Hydrogen Evolution Simulations On Transition Metals: Problem Statement
Hydrogen Evolution Simulations On Transition Metals: Problem Statement
Hydrogen Evolution Simulations On Transition Metals: Problem Statement
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
Objectives
General objectives
Justification
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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