HYDROGEN EVOLUTION SIMULATIONS ON TRANSITION METALS

Alejandro Aristizábal Sánchez; Omar Alejandro Henao Zapata

Alejandra Rendón-Calle; Santiago Builes Toro

Table of Contents
Problem statement .................................................................................................. 1
Investigation questions......................................................................................... 2
Objectives................................................................................................................ 2
General objectives ............................................................................................... 2
Specific objectives................................................................................................ 2
Reach....................................................................Error! Bookmark not defined.
Justification.............................................................................................................. 3
State of the art ..................................................................................................... 3
Methodology ............................................................................................................ 4
Schedule ................................................................................................................. 5
Budget ..................................................................................................................... 5
References .............................................................................................................. 5

Problem statement

Global energy consumption is projected to be twice the current consumption by mid-

century due to economic and population growth [1], Although this demand could be
satisfied by non-renewable fuels, the increase in CO2 emissions would contribute to
increase the effects of climate change. A plausible solution for this problematic are
fuel cells. A fuel cell is an electrochemical device capable of converting chemical
energy directly into electrical energy through chemical reactions. The H2 fuel cells
operate through a cathodic and an anodic reaction: the evolution of hydrogen (HER),
and the evolution of oxygen (OER), respectively [2].The reduction of water to H2 at
the cathode occurs in an electrocatalytic process that requires certain potential. The
difference between the required potential for the reaction and the one required
according to the thermodynamic limits is called overpotential. Catalysts are used to
accelerate the reaction rate and increase the energy efficiency, decreasing said
overpotential. HER is a possible source of clean energy. Its main advantage is that
it allows energy storage in the form of H2, so it can be used to collect energy from
intermittent sources such as wind or sunlight. However, its commercial application
is conditioned by platinum catalysts, which despite offering low overpotentials are
scarce and high-cost materials, making its implementation on a large scale not
sustainable on an economic or environmental basis. Furthermore, although
computational calculations with the density functional theory (DFT) can give detailed
information of a chemical reaction, its computational cost is still very high when
calculating all the possible combinations of: sizes, shapes and compositions of each
catalyst that you want to test.
Investigation questions

In this project some transitions metals will be computationally evaluated as catalysts

for the hydrogen evolution reaction: Ag, Au, Ir, Ni, Rh, Pt, Cu and Pd using DFT
calculations. The thermodynamic calculations of free energy of the hydrogen
adsorbed in each surface allow to determine the characteristics of adsorption and
desorption of the materials. The Sabatier principle will be used to compare the
different surfaces by means of a Volcano diagram with a descriptor calculated with
DFT and to propose the desired characteristics of viable catalysts, based on these
results.
The key to ease the computational cost is to find and develop good descriptors,
which have a high correlation with the binding energies of the reaction
intermediaries. The free energies of the reaction intermediates can be used to
evaluate catalytic activities by analysis such as that described by the Sabatier
principle. In general, the descriptors are usually electronic, for example the center of
the d-band, or geometric, such as the generalized coordination number [3].
Therefore, the research question that we want to answer in this work is: Which
descriptors allow us to design optimal catalysts for HER?

Objectives
General objectives

 Evaluate the free energies of the hydrogen evolution reaction on different

transition metals, through DFT calculations.
Specific objectives

 Calculate with DFT the lattice constants of the crystalline net of 7

transition metals: Ag, Au, Ir, Ni, Rh, Pt and Pd; with face centered cubic
(FCC) structure, in their facets (111), (110) and (100).
 Predict the hydrogen free energies of adsorption in each surface.
  Contrast the hydrogen free energies of adsorption between the different
metals using a descriptor, analyzing them according to the Sabatier
principle.
Project scope
This study focuses on the evaluation of the Gibbs free energy profiles for the
hydrogen evolution reaction on the transition metals Ag, Au, Ir, Ni, Rh, Pt, Cu and
Pd. On three Miller index surfaces (111), (110) and (100), using DFT calculations.
At first, it will be calculated the lattice constant for the eight metals in order to find
the minimum value for each to do the DFT calculations of the Gibbs free energies
on each surface. After that, they will be compared between them, using different
descriptors.

Justification

Given the reasons mentioned ut supra, it becomes necessary to develop and

implement forms of carbon neutral energy, easily stored and transported, that
replaces these obsolete energy vectors. Hydrogen H2 is a promising energy vector,
which when used in fuel cells allows energy to be obtained efficiently. The
replacement of Pt by more abundant catalysts, and therefore more economical,
would be highly beneficial for the development of fuel cells. That is why the rational
design of catalysts is proposed, as a computational tool that allows to evaluate a
priori the characteristics of materials that can favor the conditions of the reaction,
and in this way seek to synthesize materials that satisfy these characteristics. From
the theoretical point of view, it is possible to evaluate the catalytic activity of different
materials using DFT calculations. Which save costs in material synthesis, personnel
and time compared with an empirical design of the materials.
State of the art

Due to the importance of establishing a hydrogen based economy, the HER has
been studied widely experimentally [4]–[9]. Water electrolysis (2H2O ↔ 2H2 + O2)
provides an approach to sustainably produce high-purity hydrogen. The practical
widespread application of this technique is constrained by its high cost. One potential
area of improvement in this process is the development of efficient non-noble metal
electrocatalysts for the hydrogen evolution reaction that occurs at the cathode of a
water electrolysis cell. HER can operate under acidic (2H++2e- ↔ H2) or alkaline
conditions (2H2O+2e- ↔H2+2OH)[10]. An active HER catalyst will exhibit lower onset
potential on the reference electrode -RHE- (mV versus RHE). Pt-based catalysts
have superior activity for HER and replacing them is critical for providing cost-
competitive hydrogen.
However, to achieve a better understanding of the characteristics that make a
catalyst better than another, it is necessary to use theoretical methods like the DFT,
which allows to model the H2 evolution in an atomic level. These calculations allow
us to study the interactions between atoms in reactive systems and to obtain, from
a thermodynamic point of view, their lowest energy state.
For the electrocatalytic reduction of water that occurs in the fuel cells of H 2, it is
possible to calculate the free energy of H2 when being adsorbed by different catalysts
and analyze said energies according to the Sabatier principle. This principle states
that the interaction between the adsorbate and the catalytic surface must not be too
strong nor too weak. If the interaction is too strong, it results in the poisoning of the
catalyst, using up the free sites of adsorption. By the contrary, if it is too weak, high
overpotentials would be needed to carry out the adsorption. Thus, the ideal catalyst,
in accordance with this principle, has free energies near to 0.0 eV regarding the
hydrogen reference electrode [4].
These relations of activity can be plotted in a Volcano type diagram, the left side of
the Volcano corresponds to the first postulate of the Sabatier principle, relating with
the poisoning of the catalyst, whilst the right line of this diagram implies the need of
higher overpotentials, the top of this diagram must be 0.0 eV, where lies the
equilibrium between the adsorbed and free phases, though the diagram can vary
depending on the used descriptor for a given system.
At first, many parameters may affect the kinetic of a given reaction, hence possibly
being used as descriptors of the catalytic activity. However, due to the high level of
correlation between the energies of the adsorbate and its transitions states, the
number of independent descriptors reduces to a few microscopic variables that are
able to determine the macroscopic yield of the catalyst. In the case of HER it has
been demonstrated that its catalytic activity can be described by the bond strength
between the metal and hydrogen, and said descriptor can be used to build a Volcano
diagram [5], [6].

Methodology

The lattice constants of the transition metals: Ag, Au, Ir, Ni, Rh, Pt, Cu and Pd and
the adsorption energies of H2, will be calculated using VASP (Vienna Ab-initio
Simulation Package) with the exchange and correlation functional PBE (Perdew-
Burke-Erzenhof). To describe the ionic cores PAW (Projector Augmented Wave)
potentials are going to be used. The electronic density will be determined with an
energy cut 450 eV. The relaxation calculations are going to be carried out with the
quasi-Newton minimization method until the maximum force in any of the atoms is
less than $0.05 eV Å-1. Each simulation cell will have (2x2x4) in the x, y and z
dimensions because with this geometry all the adsorption sites are present, and the
z axis will have the two inferior layers fixed in their optimized positions. Said cells
are going to be repeated periodically with a separation between layers of 28 Å and
dipolar corrections will be applied in the calculations, to avoid unwanted interaction
between the cells.
All the parameters above mentioned were fixed using a convergence test, where the
parameters were changed until their alteration was not significant in the calculation
results, these convergence tests were carried out as preliminary calculations
because the objective of this work is evaluating the metals when the optimal
conditions are given, rather than setting the best simulation conditions.
Once obtained the DFT energies of each possible adsorbate-surface configuration,
the most stable adsorption sites for H2 can be determined for each metal and facet
used. The zero-point energy (ZPE) will be calculated with the vibrational frequencies
of the lesser energy states using the harmonic oscillator model. The vibrational
contributions to entropy for H2 will also be considered, according to the standard
thermodynamic tables at 298.15 K and 1 atm.
Finally, the obtained descriptor will be plotted against the current in a Volcano
diagram, to analyze it through the Sabatier principle. The descriptor chosen for this
calculations is the exchange current density, which is the rate of hydrogen evolution
per superficial area to the electrode potential, where the reaction is in equilibrium
[11].

Schedule

Budget
The license for VASP was acquired under the seedbed of research DPI (Desarrollo
de procesos de industriales) and the teacher Santiago Builes Toro the co-advisor of
this project. The calculations were made in the super computation cluster APOLO
located in EAFIT University.

References
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