Modeling Operando Electrochemical CO₂ Reduction

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(12), P. 11085 - 11130

Published: April 27, 2022

Since the seminal works on application of density functional theory and computational hydrogen electrode to electrochemical CO2 reduction (eCO2R) evolution (HER), modeling both reactions has quickly evolved for last two decades. Formulation thermodynamic kinetic linear scaling relationships key intermediates crystalline materials have led definition activity volcano plots, overpotential diagrams, full exploitation these theoretical outcomes at laboratory scale. However, recent studies hint role morphological changes short-lived in ruling catalytic performance under operating conditions, further raising bar electrocatalytic systems. Here, we highlight some novel methodological approaches employed address eCO2R HER reactions. Moving from atomic scale bulk electrolyte, first show how ab initio machine learning methodologies can partially reproduce surface reconstruction operation, thus identifying active sites reaction mechanisms if coupled with microkinetic modeling. Later, introduce potential interpret data Operando spectroelectrochemical techniques, such as Raman spectroscopy extended X-ray absorption fine structure characterization. Next, review electrolyte mass transport effects. Finally, suggest challenges near future well our perspective directions follow.

Language: Английский

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Enhancing the connection between computation and experiments in electrocatalysis

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(5), P. 374 - 381

Published: May 25, 2022

Language: Английский

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Improving the Accuracy of Atomistic Simulations of the Electrochemical Interface

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(12), P. 10651 - 10674

Published: May 6, 2022

Atomistic simulation of the electrochemical double layer is an ambitious undertaking, requiring quantum mechanical description electrons, phase space sampling liquid electrolytes, and equilibration electrolytes over nanosecond time scales. All models electrochemistry make different trade-offs in approximation electrons atomic configurations, from extremes classical molecular dynamics a complete interface with point-charge atoms to correlated electronic structure methods single electrode configuration no or electrolyte. Here, we review spectrum techniques suitable for electrochemistry, focusing on key approximations accuracy considerations each technique. We discuss promising approaches, such as enhanced configurations computationally efficient beyond density functional theory (DFT) methods, that will push simulations present frontier.

Language: Английский

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GPAW: An open Python package for electronic structure calculations

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(9)

Published: March 7, 2024

We review the GPAW open-source Python package for electronic structure calculations. is based on projector-augmented wave method and can solve self-consistent density functional theory (DFT) equations using three different wave-function representations, namely real-space grids, plane waves, numerical atomic orbitals. The representations are complementary mutually independent be connected by transformations via grid. This multi-basis feature renders highly versatile unique among similar codes. By virtue of its modular structure, code constitutes an ideal platform implementation new features methodologies. Moreover, it well integrated with Atomic Simulation Environment (ASE), providing a flexible dynamic user interface. In addition to ground-state DFT calculations, supports many-body GW band structures, optical excitations from Bethe-Salpeter Equation, variational calculations excited states in molecules solids direct optimization, real-time propagation Kohn-Sham within time-dependent DFT. A range more advanced methods describe magnetic non-collinear magnetism also now available. addition, calculate non-linear tensors solids, charged crystal point defects, much more. Recently, support graphics processing unit (GPU) acceleration has been achieved minor modifications thanks CuPy library. end outlook, describing some future plans GPAW.

Language: Английский

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The importance of a charge transfer descriptor for screening potential CO2 reduction electrocatalysts

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 5, 2023

Abstract It has been over twenty years since the linear scaling of reaction intermediate adsorption energies started to coin fields heterogeneous and electrocatalysis as a blessing curse at same time. established possibility construct activity volcano plots function single or two readily accessible descriptors, but also limited maximal catalytic conversion rate. In this work, it is found that these energy-based descriptor spaces are not applicable electrochemistry, because they lacking an important additional dimension, potential zero charge. This extra dimension arises from interaction electric double layer with intermediates which does scale energies. At example electrochemical reduction CO 2 shown addition breaks relations, opening up huge chemical space via charge-based material design. The charge explains product selectivity trends in close agreement reported experimental data highlighting its importance for electrocatalyst

Language: Английский

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Materials Screening by the Descriptor G_max(η): The Free-Energy Span Model in Electrocatalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 1740 - 1758

Published: Jan. 17, 2023

To move from fossil-based energy resources to a society based on renewables, electrode materials free of precious noble metals are required efficiently catalyze electrochemical processes in fuel cells, batteries, or electrolyzers. Materials screening operating at minimal computational cost is powerful method assess the performance potential compositions heuristic concepts. While thermodynamic overpotential combination with volcano concept refers most popular descriptor-based analysis literature, this notion cannot reproduce experimental trends reasonably well. About two years ago,

Language: Английский

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Understanding the complexity in bridging thermal and electrocatalytic methanation of CO₂

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(11), P. 3627 - 3662

Published: Jan. 1, 2023

The selective methanation of CO2 is an important research area to meet the net-zero emission targets. Furthermore, it crucial develop solutions achieve carbon neutrality, hydrogen utilization, circularity, and chemical-energy storage. This conversion can be realized via thermocatalytic multistep power-to-X route or by direct electro- (or photoelectro)-catalytic technologies. Herein, we discuss need accelerate Improving these technologies requires a better understanding catalytic chemistry complexity aspects consider in bridging electrocatalytic methanation. In this tutorial review, initially analyze fundamental question competitive adsorption key reactants regulation strategies promote overall reaction. Then, approach used guide reader differences between thermocatalysis electrocatalysis. Finally, necessary include modelling designing next-generation electrocatalysts for analyzed.

Language: Английский

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Constant inner potential DFT for modelling electrochemical systems under constant potential and bias

npj Computational Materials, Journal Year: 2024, Volume and Issue: 10(1)

Published: Jan. 5, 2024

Abstract Electrochemical systems play a decisive role in, e.g. clean energy conversion but understanding their complex chemistry remains an outstanding challenge. Constant potential and grand canonical ensemble (GCE) simulations are indispensable for unraveling the properties of electrochemical processes as function electrode potential. Currently, GCE calculations performed at density functional theory (DFT) level require fixing Fermi within simulation cell. Here, we illustrate that this method is inadequate when modeling outer sphere reactions biased two-electrode For these systems, obtained from DFT does not accurately present experimentally controlled or describe thermodynamic independent variable in GCE-DFT. To address limitation, developed implemented constant inner (CIP) offering more robust general approach to conducting GCE-DFT under bias conditions. The primary advantage CIP it uses local parameter potential, opposed global level. Through numerical analytical studies, demonstrate approaches equivalent metallic electrodes inner-sphere reactions. However, proves be versatile, can applied outer-sphere addressing limitations Fermi-level scenarios. Altogether, stands out efficient simulating interfaces first principles.

Language: Английский

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Emerging Atomistic Modeling Methods for Heterogeneous Electrocatalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8620 - 8656

Published: July 11, 2024

Heterogeneous electrocatalysis lies at the center of various technologies that could help enable a sustainable future. However, its complexity makes it challenging to accurately and efficiently model an atomic level. Here, we review emerging atomistic methods simulate electrocatalytic interface with special attention devoted components/effects have been model, such as solvation, electrolyte ions, electrode potential, reaction kinetics, pH. Additionally, relevant computational spectroscopy methods. Then, showcase several examples applying these understand design catalysts green hydrogen. We also offer experimental views on how bridge gap between theory experiments. Finally, provide some perspectives opportunities advance field.

Language: Английский

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Toward Realistic Models of the Electrocatalytic Oxygen Evolution Reaction

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(15), P. 9136 - 9223

Published: July 22, 2024

The electrocatalytic oxygen evolution reaction (OER) supplies the protons and electrons needed to transform renewable electricity into chemicals fuels. However, OER is kinetically sluggish; it operates at significant rates only when applied potential far exceeds reversible voltage. origin of this overpotential hidden in a complex mechanism involving multiple electron transfers chemical bond making/breaking steps. Our desire improve catalytic performance has then made mechanistic studies an area major scientific inquiry, though complexity understanding difficult. While historically, have relied solely on experiment phenomenological models, over past twenty years

Language: Английский

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