The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

Abidi, 2020, Atomistic modeling of electrocatalysis: are we there yet?, WIRES Comput. Mol. Sci., 10.1002/wcms.1499

Akhade, 2018, Using brønsted-evans-polanyi relations to predict electrode potential-dependent activation energies., Catal. Tod., 312, 82, 10.1016/j.cattod.2018.03.048

Ardagh, 2019, Principles of dynamic heterogeneous catalysis: surface resonance and turnover frequency response., ACS Catal., 9, 6929, 10.1021/acscatal.9b01606

Auinger, 2011, Near-surface ion distribution and buffer effects during electrochemical reactions., Phys. Chem. Chem. Phys., 13, 16384, 10.1039/C1CP21717H

Ávila, 2020, Role of the partial charge transfer on the chloride adlayers on Au (100)., ChemElectroChem, 7, 4269, 10.1002/celc.202001228

Back, , Toward a design of active oxygen evolution catalysts: insights from automated density functional theory calculations and machine learning., ACS Catal., 9, 7651, 10.1021/acscatal.9b02416

Back, , Convolutional neural network of atomic surface structures to predict binding energies for high-throughput screening of catalysts., J. Phys. Chem. Lett., 10, 4401, 10.1021/acs.jpclett.9b01428

Bard, 2010, Inner-sphere heterogeneous electrode reactions. Electrocatalysis and photocatalysis: the challenge., J. Am. Chem. Soc., 132, 7559, 10.1021/ja101578m

Basdogan, , Machine learning-guided approach for studying solvation environments., J. Chem. Theory Comput., 16, 633, 10.1021/acs.jctc.9b00605

Basdogan, , Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals., WIRES Comput. Mol. Sci., 10, 10.1002/wcms.1446

Bhattacharyya, 2021, Structure and reactivity of IrO X nanoparticles for the oxygen evolution reaction in electrocatalysis: an electronic structure theory study., J. Phys. Chem. C, 125, 4379, 10.1021/acs.jpcc.0c10092

Birdja, 2019, Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels., Nat. Energ., 4, 732, 10.1038/s41560-019-0450-y

Bligaard, 2004, The Brønsted–Evans–polanyi relation and the volcano curve in heterogeneous catalysis., J. Catal., 224, 206, 10.1016/j.jcat.2004.02.034

Bochevarov, 2013, Jaguar: a high-performance quantum chemistry software program with strengths in life and materials sciences., Int. J. Quantum Chem., 113, 2110, 10.1002/qua.24481

Briquet, 2017, A new type of scaling relations to assess the accuracy of computational predictions of catalytic activities applied to the oxygen evolution reaction., ChemCatChem, 9, 1261, 10.1002/cctc.201601662

Bumroongsakulsawat, 2014, Effect of solution pH on CO: formate formation rates during electrochemical reduction of aqueous CO2 at Sn cathodes., Electrochim. Acta, 141, 216, 10.1016/j.electacta.2014.07.057

Busch, 2016, Beyond the top of the volcano?–A unified approach to electrocatalytic oxygen reduction and oxygen evolution., Nano Energ., 29, 126, 10.1016/j.nanoen.2016.04.011

Busch, 2020, Method for the accurate prediction of electron transfer potentials using an effective absolute potential., Phys. Chem. Chem. Phys., 22, 25833, 10.1039/D0CP04508J

Busch, 2015, Linear scaling relationships and volcano plots in homogeneous catalysis–revisiting the suzuki reaction., Chem. Sci., 6, 6754, 10.1039/C5SC02910D

Calle-Vallejo, 2012, First-principles computational electrochemistry: achievements and challenges., Electrochim. Acta, 84, 3, 10.1016/j.electacta.2012.04.062

Calle-Vallejo, 2013, Oxygen reduction and evolution at single-metal active sites: comparison between functionalized graphitic materials and protoporphyrins., Surf. Sci., 607, 47, 10.1016/j.susc.2012.08.005

Carmo, 2013, A comprehensive review on PEM water electrolysis., Int. J. Hyd. Energ., 38, 4901, 10.1016/j.ijhydene.2013.01.151

Che, 2013, Nobel prize in chemistry 1912 to sabatier: organic chemistry or catalysis?, Catal. Tod., 218, 162, 10.1016/j.cattod.2013.07.006

Chen, 2017, Highly active and stable single iron site confined in graphene nanosheets for oxygen reduction reaction., Nano Energ., 32, 353, 10.1016/j.nanoen.2016.12.056

Cheng, 2008, Brønsted- evans- polanyi relation of multistep reactions and volcano curve in heterogeneous catalysis., J. Phys. Chem. C, 112, 1308, 10.1021/jp711191j

Craig, 2019, Universal scaling relations for the rational design of molecular water oxidation catalysts with near-zero overpotential., Nat. Commun., 10, 1, 10.1038/s41467-019-12994-w

Diaz-Morales, 2016, Iridium-based double perovskites for efficient water oxidation in acid media., Nat. Commun., 7, 1, 10.1038/ncomms12363

Dickens, 2017, A theoretical investigation into the role of surface defects for oxygen evolution on RuO2., J. Phys. Chem. C, 121, 18516, 10.1021/acs.jpcc.7b03481

Dubouis, 2019, The hydrogen evolution reaction: from material to interfacial descriptors., Chem. Sci., 10, 9165, 10.1039/C9SC03831K

Durst, 2014, New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism., Energ. Environ. Sci., 7, 2255, 10.1039/C4EE00440J

Exner, 2018, Activity–stability volcano plots for the investigation of nano-sized electrode materials in lithium-ion batteries., ChemElectroChem, 5, 3243, 10.1002/celc.201800838

Exner, , Activity-stability volcano plots for material optimization in electrocatalysis., ChemCatChem, 11, 3234, 10.1002/cctc.201900500

Exner, , Beyond the traditional volcano concept: overpotential-dependent volcano plots exemplified by the chlorine evolution reaction over transition-metal oxides., J. Phys. Chem. C, 123, 16921, 10.1021/acs.jpcc.9b05364

Exner, , Design criteria for oxygen evolution electrocatalysts from first principles: introduction of a unifying material-screening approach., ACS Appl. Energ. Mater., 2, 7991, 10.1021/acsaem.9b01480

Exner, , Is thermodynamics a good descriptor for the activity? Re-investigation of Sabatier’s principle by the free energy diagram in electrocatalysis., ACS Catal., 9, 5320, 10.1021/acscatal.9b00732

Exner, , Recent advancements towards closing the gap between electrocatalysis and battery science communities: the computational lithium electrode and activity–stability volcano plots., ChemSusChem, 12, 2330, 10.1002/cssc.201900298

Exner, , Comparison of the conventional volcano analysis with a unifying approach: material screening based on a combination of experiment and theory., J. Phys. Chem. C, 124, 822, 10.1021/acs.jpcc.9b10860

Exner, , Design criteria for the competing chlorine and oxygen evolution reactions: avoid the OCl adsorbate to enhance chlorine selectivity., Phys. Chem. Chem. Phys., 22, 22451, 10.1039/D0CP03667F

Exner, , Does a Thermoneutral Electrocatalyst correspond to the apex of a volcano plot for a simple two-electron process?, Angew. Chem. Int. Ed., 22, 10236, 10.1002/anie.202003688

Exner, , Overpotential-dependent volcano plots to assess activity trends in the competing chlorine and oxygen evolution reactions., ChemElectroChem, 7, 1448, 10.1002/celc.202000120

Exner, , Paradigm change in hydrogen electrocatalysis: the volcano’s apex is located at weak bonding of the reaction intermediate., Int. J. Hyd. Energ., 45, 27221, 10.1016/j.ijhydene.2020.07.088

Exner, , Recent progress in the development of screening methods to identify electrode materials for the oxygen evolution reaction., Adv. Funct. Mater., 30, 10.1002/adfm.202005060

Exner, , A universal descriptor for the screening of electrode materials for multiple-electron processes: beyond the thermodynamic overpotential., ACS Catal., 10, 12607, 10.1021/acscatal.0c03865

Exner, , Boosting the stability of RuO2 in the acidic oxygen evolution reaction by tuning oxygen-vacancy formation energies: a viable approach beyond noble-metal catalysts?, ChemElectroChem, 8, 46, 10.1002/celc.202001465

Exner, , Hydrogen electrocatalysis revisited: weak bonding of adsorbed hydrogen as design principle for active electrode materials., Curr. Opin. Electrochem., 26, 10.1016/j.coelec.2020.100673

Exner, , Why approximating electrocatalytic activity by a single free-energy change is insufficient., Electrochim. Acta, 375, 10.1016/j.electacta.2021.137975

Exner, 2014, Controlling selectivity in the chlorine evolution reaction over RuO2-based catalysts., Angew. Chem. Int. Ed., 53, 11032, 10.1002/anie.201406112

Exner, 2016, Full kinetics from first principles of the chlorine evolution reaction over a RuO2 (110) model electrode., Angew. Chem. Int. Ed., 55, 7501, 10.1002/anie.201511804

Exner, 2019, Beyond the rate-determining step in the oxygen evolution reaction over a single-crystalline IrO2 (110) model electrode: kinetic scaling relations., ACS Catal., 9, 6755, 10.1021/acscatal.9b01564

Exner, 2018, A universal approach to determine the free energy diagram of an electrocatalytic reaction., ACS Catal., 8, 1864, 10.1021/acscatal.7b03142

Fabbri, 2017, Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting., Nat. Mater., 16, 925, 10.1038/nmat4938

Fang, 2014, Tafel kinetics of electrocatalytic reactions: from experiment to first-principles., ACS Catal., 4, 4364, 10.1021/cs501312v

Frumkin, 1975, Potentials of zero total and zero free charge of platinum group metals., Electrochim. Acta, 20, 347, 10.1016/0013-4686(75)90017-1

Gao, 2015, pH effect on electrocatalytic reduction of CO2 over Pd and Pt nanoparticles., Electrochem. Commun., 55, 1, 10.1016/j.elecom.2015.03.008

Garcia, 2019, Enhancement of oxygen evolution activity of nickel oxyhydroxide by electrolyte alkali cations., Angew. Chem. Int. Ed., 58, 12999, 10.1002/anie.201905501

Gattrell, 2006, A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper., J. Electroanal. Chem., 594, 1, 10.1016/j.jelechem.2006.05.013

Gerischer, 1956, Über die Katalytische Zersetzung Von Wasserstoffsuperoxyd an metallischem platin., Z. Phys. Chem., 6, 178, 10.1524/zpch.1956.6.3_4.178

Goings, 2020, Nonequilibrium dynamics of proton-coupled electron transfer in proton wires: concerted but asynchronous mechanisms., ACS Cent. Sci., 6, 1594, 10.1021/acscentsci.0c00756

Gómez-Marín, 2014, Oxygen reduction reaction at Pt single crystals: a critical overview., Catal. Sci. Technol., 4, 1685, 10.1039/C3CY01049J

Gossenberger, 2020, Sulfate, bisulfate, and hydrogen co-adsorption on Pt (111) and Au (111) in an electrochemical environment., Front. Chem., 8, 10.3389/fchem.2020.00634

Göttle, 2017, Proton-coupled electron transfer in the electrocatalysis of CO2 reduction: prediction of Sequential Vs. Concerted pathways using DFT., Chem. Sci., 8, 458, 10.1039/C6SC02984A

Govind Rajan, 2020, Why do we use the materials and operating conditions we use for heterogeneous (Photo) electrochemical water splitting?, ACS Catal., 10, 11177, 10.1021/acscatal.0c01862

Govindarajan, 2018, Does the breaking of adsorption-energy scaling relations guarantee enhanced electrocatalysis?, Curr. Opin. Electrochem., 8, 110, 10.1016/j.coelec.2018.03.025

Greeley, 2006, Computational high-throughput screening of electrocatalytic materials for hydrogen evolution., Nat. Mater., 5, 909, 10.1038/nmat1752

Greeley, 2007, Large-scale, density functional theory-based screening of alloys for hydrogen evolution., Surf. Sci, 601, 1590, 10.1016/j.susc.2007.01.037

Groß, 2020, Theory of solid/electrolyte interfaces, Surface and Interface Science: Volume 8: Interfacial Electrochemistry, 10.1002/9783527680603.ch56

Guidelli, 2014, Defining the transfer coefficient in electrochemistry: an assessment (Iupac Technical Report)., Pure Appl. Chem., 86, 245, 10.1515/pac-2014-5026

Gupta, 2006, Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions., J. Appl. Electrochem., 36, 161, 10.1007/s10800-005-9058-y

Gurudayal, 2019, Sequential cascade electrocatalytic conversion of carbon dioxide to C–C coupled products., ACS Appl. Energ. Mater., 2, 4551, 10.1021/acsaem.9b00791

Hajiyani, 2018, Surface termination and composition control of activity of the CoxNi1–xFe2O4 (001) surface for water oxidation: insights from DFT + U calculations., ACS Catal., 8, 11773, 10.1021/acscatal.8b00574

Halck, 2014, Beyond the volcano limitations in electrocatalysis–oxygen evolution reaction., Phys. Chem. Chem. Phys., 16, 13682, 10.1039/C4CP00571F

Hammes-Schiffer, 2009, Theory of proton-coupled electron transfer in energy conversion processes., Acc. Chem. Res., 42, 1881, 10.1021/ar9001284

Hammes-Schiffer, 2010, Theory of coupled electron and proton transfer reactions., Chem. Rev., 110, 6939, 10.1021/cr1001436

Handoko, 2019, Theory-guided materials design: two-dimensional mxenes in electro-and photocatalysis., Nanoscale Horiz., 4, 809, 10.1039/C9NH00100J

Hansen, 2008, Surface pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni (111) surfaces studied by DFT., Phys. Chem. Chem. Phys., 10, 3722, 10.1039/B803956A

Hansen, 2016, pH in grand canonical statistics of an electrochemical interface., J. Phys. Chem. C, 120, 29135, 10.1021/acs.jpcc.6b09019

Hao, 2020, Dopants fixation of ruthenium for boosting acidic oxygen evolution stability and activity., Nat. Commun., 11, 1, 10.1038/s41467-020-19212-y

He, 2018, Selective electrocatalytic reduction of nitrite to dinitrogen based on decoupled proton–electron transfer., J. Am. Chem. Soc., 140, 2012, 10.1021/jacs.7b12774

He, 2020, Atomic-scale evidence for highly selective electrocatalytic N- N coupling on metallic MoS2., Proc. Natl. Acad. Sci. U.S.A., 117, 31631, 10.1073/pnas.2008429117

He, 2017, Importance of solvation for the accurate prediction of oxygen reduction activities of pt-based electrocatalysts., J. Phys. Chem. Lett., 8, 2243, 10.1021/acs.jpclett.7b01018

Heenen, 2020, Solvation at metal/water interfaces: an Ab initio molecular dynamics benchmark of common computational approaches., J. Chem. Phys., 152, 10.1063/1.5144912

Hinnemann, 2005, Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution., J. Am. Chem. Soc., 127, 5308, 10.1021/ja0504690

Holewinski, 2012, Elementary mechanisms in electrocatalysis: revisiting the ORR tafel slope., J. Electrochem. Soc., 159, 10.1149/2.022211jes

Hori, 1989, Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution., J. Chem. Soc., 85, 2309, 10.1039/F19898502309

Hörmann, 2019, Grand canonical simulations of electrochemical interfaces in implicit solvation models., J. Chem. Phys., 150, 10.1063/1.5054580

Hörmann, 2020, Electrosorption at metal surfaces from first principles., NPJ Comput. Mater., 6, 1, 10.1038/s41524-020-00394-4

Hu, 2004, Oxygen evolution reaction on IrO2-based DSA type electrodes: kinetics analysis of tafel lines and EIS., Int. J. Hyd. Energ., 29, 791, 10.1016/j.ijhydene.2003.09.007

Huang, , Non-monotonic surface charging behavior of platinum: a paradigm change., J. Phys. Chem. C, 120, 13587, 10.1021/acs.jpcc.6b03930

Huang, , Theory of electrostatic phenomena in water-filled Pt nanopores., Faraday Disc., 193, 427, 10.1039/C6FD00094K

Huang, 2018, Unifying theoretical framework for deciphering the oxygen reduction reaction on platinum., Phys. Chem. Chem. Phys., 20, 11776, 10.1039/C8CP01315B

Huang, 2019, Strategies to break the scaling relation toward enhanced oxygen electrocatalysis., Matter, 1, 1494, 10.1016/j.matt.2019.09.011

Kang, 2019, Pt-Sputtered Ti mesh electrode for polymer electrolyte membrane fuel cells., Int. J. Precis, 6, 271, 10.1007/s40684-019-00077-6

Kant, 1994, Can one electrochemically measure the statistical morphology of a rough electrode?, J. Phys. Chem., 98, 1663, 10.1021/j100057a020

Kari, 2018, Sabatier principle for interfacial (Heterogeneous) enzyme catalysis., ACS Catal., 8, 11966, 10.1021/acscatal.8b03547

Karlsson, 2016, Selectivity between oxygen and chlorine evolution in the chlor-alkali and chlorate processes., Chem. Rev., 116, 2982, 10.1021/acs.chemrev.5b00389

Kastlunger, 2018, Controlled-potential simulation of elementary electrochemical reactions: proton discharge on metal surfaces., J. Phys. Chem. C, 122, 12771, 10.1021/acs.jpcc.8b02465

Katsounaros, 2016, Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt (100)., J. Phys. Chem. Lett., 7, 387, 10.1021/acs.jpclett.5b02556

Kenmoe, 2018, Water adsorption on clean and defective anatase Tio2 (001) nanotube surfaces: a surface science approach., J. Phys. Chem. B, 122, 5432, 10.1039/C9CP06584A

Kim, 2017, High-performance pyrochlore-type yttrium ruthenate electrocatalyst for oxygen evolution reaction in acidic media., J. Am. Chem. Soc., 139, 12076, 10.1021/jacs.7b06808

Kjaergaard, 2010, Enzymatic versus inorganic oxygen reduction catalysts: comparison of the energy levels in a free-energy scheme., Inorg. Chem., 49, 3567, 10.1021/ic900798q

Klamt, 1993, COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient., J. Chem. Soc. Perkin Trans. II, 5, 799, 10.1039/P29930000799

Koper, , Structure sensitivity and nanoscale effects in electrocatalysis., Nanoscale, 3, 2054, 10.1039/C0NR00857E

Koper, , Thermodynamic theory of multi-electron transfer reactions: implications for electrocatalysis., J. Electroanal. Chem., 660, 254, 10.1016/j.jelechem.2010.10.004

Koper, , Analysis of electrocatalytic reaction schemes: distinction between rate-determining and potential-determining steps., J. Solid State Electrochem., 17, 339, 10.1007/s10008-012-1918-x

Koper, , Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis., Chem. Sci., 4, 2710, 10.1039/C3SC50205H

Koper, , Theory of the transition from sequential to concerted electrochemical proton–electron transfer., Phys. Chem. Chem. Phys., 15, 1399, 10.1039/c2cp42369c

Kortlever, , Electrochemical CO2 reduction to formic acid on a Pd-based formic acid oxidation catalyst., Catal. Tod., 244, 58, 10.1016/j.cattod.2014.08.001

Kortlever, , Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide., J. Phys. Chem. Lett., 6, 4073, 10.1021/acs.jpclett.5b01559

Kozuch, 2012, A refinement of everyday thinking: the energetic span model for kinetic assessment of catalytic cycles., WIRES Comput. Mol. Sci., 2, 795, 10.1002/wcms.1100

Kozuch, 2011, How to conceptualize catalytic cycles? The energetic span model., Acc. Chem. Res., 44, 101, 10.1021/ar1000956

Krishnamurthy, 2018, Maximal predictability approach for identifying the right descriptors for electrocatalytic reactions., J. Phys. Chem. Lett., 9, 588, 10.1021/acs.jpclett.7b02895

Kunimatsu, 2007, Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy., Electrochim. Acta, 52, 5715, 10.1016/j.electacta.2006.12.007

Laursen, 2012, Electrochemical hydrogen evolution: Sabatier’s principle and the volcano plot., J. Chem. Educ., 89, 1595, 10.1021/ed200818t

Ledezma-Yanez, 2017, Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes., Nat. Energ., 2, 1, 10.1038/nenergy.2017.31

Li, 2019, Recent progress on surface reconstruction of earth-abundant electrocatalysts for water oxidation., Small, 15, 10.1002/smll.201901980

Li, 2016, Recent advances in breaking scaling relations for effective electrochemical conversion of CO2., Adv. Energ. Mater., 6, 10.1021/jp077210j

Li, 2020, An adaptive machine learning strategy for accelerating discovery of perovskite electrocatalysts., ACS Catal., 10, 4377, 10.1021/acscatal.9b05248

Lindgren, 2020, A challenge to the G ∼0 interpretation of hydrogen evolution., ACS Catal., 10, 121, 10.1021/acscatal.9b02799

Louch, 1993, Transport to rough electrode surfaces: part 2: perturbation solution for two-dimensional steady state transport to an arbitrary surface under mixed diffusion-kinetic control., J. Electroanal. Chem., 346, 211, 10.1016/0022-0728(93)85014-8

Lum, 2018, Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu., Energ. Environ. Sci., 11, 2935, 10.1039/C8EE01501E

Man, 2011, Universality in oxygen evolution electrocatalysis on oxide surfaces., ChemCatChem, 3, 1159, 10.1002/cctc.201000397

Marshall, 2015, Avoid the quasi-equilibrium assumption when evaluating the electrocatalytic oxygen evolution reaction mechanism by tafel slope analysis., Electrochem. Commun., 61, 23, 10.1016/j.elecom.2015.09.019

Martnez-Hincapié, 2018, Peroxodisulfate reduction as a probe to interfacial charge., Electrochem. Commun., 88, 43, 10.1016/j.elecom.2018.01.012

Mathew, 2019, Implicit self-consistent electrolyte model in plane-wave density-functional theory., J. Chem. Phys., 151, 10.1063/1.5132354

Mathew, 2014, Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways., J. Chem. Phys., 140, 10.1063/1.4865107

Mefford, 2020, Interpreting Tafel behavior of consecutive electrochemical reactions through combined thermodynamic and steady state microkinetic approaches., Energ. Environ. Sci., 13, 622, 10.1039/C9EE02697E

Mehta, 2003, Review and analysis of PEM fuel cell design and manufacturing., J. Power Sources, 114, 32, 10.1016/S0378-7753(02)00542-6

Murata, 1991, Product selectivity affected by cationic species in electrochemical reduction of CO2 and CO at a Cu electrode., Bull. Chem. Soc. Jpn., 64, 123, 10.1246/bcsj.64.123

Nørskov, 2005, Trends in the exchange current for hydrogen evolution., J. Electrochem. Soc., 152, 10.1149/1.1856988

Nørskov, 2009, Towards the computational design of solid catalysts., Nat. Chem., 1, 37, 10.1038/nchem.121

Nørskov, 2004, Origin of the overpotential for oxygen reduction at a fuel-cell cathode., J. Phys. Chem. B, 108, 17886, 10.1021/jp047349j

Ooka, 2017, Competition between hydrogen evolution and carbon dioxide reduction on copper electrodes in mildly acidic media., Langmuir, 33, 9307, 10.1021/acs.langmuir.7b00696

Ooka, 2019, Shift of the optimum binding energy at higher rates of catalysis., J. Phys. Chem. Lett., 10, 6706, 10.1021/acs.jpclett.9b01796

Pajkossy, 1989, Diffusion to fractal surfaces? II. Verification of theory., Electrochim. Acta, 34, 171, 10.1016/0013-4686(89)87082-3

Pande, 2019, Computational screening of current collectors for enabling anode-free lithium metal batteries., ACS Energy Lett., 4, 2952, 10.1021/acsenergylett.9b02306

Parada, 2019, Concerted proton-electron transfer reactions in the marcus inverted region., Science, 364, 471, 10.1126/science.aaw4675

Park, 2012, A review of gas diffusion layer in PEM fuel cells: materials and designs., Int. J. Hyd. Energ., 37, 5850, 10.1016/j.ijhydene.2011.12.148

Parsons, 1951, General equations for the kinetics of electrode processes., Trans. Faraday Soc., 47, 1332, 10.1039/TF9514701332

Parsons, 1958, The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen., Trans. Faraday Soc., 54, 1053, 10.1039/TF9585401053

Pegis, 2017, Identifying and breaking scaling relations in molecular catalysis of electrochemical reactions., J. Am. Chem. Soc., 139, 11000, 10.1021/jacs.7b05642

Pérez-Gallent, 2017, Structure-and potential-dependent cation effects on CO reduction at copper single-crystal electrodes., J. Am. Chem. Soc., 139, 16412, 10.1021/jacs.7b10142

Peterson, 2012, Activity descriptors for CO2 electroreduction to methane on transition-metal catalysts., J. Phys. Chem. Lett., 3, 251, 10.1021/jz201461p

Piqué, 2020, Designing water splitting catalysts using rules of thumb: advantages, dangers and alternatives., Phys. Chem. Chem. Phys., 22, 6797, 10.1039/D0CP00896F

Retuerto, 2019, Na-doped ruthenium perovskite electrocatalysts with improved oxygen evolution activity and durability in acidic media., Nat. Commun., 10, 1, 10.1038/s41467-019-09791-w

Ringe, 2019, Understanding cation effects in electrochemical CO2 reduction., Energ. Environ. Sci., 12, 3001, 10.1039/C9EE01341E

Ringe, 2020, Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on gold., Nat. Commun., 11, 1, 10.1038/s41467-019-13777-z

Rodriguez, 2014, Electrocatalysis on gold., Phys. Chem. Chem. Phys., 16, 13583, 10.1039/C4CP00394B

Rojas-Carbonell, 2018, Effect of pH on the activity of platinum group metal-free catalysts in oxygen reduction reaction., ACS Catal., 8, 3041, 10.1021/acscatal.7b03991

Rootsaert, 1960, Interaction of formic acid vapour with tungsten., Z. Phys. Chem., 26, 16, 10.1524/zpch.1960.26.1_2.016

Rossmeisl, , Comparing electrochemical and biological water splitting., J. Phys. Chem. C, 111, 18821, 10.1021/jp077210j

Rossmeisl, 2005, Electrolysis of water on (Oxidized) metal surfaces., Chem. Phys., 319, 178, 10.1016/j.chemphys.2005.05.038

Rossmeisl, , Electrolysis of water on oxide surfaces., J. Electroanal. Chem., 607, 83, 10.1016/j.jelechem.2006.11.008

Sabatier, 1913, La Catalyse en Chimie Organique, Encyclopédie de Science Chimique Appliquée.

Sakaushi, 2020, Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid–liquid interfaces., Phys. Chem. Chem. Phys., 22, 19401, 10.1039/D0CP02741C

Sakong, 2020, Water structures on a Pt (111) electrode from Ab initio molecular dynamic simulations for a variety of electrochemical conditions., Phys. Chem. Chem. Phys., 22, 10431, 10.1039/C9CP06584A

Saveleva, 2018, Operando evidence for a universal oxygen evolution mechanism on thermal and electrochemical iridium oxides., J. Phys. Chem. Lett., 9, 3154, 10.1021/acs.jpclett.8b00810

Sayfutyarova, 2020, Excited state molecular dynamics of photoinduced proton-coupled electron transfer in anthracene–phenol–pyridine triads., J. Phys. Chem. Lett., 11, 7109, 10.1021/acs.jpclett.0c02012

Schmickler, 2010, Interfacial Electrochemistry., 10.1007/978-3-642-04937-8

Schouten, 2014, The influence of pH on the reduction of CO and CO2 to hydrocarbons on copper electrodes., J. Electroanal. Chem., 716, 53, 10.1016/j.jelechem.2013.08.033

Seitz, 2016, A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction., Science, 353, 1011, 10.1126/science.aaf5050

Sheng, 2010, Hydrogen oxidation and evolution reaction kinetics on platinum: acid Vs Alkaline electrolytes., J. Electrochem. Soc., 157, 10.1149/1.3483106

Sheng, 2015, Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy., Nat. Commun., 6, 1, 10.1038/ncomms6848

Shetty, 2020, The catalytic mechanics of dynamic surfaces: stimulating methods for promoting catalytic resonance., ACS Catal., 10, 12666, 10.1021/acscatal.0c03336

Shinagawa, 2015, Insight on tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion., Sci. Rep., 5, 10.1038/srep138012015

Shinagawa, 2019, Switching of kinetically relevant reactants for the aqueous cathodic process determined by mass-transport coupled with protolysis., ChemCatChem, 11, 5961, 10.1002/cctc.201901459

Skúlason, 2010, Modeling the electrochemical hydrogen oxidation and evolution reactions on the basis of density functional theory calculations., J. Phys. Chem. C, 114, 18182, 10.1021/jp1048887

Smith, 2020, Current and future role of haber–bosch ammonia in a carbon-free energy landscape., Energ. Environ. Sci., 13, 331, 10.1039/C9EE02873K

Song, 2020, A review on fundamentals for designing oxygen evolution electrocatalysts., Chem. Soc. Rev., 49, 2196, 10.1039/C9CS00607A

Su, 2018, Assembling ultrasmall copper-doped ruthenium oxide nanocrystals into hollow porous polyhedra: highly robust electrocatalysts for oxygen evolution in acidic media., Adv. Mater., 30, 10.1002/adma.201801351

Sumaria, 2018, Quantifying confidence in DFT predicted surface pourbaix diagrams and associated reaction pathways for chlorine evolution., ACS Catal., 8, 9034, 10.1021/acscatal.8b01432

Suntivich, , Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries., Nat. Chem., 3, 546, 10.1038/nchem.1069

Suntivich, , A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles., Science, 334, 1383, 10.1126/science.1212858

Tahir, 2017, Electrocatalytic oxygen evolution reaction for energy conversion and storage: a comprehensive review., Nano Energ., 37, 136, 10.1016/j.nanoen.2017.05.022

Tang, 2016, Mechanism of hydrogen evolution reaction on 1T-MoS2 from first principles., ACS Catal., 6, 4953, 10.1021/acscatal.6b01211

Tao, 2019, Revealing energetics of surface oxygen redox from kinetic fingerprint in oxygen electrocatalysis., J. Am. Chem. Soc., 141, 13803, 10.1021/jacs.9b01834

Theerthagiri, 2020, Fundamental aspects and recent advances in transition metal nitrides as electrocatalysts for hydrogen evolution reaction: a review., Curr. Opin. Solid State Mater. Sci., 24, 10.1016/j.cossms.2020.100805

Tichter, 2020, Finite heterogeneous rate constants for the electrochemical oxidation of Vo2+ at glassy carbon electrodes., Front. Energ. Res., 8, 10.3389/fenrg.2020.00155

Toyao, 2020, Machine learning for catalysis informatics: recent applications and prospects., ACS Catal., 10, 2260, 10.1021/acscatal.9b04186

Trasatti, 1972, Work function, electronegativity, and electrochemical behaviour of metals: III. Electrolytic hydrogen evolution in acid solutions., J. Electroanal. Chem. Interfacial Electrochem., 39, 163, 10.1016/S0022-0728(72)80485-6

Trasatti, 1987, Progress in the understanding of the mechanism of chlorine evolution at oxide electrodes., Electrochim. Acta, 32, 369, 10.1016/0013-4686(87)85001-6

Ulissi, 2016, Automated discovery and construction of surface phase diagrams using machine learning., J. Phys. Chem. Lett., 7, 3931, 10.1021/acs.jpclett.6b01254

Ulissi, 2017, Machine-learning methods enable exhaustive searches for active bimetallic facets and reveal active site motifs for CO2 reduction., ACS Catal., 7, 6600, 10.1021/acscatal.7b01648

Van Santen, 2009, Reactivity theory of transition-metal surfaces: a Brønsted- evans- polanyi linear activation energy- free-energy analysis., Chem. Rev., 110, 2005, 10.1021/cr9001808

Varela, 2016, Tuning the catalytic activity and selectivity of Cu for CO2 electroreduction in the presence of halides., ACS Catal., 6, 2136, 10.1021/acscatal.5b02550

Vinogradova, 2018, Quantifying confidence in DFT-predicted surface pourbaix diagrams of transition-metal electrode–electrolyte interfaces., Langmuir, 34, 12259, 10.1021/acs.langmuir.8b02219

Viswanathan, 2014, Unifying solution and surface electrochemistry: limitations and opportunities in surface electrocatalysis., Top. Catal., 57, 215, 10.1007/s11244-013-0171-6

Viswanathan, 2012, Universality in oxygen reduction electrocatalysis on metal surfaces., ACS Catal., 2, 1654, 10.1021/cs300227s

Vos, 2018, MnOx/IrOx as selective oxygen evolution electrocatalyst in acidic chloride solution., J. Am. Chem. Soc., 140, 10270, 10.1021/jacs.8b05382

Wang, 2009, Intrinsic kinetic equation for oxygen reduction reaction in acidic media: the double tafel slope and fuel cell applications., Faraday Disc., 140, 347, 10.1039/B802218F

Warburton, 2020, Interfacial field-driven proton-coupled electron transfer at graphite-conjugated organic acids., J. Am. Chem. Soc., 142, 20855, 10.1021/jacs.0c10632

Warren, 2010, Thermochemistry of proton-coupled electron transfer reagents and its implications., Chem. Rev., 110, 6961, 10.1021/cr100085k

Wintrich, 2019, Enhancing the selectivity between oxygen and chlorine towards chlorine during the anodic chlorine evolution reaction on a dimensionally stable anode., ChemElectroChem, 6, 3108, 10.1002/celc.201900784

Wodrich, 2018, On the generality of molecular volcano plots., ChemCatChem, 10, 1586, 10.1002/cctc.201701709

Wuttig, 2016, Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity., Proc. Natl. Acad. Sci. U.S.A., 113, E4585, 10.1073/pnas.1602984113

Xiao, 2015, A review of phosphide-based materials for electrocatalytic hydrogen evolution., Adv. Energ. Mater., 5, 10.1002/aenm.201500985

Xie, 2017, In situ growth of cobalt at cobalt-borate core–shell nanosheets as highly-efficient electrocatalysts for oxygen evolution reaction in alkaline/neutral medium., Nanoscale, 9, 16059, 10.1039/C7NR06054H

Xue, 2018, Influence of alkali metal cations on the hydrogen evolution reaction activity of Pt, Ir, Au, and Ag electrodes in alkaline electrolytes., ChemElectroChem, 5, 2326, 10.1002/celc.201800690

Yang, 2020, High-throughput identification of exfoliable two-dimensional materials with active basal planes for hydrogen evolution., ACS Energy Lett., 5, 2313, 10.1021/acsenergylett.0c00957

Yao, 2019, Algorithm screening to accelerate discovery of 2d metal-free electrocatalysts for hydrogen evolution reaction., J. Mat. Chem. A, 7, 19290, 10.1039/C9TA06286F

Zeradjanin, 2016, A critical review on hydrogen evolution electrocatalysis: re-exploring the volcano-relationship., Electroanalysis, 28, 2256, 10.1002/elan.201600270

Zhang, 2020, Advances in thermodynamic-kinetic model for analyzing the oxygen evolution reaction., ACS Catal., 10, 8597, 10.1021/acscatal.0c01906

Zhang, 2020, Understanding surface charge effects in electrocatalysis. Part I: peroxodisulfate reduction at Pt (111)., J. Phys. Chem. C, 124, 16951, 10.1021/acs.jpcc.0c02824

Zhang, 2018, Progress and perspective of electrocatalytic CO2 reduction for renewable carbonaceous fuels and chemicals., Adv. Sci., 5, 10.1002/advs.201700275

Zhang, 2019, Potential-dependent volcano plot for oxygen reduction: mathematical origin and implications for catalyst design., J. Phys. Chem. Lett., 10, 7037, 10.1021/acs.jpclett.9b02436

Zhang, 2014, Competition between CO2 reduction and H2 evolution on transition-metal electrocatalysts., ACS Catal., 4, 3742, 10.1021/cs5012298

Zheng, 2016, Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy., Sci. Adv., 2, 10.1021/jacs.0c01104

Zhou, 2020, Combining single crystal experiments and microkinetic modeling in disentangling thermodynamic, kinetic and double-layer factors influencing oxygen reduction., J. Phys. Chem. C, 124, 13672, 10.1021/acs.jpcc.0c01621

Zhu, 2020, pH-dependent hydrogen and water binding energies on platinum surfaces as directly probed through surface-enhanced infrared absorption spectroscopy., J. Am. Chem. Soc., 142, 8748, 10.1021/jacs.0c01104

Zhu, 2019, Modeling electrocatalytic oxidation of formic acid at platinum., J. Electrochem. Soc., 167, 10.1149/2.0152001JES