Proton-coupled Electron Transfer Steps Research Articles

Mechanism of glycerol oxidation on bismuth vanadate photoanodes: Influence of tantalum doping

This study investigated the mechanisms underlying the photoelectrochemical oxidation of glycerol to dihydroxyacetone (DHA) and glyceraldehyde (GLAD) on BiVO4 and Bi–O–Ta species using density functional theory calculations. The results revealed that for both products and metal-oxides, the first proton-coupled electron-transfer (PCET) step, which forms a carbon-centered radical, served as the rate-limiting step. The formation of DHA from a secondary-carbon-centered radical encountered lower energy barriers compared to the formation of GLAD from a primary-carbon-centered radical, indicating the favorability of the DHA production pathway. The differences between the energy inputs required for DHA and GLAD production were greater on the Bi–O–Ta species compared to the BiVO4. Furthermore, the production of formic acid (FA) from glycerol via GLAD, involving three H2O molecules and eight PCET steps, encountered greater energy barriers on Bi–O–Ta species than on BiVO4. These computational results confirm that the Bi–O–Ta species enhances DHA generation from glycerol while suppressing the production of unfavorable byproducts such as GLAD and FA. Correspondingly, the Ta-doped BiVO4 photoanode achieves a greater Faradaic efficiency than the BiVO4 photoanode and approximately 100% selectivity for DHA in acidic media owing to the Bi–O–Ta species formed on the surface.

Probing the Molecular Interactions of Electrochemically Reduced Vitamin B2 with CO2.

The electrochemical reduction of riboflavin (vitamin B2) in a dimethyl sulfoxide solvent was examined under a CO2 atmosphere and compared with results under an argon atmosphere. Variable-scan-rate cyclic voltammetry combined with controlled potential electrolysis (CPE) and analysis by UV-vis and EPR spectroscopies provided insights into the nature of interactions of reduced flavins with dissolved CO2. Reductive exhaustive CPE experiments under CO2 indicated an overall two-electron stoichiometry, compared to one-electron reduction under an argon atmosphere, due to the lowering of the formal one-electron reduction potential of the flavin radical anion to form the dianion, which can be rationalized by riboflavin-CO2 molecular interactions. UV-vis spectroscopic measurements confirmed complete chemical reversibility of the redox transformations over extended time scales. Digital simulation modeling of the voltammetric data enabled extraction of thermodynamic and kinetic parameters for the proposed mechanism, comprising multiple proton-coupled electron transfer steps, diamagnetic anions, radical anions, and neutral radical intermediates enroute to the fully reduced state, as well as evidence of a long-lived solution phase complex of the reduced riboflavin with CO2.

Spin-Polarized PdCu-Fe3O4 In-Plane Heterostructures with Tandem Catalytic Mechanism for Oxygen Reduction Catalysis.

Alloying has significantly upgraded the oxygen reduction reaction (ORR) of Pd-based catalysts through regulating the thermodynamics of oxygenated intermediates. However, the unsatisfactory activation ability of Pd-based alloys toward O2 molecules limits further improvement of ORR kinetics. Herein, the precise synthesis of nanosheet assemblies of spin-polarized PdCu-Fe3O4 in-plane heterostructures for drastically activating O2 molecules and boosting ORR kinetics is reported. It is demonstrated that the deliberate-engineered in-plane heterostructures not only tailor the d-band center of Pd sites with weakened adsorption of oxygenated intermediates but also endow electrophilic Fe sites with strong ability to activate O2 molecules, which make PdCu-Fe3O4 in-plane heterostructures exhibit the highest ORR specific activity among the state-of-art Pd-based catalysts so far. In situ electrochemical spectroscopy and theoretical investigations reveal a tandem catalytic mechanism on PdCu-Fe3O4─Fe sites that initially activate molecular O2 and generate oxygenated intermediates being transferred to Pd sites to finish the subsequent proton-coupled electron transfer steps.

Heterometallic Transition Metal Oxides Containing Lewis Acids as Molecular Catalysts for the Reduction of Carbon Dioxide to Carbon Monoxide with Bimodal Activity.

Electrocatalytic CO2 reduction (e-CO2RR) to CO is replete with challenges including the need to carry out e-CO2RR at low overpotentials. Previously, a tricopper-substituted polyoxometalate was shown to reduce CO2 to CO with a very high faradaic efficiency albeit at -2.5 V versus Fc/Fc+. It is now demonstrated that introducing a nonredox metal Lewis acid, preferably GaIII, as a binding site for CO2 in the first coordination sphere of the polyoxometalate, forming heterometallic polyoxometalates, e.g., [SiCuIIFeIIIGaIII(H2O)3W9O37]8-, leads to bimodal activity optimal both at -2.5 and -1.5 V versus Fc/Fc+; reactivity at -1.5 V being at an overpotential of ∼150 mV. These results were observed by cyclic voltammetry and quantitative controlled potential electrolysis where high faradaic efficiency and chemoselectivity were obtained at -2.5 and -1.5 V. A reaction with 13CO2 revealed that CO2 disproportionation did not occur at -1.5 V. EPR spectroscopy showed reduction, first of CuII to CuI and FeIII to FeII and then reduction of a tungsten atom (WVI to WV) in the polyoxometalate framework. IR spectroscopy showed that CO2 binds to [SiCuIIFeIIIGaIII(H2O)3W9O37]8- before reduction. In situ electrochemical attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) with pulsed potential modulated excitation revealed different observable intermediate species at -2.5 and -1.5 V. DFT calculations explained the CV, the formation of possible activated CO2 species at both -2.5 and -1.5 V through series of electron transfer, proton-coupled electron transfer, protonation and CO2 binding steps, the active site for reduction, and the role of protons in facilitating the reactions.

Promoting Oxygen Evolution Electrocatalysis by Coordination Engineering in Cobalt Phosphate.

Understanding the structure-activity correlation is an important prerequisite for the rational design of high-efficiency electrocatalysts at the atomic level. However, the effect of coordination environment on electrocatalytic oxygen evolution reaction (OER) remains enigmatic. In this work, the regulation of proton transfer involved in water oxidation by coordination engineering based on Co3(PO4)2 and CoHPO4 is reported. The HPO4 2- anion has intermediate pKa value between Co(II)-H2O and Co(III)-H2O to be served as an appealing proton-coupled electron transfer (PCET) induction group. From theoretical calculations, the pH-dependent OER properties, deuterium kinetic isotope effects, operando electrochemical impedance spectroscopy (EIS) and Raman studies, the CoHPO4 catalyst beneficially reduces the energy barrier of proton hopping and modulates the formation energy of high-valent Co species, thereby enhancing OER activity. This work demonstrates a promising strategy that involves tuning the local coordination environment to optimize PCET steps and electrocatalytic activities for electrochemical applications. In addition, the designed system offers a motif to understand the structure-efficiency relationship from those amino-acid residue with proton buffer ability in natural photosynthesis.

Probing the Activity and Selectivity of Nickel Carboxylethylphosphonate 2D-MOF for the Electrochemical Conversion of CO2 to Syngas

The increasing concentration of CO2 in the atmosphere is alarming for modern society and the reduction of CO2 into valuable products would be a unique solution.1 Metal–organic frameworks (MOFs), constructed from organic linkers interconnected with metal (oxide) nodes, with high porosity and large surface area, have become an emerging class of electrocatalysts for reduction of CO2.2,3 Herein, we report the synthesis and characterization of a two-dimensional nickel metal-organic framework (2D Ni-MOF) with 3-phosphopropionic acid and 4,4-bypyridine as ligands and Ni2+ as the node (figure 1). The electrocatalytic activity of this material is explored for the electrochemical CO2 reduction reaction (CO2RR). An onset potential for the electrochemical reduction CO2 activity of -0.51 V vs RHE was observed which is 70 mV more positive than the HER in Ar-saturated electrolyte suggesting an efficient CO2 reduction. This catalyst showed a high current density of 33.5 mA cm-2 at 1.01 V vs RHE, exhibiting superior performance to most of the MOFs tested so far for CO2 reduction (figure 2a and b). Long term electrolysis at -0.8 V (vs RHE) yielded a current density of ∼10 mA cm-2 with high selectivity towards the formation of CO and H2 with an average production ratio of 30:70%, respectively (figure 2c and d). This new Ni-MOF catalyst retained its crystallinity and morphology after electrolysis as confirmed by powder XRD, HRTEM, FT-IR and Raman spectroscopy, indicating promising stability of the catalyst.Density functional theory (DFT) was employed to calculate adsorption-free energy of the reaction intermediates to identify the active catalytic sites responsible for CO2 reduction in our 2D Ni-MOF structure. Findings show that the catalyst more readily reduces H* to H2 (with a limiting potential of 0.48 eV) than CO2 to COOH* (limiting potential of 0.78 eV). The reaction mechanism upon which this calculation was based begins with the removal of the H2O molecule bound to the Ni (II) site, followed by CO2 adsorption and the two proton-coupled electron transfer steps yielded COOH* and then CO & H2O. The H2O is more strongly adsorbed to the Ni (II) site than CO which closes the mechanistic cycle. Reference 1. M. J. B. Kabeyi and O. A. Olanrewaju, Frontiers in Energy Research, 2022, 9.2. B.-X. Dong, S.-L. Qian, F.-Y. Bu, Y.-C. Wu, L.-G. Feng, Y.-L. Teng, W.-L. Liu and Z.-W. Li, ACS Applied Energy Materials, 2018, 1, 4662-4669.3. J.-X. Wu, S.-Z. Hou, X.-D. Zhang, M. Xu, H.-F. Yang, P.-S. Cao and Z.-Y. Gu, Chemical Science, 2019, 10, 2199-2205. Figure 1

Mechanisms for Methane and Ammonia Oxidation by Particulate Methane Monooxygenase.

Particulate MMO (pMMO) catalyzes the oxidation of methane to methanol and also ammonia to hydroxylamine. Experimental characterization of the active site has been very difficult partly because the enzyme is membrane-bound. However, recently, there has been major progress mainly through the use of cryogenic electron microscopy (cryoEM). Electron paramagnetic resonance (EPR) and X-ray spectroscopy have also been employed. Surprisingly, the active site has only one copper. There are two histidine ligands and one asparagine ligand, and the active site is surrounded by phenyl alanines but no charged amino acids in the close surrounding. The present study is the first quantum chemical study using a model of that active site (CuD). Low barrier mechanisms have been found, where an important part is that there are two initial proton-coupled electron transfer steps to a bound O2 ligand before the substrate enters. Surprisingly, this leads to large radical character for the oxygens even though they are protonated. That result is very important for the ability to accept a proton from the substrates. Methods have been used which have been thoroughly tested for redox enzyme mechanisms.

Oxidation mechanism of iodate to metaperiodate on a tungsten trioxide photoanode

The mechanisms involved in the photoelectrochemical oxidation of iodate (IO3−) to metaperiodate (IO4−) and H2O to O2 on WO3 were investigated using density functional theory. The oxygen evolution reaction (OER) included four proton-coupled electron transfer (PCET) steps via H2O2 intermediates. After the first PCET of the rate-limiting step, instead of H2O adsorption, IO3− was adsorbed and the second PCET step generated IO4− species (PI1 mechanism). Although another mechanism, PI2, with the two PCET steps followed by the IO3− adsorption was found, IO4− was energetically generated via PI1 rather than via PI2. Based on the free energy changes in the PCET steps, alkaline cations such as Li+, Na+, and K+ on WO3 suppressed the OER process. In addition, Na+ promoted the IO3− adsorption and subsequent PCET step of PI1. The computational results verified that using NaIO3 aqueous solution on WO3 effectively inhibits OER and facilitates IO4− generation, resulting in a higher (lower) selectivity of IO4− (O2) than using LiIO3 and KIO3 aqueous solutions.

Four Generations of Volcano Plots for the Oxygen Evolution Reaction: Beyond Proton-Coupled Electron Transfer Steps?

ConspectusDue to its importance for electrolyzers or metal-air batteries for energy conversion or storage, there is huge interest in the development of high-performance materials for the oxygen evolution reaction (OER). Theoretical investigations have aided the search for active material motifs through the construction of volcano plots for the kinetically sluggish OER, which involves the transfer of four proton-electron pairs to form a single oxygen molecule. The theory-driven volcano approach has gained unprecedented popularity in the catalysis and energy communities, largely due to its simplicity, as adsorption free energies can be used to approximate the electrocatalytic activity by heuristic descriptors.In the last two decades, the binding-energy-based volcano method has witnessed a renaissance with special concepts being developed to incorporate missing factors into the analysis. To this end, this Account summarizes and discusses the different generations of volcano plots for the example of the OER. While first-generation methods relied on the assessment of the thermodynamic information for the OER reaction intermediates by means of scaling relations, the second and third generations developed strategies to include overpotential and kinetic effects into the analysis of activity trends. Finally, the fourth generation of volcano approaches allowed the incorporation of various mechanistic pathways into the volcano methodology, thus paving the path toward data- and mechanistic-driven volcano plots in electrocatalysis.Although the concept of volcano plots has been significantly expanded in recent years, further research activities are discussed by challenging one of the main paradigms of the volcano concept. To date, the evaluation of activity trends relies on the assumption of proton-coupled electron transfer steps (CPET), even though there is experimental evidence of sequential proton-electron transfer (SPET) steps. While the computational assessment of SPET for solid-state electrodes is ambitious, it is strongly suggested to comprehend their importance in energy conversion and storage processes, including the OER. This can be achieved by knowledge transfer from homogeneous to heterogeneous electrocatalysis and by focusing on the material class of single-atom catalysts in which the active center is well defined. The derived concept of how to analyze the importance of SPET for mechanistic pathways in the OER over solid-state electrodes could further shape our understanding of the proton-electron transfer steps at electrified solid/liquid interfaces, which is crucial for further progress toward sustainable energy and climate neutrality.

Promoted selectivity of photocatalytic CO2 reduction to C2H4 via hybrid CuxCoSy possessing dual unsaturated sites

Ethylene production by CO2 reduction is sluggish because the repulsive dipole-dipole interaction and 12 proton-coupled electron-transfer steps consecutively. Amorphous structured photocatalysts possess few grain boundaries and abundant unsaturated sites, accelerating the reaction efficiency from the angle of dynamics and thermodynamics, which still not yet be used in PCR to C2 products currently. Herein, an amorphous CuxCoSy composed of the minority crystalline CuCo2S4 is fabricated to realize an excellent C2H4 selectivity in terms of Relectron (94.9%). Unsaturated Co and S play the key roles in the improved efficiency of C2H4 generation. C-C coupling is achieved via shortening Co-S bonds distance, and *CO-*CO coupling barrier is decreased by more electrons accumulated on unsaturated S. Water is adsorbed on Co adjacent to S and provide protons for *COCO to form *CH2 = C. This work paves a new way for broadening the efficient of C2H4 photocatalytic evolution using amorphous photocatalyst.

(Invited) Crosscutting Materials and Molecular Catalysts in Hybrid Photoelectrodes for Liquid Solar Fuel Production

The Solar Hub entitled the C enter for Hybrid Approaches in Solar Energy to Liquid Fuels, or CHASE, is advancing the quest for liquid fuels from water, nitrogen, and/or carbon dioxide feedstocks with sunlight as the only energy source. To realize this quest, CHASE utilizes hybrid photoelectrodes based on molecular catalysts integrated with visible light absorbing semiconductors with controlled microenvironments to achieve liquid solar fuel production. These crosscutting materials serve as hybrid photoelectrodes in photoelectrochemical cells. This presentation will focus on recent advances on photocatalysis at hybrid Si interfaces with particular attention to the individual electron transfer and proton coupled electron transfer step(s) relevant to water oxidation and carbon dioxide reduction catalysis. The impact of CHASE findings on solar energy conversion and the quest for liquid solar fuels will be discussed.

Cations Determine the Mechanism and Selectivity of Alkaline Oxygen Reduction Reaction on Pt(111)**

AbstractThe proton‐coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long‐standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR‐PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well‐defined Pt(111). We unveil a dual‐cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt−O and Pt−OH overlayers and ii) the competition between inner‐ and outer‐sphere PCET steps. The cation‐dependent transition from Pt−O to Pt−OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes.

Cations Determine the Mechanism and Selectivity of Alkaline Oxygen Reduction Reaction on Pt(111).

The proton-coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long-standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR-PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well-defined Pt(111). We unveil a dual-cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt-O and Pt-OH overlayers and ii) the competition between inner- and outer-sphere PCET steps. The cation-dependent transition from Pt-O to Pt-OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes.

Iridium-Catalyzed Hydrogenation of a Phenoxy Radical to the Phenol: Overcoming Catalyst Deactivation with Visible Light Irradiation.

Piano-stool iridium hydride complexes bearing phenylpyridine ligands are effective precatalysts for promoting the formation of element-hydrogen bonds using H2 as the stoichiometric H-atom source. Irradiation with blue light resulted in a profound enhancement of catalyst turnover for the iridium-catalyzed hydrogenation of the aryloxyl radical 2,4,6-tBu3-C6H2O• to the corresponding phenol. Monitoring the progress of the reaction revealed the formation of an iridium 3,3-dimethyl-2,3-dihydrobenzofuranyl compound arising from two C-H activation events following the proton-coupled electron transfer (PCET) step. Under thermal conditions, this compound was inactive for catalytic aryloxide hydrogenation, representing a deactivation pathway. Irradiation with blue light under H2 released the free heterocycle and regenerated the piano-stool iridium hydride precatalyst, establishing a pathway for catalyst recovery and overall enhanced turnover.

Revealing the role of double-layer microenvironments in pH-dependent oxygen reduction activity over metal-nitrogen-carbon catalysts

A standing puzzle in electrochemistry is that why the metal-nitrogen-carbon catalysts generally exhibit dramatic activity drop for oxygen reduction when traversing from alkaline to acid. Here, taking FeCo-N6-C double-atom catalyst as a model system and combining the ab initio molecular dynamics simulation and in situ surface-enhanced infrared absorption spectroscopy, we show that it is the significantly distinct interfacial double-layer structures, rather than the energetics of multiple reaction steps, that cause the pH-dependent oxygen reduction activity on metal-nitrogen-carbon catalysts. Specifically, the greatly disparate charge densities on electrode surfaces render different orientations of interfacial water under alkaline and acid oxygen reduction conditions, thereby affecting the formation of hydrogen bonds between the surface oxygenated intermediates and the interfacial water molecules, eventually controlling the kinetics of the proton-coupled electron transfer steps. The present findings may open new and feasible avenues for the design of advanced metal-nitrogen-carbon catalysts for proton exchange membrane fuel cells.

Correlations between the Electronic Structure and Energetics of the Catalytic Steps in Homogeneous Water Oxidation Catalysis.

The development of an efficient electrocatalyst for the water oxidation reaction is limited by unfavorable scaling relations between catalytic intermediates, resulting in an overpotential. In contrast to heterogeneous catalysts, the electronic structure of homogeneous catalysts can be modified to a great extent due to a tailored ligand design. However, studies utilizing the tunability of organic ligands have rarely been conducted in a systematic manner and, as of yet, have not produced catalytic paths that avoid the aforementioned unfavorable scaling relations. To investigate the influence of electron-donating groups (EDGs) or electron-withdrawing groups (EWGs) on elementary steps in electrochemical water oxidation catalysis, cis-[Ru(bpy)2(H2O)]2+ (bpy = 2,2'-bipyridine) was selected as the scaffold that was modified with methyl, methoxy, chloro, and trifluoromethyl groups. This catalyst can undergo several electron transfer (ET), proton transfer (PT), and proton-coupled electron transfer (PCET) steps that were all probed experimentally. In this systematic study, it was found that PCET steps are relatively insensitive with respect to the presence of EDGs or EWGs, while the decoupled ET and PT steps are more heavily affected. However, the influence of the substituents decreases with an increasing oxidation state of Ru due to a lack of d-electrons available at the Ru center for π-backbonding to the bipyridine ligand. Therefore, the RuV/VI redox couple appears to be relatively unaffected by the substituent. Nevertheless, the implementation of EWGs can shift all oxidation events to a very narrow potential window. Not only do our findings illustrate how electronic substituents affect the entire potential energy landscape of the catalytic water oxidation reaction, but they also show that the cis-[Ru(bpy)2(H2O)]2+ compounds follow different design rules and scaling relations, as has been reported for every other oxygen evolution catalyst thus far.

Boosting the Proton-coupled Electron Transfer via Fe-P Atomic Pair for Enhanced Electrochemical CO2 Reduction.

Single-atom catalysts exhibit superior CO2 -to-CO catalytic activity, but poor kinetics of proton-coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe-P atom paired catalyst onto nitrogen doped graphitic layer (Fe1 /PNG) to accelerate PCET step. Fe1 /PNG delivers an industrial CO current of 1 A with FECO over 90 % at 2.5 V in a membrane-electrode assembly, overperforming the CO current of Fe1 /NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe-P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO2 , and enhancing the activity of CO2 reduction. This atom-pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single-atom catalysts.

Boosting the Proton‐coupled Electron Transfer via Fe−P Atomic Pair for Enhanced Electrochemical CO2 Reduction

AbstractSingle‐atom catalysts exhibit superior CO2‐to‐CO catalytic activity, but poor kinetics of proton‐coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe−P atom paired catalyst onto nitrogen doped graphitic layer (Fe1/PNG) to accelerate PCET step. Fe1/PNG delivers an industrial CO current of 1 A with FECO over 90 % at 2.5 V in a membrane‐electrode assembly, overperforming the CO current of Fe1/NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe−P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO2, and enhancing the activity of CO2 reduction. This atom‐pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single‐atom catalysts.

Unveiling the Hidden Energy Profiles of the Oxygen Evolution Reaction via Machine Learning Analyses.

The oxygen evolution reaction (OER) is a crucial electrochemical process for hydrogen production in water electrolysis. However, due to the involvement of multiple proton-coupled electron transfer steps, it is challenging to identify the specific elementary reaction that limits the rate of the OER. Here we employed a machine-learning-based approach to extract the reaction pathway exhaustively from experimental data. Genetic algorithms were applied to search for thermodynamic and kinetic parameters using the current-electrochemical potential relationship of the OER. Interestingly, analysis of the datasets revealed the energy state distributions of reaction intermediates, which likely originated in the interactions among intermediates or the distribution of multiple sites. Through our exhaustive analyses, we successfully uncovered the hidden energy profiles of the OER. This approach can reveal the reaction pathway to activate for efficient hydrogen production, which facilitates the design of catalysts.

How data-driven approaches advance the search for materials relevant to energy conversion and storage

Materials discovery for proton-coupled electron transfer steps is governed by theoretical predictions using the density functional theory approximation. This method underestimates the complexity of the dynamic solid/liquid interface encountered during catalytic processes under bias. In the present perspective article, it is discussed how data-science approaches improve the analysis of the elementary steps at electrified solid/liquid interfaces by using the popular volcano concept as a tool for communication.