,3 24,9 20,1 124
25)
Fe/CNT 1 300 21800 0,5 11,2 17,9 41,6 4,7 7,1 125
Fe/carbon black 1 300 21800 0,5 8,8 21 38,1 3,4 5,6 125
Fe/SBA-15 (reduc. H2) 1 300 21800 0,5 2,3 25,5 39,5 0,9 4,3 125
Fe/SiO2 1 300 21800 0,5 4 25,8 38,1 1,5 6,4 125
Fe–Cu–Al + ZSM-5
2 300 (4) 3600 10 96,9 8,7 34,4 5,4 19,1 9,9 33,3 3,7 126
(dual bed)(3)
Fe50Mn50 (5 %)/Al2O3 1 360 2700 6 84 19,8 59,2 40,1 13,2 5,9 49,7 127
300-
Mn-Co/H-5A zeolite 4 1 40,9 0,2 85,8 35,1 128
400
(1) -1 (2) -1
28 g mol h 2000 ml/gcat h .
(3)
1st bed FT catalyst, 2nd bed selective cracking of long chain hydrocarbon. FT = 6K/100Fe–6Cu–16AlOx; cracking = ZSM-5 (SiO2/Al2O3 = 280)
(4)
cracking at 500°C with 0.15g catalyst

8 | Energy Environ. Sci., [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
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dioxide. It would be desirable, for example, to have a novel FT hydrocarbons is apparently not possible. It is thus necessary to
catalyst able to directly and selectively convert CO2 and H2 to limit the chain growth or circumvent the propagation reaction.
short-chain olefins, or novel methanol catalysts able to directly Overall, yields up to over 55% in C2-C4 olefins have been
convert CO2 without the presence of RWGS reaction. Therefore, 45 observed, but together with C2-C4 alkanes, methane and C5+
5 even if the methanol, MTO and FT catalysts are well-established, products (Table 1).120-128 These conditions are still not
and current methanol and FT processes operate in the presence of satisfactory to produce olefins for the chemical sector. A further
some CO2 (typically around 3%) which promotes the reaction significant improvement using the same approach is unlikely.
rate, converting pure CO2 would require to develop novel or Therefore, either a step forward in the understanding the reaction

Energy & Environmental Science Accepted Manuscript


improved catalysts. Maximize selectivity to short-chain olefins, 50 mechanism to determine how to control more effectively the
10 and possibly also their relative ratio of formation (currently it is chain growth, or exploration of new pathways to convert syngas
preferable to form propylene over ethylene) is another challenge. to olefins is necessary.
The conversion of syngas to short-chain olefins was reviewed
Catalysts for olefins synthesis from CO2 through a FT-type
recently.108 While the earlier reviews on this topic date back to
reaction
1987109 and 1990,110 there still is significant industrial interest
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15 currently ongoing,111 mostly driven by the goal of producing 55 Starting from CO2 + H2 to produce short-chain olefins instead
high-octane gasoline components (by oligomerization/ than from syngas, would require the presence of a bifunctional
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isomerization of short-chain olefins from FT), in contrast with the catalyst that combines reverse water-gas-shift (RWGS) and
middle distillate (diesel) produced with the conventional process, Fischer–Tropsch chain growth activity.129 U.S. military are
as seen for example in the Synthol process by SASOL in South actively investigating this direction of research to produce jet
20 Africa. Produce short-chain olefins for the petrochemical market 60 fuel.130 Dorner et al.129a showed that using a Fe/Mn/K FT
has even more strict requirements with respect to the use as catalysts deposited over a Ce-modified alumina it is possible to
feedstock to produce gasoline components. The FT catalyst obtain in one-step about 62% selectivity to C2-C5+ hydrocarbons
should be modified in order to minimize the formation of alkanes (olefin/paraffin ratio of 4.4) at about 50% CO2 conversion
(especially CH4), and increase selectivity to C2-C3 olefins. (290°C, H2:CO2 ratio of 3:1, 13 atm). Yields in short-chain
25 Some of the underpinning fundamental open issues regarding 65 olefins are thus still low in comparison with the best data for
the selectivity to short-chain olefins through FT are still not short-chain olefins from syngas reported in Table 1 as well as in
solved, although progresses in mechanism proposals and earlier reviews.109,110,131 There is thus ample space to improve the
understanding112-115, structure-activity relationship related to, for performances. Also in this case a better understanding of the
example Fe or Co catalysts nanoparticle size,116-118 and reactor surface chemistry is necessary.
30 design considerations119,120 are being addressed. A better 70 There are two main differences between the use of a CO2+H2
understanding of the overall mechanistic aspects would be feed and a syngas feed, besides the need of centers for RWGS or
relevant to control the chain growth and maximize the selectivity sites able to directly dissociate CO2 to form "C1" type species as
to short-chain olefins, even if all the actual studies have not those involved in the FT mechanism.
attempted to identify the catalyst designing factors to maximize Sai Prasad et al.132 used a Fe/Cu/Al/K catalyst at 300°C and
35 the selectivity to short-chain olefins. Due to the presence of many 75 one atmosphere to convert a CO/CO2/H2 syngas. About 85%
competing reactions, there is no linear dependence between any selectivity to alkene in the C2-C4 fraction (about 40% of the
single parameter and the observed catalytic performances. For FT whole hydrocarbon fraction) was observed. Zhao et al.133 studied
reaction there is thus an intermediate optimal window, which the kinetics of short-chain alkene syntheses by CO2
depends on the fraction desired, as shown in Figure 4. Based on hydrogenation over Fe-Ni catalysts, observing that the presence
40 this distribution, a selective synthesis of short-chain olefins (C2- 80 of CO2 in the feed stream has a negative effect on catalyst
C4) without the significant formation of methane and >C4 stability and on the formation of heavy hydrocarbons. The data
cannot be extrapolated to the case of the conversion of CO2 to
short-chain olefins and used to optimize this reaction. Specific
studies on these aspects are necessary to consider feasible this
85 reaction pathway.

Catalysts for olefins synthesis from CO2 through alternative paths


Short-chain olefins may be obtained also via conversion of
methanol/DME on multifunctional catalysts instead that through
the FT mechanism. Introducing Rh centers in the zeolite leads to
90 the selective synthesis of lower olefins, particularly ethylene.134
Ethanol forms through both the DME isomerization and methanol
homologation catalyzed by Rh and then ethanol easily dehydrated
(on controlled acidity zeolites) to ethylene. This is an interesting
pathway potentially avoiding the problems of selectivity
95 discussed in FT mechanism. Since this pathway can use MeOH
Fig. 4 Schematics of the changes in the reaction rates of key reaction
or DME obtained from CO2, it is tantamount to a CO2  olefins
steps as a function of Metal–Carbon interaction energies. (Adapted from
ref.112). conversion route avoiding FT mechanism.

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performances of the process and concomitant recycling CH4,


short-chain alkanes, >C5 hydrocarbons produced, while CO and
45 CO2 are recycled to the rWGS unit. A techno-economic analysis
of this possibility107 indicates that for a predicted renewable H2
cost as target for the year 2020 (2-3 US$/kg H2), the process is
economically viable. Current r-H2 cost is still higher, but
nevertheless in a range that makes the possibility to produce
short-chain olefins from CO2 as an interesting one.

Energy & Environmental Science Accepted Manuscript


50

Comparison of the routes and outlooks


The production of short-chain olefins from CO2+H2 via syngas
and then modified FT catalysts is potentially simpler, but gives
Fig. 5 Performances of UOP/Hydro MTO process and their integration rise to a broader distribution of olefins which is appearing
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

with Total/UOP olefin cracking (OC) unit using two types of zeolites, the 55 challenging to further improve. The route passing through
second tailored to enhance propylene formation. (Adapted from ref. 136). methanol (DME) and MTO/MTP processes is more complex, but
it is based on already established catalysts/ processes, whose
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Methanol-to-olefin (MTO) or the variation methanol-to-


economics are interesting for very large scale plants. The use of
propylene (MTP) are also known processes, since the first
CO2+H2 instead of syngas causes lower rates and selectivities in
discovery of methanol-to-hydrocarbon reactions in the early
60 both cases. It would be thus necessary to develop novel and more
1970s using ZSM-5 (MFI) catalysts and the significant step
specific catalysts containing selective sites for short-chain olefins
5 forward in the 1980s by the scientists at Union Carbide that
directly by hydrogenation of CO2. An interesting route, still
discovered narrow-pore zeo-type material SAPO-34 showing
largely not explored, involves the possibility to have a mixed
excellent behavior for the conversion of methanol to ethylene and
mechanism between that present in methanol synthesis137 leading
propylene.135 The process was developed commercially by
65 to the formation of formate (HCOO) surface species from
UOP/Norsk Hydro. The advanced MTO process integrates an
chemisorbed CO2 and H, and that for FT reaction previously
10 Olefin Cracking Process (Total/UOP) to increase the carbon
discussed, with a key step of C-C bond formation between the
selectivity from methanol to C2-C3 olefins to about 85–90%.
surface formate and "C1" type species deriving from CO
With the integrated process, C4 to C6+ olefins generated as by-
dissociation. A similar mechanism was proposed originally from
products from the MTO unit can be fed to the olefin cracking
70 Izumi138 to explain the selective synthesis of ethanol from CO2 +
(OC) unit to convert them to the C2-C3 olefins. The combined
H2 on [Rh10Se]/TiO2 catalysts. Rh/SiO2 and Rh-Fe/SiO2 are
15 process has great flexibility to adapt the propylene/ethylene
active in the hydrogenation of CO2 to ethanol, although
ratios. Nearly an 80% reduction in C4+ by-product formation and
selectivities to ethanol are 30% at the best. In CO2 hydrogenation
a 20% increase in short-chain olefin yield can be achieved (Figure
over supported [Rh10Se] clusters, selectivity up to over 80% was
5).136
75 observed, even if the conversion was not given. The ethanol may
Methanol-to-propylene (MTP) process developed by Lurgi
be then easily dehydrated to selectively form ethylene.
20 was recently put into commercial operation for the first time at
Although further improvements in catalysts, reactor design and
two facilities in China. It is based on the use of a ZSM-5 based
process operations are necessary, these results show that it should
zeolite catalyst able to give about 70% yield (97% selectivity) at
be possible to modify FT or methanol catalysts to selectively
about 425°C and nearly atmospheric pressure. Gasoline-range
80 form short-chain olefins, or even develop new type of catalysts
byproducts are recycled. Periodic regeneration after about 20-25
based on a novel reaction It is reasonable to consider a further
25 days operations is necessary.
optimization with a target in selective synthesis of short-chain
The conversion of CO2 to short-chain olefins via methanol
olefins over 80% at higher productivity.
(DME) formation therefore has the advantages over the modified
FT route of i) being at least partly already commercially
established and ii) giving rise to a more tuned and narrow Solar fuels from CO2: a complementary route to
30 distribution of short-chain olefins. However, several further 85 introduce renewable energy in the chemical
improvement steps are necessary, with a consequent increase in production chain
the costs. Results on the development of multifunctional catalysts Chemical industry is energy intensive, but as discussed in the
able to combine the characteristics necessary for the various steps introduction, the use of electrical energy from RE sources is not
are still limited and not very successful up to now. the optimal approach to lower the carbon footprint. On the
35 Techno-economic assessment 90 contrary, the use of fuels which incorporate RE sources (here
briefly indicated as solar fuels from CO2) is a complementary
Regarding the assessment of the production of short-chain olefins valuable approach to the use of low carbon footprint raw
from CO2, the process flow-sheet is based on a first step of materials. However, fuels have a lower added-value with respect
production of H2 by electrolysis, either using PEM electrolyzers to raw materials for petrochemistry, and thus is even more critical
or high-temperature SOEC, and electrical energy deriving from 95 the cost-competiveness with fossil fuels. With the progressive
40 RE.107 The core of the process is the combination of RWGS and shortage of fossil fuels (the great impact on the environment of
modified FT reactions with inorganic membranes permeo- shale gas and coal production puts a great question mark on their
selective to water integrated in the reactors to improve the long-term use), we expect that the cost differential between fossil

10 | Energy Environ. Sci., [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
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and solar fuels will decrease. Thus, solar fuels from CO2 will fuels, lubrificants and chemicals (in addition to short-chain
become progressively cost-competitive in a medium-long term 55 olefins discussed in the previous section), depending on catalyst,
perspective, but it is expected that raw materials deriving from operative conditions and downstream processes. In terms of use
CO2 will be earlier introduced commercially in the chemical of the FT reaction for introducing RE in the chemical production
5 industry value chain. chain, the main limit of this process is the broad distribution of
products formed, which determines large costs of separation (and
Conversion of CO2 to DME
60 downstream processes) and the need of large capacity plants.
Extension of methanol systems to DME (dimethyl ether, a Even if there are commercial plants for the production of

Energy & Environmental Science Accepted Manuscript


potentially valuable liquid fuel, substitute of LPG), can be chemicals based on FT reaction, although based on syngas (for
obtained by shifting the equilibrium with hybrid catalysts (eq. 8): example, the Sasol FT refinery at Sasolburg, South Africa), the
use of CO2 via FT reaction should be focused either on the
10 2CH3OH  CH3OCH3 + H2O (8)
65 selective synthesis of short-chain olefins (as discussed before) or
In the presence of acid sites, DME could be easy formed from instead on the synthesis of hydrocarbons to be used as fuels for
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

methanol by water elimination on mild acid sites. DME could be the energy needs in chemical industry.
preferable to methanol for the consecutive step of short-chain
Conversion of CO2 to methane (SNG)
olefin formation. It is possible also to develop core-shell
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15 catalysts, with a methanol catalyst core and a zeolite shell with The reaction of CO2 methanation, that is the hydrogenation of
controlled acidity to synthetize directly DME from syngas.139 70 CO2 to methane (eq. 10), has been known from over a century as
Other type of bifunctional catalysts recently investigated include the Sabatier reaction, but has received a renewed interest recently,
CuO-ZnO-Al2O3/γ-Al2O3,140 CuO-ZnO-Al2O3-ZrO2 + HZSM- for the use as chemical storage of the excess of electrical energy
5141 and CuO-ZnO-Al2O3/HZSM-5.142 (used to generate by electrolysis the H2 necessary in the
synthesis) produced during night by wind factories.173,174 The
20 Conversion of CO2 to FT liquid products
75 wind to SNG concept (also called power-to-gas, P2G) is based on
Although Fischer-Tropsch synthesis (FT, eq. 9) has been known the use of existing gas grid infrastructures for storing and
for over a century, the need to produce fuels from alternative raw converting the generated fuel to electricity, and in particular the
materials has recently renewed the interest on this process to use of wind-generated electricity, the further expansion of which
produce middle distillate from natural gas (gas-to-liquid process, is currently restricted by the capacity of the electricity grids
25 GTL), coal (coal-to-liquid process, CTL) and biomass (biomass- 80 (Figure 6).174 Solar electricity or any other type of renewable
to-liquid, BTL).143 A number of reviews have been published electricity can be also used for the process. RCO2 AS (Norway)
recently on the various aspects of FT reaction, from the reaction has developed a pilot scale a process based on recovery of CO2
mechanism144-148 to the catalyst and process design149-154 and the from flue gas and its conversion to methane using renewable
effect of water and CO2 on the reaction155-159 or the development H2.175 The estimated cost (US$/mt of CO2) were in the 41-45
30 of novel type of catalysts based on homogeneous catalysts160,161 85 range with respect to costs to CO2 sequestration estimated in the
or zeolites and periodic mesoporous silicas162 in order to tune the 60-100 range. Although methane produced from CO2 according
selectivity. to above routes is considered as a way to use off-peak excess RE
or to increase the overall efficiency of combustion process, this
CO + H2 → CnH2n + CnH2n+2 + H2O + CO2 (n = 1,2,...) (9)
renewable SNG can be also used in chemical industry to lower
The FT mechanism it is known to be significantly influenced 90 the carbon footprint. Due to the difficulty in the direct conversion
35 by the presence of CO2 and of water (formed from RWGS, eq. 1). of methane to chemicals (not via syngas), the use as raw material
The effect of water was reviewed recently by Dalai and Davis, 163 for the chemical industry is instead not convenient currently, at
while Botes155 reviewed the effect of water and CO2 on FT least up to when new breakthrough discoveries in the direct
reaction kinetics, Srinivas et al.158 the use of CO2-rich syngas, methane conversion to chemicals will change the game.
and Blekkan et al.159 the effect of water on cobalt FT catalyst 95 The Sabatier reaction requires a 4:1=H2:CO2 ratio, thus higher
40 reactivity. than the conversion of CO2 to formic acid, methanol or FT
A number of recent studies have been dedicated to the effect of products.
CO2 on FT synthesis. A low K content is suitable for increasing
hydrocarbon yield.164-166 For cobalt and iron catalysts, a CO2 + 4 H2  CH4 + 2 H2O (10)
significant increase in methane formation was noted upon Although catalysts has been known for a long time, a renewed
45 switching feed from syngas to the CO2 + H2.167-170 Similar results 100 interest in their improvement is fostered by the need to develop
were observed for Fe/Co catalysts.170 It was also observed that catalysts active at lower temperatures and suitable for the
CO and CO2 hydrogenation show different product distributions, compact devices to be used in the electrical-to-energy conversion
e.g. Anderson-Schulz-Flory (ASF) trends.171,172 There are strategy outlined in Figure 6. The need of a fast start and
conflicting indications on the role of CO2 and on the preferable shutdown, the enhanced resistance to deactivation due to these
50 conditions to hydrogenate CO2, in part because the effect of water 105 fast cycling modes, and the need to be integrated into
is not accounted for, although water influences the rate of CO2 microreactors are among the additional constraints necessary to
hydrogenation and inhibits the rate of FT reaction. the development of compact devices for a distributed use.
It should be remarked that FT reaction may give rise to liquid

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40 73000 h-1) with Ir(III) trishydride PNP ligands catalysts.187 Non


precious-metal Fe based homogeneous catalysts have also been
developed.188 New recent developments include:
- the development of cyclometalated organoiridium complex as
efficient catalyst for the interconversion between hydrogen
45 and formic acid at ambient temperature and pressure
(depending on pH),189 allowing the use of a single one-pot
solution for the reversible storage of H2;

Energy & Environmental Science Accepted Manuscript


- the use of a homogeneous Ir catalyst with a proton-responsive
ligand,190 also for the reversible and recyclable hydrogen
50 storage under mild conditions.
Obtaining formates or formamides derives from the necessity to
add a base such as KOH or amine to drive the endorgonic (even if
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

exothermic) reduction of CO2 to HCOOH, through the further


formation of the salts/formamide. The successive step of formic
acid recovery has been recently described,191 with further
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55
Fig. 6 Wind to SNG (power-to-gas) concept for bidirectional coupling of
the electricity and gas grids with a link to the mobility sector. See development of continuous-flow hydrogenation of carbon dioxide
glossary for acronyms. (Adapted from ref.174) to pure formic acid in a single processing unit.192 Zhao and
Ferenc193 instead reported that free formic acid was produced in
The catalysts used have some similarities to those for CO2 hydrogenation of carbon dioxide dissolved in aqueous sodium
reforming. 10wt%Ni/CeO2 shows a high CO2 methanation 60 formate solutions under H2 and CO2 pressure with the water-
activity and high CH4 selectivity at low temperatures.176 Rh/γ- soluble rhodium-phosphine complex, [RhCl(mtppms)3] (mtppms
Al2O3 catalysts, another good catalyst in reforming, shows also = monosulfonated triphenylphosphine) as catalyst.
5 good performances in CO2 methanation at low temperatures.177 There are some new interesting alternative approaches under
Operando-DRIFTS experiments showed that CO2 is readily development for the hydrogenation of CO2 to HCOOH:
dissociated on the latter catalysts at 50°C giving rise to different 65 - The use of tandem photoelectrocatalytic reactions, in
Rh carbonyls and formate species.177 There is thus a link between particular the concurrent reduction of CO2 and photo-
CO2 and CO methanation catalysts, the latter being often based oxidation of methyl orange using nitrogen-doped TiO2.194
10 on supported Ru catalysts,178 for which CO2 methanation - The coupling of a photocatalyst and an enzyme, in particular
similarly proceeds via dissociation to COad, and subsequent for the reoxidation of NAD+ to NADH cofactor, the latter
methanation.179 70 used by a formate dehydrogenation enzyme active in the
Ru-doped ceria also shows interesting performances in CO2 reduction of CO2 to formic acid.195 It is used a graphene-
methanation.180 A conversion of 55% of CO2 with a 99% based photocatalyst with covalently bonded the chromophore
15 selectivity for methane at a temperature of 450°C was observed (anthraquinone substituted porphyrin) as an electron donor,
over Ce0.95Ru0.05O2 catalyst.180 The performances are quite and rhodium complex supported on graphene (acting as
similar to those of Pd-MgO/SiO2 catalysts, even if probably there 75 electron conductor) to mediate the transfers electrons and a
are differences in the reaction mechanism.181 A recent result hydride to NAD+, which gets converted to NADH.
showed that on very narrow Ru particles supported on TiO2 - The development of advanced photoelectrodes, in particular
20 (mean diameter 2.5 nm) it is possible to realize the methanation of AlGaN/GaN photoelectrode.196 Light illumination of a
of CO2 with a 100% yield at very low temperatures (ca. 160°C), GaN photoelectrode creates separation of the electron-hole
about 200°C lower than a similar catalyst having a broader and 80 pairs that drive water oxidation and CO2 reduction reactions.
larger Ru nanoparticles distribution.182 Particle size is thus a key The doped AlGaN acts as photoabsorption layer promoting
parameter to control to develop highly active catalysts, although the production rate of formic acid by CO2 conversion.
25 an effective mechanism for the long-term stabilization of very - The application of ionic liquids to promote the
small nanoparticles must still be found. electrocatalytic reduction of CO2 to formic acid.197
Conversion of CO2 to formic acid 85 - The use of a microbial electrolysis cell (MEC) driven by a
microbial fuel cell (MFC).198 The electrodes were based on
Formation of formic acid from CO2 and H2 (see Fig. 1a) to store
multi-walled carbon nanotubes, MWCNT, and Co tetra-
(and eventually transport) H2 in a liquid form,183,184 extends the
amino phthalocyanine (CoTAPc) composite. The new
30 portfolio of possible reactions for using H2 deriving from
electrodes significantly decreased the overpotential of CO2
renewable sources, and hence the RE share, in the chemical
90 reduction and as cathode successfully reduce CO2 to formic
industry. There are scarce reports of direct attempts of producing
acid (production rate of up to about 21 mg∙L-1∙h-1) in an MEC
formic acid by direct CO2 electroreduction at pilot scale.4
driven by a single MFC. The MWCNT/CoTAPc composite
Homogeneous catalysts have been the most successful in the
electrode reached the maximum Faraday efficiency at the
35 reduction of CO2 to formic acid derivatives, such as formamides
cathode potential of about -0.5 V vs. Ag/AgCl. The coupling
or formates. While the first hydrogenation of CO2 into
95 of the catalytic electrode and the bioelectrochemical system
formamides dates back several decades,185 use of supercritical
allows the reduction of CO2 in the absence of external energy
CO2186 and chelating phosphine have dramatically improved the
input.
rates to formates to turnover numbers as high as 350000 (TOF =

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There are also interesting developments in the photochemical and


photoelectrochemical reduction of CO2 recently reviewed by
Kumar et al.63 An issue is the reduction of the overpotential, but it
was shown that modified Cu electrodes (resulting from the
5 reduction of thick Cu2O films) allow the CO2 reduction at low
overpotentials.199 There are thus exciting novel routes to produce
formic acid, but still to consolidate in terms of effective practical
applicability. The homogeneous catalysts described before appear

Energy & Environmental Science Accepted Manuscript


the only applicable for now to the reversible storage of H2.
10 However, several open questions still remain regarding costs,
stability, safety, productivities and time response for the practical
applicability of devices for H2 storage based on this concept.
The other approaches described above are suited for the
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

synthesis of formic acid, although this is not a large scale use


15 product and the development of formic acid fuelled fuel cells still
shows a number of challenges.200 It is thus preferable to use
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conventional H2 fuel cells, and use formic acid for the storage and Fig. 7 Indicative timeline for the use of CO2 and RE to increase resource
transport of renewable H2.201 This is an option interesting to and energy efficiency in chemical production chain.
couple with other direct sources of renewable electrical energy
20 (photovoltaic, wind, etc.) to guarantee a constant in time supply microreactors for power-to-gas or to methanol conversion). It is
of electrical energy, and favour in this way the use of RE in also necessary to improve current electrolyzers (efficiency is still
process industry. For safety and energy density aspects, the use of 60 low). In addition to improve cell engineering (aspects where
r-H2 for the conversion of CO2 to methanol (used then in direct research is most focused), there is the need of better
methanol fuel cell, DMFC) rather than the H2 reversible storage electrocatalysts design, starting from the understanding on how to
25 as formic acid (with use in conventional PEM fuel cells) was decrease the overpotential in H2 generation from water
suggested to preferable.29c However, for conclusive detailed electrolysis. It may be reasonable to assume that at least 5-10
techno-economic assessment studies are necessary. Worth to 65 years could be necessary. Further improvements in electrolyzer
note, the recent market research report “Methanol: 2012 World technology and engineering (stack capital reduction by optimal
Market Outlook and Forecast”203 indicated that methanol based design of electrodes and electrolyzer cell, cost reduction for
30 fuel cells will be the most prominent growth segment for the larger scale production), however, could be achieved in shorter
methanol market. time (3-5 years) and this will also decrease the cost. Avoiding the
70 use on noble metals in electrodes is another clear target, also
A roadmap for CO2 use in relation to RE reasonably requiring longer time (around a decade), given the
need for basic research.
The discussion of a detailed roadmap for the use of CO2 in A first major contribution to decrease the costs will be to
relation to the issue of introducing RE in the chemical production eliminate one of the steps in the current 3 step REchemical
35 chain is out of the scope and limits of this perspective paper. 75 approach. There are two possible options. The first solution is to
Nevertheless, it is useful to present an indicative timeline integrate the catalysts for water oxidation (to O2, protons and
summarizing some of the main steps, which help define the future electrons) and H2 generation (using the protons and electrons
prospects in this field. Figure 7 reports a graphical representation generated in the other step) in a photovoltaic cell. There are
of this timeline and concise roadmap. already advanced studies in this 2-step direction, solar  H2 
40 The current situation requires the 3-step strategy: step 1) the 80 chemical (see the review19 for more details), but it is necessary to
production of electrical energy through renewable sources, step have a breakthrough in the productivities and cost/efficiency
2) the electrolysis of water to produce H2, and step 3) the use of (more relevant than the generally studied factor of quantum
H2 for the catalytic conversion of CO2 to products such as efficiency). Physically separated productions of O2 and H2 in the
methanol, methane, formic acid which could be used either as device are necessary for safety and separation cost motivations.
45 energy vectors or raw materials for chemical industry. These 85 This aspect requires a different design from those often currently
processes are currently economics only when rather cheap investigated, and the presence of a proton-conductive membrane
electrical energy is available (below about 0.05 $/kWh). This to separate the reactions producing O2 and H2.19 There is the need
target is possible in some remote areas (where, for example, the to develop more productive and stable catalysts for water
electricity may be produced by hydropower, but there is no local oxidation, while the catalysts for H2 evolution are less critical (to
50 use and transport through the grid is impossible) or for "excess" 90 note that several studies focus instead on this aspect). The
electrical energy, e.g. unused sources (for example, in wind or hydrogen produced in these devices is then used for the catalytic
nuclear power during night). The main elements of these conversion of CO2. It may be estimated than within a decade the
technologies are available, but there is still the need to develop production of r-H2 by this route at competitive costs should
improved catalysts (more productive catalysts for CO2 conversion become available (less than 2-3 $/kg), making in turn also
55 to methanol or methane, heterogeneous and cheaper catalysts for 95 potentially attractive to produce short-chain olefins and other
the reversible synthesis of formic acid to store H2, etc.) as well chemicals from CO2.
related technologies (for example, compact devices using The other possible approach is based on inverse (methanol)

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Energy & Environmental Science Page 14 of 19

fuels cells, another 2-step strategy (RE  electricity  which can be easily integrated into the actual chemical
methanol). In a direct methanol fuel cell, methanol is converted to production. It is thus clear from this perspective that CO2
CO2 at the anode with production of protons and electrons which 60 conversion is the natural option by which this task of introducing
reduce oxygen to water at the cathode side. Electrical energy is RE into the chemical production chain can be realized. In fact, the
5 produced. In an inverse methanol fuel cell the process is formally conversion of CO2 to products such as those discussed in the
inverted, by feeding electrical energy and CO2 to produce review (short-chain olefins, methanol, formic acid, methane, etc.)
methanol. However, the electrocatalysts on both sides of the cell could be realized through the use of RE, and these products of
are completely different and still have to be developed. There are CO2 conversion are all well compatible with currently established

Energy & Environmental Science Accepted Manuscript


65

thus common aspects in the cell engineering, but different types chemical industry. The CO2 conversion is thus an effective link
10 of electrocatalysts. By tuning the CO2 reduction electrocatalyst, between needs and requirements in RE injection in the current
products other than methanol could be formed. This is a new area energy infrastructure, even if this problem is only starting to be
of development and only preliminary attempts are currently recognized.
present in literature on this direction. More than 10 years thus 70 There clearly are numerous technical and economic barriers to
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

appear necessary to make this technology mature. overcome before reaching this objective. We have analysed here
15 The final, long-term objective should be to develop direct 1- the status of research in this direction, with a focus on catalysis
step (REchemical) devices which perform all these steps in a and the open problems to be solved, among which the related
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single unit, acting as a kind of artificial leaf,19 eventually also mechanistic aspects, because conceptually new catalysts could be
integrating the step of CO2 capture from the atmosphere. With 75 developed only by a fundamental understanding of the catalytic
respect to natural leaves, these man-made devices should allow chemistry.
20 an intensified production, be cost-competitive and able to tune the The catalytic chemistry of RWGS reaction and the following
conversion of CO2 to the specific type of required products transformation to methanol/DME, or hydrocarbons via Fischer-
(chemicals, fuels). Their use will allow a distributed energy (or Tropsch (FT), and the subsequent production of gasoline
chemical) production, but there are many challenges in terms of 80 (methanol-to-gasoline, MTG) or of diesel via hydrocracking of
electrocatalysts, nanodesign of elements and interfaces, charge the alkanes produced in FT process (using Co-based catalysts) are
25 transport and separation, etc. It is thus still a vision, whose well established, even if there is still need of development, due to
realization should be possible only through the development of the change of feed composition starting from CO2 instead than
the next-generation catalysts, nanomaterials and nanosystems for from syngas, as commented before. Also in terms of process
energy. The realization of this vision and related knowledge on 85 development most of the knowledge necessary is available.
materials, nanodevices and catalysts can thus become one of the Minor technological barrier to develop these routes are thus
30 driving factors for a sustainable future of chemical industry, present. Only for the synthesis of formic acid, either catalytically
because this area has the potential to become a game changer for or electrocatalytically, there still is need of development in terms
chemistry. of productivity and stability, even if relevant progresses have
90 been made recently in this field.204
Future prospects and conclusions The use of CO2 as the carbon-source for the production of
short-chain olefins (ethylene, propylene) is an effective way to
With the global consumption of primary energy today
introduce renewable energy in the chemical industry value chain,
35 approaching 500 exajoules (EJ), largely through the use of oil, improve resource efficiency and limit greenhouse gas emissions.
natural gas and coal resources, it is imperative to diminish in 95 There are different possible routes, but in all cases there is the
coming years this reliance on fossil fuels to meet two emerging need of a significant progress in catalyst design.
pressures:
The key for all these short-to-medium term reactions is the
- To reduce the dependence on fossil fuels, even taking into
production of r-H2 at competitive costs, and for this reason part of
40 consideration the new opportunities deriving from shale
this review was dedicated to analyse the technical, economic and
gases, in order to decrease related geopolitical pressures 100 environmental aspects of the production of renewable H2. Also in
(energy security). this case, a key enabling factor is the development of new
- To reduce the flow of carbon dioxide and other greenhouse electrocatalysts with ideally zero overpotential in the production
gases into the atmosphere (socio-environment security).
of H2 from water. This requires a better fundamental
45 A major shift in a vital underpinning technology such as power
understanding of this old, but still challenging question.
generation takes decades. The imperative necessity to accelerate
105 The issue of introduction of RE into the chemical production
the introduction of RE in the energy system is thus out of chain thus opens new challenges and interesting research
discussion.203 Chemical production and related value chain are perspectives, with the development of conceptually new catalysts
thus facing the urgent need of increasing the use of RE, but through their better understanding as the enabling factor.
50 current RE production systems (solar PV panels, wind power,
etc.) generate essentially electrical energy which does not match
Acknowledgements
well the energy needs of current chemical production, as
discussed in the introduction. Large storage of electrical energy 110 The authors wish to thank all members of the Cefic CO2 Initiative
and the discontinuous electrical energy production through RE (in particular, Dr. E. D'Hooghe) whose fruitful discussions have
55 devices are two main issues. The possibility of effective contributed to elaborate the concepts presented in this perspective
introduction of RE into the chemical production value chain thus paper. EAQ gratefully acknowledges the CPE Lyon sustainable
requires the use of RE to produce chemicals and energy vectors development chair and its sponsor the DOW Chemical company.

14 | Energy Environ. Sci., [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
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Energy & Environmental Science Accepted Manuscript


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18 | Energy Environ. Sci., [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
View Article Online
Page 19 of 19 Energy & Environmental Science

CV 60 GRAPHICAL ABSTRACT
Gabriele Centi completed his industrial The options and catalysts for using CO2 to introduce renewable
chemistry studies at the University of energy in the chemical production value chain are discussed.
Bologna (Italy) and is actually
5 Professor of Industrial Chemistry at

the University of Messina (Italy). He is

Energy & Environmental Science Accepted Manuscript


a former President of the European
Federation of Catalysis Societies, and
was Co-ordinator of the European
10 Network of Excellence on catalysis

IDECAT. He is co-Chairman of the


Editorial Board of ChemSusChem and
Published on 03 April 2013 on http://pubs.rsc.org | doi:10.1039/C3EE00056G

Chief Editor of the book series Studies


in Surface Science and Catalysis (Elsevier) and Green Energy
Downloaded by Mount Allison University on 25/04/2013 12:23:15.

15 (De Gruyter). His research interests lie in the development of


industrial heterogeneous catalysts for sustainable chemical
65
processes, environmental protection, and clean energy.

Elsje Alessandra Quadrelli earned her


undergraduate Laurea degree in
20
AUTHORS ADDRESS
chemistry from Scuola Normale 70
Superiore di Pisa (Italy) and her Ph.D. G. Centi, S. Perathoner
from University of Maryland (US). Dept. of Electronic Engineering, Industrial Chemistry and
She is currently a confirmed CNRS Engineering, Section Industrial Chemistry, University of Messina
25 researcher in the field of catalysis and and INSTM/CASPE (Laboratory of Catalysis for Sustainable
organometallic chemistry and head of 75 Production and Energy),
the sustainable development chair of V.le F. Stagno D'Alcontres 31
École Supérieure de Chimie Physique 98166 Messina (Italy),
centi@unime.it, perathon@unime.it
Électronique de Lyon (CPE Lyon, France), a sponsored chair by
30 the DOW France Chemical company. She co-chairs the 80 E. A. Quadrelli
decarbonated energies workgroup of the French competitive CPE Lyon and CNRS, Université de Lyon; ICL, C2P2 UMR
cluster AXELERA. Her current research interests are N2 and SiH4 5265 LCOMS (CNRS – CPE Lyon – Univ. Lyon 1)
activation by silica-supported organometallic complexes and by Ecole Supérieure de Chimie Physique Electronique de Lyon
novel functional materials such as metal organic frameworks. She 43 Bd du 11 Novembre 1918
35 founded and chairs the “CO2 Forum (Large volume CO2 85 69616 Villeurbanne, France
recycling)” in Lyon. quadrelli@cpe.fr

All the three authors are corresponding authors


Siglinda Perathoner took her degree in
40 Chemistry at the University of
Bologna (Italy) in 1984 and her PhD
in Chemical Science in 1988 working
on photophysics and photochemistry
of supramolecular systems. From
45 2001 she joined the University of

Messina and is associate professor of


Industrial Chemistry presently. Her
recent research interests include
nanostructured zeolites, catalytic
50 membranes, catalysts for waste water purification and
remediation, photo(electro)catalytic conversion of carbon
dioxide, and fuel cells.

55

This journal is © The Royal Society of Chemistry [year] Energy Environ. Sci., [year], [vol], 00–00 | 19