The electrochemical hydrogen evolution reaction is catalyzed most effectively by the Pt group metals. As H2 is considered as a future energy carrier, the need for these catalysts will increase and alternatives to the scarce and expensive Pt group catalysts will be needed. We analyze the ability of different metal surfaces and of the enzymes nitrogenase and hydrogenase to catalyze the hydrogen evolution reaction and find a necessary criterion for high catalytic activity. The necessary criterion is that the binding free energy of atomic hydrogen to the catalyst is close to zero. The criterion enables us to search for new catalysts, and inspired by the nitrogenase active site, we find that MoS2 nanoparticles supported on graphite are a promising catalyst. They catalyze electrochemical hydrogen evolution at a moderate overpotential of 0.1−0.2 V.

Biomimetic Hydrogen Evolution: MoS2 Nanoparticles as Catalyst for Hydrogen Evolution

The pace of materials discovery for heterogeneous catalysts and electrocatalysts could, in principle, be accelerated by the development of efficient computational screening methods. This would require an integrated approach, where the catalytic activity and stability of new materials are evaluated and where predictions are benchmarked by careful synthesis and experimental tests. In this contribution, we present a density functional theory-based, high-throughput screening scheme that successfully uses these strategies to identify a new electrocatalyst for the hydrogen evolution reaction (HER). The activity of over 700 binary surface alloys is evaluated theoretically; the stability of each alloy in electrochemical environments is also estimated. BiPt is found to have a predicted activity comparable to, or even better than, pure Pt, the archetypical HER catalyst. This alloy is synthesized and tested experimentally and shows improved HER performance compared with pure Pt, in agreement with the computational screening results.

Computational high-throughput screening of electrocatalytic materials for hydrogen evolution

Over the past decade the theoretical description of surface reactions has undergone a radical development. Advances in density functional theory mean it is now possible to describe catalytic reactions at surfaces with the detail and accuracy required for computational results to compare favourably with experiments. Theoretical methods can be used to describe surface chemical reactions in detail and to understand variations in catalytic activity from one catalyst to another. Here, we review the first steps towards using computational methods to design new catalysts. Examples include screening for catalysts with increased activity and catalysts with improved selectivity. We discuss how, in the future, such methods may be used to engineer the electronic structure of the active surface by changing its composition and structure.

Towards the computational design of solid catalysts

During the past decade, computer simulations based on a quantum-mechanical description of the interactions between electrons and between electrons and atomic nuclei have developed an increasingly important impact on solid-state physics and chemistry and on materials science—promoting not only a deeper understanding, but also the possibility to contribute significantly to materials design for future technologies. This development is based on two important columns: (i) The improved description of electronic many-body effects within density-functional theory (DFT) and the upcoming post-DFT methods. (ii) The implementation of the new functionals and many-body techniques within highly efficient, stable, and versatile computer codes, which allow to exploit the potential of modern computer architectures. In this review, I discuss the implementation of various DFT functionals [local-density approximation (LDA), generalized gradient approximation (GGA), meta-GGA, hybrid functional mixing DFT, and exact (Hartree-Fock) exchange] and post-DFT approaches [DFT + U for strong electronic correlations in narrow bands, many-body perturbation theory (GW) for quasiparticle spectra, dynamical correlation effects via the adiabatic-connection fluctuation-dissipation theorem (AC-FDT)] in the Vienna ab initio simulation package VASP. VASP is a plane-wave all-electron code using the projector-augmented wave method to describe the electron-core interaction. The code uses fast iterative techniques for the diagonalization of the DFT Hamiltonian and allows to perform total-energy calculations and structural optimizations for systems with thousands of atoms and ab initio molecular dynamics simulations for ensembles with a few hundred atoms extending over several tens of ps. Applications in many different areas (structure and phase stability, mechanical and dynamical properties, liquids, glasses and quasicrystals, magnetism and magnetic nanostructures, semiconductors and insulators, surfaces, interfaces and thin films, chemical reactions, and catalysis) are reviewed. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008

Ab-initio simulations of materials using VASP: Density-functional theory and beyond.

UV-Visible ار راد ن .د TiO2 ( تیفرظ راون مان هب نورتکلا یاراد یژرنا زارت لماش VB و ) رگید زارت ی یژرنا اب ( ییاناسر راون مان هب نورتکلا زا یلاخ و رتلااب VB یم ) .دشاب ت ود نیا نیب یژرنا توافت یژرنا فاکش زار ، پگ دناب هدیمان یم .دوش هک ینامز زا نورتکلا لاقتنا VB هب VB یم ماجنا دریگ ، TiO2 اب ودح یژرنا بذج د ev 2 / 3 ، نورتکلا تفج کی دیلوت یم هرفح .دیامن و نورتکلا هرفح ی نا اب هدش دیلوت یم کرتشم حطس هب لاقت ثعاب دناوت شنکاو ماجنا اه یی ددرگ . TiO2 دربراک ،دراد یدایز یاه هلمج زا یم ناوت اوه یگدولآ هیفصت یارب (CO2) و بآ و ... نآ زا هدافتسا درک .

Advanced Nanoarchitectures for Solar Photocatalytic Applications

Use of DFT to achieve a rational understanding of acid–basic properties of γ-alumina surfaces

Hydroxyl Groups on γ-Alumina Surfaces: A DFT Study

The topotactic transformation of boehmite (AlOOH) taking place under calcination and leading to γ-alumina (γ-Al2O3) has been investigated theoretically and a step-by-step mechanism for the structural transformation is proposed This mechanism reveals two major steps First, the structural collapse of boehmite occurs, after hydrogen transfers and water extraction Then, through an aluminum migration process, the γ-alumina characteristics appear The proposed mechanism demonstrates the existence of an equilibrium structure for γ-alumina containing 25−31% of tetrahedral aluminum sites in agreement with nuclear magnetic resonance (NMR) results Temperature effects on the thermodynamic stability of the different structures involved in the mechanism has been investigated Theoretically simulated X-ray diffraction (XRD) patterns confirm the validity of our model structures According to this mechanism, a coherent skeleton of γ-alumina inherited from the original AlOOH network is constructed This skeleton can be

Theoretical Study of the Dehydration Process of Boehmite to γ-Alumina

A geometrical model of the active phase of hydrotreating catalysts

Hydroxyl Groups on γ-Alumina Surfaces: A DFT Study M. Digne,∗,†,‡ P. Sautet,∗,† P. Raybaud,‡,1 P. Euzen,§ and H. Toulhoat# ∗Laboratoire de Chimie Theorique et des Materiaux Hybrides, Ecole Normale Superieure de Lyon, 46 allee d’Italie, 69364 Lyon Cedex 07, France; †Institut de Recherches sur la Catalyse, Centre National de la Recherche Scientifique, 2 avenue Albert Einstein, 69626 Villeurbanne Cedex, France; and ‡Division Chimie et Physico-Chimie Appliquees, §Division Cinetique et Catalyse, and #Direction Scientifique, Institut Francais du Petrole, 1-4 avenue de Bois-Preau, 92852 Rueil-Malmaison Cedex, France

Hervé Toulhoat

Papers

Use of DFT to achieve a rational understanding of acid–basic properties of γ-alumina surfaces

Hydroxyl Groups on γ-Alumina Surfaces: A DFT Study

Theoretical Study of the Dehydration Process of Boehmite to γ-Alumina

A geometrical model of the active phase of hydrotreating catalysts

PRIORITY COMMUNICATION Hydroxyl Groups on γ-Alumina Surfaces: A DFT Study