How to cite this WIREs title:
WIREs Comput Mol Sci

Impact Factor: 16.778

Atomistic modeling of electrocatalysis: Are we there yet?

Overview

Nawras Abidi, Kang Rui Garrick Lim, Zhi Wei Seh, Stephan N. Steinmann

Published Online: Aug 26 2020

DOI: 10.1002/wcms.1499

Full article on Wiley Online Library: HTML PDF

Can't access this content? Tell your librarian.

Abstract Electrified interfaces play a prime role in energy technologies, from batteries and capacitors to heterogeneous electrocatalysis. The atomistic understanding and modeling of these interfaces is challenging due to the structural complexity and the presence of the electrochemical potential. Including the potential explicitly in the quantum mechanical simulations is equivalent to simulating systems with a surface charge. For realistic relationships between the potential and the surface charge (i.e., the capacity), the solvent and counter charge need to be considered. The solvent and electrolyte description are limited by the computational power: either molecules or ions are included explicitly or implicit solvent and electrolyte descriptions are adopted. The first option is limited by the phase‐space sampling that is at least 10 times too small to reach convergence, while the second is missing a realistic structuring of the interface. Both approaches suffer from a lack of validation against directly comparable experimental data. Furthermore, the limitations of density functional theory in terms of accuracy are critical for these metal/liquid interfaces. Nevertheless, the atomistic insight in electrocatalytic interfaces allows insights with unprecedented details. The joint theoretical and experimental efforts to design non‐noble hydrogen evolution catalysts are discussed as an example for the success of theory to spur and accelerate experimental discoveries. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Electronic Structure Theory > Density Functional Theory

Left: Scaling relationship for OH* and OOH* over various oxides, superposed on a heat map of activity as a function of these two variables. Note that the optimum (brightest color) is does not lie on the scaling line (a). Right: Examples of how to overcome the scaling relation by introducing adsorbate specific stabilizations. Bifunctionality (b) on alloys or mixed metal/oxide/sulfide catalysts, promoters in terms of specifically adsorbed ions (c), ligands (d), or electrolyte molecules (e) can stabilize various adsorbates specifically. Three‐dimensional active sites such as interfaces between two materials (f) or confinement (g) can also provide opportunities to break scaling relationships. Differently colored circles indicate distinct elements. Reproduced from Reference 54. Copyright Nature Publishing Group

[ Normal View | Magnified View ]

Reconciling theory with experiment results for hydrogen evolution reaction (HER) electrocatalysts. (a) (top) Experimental i₀ plotted against theoretically calculated ΔG_H for various transition metal surfaces, compared against the proposed kinetic model (below). Open circles represent single crystal data. Reproduced from Reference 46. Copyright IOP science. (b) Experimental HER data of Pt (black), BiPt alloy precursor (Pt‐Bi_ir, red dash), and the synthesized BiPt alloy (blue dots). Modified from Reference 47. Copyright Nature Publishing Group. (c) Color contour plot of stability (measured by surface energy per unit cell γ) with varying levels of strain and S vacancies. Black line illustrates combinations of strain and S vacancies for ΔG_H = 0. (d) HER data of Au substrate, Pt control, and 2H‐MoS₂ (pristine and with various treatments). (c) and (d) reproduced from Reference 229. Copyright Nature Publishing Group. (e) (left) Theoretical volcano plot of MXenes (Ti₂C and Mo₂C marked out with red stars) and (right) HER activity of Ti₂CT_x and Mo₂CT_x. Modified from Reference 246. Copyright American Chemical Society. (f) Comparison of theoretical and experimental overpotential at −10 mA cm⁻² for various MXenes after considering –F coverage on basal planes. Dashed line indicates complete agreement. Reproduced from Reference 247. Copyright American Chemical Society

[ Normal View | Magnified View ]

Mean average deviations (MADs) for eight diverse test sets. The performance for PBE (blue) and the dispersion corrected PBE‐dDsC (pink) are shown. The data for surface adsorption is taken from Reference (206). The E_adsPt_Small refers to H, O, and CO adsorption on Pt.¹¹¹ E_adsPt_Org. contains methane, ethane, ethylidyne, cyclohexene, benzene, and naphtalene on Pt(111). The other test sets are extracted from GMTKN24.²⁰⁷ The PBE‐dDsC data were published in Reference (208). ISOL22 assesses isomerization energies of large organic molecules. DARC stands for Diels‐Alder reaction energies, while AL2X contains dimerization energies of AlX3 species. ISO34 determines isomerization energies of small organic molecules while S22 is dedicated to weak intermolecular interactions. BSR36 measures bond separation energies of alkanes, that is, hydrogenation reactions of alkanes to methane

[ Normal View | Magnified View ]

Schematic plot of the overpotential (η) versus the logarithm of the current density (pink). The Tafel slope and the exchange current density i₀ as determined by the linear fit (Tafel approximation) are indicated (blue)

[ Normal View | Magnified View ]

Model Free Energy surface in terms of the adsorbate, nuclear coordinate (x‐axis), and the electrolyte arrangement coordinate (y‐axis). Early and late transition states with respect to the electrolyte coordinate can be distinguished

[ Normal View | Magnified View ]

Comparison of computational hydrogen electrode (CHE) (horizontal lines and solid points) and grand‐canonical density functional theory (GC‐DFT) (empty crosses and thick lines) results for the energy difference of two intermediates during the oxygen evolution reaction (OER) over CoOOH (a semiconductor) in basic conditions. The intermediate in pink (crosses) has O₂ bound to the catalyst, while O₂ is desorbed in the intermediate in blue (plus signs). The desorbing O₂ molecule is highlighted in pale red in the structural representation, which also exemplifies the use of symmetric unit cells to avoid surface dipole moments and obtain unambigious workfunctions. The data is taken from Reference 64

[ Normal View | Magnified View ]

Representation of the key contributions introducing various descriptions of the electrocatalytic interface. The superscript refers to the reference to the corresponding article, while the year is given below the lead author name. The gray scale highlights the chronological ordering. Note, that other groups have applied these techniques in various contexts and some of the methods have been developed several times independently with slight variations, but we have tried to highlight the earliest contributions. The horizontal axis is indicative of the treatment of the solvent, with the black line symbolizing the electrostatic potential. (a) corresponds to vacuum, (b) the combination of a small number of solvent molecules at the vacuum interface, (c) the use of an implicit solvent, (d) the combination of implicit solvent (light blue) and explicit solvent molecules, and (e) the use of a fully explicit description of the liquid phase. The computational hydrogen electrode (CHE) cornerstone is highlighted in bold. The vertical axis represents the description of the electrochemical potential. Constant charge approaches typically work with neutral surfaces. Constant electric fields can be used as a proxy for the electrochemical potential under certain assumptions (typically the thickness of the double layer). Truly constant potential approaches are typically relying on grand‐canonical density functional theory (GC‐DFT)

[ Normal View | Magnified View ]

References

Lewis, NS, Nocera, DG. Powering the planet: Chemical challenges in solar energy utilization. Proc Natl Acad Sci. 2006;103(43):15729–15735.
Bockris, JO. Hydrogen no longer a high cost solution to global warming: New ideas. Int J Hydrog Energy. 2008;33(9):2129–2131.
Seshadri, G, Lin, C, Bocarsly, AB. A new homogeneous electrocatalyst for the reduction of carbon dioxide to methanol at low overpotential. J Electroanal Chem. 1994;372(1):145–150.
Yan, Y, Zeitler, EL, Gu, J, Hu, Y, Bocarsly, AB. Electrochemistry of aqueous pyridinium: Exploration of a key aspect of electrocatalytic reduction of CO2 to methanol. J Am Chem Soc. 2013;135(38):14020–14023.
Neri, G, Donaldson, PM, Cowan, AJ. The role of electrode–catalyst interactions in enabling efficient CO ₂ reduction with Mo(bpy)(CO) ₄ as revealed by vibrational sum‐frequency generation spectroscopy. J Am Chem Soc. 2017;139(39):13791–13797.
Franco, AA, Rucci, A, Brandell, D, et al. Boosting rechargeable batteries R%26D by multiscale modeling: Myth or reality? Chem Rev. 2019;119(7):4569–4627.
Lautar, AK, Hagopian, A, Filhol, J‐S. Modeling interfacial electrochemistry: Concepts and tools. Phys Chem Chem Phys. 2020;22:10569–10580.
Norskov, JK, Bligaard, T, Rossmeisl, J, Christensen, CH. Towards the computational design of solid catalysts. Nat Chem. 2009;1(1):37–46.
Seh, ZW, Kibsgaard, J, Dickens, CF, Chorkendorff, I, Nørskov, JK, Jaramillo, TF. Combining theory and experiment in electrocatalysis: Insights into materials design. Science. 2017;355(6321):eaad4998.
Stampfl, C, Veronica Ganduglia‐Pirovano, M, Reuter, K, Scheffler, M. Catalysis and corrosion: The theoretical surface‐science context. Surf Sci. 2002;500(1):368–394.
Taylor, CD. Corrosion informatics: An integrated approach to modelling corrosion. Corros Eng Sci Technol. 2015;50(7):490–508.
Merola, C, Cheng, H‐W, Schwenzfeier, K, et al. In situ nano‐ to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface. Proc Natl Acad Sci. 2017;114(36):9541–9546.
Nace‐International‐Report.pdf [Internet]. [cited 2019]. Available from: http://impact.nace.org/documents/Nace-International-Report.pdf.
Heiskanen, SK, Kim, J, Lucht, BL. Generation and evolution of the solid electrolyte interphase of lithium‐ion batteries. Joule. 2019;3(10):2322–2333.
Kopač Lautar, A, Bitenc, J, Rejec, T, Dominko, R, Filhol, J‐S, Doublet, M‐L. Electrolyte reactivity in the double layer in mg batteries: An interface potential‐dependent DFT study. J Am Chem Soc. 2020;142(11):5146–5153.
Simon, P, Gogotsi, Y. Materials for electrochemical capacitors. Nat Mater. 2008;7(11):845–854.
Zhan, C, Lian, C, Zhang, Y, et al. Computational insights into materials and interfaces for capacitive energy storage. Adv Sci. 2017;4(7):1700059.
Burdyny, T, Smith, WA. CO ₂ reduction on gas‐diffusion electrodes and why catalytic performance must be assessed at commercially‐relevant conditions. Energy Environ Sci. 2019;12(5):1442–1453.
Laguna‐Bercero, MA. Recent advances in high temperature electrolysis using solid oxide fuel cells: A review. J Power Sources. 2012;203(0):4–16.
Vayenas, CG, Bebelis, S, Yentekakis, IV, Lintz, H‐G. Non‐faradaic electrochemical modification of catalytic activity: A status report. Catal Today. 1992;11(3):303–438.
Pander, JE, Baruch, MF, Bocarsly, AB. Probing the mechanism of aqueous CO2 reduction on post‐transition‐metal electrodes using ATR‐IR spectroelectrochemistry. ACS Catal. 2016;6(11):7824–7833.
Subbaraman, R, Tripkovic, D, Chang, K‐C, et al. Trends in activity for the water electrolyser reactions on 3D M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat Mater. 2012;11(6):550–557.
Benck, JD, Hellstern, TR, Kibsgaard, J, Chakthranont, P, Jaramillo, TF. Catalyzing the hydrogen evolution reaction (HER) with molybdenum sulfide nanomaterials. ACS Catal. 2014;4(11):3957–3971.
Yu, P, Wang, F, Shifa, TA, et al. Earth abundant materials beyond transition metal dichalcogenides: A focus on electrocatalyzing hydrogen evolution reaction. Nano Energy. 2019;58:244–276.
Dasgupta, A, Rioux, RM. Intermetallics in catalysis: An exciting subset of multimetallic catalysts. Catal Today. 2019;330:2–15.
Handoko, AD, Steinmann, SN, Seh, ZW. Theory‐guided materials design: Two‐dimensional MXenes in electro‐ and photocatalysis. Nanoscale Horiz. 2019;4(4):809–827.
Wu, G, Zelenay, P. Nanostructured nonprecious metal catalysts for oxygen reduction reaction. Acc Chem Res. 2013;46(8):1878–1889.
Masa, J, Xia, W, Muhler, M, Schuhmann, W. On the role of metals in nitrogen‐doped carbon electrocatalysts for oxygen reduction. Angew Chem Int Ed. 2015;54(35):10102–10120.
Leung, K. DFT modelling of explicit solid–solid interfaces in batteries: Methods and challenges. Phys Chem Chem Phys. 2020;22:10412–10425.
Wu, C, Schmidt, DJ, Wolverton, C, Schneider, WF. Accurate coverage‐dependence incorporated into first‐principles kinetic models: Catalytic NO oxidation on Pt (111). J Catal. 2012;286:88–94.
Reuter, K. Ab initio thermodynamics and first‐principles microkinetics for surface catalysis. Catal Lett. 2016;146(3):541–563.
Stamenkovic, VR, Strmcnik, D, Lopes, PP, Markovic, NM. Energy and fuels from electrochemical interfaces. Nat Mater. 2017;16(1):57–69.
Ong, BC, Kamarudin, SK, Basri, S. Direct liquid fuel cells: A review. Int J Hydrog Energy. 2017;42(15):10142–10157.
Zhu, DD, Liu, JL, Qiao, SZ. Recent advances in inorganic heterogeneous electrocatalysts for reduction of carbon dioxide. Adv Mater. 2016;28(18):3423–3452.
Cui, X, Tang, C, Zhang, Q. A review of Electrocatalytic reduction of dinitrogen to ammonia under ambient conditions. Adv Energy Mater. 2018;8(22):1800369.
Steinmann, SN, Michel, C, Schwiedernoch, R, Wu, M, Sautet, P. Electro‐carboxylation of butadiene and ethene over Pt and Ni catalysts. J Catal. 2016;343:240–247.
Wang, C‐Y. Fundamental models for fuel cell engineering. Chem Rev. 2004;104(10):4727–4766.
Weber, AZ, Newman, J. Modeling transport in polymer‐electrolyte fuel cells. Chem Rev. 2004;104(10):4679–4726.
Bernardi, DM, Verbrugge, MW. A mathematical model of the solid‐polymer‐electrolyte fuel cell. J Electrochem Soc. 1992;139(9):2477–2491.
Jahnke, T, Futter, G, Latz, A, et al. Performance and degradation of proton exchange membrane fuel cells: State of the art in modeling from atomistic to system scale. J Power Sources. 2016;304:207–233.
Costentin, C, Savéant, J‐M, Tard, C. Catalysis of CO ₂ electrochemical reduction by protonated pyridine and similar molecules. Useful lessons from a methodological misadventure. ACS Energy Lett. 2018;3(3):695–703.
Quaino, P, Juarez, F, Santos, E, Schmickler, W. Volcano plots in hydrogen electrocatalysis—Uses and abuses. Beilstein J Nanotechnol. 2014;5(1):846–854.
Sabatier, F. La catalyse en chimie organique. Paris, France: Berauge, 1920.
Parsons, R. The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen. Trans Faraday Soc. 1958;54(0):1053–1063.
Trasatti, S. Work function, electronegativity, and electrochemical behaviour of metals: III. Electrolytic hydrogen evolution in acid solutions. J Electroanal Chem Interfacial Electrochem. 1972;39(1):163–184.
Nørskov, JK, Bligaard, T, Logadottir, A, et al. Trends in the exchange current for hydrogen evolution. J Electrochem Soc. 2005;152(3):J23.
Greeley, J, Jaramillo, TF, Bonde, J, Chorkendorff, I, Norskov, JK. Computational high‐throughput screening of electrocatalytic materials for hydrogen evolution. Nat Mater. 2006;5(11):909–913.
Norskov, JK, Christensen, CH. Toward efficient hydrogen production at surfaces. Science. 2006;312(5778):1322–1323.
Monyoncho, EA, Steinmann, SN, Sautet, P, Baranova, EA, Michel, C. Computational screening for selective catalysts: Cleaving the CC bond during ethanol electro‐oxidation reaction. Electrochim Acta. 2018;274:274–278.
Abild‐Pedersen, F, Greeley, J, Studt, F, et al. Scaling properties of adsorption energies for hydrogen‐containing molecules on transition‐metal surfaces. Phys Rev Lett. 2007;99(1):016105.
Montemore, MM, Medlin, JW. Scaling relations between adsorption energies for computational screening and design of catalysts. Cat Sci Technol. 2014;4(11):3748–3761.
Calle‐Vallejo, F, Loffreda, D, Koper, MTM, Sautet, P. Introducing structural sensitivity into adsorption‐energy scaling relations by means of coordination numbers. Nat Chem. 2015;7(5):403–410.
Vojvodic, A, Nørskov, JK. New design paradigm for heterogeneous catalysts. Natl Sci Rev. 2015;2(2):140–143.
Montoya, JH, Seitz, LC, Chakthranont, P, Vojvodic, A, Jaramillo, TF, Nørskov, JK. Materials for solar fuels and chemicals. Nat Mater. 2017;16(1):70–81.
Pérez‐Ramírez, J, López, N. Strategies to break linear scaling relationships. Nat Catal. 2019;2(11):971–976.
Fletcher, S. Tafel slopes from first principles. J Solid State Electrochem. 2009;13(4):537–549.
Gnanamuthu, DS, Petrocelli, JV. A generalized expression for the Tafel slope and the kinetics of oxygen reduction on noble metals and alloys. J Electrochem Soc. 1967;114(10):1036.
Holewinski, A, Linic, S. Elementary mechanisms in Electrocatalysis: Revisiting the ORR Tafel slope. J Electrochem Soc. 2012;159(11):H864–H870.
Shinagawa, T, Garcia‐Esparza, AT, Takanabe, K. Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion. Sci Rep. 2015;5(1):13801.
Norskov, JK, Rossmeisl, J, Logadottir, A, et al. Origin of the overpotential for oxygen reduction at a fuel‐cell cathode. J Phys Chem B. 2004;108(46):17886–17892.
Koper, MTM, Lukkien, JJ, Jansen, APJ, van Santen, RA. Lattice gas model for CO electrooxidation on Pt−Ru bimetallic surfaces. J Phys Chem B. 1999;103(26):5522–5529.
Chun, H‐J, Apaja, V, Clayborne, A, Honkala, K, Greeley, J. Atomistic insights into nitrogen‐cycle electrochemistry: A combined DFT and kinetic Monte Carlo analysis of NO electrochemical reduction on Pt(100). ACS Catal. 2017;7(6):3869–3882.
Rossmeisl, J, Logadottir, A, Norskov, JK. Electrolysis of water on (oxidized) metal surfaces. Chem Phys. 2005;319(1–3):178–184.
Curutchet, A, Colinet, P, Michel, C, Steinmann, SN, Bahers, TL. Two‐sites are better than one: Revisiting the OER mechanism on CoOOH by DFT with electrode polarization. Phys Chem Chem Phys. 2020;22(13):7031–7038.
Exner, KS, Sohrabnejad‐Eskan, I, Over, H. A universal approach to determine the free energy diagram of an electrocatalytic reaction. ACS Catal. 2018;8(3):1864–1879.
Exner, KS. Is thermodynamics a good descriptor for the activity? Re‐investigation of Sabatier`s principle by the free energy diagram in electrocatalysis. ACS Catal. 2019;9:5320–5329.
Exner, KS. Design criteria for oxygen evolution electrocatalysts from first principles: Introduction of a unifying material‐screening approach. ACS Appl Energy Mater. 2019;2(11):7991–8001.
Bockris, JO. Overpotential. A lacuna in scientific knowledge. J Chem Educ. 1971;48(6):352.
Anderson, AB. Molecular orbital theory for catalysis. Structures, energy levels, and reactions of acetylene with Ni2(COD)2(RCCR), Ni2(C5H5)2(RCCR), and the nickel(111) surface. J Am Chem Soc. 1978;100(4):1153–1159.
Anderson, AB, Kötz, R, Yeager, E. Theory for C—N− and Ag—C vibrational frequency dependence on potential: Cyanide on a silver electrode. Chem Phys Lett. 1981;82(1):130–134.
Anderson, AB, Ray, NK. Structures and reactions of hydronium, water, and hydroxyl on an iron electrode. Potential dependence. J Phys Chem. 1982;86(4):488–494.
Nakatsuji, H. Dipped adcluster model for chemisorptions and catalytic reactions on a metal surface. J Chem Phys. 1987;87(8):4995–5001.
Santos, E, Schmickler, W. Changes in the surface energy during the reconstruction of Au(100) and Au(111) electrodes. Chem Phys Lett. 2004;400(1):26–29.
Bureau, C, Lécayon, G. On a modeling of voltage‐application to metallic electrodes using density functional theory. J Chem Phys. 1997;106(21):8821–8829.
Anderson, AB, Kang, DB. Quantum chemical approach to redox reactions including potential dependence: Application to a model for hydrogen evolution from diamond. J Phys Chem A. 1998;102(29):5993–5996.
Khan, SUM, Bockris, JO. Electronic states in solution and charge transfer. J Phys Chem. 1983;87(14):2599–2603.
Anderson, AB, Albu, TV. Ab initio determination of reversible potentials and activation energies for outer‐sphere oxygen reduction to water and the reverse oxidation reaction. J Am Chem Soc. 1999;121(50):11855–11863.
Anderson, AB, Albu, TV. Catalytic effect of platinum on oxygen reduction an ab initio model including electrode potential dependence. J Electrochem Soc. 2000;147(11):4229–4238.
Bureau, C, Kranias, S, Crispin, X, Bredas, J‐L. DFT modeling of stark‐tuning effect: CO on polarized Pd(100) as a probe for double‐layer electrostatic effects in electrochemistry. In: Hernández‐Laguna, A, Maruani, J, McWeeny, R, Wilson, S, editors. Quantum systems in chemistry and physics volume 2: Advanced problems and complex systems Granada, Spain, 1998. Dordrecht: Springer Netherlands, 2000; p. 169–192. (Progress in Theoretical Chemistry and Physics).
Crispin, X, Geskin, VM, Bureau, C, Lazzaroni, R, Schmickler, W, Brédas, JL. A density functional model for tuning the charge transfer between a transition metal electrode and a chemisorbed molecule via the electrode potential. J Chem Phys. 2001;115(22):10493–10499.
Koper, MTM, van Santen, RA, Wasileski, SA, Weaver, MJ. Field‐dependent chemisorption of carbon monoxide and nitric oxide on platinum‐group (111) surfaces: Quantum chemical calculations compared with infrared spectroscopy at electrochemical and vacuum‐based interfaces. J Chem Phys. 2000;113(10):4392–4407.
Liu, P, Logadottir, A, Nørskov, JK. Modeling the electro‐oxidation of CO and H2/CO on Pt, Ru, PtRu and Pt3Sn. Electrochim Acta. 2003;48(25–26):3731–3742.
Vuilleumier, R, Sprik, M, Alavi, A. Computation of electronic chemical potentials using free energy density functionals. J Mol Struct. 2000;506:11.
Lozovoi, AY, Alavi, A, Kohanoff, J, Lynden‐Bell, RM. Ab initio simulation of charged slabs at constant chemical potential. J Chem Phys. 2001;115(4):1661–1669.
Lozovoi, AY, Alavi, A. Reconstruction of charged surfaces: General trends and a case study of Pt(110) and Au(110). Phys Rev B. 2003;68(24):245416.
Blumberger, J, Bernasconi, L, Tavernelli, I, Vuilleumier, R, Sprik, M. Electronic structure and solvation of copper and silver ions: A theoretical picture of a model aqueous redox reaction. J Am Chem Soc. 2004;126(12):3928–3938.
Tateyama, Y, Blumberger, J, Sprik, M, Tavernelli, I. Density‐functional molecular‐dynamics study of the redox reactions of two anionic, aqueous transition‐metal complexes. J Chem Phys. 2005;122(23):234505.
Anderson, AB. Theory at the electrochemical interface: Reversible potentials and potential‐dependent activation energies. Electrochim Acta. 2003;48(25):3743–3749.
Roques, AB, Jérôme, A. Theory for the potential shift for OHads formation on the Pt skin on Pt3Cr(111) in acid. J Electrochem Soc. 2004;151(3):E85.
Roques, J, Anderson, AB. Electrode potential‐dependent stages in OHads formation on the Pt3Cr alloy (111) surface. J Electrochem Soc. 2004;151:E340.
Sha, Y, Yu, TH, Liu, Y, Merinov, BV, Goddard, WA. Theoretical study of solvent effects on the platinum‐catalyzed oxygen reduction reaction. J Phys Chem Lett. 2010;1(5):856–861.
Sakong, S, Naderian, M, Mathew, K, Hennig, RG, Groß, A. Density functional theory study of the electrochemical interface between a Pt electrode and an aqueous electrolyte using an implicit solvent method. J Chem Phys. 2015;142(23):234107.
Stamenkovic, V, Mun, BS, Mayrhofer, KJJ, et al. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angew Chem Int Ed. 2006;45(18):2897–2901.
Morgan, BJ, Watson, GW. A DFT+U description of oxygen vacancies at the TiO2 rutile (110) surface. Surf Sci. 2007;601(21):5034–5041.
Kuo, T‐J, Huang, MH. Gold‐catalyzed low‐temperature growth of cadmium oxide nanowires by vapor transport. J Phys Chem B. 2006;110(28):13717–13721.
Nilekar, AU, Mavrikakis, M. Improved oxygen reduction reactivity of platinum monolayers on transition metal surfaces. Surf Sci. 2008;602(14):L89–L94.
Man, IC, Su, H‐Y, Calle‐Vallejo, F, et al. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem. 2011;3(7):1159–1165.
Song, G‐L, Unocic, KA. The anodic surface film and hydrogen evolution on Mg. Corros Sci. 2015;98:758–765.
Liu, Y, Liu, S, Che, Z, et al. Concave octahedral Pd@PdPt electrocatalysts integrating core–shell, alloy and concave structures for high‐efficiency oxygen reduction and hydrogen evolution reactions. J Mater Chem A. 2016;4(42):16690–16697.
Ekspong, J, Sharifi, T, Shchukarev, A, Klechikov, A, Wågberg, T, Gracia‐Espino, E. Stabilizing active edge sites in semicrystalline molybdenum sulfide by anchorage on nitrogen‐doped carbon nanotubes for hydrogen evolution reaction. Adv Funct Mater. 2016;26(37):6766–6776.
Karamad, M, Hansen, HA, Rossmeisl, J, Nørskov, JK. Mechanistic pathway in the electrochemical reduction of CO2 on RuO2. ACS Catal. 2015;5(7):4075–4081.
Chen, LD, Urushihara, M, Chan, K, Nørskov, JK. Electric field effects in electrochemical CO2 reduction. ACS Catal. 2016;6(10):7133–7139.
Liu, S, Yang, H, Huang, X, et al. Identifying active sites of nitrogen‐doped carbon materials for the CO2 reduction reaction. Adv Funct Mater. 2018;28(21):1800499.
Montoya, JH, Tsai, C, Vojvodic, A, Nørskov, JK. The challenge of electrochemical ammonia synthesis: A new perspective on the role of nitrogen scaling relations. ChemSusChem. 2015;8(13):2180–2186.
Choi, C, Back, S, Kim, N‐Y, Lim, J, Kim, Y‐H, Jung, Y. Suppression of hydrogen evolution reaction in electrochemical N2 reduction using single‐atom catalysts: A computational guideline. ACS Catal. 2018;8(8):7517–7525.
Kwon, Y, Lai, SCS, Rodriguez, P, Koper, MTM. Electrocatalytic oxidation of alcohols on gold in alkaline media: Base or gold catalysis? J Am Chem Soc. 2011;133(18):6914–6917.
Calle‐Vallejo, F, Koper, MTM. Theoretical considerations on the electroreduction of CO to C₂ species on Cu(100) electrodes. Angew Chem Int Ed. 2013;52(28):7282–7285.
Katsounaros, I, Chen, T, Gewirth, AA, Markovic, NM, Koper, MTM. Evidence for decoupled electron and proton transfer in the electrochemical oxidation of Ammonia on Pt(100). J Phys Chem Lett. 2016;7(3):387–392.
Goodpaster, JD, Bell, AT, Head‐Gordon, M. Identification of possible pathways for C–C bond formation during electrochemical reduction of CO₂: New theoretical insights from an improved electrochemical model. J Phys Chem Lett. 2016;7(8):1471–1477.
Nie, X, Esopi, MR, Janik, MJ, Asthagiri, A. Selectivity of CO2 reduction on copper electrodes: The role of the kinetics of elementary steps. Angew Chem Int Ed. 2013;52(9):2459–2462.
Fang, Y‐H, Wei, G‐F, Liu, Z‐P. Constant‐charge reaction theory for potential‐dependent reaction kinetics at the solid‐liquid interface. J Phys Chem C. 2014;118(7):3629–3635.
Chan, K, Nørskov, JK. Electrochemical barriers made simple. J Phys Chem Lett. 2015;6(14):2663–2668.
Steinmann, SN, Michel, C, Schwiedernoch, R, Filhol, J‐S, Sautet, P. Modeling the HCOOH/CO2 electrocatalytic reaction: When details are key. ChemPhysChem. 2015;16(11):2307–2311.
Taylor, CD, Wasileski, SA, Filhol, J‐S, Neurock, M. First principles reaction modeling of the electrochemical interface: Consideration and calculation of a tunable surface potential from atomic and electronic structure. Phys Rev B. 2006;73(16):165402.
Filhol, J‐S, Neurock, M. Elucidation of the electrochemical activation of water over Pd by first principles. Angew Chem Int Ed. 2006;45(3):402–406.
Taylor, C, Kelly, RG, Neurock, M. First‐principles calculations of the electrochemical reactions of water at an immersed Ni(111)/H2O interface. J Electrochem Soc. 2006;153(12):E207–E214.
Lespes, N, Filhol, J‐S. Using implicit solvent in ab initio electrochemical modeling: Investigating Li+/Li electrochemistry at a Li/solvent interface. J Chem Theory Comput. 2015;11(7):3375–3382.
Steinmann, SN, Michel, C, Schwiedernoch, R, Sautet, P. Impacts of electrode potentials and solvents on the electroreduction of CO2: A comparison of theoretical approaches. Phys Chem Chem Phys. 2015;17(21):13949–13963.
Otani, M, Sugino, O. First‐principles calculations of charged surfaces and interfaces: A plane‐wave nonrepeated slab approach. Phys Rev B. 2006;73(11):115407.
Otani, M, Hamada, I, Sugino, O, Morikawa, Y, Okamoto, Y, Ikeshoji, T. Electrode dynamics from first principles. J Phys Soc Jpn. 2008;77(2):024802.
Bonnet, N, Morishita, T, Sugino, O, Otani, M. First‐principles molecular dynamics at a constant electrode potential. Phys Rev Lett. 2012;109(26):266101.
Haruyama, J, Ikeshoji, T, Otani, M. Electrode potential from density functional theory calculations combined with implicit solvation theory. Phys Rev Mater. 2018;2(9):095801.
Rossmeisl, J, Norskov, JK, Taylor, CD, Janik, MJ, Neurock, M. Calculated phase diagrams for the electrochemical oxidation and reduction of water over Pt(111). J Phys Chem B. 2006;110(43):21833–21839.
Rossmeisl, J, Skulason, E, Bjorketun, ME, Tripkovic, V, Norskov, JK. Modeling the electrified solid‐liquid interface. Chem Phys Lett. 2008;466(1–3):68–71.
Skúlason, E, Tripkovic, V, Björketun, ME, et al. Modeling the electrochemical hydrogen oxidation and evolution reactions on the basis of density functional theory calculations. J Phys Chem C. 2010;114(42):18182–18197.
Hansen, MH, Rossmeisl, J. pH in grand canonical statistics of an electrochemical interface. J Phys Chem C. 2016;120(51):29135–29143.
Hansen, MH, Nilsson, A, Rossmeisl, J. Modelling pH and potential in dynamic structures of the water/Pt(111) interface on the atomic scale. Phys Chem Chem Phys. 2017;19(34):23505–23514.
Cohen, AJ, Mori‐Sánchez, P. Dramatic changes in electronic structure revealed by fractionally charged nuclei. J Chem Phys. 2014;140(4):044110.
Chen, Y, Roux, B. Constant‐pH hybrid nonequilibrium molecular dynamics–Monte Carlo simulation method. J Chem Theory Comput. 2015;11(8):3919–3931.
Radak, BK, Chipot, C, Suh, D, et al. Constant‐pH molecular dynamics simulations for large biomolecular systems. J Chem Theory Comput. 2017;13(12):5933–5944.
Bagger, A, Arán‐Ais, RM, Halldin Stenlid, J, et al. Ab initio cyclic voltammetry on Cu(111), Cu(100) and Cu(110) in acidic, neutral and alkaline solutions. ChemPhysChem. 2019;20(22):3096–3105.
Jinnouchi, R, Anderson, AB. Electronic structure calculations of liquid‐solid interfaces: Combination of density functional theory and modified Poisson‐Boltzmann theory. Phys Rev B. 2008;77(24):245417.
Fang, Y‐H, Liu, Z‐P. Mechanism and Tafel lines of electro‐oxidation of water to oxygen on RuO2(110). J Am Chem Soc. 2010;132(51):18214–18222.
Letchworth‐Weaver, K, Arias, TA. Joint density functional theory of the electrode‐electrolyte interface: Application to fixed electrode potentials, interfacial capacitances, and potentials of zero charge. Phys Rev B. 2012;86(7):075140.
Ringe, S, Oberhofer, H, Hille, C, Matera, S, Reuter, K. Function‐space‐based solution scheme for the size‐modified Poisson‐Boltzmann equation in full‐potential DFT. J Chem Theory Comput. 2016;12(8):4052–4066.
Fisicaro, G, Genovese, L, Andreussi, O, Marzari, N, Goedecker, S. A generalized Poisson and Poisson‐Boltzmann solver for electrostatic environments. J Chem Phys. 2016;144(1):014103.
Sundararaman, R, Goddard, WA, Arias, TA. Grand canonical electronic density‐functional theory: Algorithms and applications to electrochemistry. J Chem Phys. 2017;146(11):114104.
Mathew, K, Kolluru, VSC, Mula, S, Steinmann, SN, Hennig, RG. Implicit self‐consistent electrolyte model in plane‐wave density‐functional theory. J Chem Phys. 2019;151(23):234101.
Petrosyan, SA, Rigos, AA, Arias, TA. Joint density‐functional theory: Ab initio study of Cr2O3 surface chemistry in solution. J Phys Chem B. 2005;109(32):15436–15444.
Gunceler, D, Letchworth‐Weaver, K, Sundararaman, R, Schwarz, KA, Arias, TA. The importance of nonlinear fluid response in joint density‐functional theory studies of battery systems. Model Simul Mater Sci Eng. 2013;21(7):074005.
Melander, MM, Kuisma, MJ, Christensen, TEK, Honkala, K. Grand‐canonical approach to density functional theory of electrocatalytic systems: Thermodynamics of solid‐liquid interfaces at constant ion and electrode potentials. J Chem Phys. 2018;150(4):041706.
Kastlunger, G, Lindgren, P, Peterson, AA. Controlled‐potential simulation of elementary electrochemical reactions: Proton discharge on metal surfaces. J Phys Chem C. 2018;122(24):12771–12781.
Steinmann, SN, Sautet, P. Assessing a first‐principles model of an electrochemical interface by comparison with experiment. J Phys Chem C. 2016;120(10):5619–5623.
Shang, R, Steinmann, SN, Xu, B‐Q, Sautet, P. Mononuclear Fe in N‐doped carbon: Computational elucidation of active sites for electrochemical oxygen reduction and oxygen evolution reactions. Cat Sci Technol. 2020;10(4):1006–1014.
Abidi, N, Bonduelle‐Skrzypczak, A, Steinmann, SN. Revisiting the active sites at the MoS2/H2O interface via grand‐canonical DFT: The role of water dissociation. ACS Appl Mater Interfaces. 2020;12:31401–31410.
Hajar, YM, Treps, L, Michel, C, Baranova, EA, Steinmann, SN. Theoretical insight into the origin of the electrochemical promotion of ethylene oxidation on ruthenium oxide. Cat Sci Technol. 2019;9(21):5915–5926.
Panaritis, C, Michel, C, Couillard, M, Baranova, EA, Steinmann, SN. Elucidating the role of electrochemical polarization on the selectivity of the CO2 hydrogenation reaction over Ru. Electrochim Acta. 2020;350:136405.
Wang, P, Steinmann, SN, Fu, G, Michel, C, Sautet, P. Key role of anionic doping for H2 production from formic acid on Pd(111). ACS Catal. 2017;7(3):1955–1959.
Lluch, JM. Perspective on “on the theory of oxidation—Reduction reactions involving electron transfer. I.”. In: Cramer, CJ, Truhlar, DG, editors. Theoretical chemistry accounts: New century issue. Berlin and Heidelberg, Germany: Springer, 2001; p. 231–233.
Hush, NS. Adiabatic rate processes at electrodes. I. Energy‐charge relationships. J Chem Phys. 1958;28(5):962–972.
Kornyshev, AA, Vilfan, I. Phase transitions at the electrochemical interface. Electrochim Acta. 1995;40(1):109–127.
Santos, E, Koper, MTM, Schmickler, W. A model for bond‐breaking electron transfer at metal electrodes. Chem Phys Lett. 2006;419(4):421–425.
Santos, E, Schmickler, W. Fundamental aspects of electrocatalysis. Chem Phys. 2007;332(1):39–47.
Santos, E, Koper, MTM, Schmickler, W. Bond‐breaking electron transfer of diatomic reactants at metal electrodes. Chem Phys. 2008;344(1):195–201.
Anderson, PW. Localized magnetic states in metals. Phys Rev. 1961;124(1):41–53.
Newns, DM. Self‐consistent model of hydrogen chemisorption. Phys Rev. 1969;178(3):1123–1135.
Santos, E, Lundin, A, Pötting, K, Quaino, P, Schmickler, W. Model for the electrocatalysis of hydrogen evolution. Phys Rev B. 2009;79(23):235436.
Staub, R, Iannuzzi, M, Khaliullin, RZ, Steinmann, SN. Energy decomposition analysis for metal surface–Adsorbate interactions by block localized wave functions. J Chem Theory Comput. 2019;15(1):265–275.
Santos, E, Quaino, P, Schmickler, W. Theory of electrocatalysis: Hydrogen evolution and more. Phys Chem Chem Phys. 2012;14(32):11224–11233.
Marcus, RA, Siders, P. Theory of highly exothermic electron transfer reactions. J Phys Chem. 1982;86(5):622–630.
Mills, JN, McCrum, IT, Janik, MJ. Alkali cation specific adsorption onto fcc(111) transition metal electrodes. Phys Chem Chem Phys. 2014;16(27):13699–13707.
Saleheen, M, Heyden, A. Liquid‐phase modeling in heterogeneous catalysis. ACS Catal. 2018;8(3):2188–2194.
Schweitzer, B, Steinmann, SN, Michel, C. Can microsolvation effects be estimated from vacuum computations? A case‐study of alcohol decomposition at the H2O/Pt(111) interface. Phys Chem Chem Phys. 2019;21(10):5368–5377.
Cantu, DC, Padmaperuma, AB, Nguyen, M‐T, et al. A combined experimental and theoretical study on the activity and selectivity of the electrocatalytic hydrogenation of aldehydes. ACS Catal. 2018;8(8):7645–7658.
Sakong, S, Forster‐Tonigold, K, Gross, A. The structure of water at a Pt(111) electrode and the potential of zero charge studied from first principles. J Chem Phys. 2016;144(19):194701.
Bellarosa, L, Garcia‐Muelas, R, Revilla‐Lopez, G, Lopez, N. Diversity at the water‐metal Interface: Metal, water thickness, and confinement effects. ACS Cent Sci. 2016;2(2):109–116.
Le, J, Iannuzzi, M, Cuesta, A, Cheng, J. Determining potentials of zero charge of metal electrodes versus the standard hydrogen electrode from density‐functional‐theory‐based molecular dynamics. Phys Rev Lett. 2017;119(1):016801.
Cheng, T, Xiao, H, Goddard, WA. Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free‐energy calculations at 298 K. Proc Natl Acad Sci. 2017;114(8):1795–1800.
Steinmann, SN, Ferreira De Morais, R, Götz, AW, et al. Force field for water over Pt(111): Development, assessment, and comparison. J Chem Theory Comput. 2018;14(6):3238–3251.
van, D, Adri, CT, Bryantsev, VS, et al. Development and validation of a ReaxFF reactive force field for Cu Cation/water interactions and copper metal/metal oxide/metal hydroxide condensed phases. J Phys Chem A. 2010;114(35):9507–9514.
Cheng, T, Xiao, H, Goddard, WA. Reaction mechanisms for the electrochemical reduction of CO2 to CO and Formate on the Cu(100) surface at 298 K from quantum mechanics free energy calculations with explicit water. J Am Chem Soc. 2016;138(42):13802–13805.
Cheng, TH, Fortunelli, A, Goddard, WA III. Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics. Proc Natl Acad Sci. 2019;116(16):7718–7722.
Clabaut, P, Fleurat‐Lessard, P, Michel, C, Steinmann, SN. Ten facets, one force field: The GAL19 force field for water–Noble metal interfaces. J Chem Theory Comput. 2020;16:4565–4578.
Cramer, CJ, Truhlar, DG. Implicit solvation models: Equilibria, structure, spectra, and dynamics. Chem Rev. 1999;99(8):2161–2200.
Fattebert, J‐L, Gygi, F. First‐principles molecular dynamics simulations in a continuum solvent. Int J Quantum Chem. 2003;93(2):139–147.
Ramirez, R, Borgis, D. Density functional theory of solvation and its relation to implicit solvent models. J Phys Chem B. 2005;109(14):6754–6763.
Jeanmairet, G, Levesque, M, Vuilleumier, R, Borgis, D. Molecular density functional theory of water. J Phys Chem Lett. 2013;4(4):619–624.
Réocreux, R, Jiang, T, Iannuzzi, M, Michel, C, Sautet, P. Structuration and dynamics of interfacial liquid water at hydrated γ‐alumina determined by ab initio molecular simulations: Implications for nanoparticle stability. ACS Appl Nano Mater. 2018;1(1):191–199.
Limmer, DT, Willard, AP, Madden, P, Chandler, D. Hydration of metal surfaces can be dynamically heterogeneous and hydrophobic. Proc Natl Acad Sci U S A. 2013;110(11):4200–4205.
Gauthier, JA, Ringe, S, Dickens, CF, et al. Challenges in modeling electrochemical reaction energetics with polarizable continuum models. ACS Catal. 2019;9(2):920–931.
Sun, G, Sautet, P. Metastable structures in cluster catalysis from first‐principles: Structural ensemble in reaction conditions and metastability triggered reactivity. J Am Chem Soc. 2018;140(8):2812–2820.
Marcus, RA. On the theory of oxidation‐reduction reactions involving electron transfer. I. J Chem Phys. 1956;24(5):966–978.
Staub, R, Steinmann, SN. Parameter‐free coordination numbers for solutions and interfaces. J Chem Phys. 2020;152(2):024124.
Sundararaman, R, Goddard, WA. The charge‐asymmetric nonlocally determined local‐electric (CANDLE) solvation model. J Chem Phys. 2015;142(6):064107.
Garcia‐Ratés, M, López, N. Multigrid‐based methodology for implicit solvation models in periodic DFT. J Chem Theory Comput. 2016;12(3):1331–1341.
Fisicaro, G, Genovese, L, Andreussi, O, et al. Soft‐sphere continuum solvation in electronic‐structure calculations. J Chem Theory Comput. 2017;13(8):3829–3845.
Li, Q, García‐Muelas, R, López, N. Microkinetics of alcohol reforming for H2 production from a FAIR density functional theory database. Nat Commun. 2018;9(1):526.
Desai, SK, Pallassana, V, Neurock, M. A periodic density functional theory analysis of the effect of water molecules on deprotonation of acetic acid over Pd(111). J Phys Chem B. 2001;105(38):9171–9182.
Vatti, AK, Todorova, M, Neugebauer, J. Ab initio determined phase diagram of clean and solvated muscovite mica surfaces. Langmuir. 2016;32(4):1027–1033.
Andreussi, O, Hörmann, NG, Nattino, F, Fisicaro, G, Goedecker, S, Marzari, N. Solvent‐aware interfaces in continuum solvation. J Chem Theory Comput. 2019;15(3):1996–2009.
Moine, E, Privat, R, Sirjean, B, Jaubert, J‐N. Estimation of solvation quantities from experimental thermodynamic data: Development of the comprehensive compSol databank for pure and mixed solutes. J Phys Chem Ref Data Monogr. 2017;46(3):033102.
Andreussi, O, Dabo, I, Marzari, N. Revised self‐consistent continuum solvation in electronic‐structure calculations. J Chem Phys. 2012;136(6):064102.
Sundararaman, R, Schwarz, KA, Letchworth‐Weaver, K, Arias, TA. Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz. J Chem Phys. 2015;142(5):054102.
Ringe, S, Oberhofer, H, Reuter, K. Transferable ionic parameters for first‐principles Poisson‐Boltzmann solvation calculations: Neutral solutes in aqueous monovalent salt solutions. J Chem Phys. 2017;146(13):134103.
Truscott, M, Andreussi, O. Field‐aware interfaces in continuum solvation. J Phys Chem B. 2019;123(16):3513–3524.
Steinmann, SN, Sautet, P, Michel, C. Solvation free energies for periodic surfaces: Comparison of implicit and explicit solvation models. Phys Chem Chem Phys. 2016;18(46):31850–31861.
Akinola, J, Barth, I, Goldsmith, BR, Singh, N. Adsorption energies of oxygenated aromatics and organics on rhodium and platinum in aqueous phase. ACS Catal. 2020;10:4929–4941.
Møller, C, Plesset, MS. Note on an approximation treatment for many‐electron systems. Phys Rev. 1934;46(7):618–622.
VandeVondele, J, Hutter, J. An efficient orbital transformation method for electronic structure calculations. J Chem Phys. 2003;118(10):4365–4369.
Mohr, S, Ratcliff, LE, Boulanger, P, et al. Daubechies wavelets for linear scaling density functional theory. J Chem Phys. 2014;140(20):204110.
Kohn, W, Sham, LJ. Self‐consistent equations including exchange and correlation effects. Phys Rev. 1965;140(4A):A1133–A1138.
Kühne, TD. Second generation car–Parrinello molecular dynamics. WIREs Comput Mol Sci. 2014;4(4):391–406.
Lin, L, Chen, M, Yang, C, He, L. Accelerating atomic orbital‐based electronic structure calculation via pole expansion and selected inversion. J Phys Condens Matter. 2013;25(29):295501.
Mohr, S, Eixarch, M, Amsler, M, Mantsinen, MJ, Genovese, L. Linear scaling DFT calculations for large tungsten systems using an optimized local basis. Nucl Mater Energy. 2018;15:64–70.
Hu, Q‐M, Reuter, K, Scheffler, M. Towards an exact treatment of exchange and correlation in materials: Application to the “CO adsorption puzzle” and other systems. Phys Rev Lett. 2007;98(17):176103.
Gautier, S, Steinmann, SN, Michel, C, Fleurat‐Lessard, P, Sautet, P. Molecular adsorption at Pt(111). How accurate are DFT functionals? Phys Chem Chem Phys. 2015;17(43):28921–28930.
Goerigk, L, Grimme, S. A general database for main group thermochemistry, kinetics, and noncovalent interactions—Assessment of common and reparameterized (meta‐)GGA density functionals. J Chem Theory Comput. 2010;6(1):107–126.
Steinmann, SN, Corminboeuf, C. Comprehensive benchmarking of a density‐dependent dispersion correction. J Chem Theory Comput. 2011;7(11):3567–3577.
Perdew, JP, Burke, K, Ernzerhof, M. Generalized gradient approximation made simple. Phys Rev Lett. 1996;77(18):3865–3868.
Zhang, Y, Yang, W. Comment on “generalized gradient approximation made simple.”. Phys Rev Lett. 1998;80(4):890.
Hammer, B, Hansen, LB, Norskov, JK. Improved adsorption energetics within density‐functional theory using revised Perdew‐Burke‐Ernzerhof functionals. Phys Rev B. 1999;59(11):7413–7421.
Perdew, JP, Ruzsinszky, A, Csonka, GI, et al. Restoring the density‐gradient expansion for exchange in solids and surfaces. Phys Rev Lett. 2008;100(13):136406.
Gillan, MJ, Alfè, D, Michaelides, A. Perspective: How good is DFT for water? J Chem Phys. 2016;144(13):130901.
Chen, Y, Huang, Y, Cheng, T, Goddard, WA. Identifying active sites for CO2 reduction on dealloyed gold surfaces by combining machine learning with multiscale simulations. J Am Chem Soc. 2019;141(29):11651–11657.
Schmidt, PS, Thygesen, KS. Benchmark database of transition metal surface and adsorption energies from many‐body perturbation theory. J Phys Chem C. 2018;122(8):4381–4390.
Goerigk, L, Hansen, A, Bauer, C, Ehrlich, S, Najibi, A, Grimme, S. A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions. Phys Chem Chem Phys. 2017;19(48):32184–32215.
Cohen, AJ, Mori‐Sanchez, P, Yang, W. Insights into current limitations of density functional theory. Science. 2008;321(5890):792–794.
Ruzsinszky, A, Perdew, JP, Csonka, GI, Vydrov, OA, Scuseria, GE. Spurious fractional charge on dissociated atoms: Pervasive and resilient self‐interaction error of common density functionals. J Chem Phys. 2006;125(19):194112.
Patra, A, Bates, JE, Sun, J, Perdew, JP. Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality. Proc Natl Acad Sci. 2017;114(44):E9188–E9196.
Le Bahers, T, Rérat, M, Sautet, P. Semiconductors used in photovoltaic and photocatalytic devices: Assessing fundamental properties from DFT. J Phys Chem C. 2014;118(12):5997–6008.
Bjorketun, ME, Zeng, Z, Ahmed, R, Tripkovic, V, Thygesen, KS, Rossmeisl, J. Avoiding pitfalls in the modeling of electrochemical interfaces. Chem Phys Lett. 2013;555(0):145–148.
Chu, S, Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature. 2012;488(7411):294–303.
Khan, K, Tareen, AK, Aslam, M, et al. Recent advances in two‐dimensional materials and their nanocomposites in sustainable energy conversion applications. Nanoscale. 2019;11(45):21622–21678.
Lindgren, P, Kastlunger, G, Peterson, AA. A challenge to the G ∼ 0 interpretation of hydrogen evolution. ACS Catal. 2020;10(1):121–128.
Hinnemann, B, Moses, PG, Bonde, J, et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J Am Chem Soc. 2005;127(15):5308–5309.
Jaramillo, TF, Jørgensen, KP, Bonde, J, Nielsen, JH, Horch, S, Chorkendorff, I. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science. 2007;317(5834):100–102.
Benck, JD, Chen, Z, Kuritzky, LY, Forman, AJ, Jaramillo, TF. Amorphous molybdenum sulfide catalysts for electrochemical hydrogen production: Insights into the origin of their catalytic activity. ACS Catal. 2012;2(9):1916–1923.
Kibsgaard, J, Chen, Z, Reinecke, BN, Jaramillo, TF. Engineering the surface structure of MoS 2 to preferentially expose active edge sites for electrocatalysis. Nat Mater. 2012;11(11):963–969.
Li, H, Tsai, C, Koh, AL, et al. Activating and optimizing MoS 2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat Mater. 2016;15(1):48–53.
Voiry, D, Yang, J, Chhowalla, M. Recent strategies for improving the catalytic activity of 2D TMD nanosheets toward the hydrogen evolution reaction. Adv Mater. 2016;28(29):6197–6206.
Voiry, D, Shin, HS, Loh, KP, Chhowalla, M. Low‐dimensional catalysts for hydrogen evolution and CO 2 reduction. Nat Rev Chem. 2018;2(1):1–17.
Voiry, D, Salehi, M, Silva, R, et al. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 2013;13(12):6222–6227.
Lukowski, MA, Daniel, AS, Meng, F, Forticaux, A, Li, L, Jin, S. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J Am Chem Soc. 2013;135(28):10274–10277.
Voiry, D, Yamaguchi, H, Li, J, et al. Enhanced catalytic activity in strained chemically exfoliated WS 2 nanosheets for hydrogen evolution. Nat Mater. 2013;12(9):850–855.
Chhowalla, M, Shin, HS, Eda, G, Li, L‐J, Loh, KP, Zhang, H. The chemistry of two‐dimensional layered transition metal dichalcogenide nanosheets. Nat Chem. 2013;5(4):263–275.
Di, J, Yan, C, Handoko, AD, Seh, ZW, Li, H, Liu, Z. Ultrathin two‐dimensional materials for photo‐ and electrocatalytic hydrogen evolution. Mater Today. 2018;21(7):749–770.
Hantanasirisakul, K, Gogotsi, Y. Electronic and optical properties of 2D transition metal carbides and nitrides (MXenes). Adv Mater. 2018;30(52):1804779.
Anasori, B, Lukatskaya, MR, Gogotsi, Y. 2D metal carbides and nitrides (MXenes) for energy storage. Nat Rev Mater. 2017;2(2):1–17.
Naguib, M, Mochalin, VN, Barsoum, MW, Gogotsi, Y. 25th anniversary article: MXenes: A new family of two‐dimensional materials. Adv Mater. 2014;26(7):992–1005.
Gogotsi, Y, Anasori, B. The rise of MXenes. ACS Nano. 2019;13(8):8491–8494.
Deysher, G, Shuck, CE, Hantanasirisakul, K, et al. Synthesis of Mo4VAlC4 MAX phase and two‐dimensional Mo4VC4 MXene with five atomic layers of transition metals. ACS Nano. 2020;14(1):204–217.
Halim, J, Kota, S, Lukatskaya, MR, et al. Synthesis and characterization of 2D molybdenum carbide (MXene). Adv Funct Mater. 2016;26(18):3118–3127.
Naguib, M, Mashtalir, O, Carle, J, et al. Two‐dimensional transition metal carbides. ACS Nano. 2012;6(2):1322–1331.
Fredrickson, KD, Anasori, B, Seh, ZW, Gogotsi, Y, Vojvodic, A. Effects of applied potential and water intercalation on the surface chemistry of Ti2C and Mo2C MXenes. J Phys Chem C. 2016;120(50):28432–28440.
Pandey, M, Thygesen, KS. Two‐dimensional MXenes as catalysts for electrochemical hydrogen evolution: A computational screening study. J Phys Chem C. 2017;121(25):13593–13598.
Seh, ZW, Fredrickson, KD, Anasori, B, et al. Two‐dimensional molybdenum carbide (MXene) as an efficient electrocatalyst for hydrogen evolution. ACS Energy Lett. 2016;1(3):589–594.
Handoko, AD, Fredrickson, KD, Anasori, B, et al. Tuning the basal plane functionalization of two‐dimensional metal carbides (MXenes) to control hydrogen evolution activity. ACS Appl Energy Mater. 2018;1(1):173–180.
Li, P, Zhu, J, Handoko, AD, et al. High‐throughput theoretical optimization of the hydrogen evolution reaction on MXenes by transition metal modification. J Mater Chem A. 2018;6(10):4271–4278.
Kuznetsov, DA, Chen, Z, Kumar, PV, et al. Single site cobalt substitution in 2D molybdenum carbide (MXene) enhances catalytic activity in the hydrogen evolution reaction. J Am Chem Soc. 2019;141(44):17809–17816.
Zhang, J, Zhao, Y, Guo, X, et al. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction. Nat Catal. 2018;1(12):985–992.
Ramalingam, V, Varadhan, P, Fu, H‐C, et al. Heteroatom‐mediated interactions between ruthenium single atoms and an MXene support for efficient hydrogen evolution. Adv Mater. 2019;31(48):1903841.
Le, TA, Bui, QV, Tran, NQ, et al. Synergistic effects of nitrogen doping on MXene for enhancement of hydrogen evolution reaction. ACS Sustain Chem Eng. 2019;7(19):16879–16888.
Qu, G, Zhou, Y, Wu, T, et al. Phosphorized MXene‐phase molybdenum carbide as an Earth‐abundant hydrogen evolution electrocatalyst. ACS Appl Energy Mater. 2018;1(12):7206–7212.
Li, S, Tuo, P, Xie, J, et al. Ultrathin MXene nanosheets with rich fluorine termination groups realizing efficient electrocatalytic hydrogen evolution. Nano Energy. 2018;47:512–518.
Jiang, Y, Sun, T, Xie, X, et al. Oxygen‐functionalized ultrathin Ti3C2Tx MXene for enhanced electrocatalytic hydrogen evolution. ChemSusChem. 2019;12(7):1368–1373.
Zhan, C, Sun, W, Xie, Y, Jiang, D, Kent, PRC. Computational discovery and design of MXenes for energy applications: Status, successes, and opportunities. ACS Appl Mater Interfaces. 2019;11(28):24885–24905.
Ling, C, Shi, L, Ouyang, Y, Wang, J. Searching for highly active catalysts for hydrogen evolution reaction based on O‐terminated MXenes through a simple descriptor. Chem Mater. 2016;28(24):9026–9032.
Ling, C, Shi, L, Ouyang, Y, Chen, Q, Wang, J. Transition metal‐promoted V2CO2 (MXenes): A new and highly active catalyst for hydrogen evolution reaction. Adv Sci. 2016;3(11):1600180.
Yang, X, Gao, N, Zhou, S, Zhao, J. MXene nanoribbons as electrocatalysts for the hydrogen evolution reaction with fast kinetics. Phys Chem Chem Phys. 2018;20(29):19390–19397.
Rossmeisl, J, Chan, K, Skúlason, E, Björketun, ME, Tripkovic, V. On the pH dependence of electrochemical proton transfer barriers. Catal Today. 2016;262:36–40.
McCrum, IT, Janik, MJ. pH and alkali cation effects on the Pt cyclic voltammogram explained using density functional theory. J Phys Chem C. 2016;120(1):457–471.
Ledezma‐Yanez, I, Wallace, WDZ, Sebastián‐Pascual, P, Climent, V, Feliu, JM, Koper, MTM. Interfacial water reorganization as a pH‐dependent descriptor of the hydrogen evolution rate on platinum electrodes. Nat Energy. 2017;2(4):17031.
Cheng, T, Wang, L, Merinov, BV, Goddard, WA. Explanation of dramatic pH‐dependence of hydrogen binding on noble metal electrode: Greatly weakened water adsorption at high pH. J Am Chem Soc. 2018;140(25):7787–7790.
Lamoureux, PS, Singh, AR, Chan, K. pH effects on hydrogen evolution and oxidation over Pt(111): Insights from first‐principles. ACS Catal. 2019;9(7):6194–6201.
Liu, L, Liu, Y, Liu, C. Enhancing the understanding of hydrogen evolution and oxidation reactions on Pt(111) through ab initio simulation of electrode/electrolyte kinetics. J Am Chem Soc. 2020;142(11):4985–4989.
Handoko, AD, Wei, F, Jenndy, YBS, Seh, ZW. Understanding heterogeneous electrocatalytic carbon dioxide reduction through operando techniques. Nat Catal. 2018;1(12):922–934.
Handoko, AD, Khoo, KH, Tan, TL, Jin, H, Seh, ZW. Establishing new scaling relations on two‐dimensional MXenes for CO2 electroreduction. J Mater Chem A. 2018;6(44):21885–21890.
Chen, H, Handoko, AD, Xiao, J, et al. Catalytic effect on CO2 electroreduction by hydroxyl‐terminated two‐dimensional MXenes. ACS Appl Mater Interfaces. 2019;11(40):36571–36579.
Lai, Y, Jones, RJR, Wang, Y, Zhou, L, Gregoire, JM. Scanning electrochemical flow cell with online mass spectroscopy for accelerated screening of carbon dioxide reduction Electrocatalysts. ACS Comb Sci. 2019;21(10):692–704.
Magnussen, OM, Hotlos, J, Nichols, RJ, Kolb, DM, Behm, RJ. Atomic structure of Cu adlayers on Au(100) and Au(111) electrodes observed by in situ scanning tunneling microscopy. Phys Rev Lett. 1990;64(24):2929–2932.
Cai, W‐B, Wan, L‐J, Noda, H, Hibino, Y, Ataka, K, Osawa, M. Orientational phase transition in a pyridine adlayer on gold(111) in aqueous solution studied by in situ infrared spectroscopy and scanning tunneling microscopy. Langmuir. 1998;14(111):6992–6998.
Khairunnisa, A, Liao, W, Yau, S. Adsorption and electrochemical polymerization of pyrrole on Au(100) electrodes as examined by in situ scanning tunneling microscopy. J Phys Chem C. 2016;120(46):26425–26434.
Vu, T‐H, Wandlowski, T. CV and in situ STM study the adsorption behavior of benzoic acid at the electrified Au(100)| HClO4 interface: Structure and dynamics. J Electroanal Chem. 2016;776:40–48.
Vu, T‐H, Wandlowski, T. Self‐assembled structures of benzoic acid on au(111) surface. J Electron Mater. 2017;46(6):3463–3471.
Lelaidier, T, Leoni, T, Ranguis, A, D`Aléo, A, Fages, F, Becker, C. Adsorption and growth of bis‐pyrene molecular layers on Au(111) studied by STM. J Phys Chem C. 2017;121(13):7214–7220.
Monyoncho, EA, Steinmann, SN, Michel, C, Baranova, EA, Woo, TK, Sautet, P. Ethanol electro‐oxidation on palladium revisited using polarization modulation infrared reflection absorption spectroscopy (PM‐IRRAS) and density functional theory (DFT): Why is it difficult to break the C‐C bond? ACS Catal. 2016;6(8):4894–4906.
Steinmann, SN, Wei, Z‐Y, Sautet, P. Theory and experiments join forces to characterize the electrocatalytic interface. Proc Natl Acad Sci. 2019;116(16):7611–7613.
Fang, Y, Ding, S, Zhang, M, et al. Revisiting the atomistic structures at the interface of Au(111) electrode‐sulfuric acid solution. J Am Chem Soc. 2020;142:9439–9446.
Valette, G. Double layer on silver single crystal electrodes in contact with electrolytes having anions which are slightly specifically adsorbed: Part III. The (111) face. J Electroanal Chem Interfacial Electrochem. 1989;269(1):191–203.
Sundararaman, R, Schwarz, K. Evaluating continuum solvation models for the electrode‐electrolyte interface: Challenges and strategies for improvement. J Chem Phys. 2017;146(8):084111.
Sottomayor, MJ, Coelho, V, Ferreira, AP, et al. Parameters of n‐hexanol adsorption on Au (111). Comparison between differential capacity and chronocoulometry results. Electrochim Acta. 1999;45(4):775–787.
Foresti, ML, Innocenti, M, Guidelli, R, Hamelin, A. Electrochemical investigation of 1,5‐pentanediol adsorption on the Ag(111) and Ag(110) faces. J Electroanal Chem. 1999;467(1):217–229.
Chen, A, Shi, Z, Bizzotto, D, Lipkowski, J, Pettinger, B, Bilger, C. Iodide adsorption at the Au(111) electrode surface. J Electroanal Chem. 1999;467(1):342–353.
Garcia‐Araez, N, Climent, V, Herrero, E, Feliu, J, Lipkowski, J. Thermodynamic studies of bromide adsorption at the Pt(111) electrode surface perchloric acid solutions: Comparison with other anions. J Electroanal Chem. 2006;591(2):149–158.
Shi, Z, Lipkowski, J, Mirwald, S, Pettinger, B. Electrochemical and second harmonic generation study of SO2−4 adsorption at the Au(111) electrode. J Electroanal Chem. 1995;396(1):115–124.
Herrero, E, Mostany, J, Feliu, JM, Lipkowski, J. Thermodynamic studies of anion adsorption at the Pt(111) electrode surface in sulfuric acid solutions. J Electroanal Chem. 2002;534(1):79–89.
Mostany, J, Martínez, P, Climent, V, Herrero, E, Feliu, JM. Thermodynamic studies of phosphate adsorption on Pt(111) electrode surfaces in perchloric acid solutions. Electrochim Acta. 2009;54(24):5836–5843.
Wandlowski, T, Hölzle, MH. Structural and thermodynamic aspects of phase transitions in uracil adlayers. A chronocoulometric study. Langmuir. 1996;12(26):6604–6615.
Li, H‐Q, Roscoe, SG, Lipkowski, J. Electrochemical studies of the benzoate adsorption on Au (111) electrode. J Solut Chem. 2000;29(10):987–1005.
Schmickler, W, Guidelli, R. The partial charge transfer. Electrochim Acta. 2014;127:489–505.

Access to this WIREs title is by subscription only.

Recommend to Your
Librarian Now!

The latest WIREs articles in your inbox

Sign Up for Article Alerts