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

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(9), P. 1336 - 1345

Published: April 15, 2024

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

Language: Английский

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Revolutionizing electrochemical CO₂ reduction to deeply reduced products on non-Cu-based electrocatalysts

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(15), P. 5336 - 5364

Published: Jan. 1, 2024

Producing deeply reduced (>2 e − per carbon atom) products from the electrochemical CO 2 reduction reaction on non-Cu-based catalysts is an attractive and sustainable approach for utilization.

Language: Английский

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Steering CO Selectivity in CO₂ Electroreduction over Silver Microtubular Gas-Diffusion Electrodes via Surface Reconstruction

Energy & Fuels, Journal Year: 2024, Volume and Issue: 38(11), P. 10096 - 10105

Published: May 10, 2024

An efficient gas diffusion electrode (GDE) is crucial for enhancing mass transport involving gas-phase CO2 conversion in the electrochemical reduction reaction (CO2RR). Microtubular hollow fiber GDE (HFGDE) with a porous hierarchical wall has garnered significant attention, which can modulate triple-phase zone and improve performance of CO2RR. Simultaneously, engineering nano/microstructure surfaces electrocatalysts have been demonstrated to effectively enhance selectivity activity Here, we developed microparticle Ag-based HFGDE via an situ oxidation–reduction method. Both CO showed enhancement over pristine thermal reduced Ag without surface reconstruction. At −1.2 V vs RHE, faradaic efficiency 94%, partial current density 83.4 mA cm–2, surpassing that treatment electrodes, only 26% 12.3 cm–2. The distinctive reconstruction on electrocatalyst could be attributed decreasing activation energy barrier rate-limiting step initial electron/proton transfer. This work represents facile strategy as advanced materials conversion.

Language: Английский

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Insights into Electrochemical Nitrate Reduction to Nitrogen on Metal Catalysts for Wastewater Treatment

Environmental Science & Technology, Journal Year: 2025, Volume and Issue: 59(6), P. 3263 - 3275

Published: Jan. 6, 2025

Electrocatalytic nitrate reduction reaction (NO3RR) to harmless nitrogen (N2) presents a viable approach for purifying NO3–-contaminated wastewater, yet most current electrocatalysts predominantly produce ammonium/ammonia (NH4+/NH3) due challenges in facilitating N–N coupling. This study focuses on identifying metal catalysts that preferentially generate N2 and elucidating the mechanistic origins of their high selectivity. Our evaluation 16 commercially available metals reveals only Pb, Sn, In demonstrated substantial selectivity (79.3, 70.0, 57.0%, respectively, under conditions 6 h electrolysis, density 10 mA/cm2, an initial NO3–-N concentration 100 mg/L), while others largely favored NH4+ production. Comprehensive experimental theoretical analyses indicate NH4+-selective (e.g., Co) exhibited water activity enhances •H coverage, thereby promoting hydrogenation NO3– through hydrogen atom transfer mechanism. contrast, N2-selective catalysts, with lower activity, promoted formation N-containing intermediates, which likely undergo dimerization form via proton-coupled electron Enhancing adsorption was beneficial improve by competitively reducing coverage. findings highlight crucial role NO3RR performance offer rational design enhanced

Language: Английский

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Theoretical Insights into the Selectivity of Single-Atom Fe–N–C Catalysts for Electrochemical NO_x Reduction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

Single-atom Fe-N-C catalysts have attracted significant attention in the NOx reduction reaction (NOxRR). However, origin of their selectivity NOxRR remains unclear, impeding further advancements application. Herein, we investigate potential-driven competitive mechanism for NH3 and NH2OH production over single-atom pyridinic-FeN4 pyrrolic-FeN4 sites using constant-potential density functional theory calculations. The is linked to switching Fe 3d orbitals as they interact with intermediates. between determined by applied potentials. predominantly generates at higher potentials (-0.6 -1.2 V, vs SHE), while favored lower (0.6 -0.6 V). shows a similar potential-dependent product distribution, crossover potential -1.0 V. selectivity-determining intermediates (SDIs) are *NH2OH *NH2 + *OH. governed interacting SDIs, from dumbbell-shaped 3dz2 four-leaf clover-like 3dxz, 3dyz, 3dx2-y2, which plays crucial role controlling distribution based on These findings offer new insights into NOxRR.

Language: Английский

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Doping and defect engineering in carbon-based electrocatalysts for enhanced electrochemical CO2 reduction: From 0D to 3D materials

Advances in Colloid and Interface Science, Journal Year: 2025, Volume and Issue: 339, P. 103429 - 103429

Published: Feb. 6, 2025

Language: Английский

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Electrifying CO₂ Coupling With Small Molecules

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Abstract Carbon capture and utilization (CCU) is pivotal for low‐carbon industry. Among varied techniques, coupling of carbon dioxide (CO 2 ) with small molecules to generate valuable‐added chemicals using renewable electricity stands out thanks its cost‐effectiveness sustainability. This review first highlights recent strategies in catalyst preparation improving the efficiency selectivity electrochemical reactions, including heterostructure catalysts, bimetallic defect engineering, coordination complexes. The progresses on mechanism investigation C─N, C─O, C─C situ spectroscopies online mass spectrometry are subsequently summarized. In addition, electrolyzer design techno–economic analysis about process optimization integration energy stressed. Finally, future challenges optimization, reaction elucidation, scale‐up implementation discussed.

Language: Английский

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Insights into Electrochemical CO₂ Reduction on Metallic and Oxidized Tin Using Grand-Canonical DFT and In Situ ATR-SEIRA Spectroscopy

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8353 - 8365

Published: May 14, 2024

Electrochemical CO2 reduction (CO2R) to formate is an attractive carbon emissions mitigation strategy due the existing market and price for formic acid. Tin effective electrocatalyst CO2R formate, but underlying reaction mechanism whether active phase of tin metallic or oxidized during openly debated. In this report, we used grand-canonical density functional theory attenuated total reflection surface-enhanced infrared absorption spectroscopy identify differences in vibrational signatures surface species on fully surfaces. Our results show that feasible both tin. We propose key difference between each termination catalyzed by surfaces limited electrochemical activation CO2, whereas slow reductive desorption formate. While exact degree oxidation unlikely be either oxidized, study highlights limiting behavior these two lays out features our predict will promote rapid catalysis. Additionally, highlight power integrating high-fidelity quantum mechanical modeling spectroscopic measurements elucidate intricate electrocatalytic pathways.

Language: Английский

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Cation Effects on the Adsorbed Intermediates of CO₂ Electroreduction Are Systematic and Predictable

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8814 - 8822

Published: May 23, 2024

The electrode–electrolyte interface, and in particular the nature of cation, has considerable effects on activity product selectivity electrochemical reduction CO2. Therefore, to improve electrocatalysis this challenging reaction, it is paramount ascertain whether cation adsorbed intermediates are systematic. Here, DFT calculations used show that K+, Na+, Mg2+, single carbon CO2 can either be stabilizing or destabilizing depending metal adsorbate. Because systematic trends observed, accurately predicted simple terms for a wide variety metals, cations species. These results then applied CO four different catalytic surfaces (Au, Ag, Cu, Pd) activation weak-binding metals consistently observed by virtue stabilization key intermediate *COOH.

Language: Английский

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Catalyst Design and Engineering for CO₂‐to‐Formic Acid Electrosynthesis for a Low‐Carbon Economy

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 12, 2024

Abstract Formic acid (FA) has emerged as a promising candidate for hydrogen energy storage due to its favorable properties such low toxicity, flammability, and high volumetric capacity under ambient conditions. Recent analyses have suggested that FA produced by electrochemical carbon dioxide (CO 2 ) reduction reaction (eCO RR) using low‐carbon electricity exhibits lower fugitive (H emissions global warming potential (GWP) during the H carrier production, transportation processes compared those of other alternatives like methanol, methylcyclohexane, ammonia. eCO RR can enable industrially relevant current densities without need pressures, temperatures, or auxiliary sources. However, widespread implementation is hindered requirement highly stable selective catalysts. Herein, aim explore evaluate catalyst engineering in designing nanostructured catalysts facilitate economically viable production FA.

Language: Английский

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