Artificialphotosynthesisfor

Artificialphotosynthesisfor
solarfuels
solarfuels
Stenbjrn Styring
Uppsala university

Swedish Consortium for

Artificial Photosynthesis
1994-

Sw.
Sw.Energy
Energyagency,
agency,Knut
Knutand
andAlice
AliceWallenberg
WallenbergFoundation;
Foundation;EU;
EU;VR
VR

The
The global
global concept
concept

Global energy use

Nuclear
Biomass
Hydro
others.....

2011; ca 17 TW years

Fossil
80%
0

10

TW

20

30

40

Local
Local vs.
vs. global
global concept
concept

Energy supply 2008, Sweden:

Hydro Biomass
Fossil

Nuclear
33

32

12 23

% of total

Local
Local vs.
vs. global
global concept
concept

Energy supply 2008, Sweden:

Hydro Biomass
Fossil

Nuclear
33

32

12 23

% of total

Energy supply 2008; Germany

Fossil
82

11 7% of total

The
The global
global concept
concept

Fossil

2050

Fossil

2011: 17 TW

80%
0

10

TW

20

30

40

The
The global
global concept
concept

Note!
Note!This
This comes
comes from
from people
people that
that dont
dont use
use energy
energy
today.
today.They
They can
can not
not solve
solve this
this by
by saving
saving energy!!!
energy!!!
Fossil

2050

Fossil

2011: 17 TW

80%
0

10

TW

20

30

40

Renewable technologies (Sims et al, IPCC 2007) Electricity

Technologically mature with markets
hydroelectric; geothermal;
in at least some countries
woody biomass; onshore wind
landfill gas; bioethanol; silicon
solar cells.....
Technologically mature with small, new
solid waste energy in towns;
markets in few countries
biodiesel; offshore wind; heat
concentrating solar dishes...
Under technological development
thin film PV; tidal change; wave
demonstration plants, upcoming
biomass gasification; pyrolysis; bioethanol from lignocellulose; thermal towers.......

Many give electricity

Everything is not electricity

Total production
2011; ca 17 TW years

Fossil
80%
10

TW

20

Everything is not electricity

Final consumtion
Electricity 17%

Total production
Fossil
80%
10

TW

20

Everything is not electricity

Final consumtion
Electricity 17%
The rest, 83% is used as
fuel for many things
Total production
Fossil
80%
10

TW

20

Critical
Critical insights
insights

1. Electricity is an energy carrier. It is used to

carry a minor part of the energy in the world.

Critical
Critical insights
insights

1. Electricity is an energy carrier. It is used to

carry a minor part of the energy in the world.
2. Biomass is limited on a global scale. Although
important in many regions, there is not enough
to replace fossile fuels.

Renewable technologies

Biomass derived

Technologically mature with markets

hydroelectric; geothermal;
in at least some countries
woody biomass; onshore wind
landfill gas; bioethanol; silicon
solar cells.....
Technologically mature with small, new
solid waste energy in towns;
markets in few countries
biodiesel; offshore wind; heat
concentrating solar dishes...
Under technological development
thin film PV; tidal change; wave
demonstration plants, upcoming
biomass gasification; pyrolysis; bioethanol from lignocellulose; thermal towers.......

Many give electricity.

All fuel technologies are
based on biomass

Research stage

Critical
Critical insights
insights

1. Electricity is an energy carrier. It is used to

carry a minor part of the energy in the world.
2. Biomass is limited on a global scale. Although
important in many regions, there is not enough
to replace fossile fuels.
3. Need for fuels from other renewable resources
than biomass

Solar Energy, Options

Converted solar
energy;
Oil,biomass.

Solar fuel
for storage

!!
Heat;
Low temp
High temp

!!

!?

Solar cells
Electricity

12

Theenergysystemlocalversusglobalaspects;theplacefor
solarenergy;needforfuel
Variousconceptsforsolarfuels
OurscienceintheSwedishConsortiumforArtificial
Photosynthesis

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar

Sustainable methods to make solar fuels/hydrogen

Solarenergy
energyand
andwater
water
Solar
Direct methods

Indirect
Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Sustainable methods to make solar fuels/hydrogen

Solarenergy
energyand
andwater
water
Solar
Indirect

Photovoltaics
ElectrolysisH2
Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Sustainable methods to make solar fuels/hydrogen

Indirect
Photovoltaics

Leads to discussions about

the hydrogen society

ElectrolysisH2

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar

Sustainable methods to make solar fuels/hydrogen

Indirect
Photovoltaics

ElectrolysisH2

C-based fuel
From H2 and CO2

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar

Sustainable methods to make solar fuels/hydrogen

Indirect

Biomass

Conversion
Pyrol.,ferm., chop wood etc

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar

Sustainable methods to make solar fuels/hydrogen

Solarenergy
energyand
andwater
water
Solar
Indirect

Photosynthesis
Biomass
Conversion

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Sustainable methods to make solar fuels/hydrogen

Indirect
Photovoltaics

ElectrolysisH2

Photosynthesis

Biomass

C-based fuel
From H2 and CO2

Conversion
Pyrolysis, ferment., etc

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar

Sustainable methods to make solar fuels/hydrogen

Sustainable methods to make solar fuels/hydrogen

Electricity
Electricity

Electrolysis
Electrolysis

Solar cells in Sala/Heby

Two systems -solar cells and

electrolyser

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar

Indirect

Sustainable methods to make solar fuels/hydrogen

Biomass,
Biomass,
Trees;
Trees;
Waste;
Waste;
Grasses
Grasses

Conversion
Conversion

Several systems must

be integrated

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar

Indirect

Solarenergy
energyand
andwater
water
Solar

Indirect

General - Extra systems cost

Losses in extra step(s)
Electricity
Electricity

Electrolysis
Electrolysis

Solar cells in Sala/Heby

Biomass,
Biomass,
Waste;
Waste;
Trees;
Trees;
Grasses
Grasses

Conversion
Conversion

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Sustainable methods to make solar fuels/hydrogen

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar
Direct methods

Thermochemical cycles (CSP for H2)

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energyand
andwater
water
Solar
Direct methods

Direct methods

Solarenergy
energyand
andwater
water
Solar

Artificial Photosynthesis in molecular systems

Artificial Photosynthesis in materials and nanosystems

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Thermochemical cycles (CSP for H2)

2
H2O +
O2 + 4 H

Joining
Joining in
in cells
cells
H+
H+

e-

e-

e-

e-

4 H+
2 H2

Direct methods

Artificial Photosynthesis in molecular systems

Solarenergy
energy
Solar

Artificial Photosynthesis in materials and nanosystems

System costs might become lower
in a direct process

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Thermochemical cycles (CSP for H2)

Semi-direct
Light reactions
NADPH & ATP

Photosynthesis
(compartmentalized)

Dark reactions
H2, alcohols etc

Photobiological processes not harvesting the organism

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Solarenergy
energy
Solar

Excreted

Photobiological
Photobiological hydrogen
hydrogen and
and fuel
fuel
production
production using
using living
living organisms.
organisms.

Vegetative cells

H2 forming heterocyst

Cyanobacterium Nostoc

Green algae
Chlamydomonas
Can make hydrogen
under special
conditions

Mixing biological and non-biological parts

Solarenergy
energy
Solar

H2ses Ru
TiO2
etc

PSII
PSII

Pt PSI
PSI

Hybrides
Enzyme & metal catalysts

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Something in between

Direct methods

Solarenergy
energyand
andwater
water
Solar

Artificial Photosynthesis in materials and nanosystems

Thermochemical cycles (CSP for H2)
Semi-direct
Light reactions
NADPH & ATP

Photosynthesis
(compartmentalized)

Dark reactions
H2, alcohols etc

Indirect
Photovoltaics

ElectrolysisH2

Photosynthesis

Biomass

C-based fuel
From H2 and CO2

Conversion
Pyrolysis, ferment., etc

Solarfuel;
fuel;hydrogen
hydrogenor
orcarbon
carbonbased
based
Solar

Artificial Photosynthesis in molecular systems

Theenergysystemlocalversusglobalaspects;theplacefor
solarenergy;needforfuel
Variousconceptsforsolarfuels
AlittleonourscienceintheSwedishConsortiumforArtificial
Photosynthesis

We follow two branches to Solar hydrogen,

common link biochemistry, biophysics

H2O

P
P

H2

Photobiological hydrogen production in photosynthetic

microorganisms

H2O

Design of organisms
Synthetic biology, genomics,
metabolomics
P
P

H2

Artificial photosynthesis, synthetic

light driven catalytic chemistry

H2O
Fe
Ru

Fe

Mn
C
o

Mn

P
P

Design and synthesis

Spectroscopy

H2

Artificial photosynthesis:
Target fuel from solar energy and water!
Visionary but how?

Artificial photosynthesis - manmade:

Visionary but how?
Idea for a short cut:
Mimic (copy) principles in natural enzymes
Method
Biomimetic chemistry

Photosystem II the wunderkind in nature!

O2

P
O2

O2
O2

O2

O2
O2

? Secret of life
Element: Mn
Atomic weight: 55

Mn
Mn

Water

Mn

Mn

Four manganese atoms

are the secret behind
the splitting of water

Water oxidation - the main players

TyrZ 161

His 190

Gln 165
OH

Glu 189
Asp 170

Ca
Mn

Mn

Mn Mn

Supramolecular chemistry
chemical LEGO
2 H 2O

4H

D
O2 +4H

Link

e-

Link

e-

A
2 H2

light
N
N
N

Ru
N

Ruthenium instead
of chlorophyll

Supramolecular chemistry
chemical LEGO
2 H 2O

4H

D
O2 +4H

Link

e-

Link

e-

light
N

Mn

Link

Mn
Manganese as in
Photosystem II

N
N

Ru
N

A
2 H2

Mn2(II/II) BPMP has been connected to Ru and

electron acceptors
C8H17
N

O O

NDI acceptor O

C8H17
O

Mn

Mn
N

3+

N
N
N

Ru

N
N
N

Ru

NH

EtO2C

Me

NH
EtO2C

Mn Mn
N O OO O N

N
Mn

N
Mn

N O O O O N
Me Me

Mw 2800

We seek catalysts based on abundant metals,

Mn-based systems have potential
- The Mn4 cluster works in Photosystem II
- It is the most efficient and stable
part of PSII electron transfer
Co-based systems have potential
- We seek molecular systems
- We seek light driven systems

Cobalt as a water oxidation catalyst

Kanan and Nocera, Science 2008, 321, 5892, 10721075

Yin, Tan, Besson, Geletii, Musaev, Kuznetsov, Luo,

Hardcastle and Hill, Science 2010, 328, 342-345

Photo-driven
Photo-driven O
O22 evolution
evolution
with
with aa new
newCo-nanoparticle
Co-nanoparticle

O
O PO

O
P OO

Co(III) oxide
ON
50 % light
OFF

ON

1 O2/Co
100 % light

Development
Development of
of aa Co-ligand
Co-ligand system
system
for
foruse
use in
in the
the split
split cell.
cell.
1. Link the Ru-sensitizer with ligand

2
H2O +
O2 + 4 H

C
o

e-

R
u

H4M2P (M2P for short)

methyldiphosphonic acid

Development
Development of
of aa Co-ligand
Co-ligand system
system
for
foruse
use in
in the
the split
split cell.
cell.
1. Link the Ru-sensitizer with ligand

2
H2O +
O2 + 4 H

C
o

e-

R
u

H4M2P (M2P for short)

methyldiphosphonic acid

Ru(M2P)
1. Synthesized and characterized.

Development
Development of
of aa Co-ligand
Co-ligand system
system
for
foruse
use in
in the
the split
split cell.
cell.
Isolated Ru(M2P)Co

65 g Ru(M2P)Co
(ca 40 M Ru)
6 mM S2O8225 mM Pi (pH 8.4)

+ Pi buffer
+ persulfate
+ light
Photocatalytic oxygen
evolution!

Ca 1 turnover

Development
Development of
of aa Co-ligand
Co-ligand system
system
for
foruse
use in
in the
the split
split cell.
cell.
1. Link the Ru-sensitizer with ligand H M2P (M2P for short)
2. Can it bind Co and is it active? methyldiphosphonic acid

2
H2O +
O2 + 4 H

C
o

e-

R
u

Ru(M2P)
1. Synthesized and characterized.
2. Yes, it binds Co and the system
is photo-catalytic!

Supramolecular chemistry
chemical LEGO
2 H 2O

4H

D
O2 +4H

e-

Link

e-

light

Cobolt
Co(III)
oxide

Link

Mn

Link

Mn

N
N

Ru
N

A
2 H2

Supramolecular chemistry
chemical LEGO
2 H 2O

4H

D
O2 +4H

e-

Link

e-

light

Cobolt
Co(III)
oxide

Link

Mn

Link

Mn
Manganese like
Photosystem II

N
N

Ru
N

A
2 H2

NC
OC
S
Cys

CO

O
C

Fe
Fe

CN

Fe
Fe
S

S
NH

Hydrogenases: Enzymes
that can make and handle
hydrogen

Many complexes making hydrogen!!

Hydrogen formation.
Electrochemistry under very
acidic conditions

Br

-12

N
S S
OC

Fe
OC

Our complex

15

-8

10

Fe
CO

20

turnovers

25

CO

CO

-4

CO

Background
0
0

200

400

seconds

600

Diiron complexes with aromatic dithiolate ligands

quinoxaline

carborane

Aromatic dithiolate ligands

Tuning for catalysis at milder potentials

Bimolecular approach
1

H2

e-

e3
Ascorbic acid

Fe2(-Cl2-bdt)(CO)6
Ru(bpy)32+

H+

An interesting development complexes with only

one Fe can also make hydrogen.

S S
FeII CO
Ph2P

PPh2

N
O

Hydrogen at low overpotential

Supramolecular chemistry
chemical LEGO
2 H 2O

4H

D
O2 +4H

e-

Link

e-

A
2 H2

light

Cobolt
Co(III)
oxide

Link

Mn

Link

Mn

N
N

Ru
N

Fe
Fe

Fe

We have water oxididation catalyst

Co-nanoparticle

We have many hydrogen forming catalysts

We can drive them with light!

Can we combine them?

Fe-complexes

AASplit-cell
Split-cellfor
forcomplete
completewater
wateroxidation/fuel
oxidation/fuelformation
formation
with
withcatalysts
catalystsof
ofearth
earthabundant
abundantelements
elementsfrom
fromour
ourlaboratory
laboratory

e-

e-

e2-

a)

e-

O3P
N
N

2-

TiO2

O3P

N
Ru
N

O2 + 4H+

4H+

b)
H
N

[4Fe-4S]
Cys S

2 H2O

2 H2

c)

SS

S SH

SS

R2N
F2 O
B
OO
N
Ph N I

etBu

Co

N Ph
Fep Fed
I
I Ph N
Me
P
PMe
Fe
Fe
OC
O
3
OC
3
O
C CN
B
NC O CO
OC CO PR2 PR2
F2
NCMe
X3
X1
X2
NR

e-

OAr
O

N
tBu O

CO2H

Ar =

OAr 1

OO

Oct N

NN

OO

OAr
O

OAr

NiO
CO H
2

H2 by photosynthesis
Water as substrate

Organisms
in Bioreactors
Soon
-will work
-explored by many

Artificial
Systems

H2 by photosynthesis
Water as substrate

Bioreactors

Artificial
Systems

Long term
Soon
- big potential
-will work
-explored by many - more unproven