Activity versus stability of atomically dispersed transition-metal electrocatalysts

Nature Reviews Materials, Journal Year: 2024, Volume and Issue: 9(9), P. 643 - 656

Published: July 31, 2024

Language: Английский

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Hierarchically Ordered Pore Engineering of Metal–Organic Framework‐Based Materials for Electrocatalysis

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(27)

Published: April 17, 2024

Abstract Ordered pore engineering that embeds uniform pores with periodic alignment in electrocatalysts opens up a new avenue for achieving further performance promotion. Hierarchically ordered porous metal–organic frameworks (HOP‐MOFs) possessing multilevel distribution are the promising precursors exploration of electrocatalysts, while scalable acquisition HOP‐MOFs editable components and adjustable size regimes is critical. This review presents recent progress on hierarchically MOF‐based materials enhanced electrocatalysis. The synthetic strategies different regimes, including self‐assembly guided by reticular chemistry, surfactant, nanoemulsion, nanocasting, first introduced. Then applications as exploring summarized, selecting representatives to highlight boosted performance. Especially, intensification molecule ion transport integrated optimized electron transfer site exposure over derivatives emphasized clarify directional integration effect endowed engineering. Finally, remaining scientific challenges an outlook this field proposed. It hoped will guide nanocatalysts boosting catalytic promoting practical applications.

Language: Английский

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Regulating Spin Polarization via Axial Nitrogen Traction at Fe‐N5 Sites Enhanced Electrocatalytic CO2 Reduction for Zn‐CO2 Batteries

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 18, 2024

Abstract Single Fe sites have been explored as promising catalysts for the CO 2 reduction reaction to value‐added CO. Herein, we introduce a novel molten salt synthesis strategy developing axial nitrogen‐coordinated Fe‐N 5 on ultrathin defect‐rich carbon nanosheets, aiming modulate pathway precisely. This distinctive architecture weakens spin polarization at sites, promoting dynamic equilibrium of activated intermediates and facilitating balance between *COOH formation *CO desorption active site. Notably, synthesized FeN , supported in nitrogen‐doped (FeN @DNC), exhibits superior performance RR, achieving Faraday efficiency 99 % production (−0.4 V vs. RHE) an H‐cell, maintaining 98 current density 270 mA cm −2 (−1.0 flow cell. Furthermore, @DNC catalyst is assembled reversible Zn−CO battery with cycle durability 24 hours. In situ IR spectroscopy functional theory (DFT) calculations reveal that N coordination traction induces transformation crystal field local symmetry, therefore weakening central atom lowering energy barrier desorption.

Language: Английский

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Feasibility of Active and Durable Lattice Oxygen‐Mediated Oxygen Evolution Electrocatalysts in Proton Exchange Membrane Water Electrolyzers Through d⁰ Metal Ion Incorporation

Small, Journal Year: 2025, Volume and Issue: unknown

Published: March 28, 2025

Abstract The primary hurdle faced in the practical application of proton exchange membrane water electrolyzer (PEMWE) involves improving intrinsic kinetic activity oxygen evolution reaction (OER) electrocatalysts while concurrently enhancing their durability. Although based on lattice oxygen‐mediated mechanism (LOM) have potential to significantly enhance OER without being restricted by scaling relationships, they are neglected acidic electrolytes due limited In this study, an innovative approach is presented simultaneously promote activation and improve durability LOM‐based incorporating d 0 metal ions into RuO 2 electrocatalyst. Leveraging unique electronic properties ion, O 2p band center Ru‐O covalency electrocatalyst successfully engineered, resulting change mechanism. Furthermore, a single cell PEMWE, demonstrates outstanding performance, achieving 3.0 A cm −2 at 1.81 V maintaining for 100 h 200 mA , surpassing commercial . This strategy challenges traditional viewpoint that suppressing essential PEMWE durability, offering new perspectives development electrolytes.

Language: Английский

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Ethylene Electrosynthesis via Selective CO₂ Reduction: Fundamental Considerations, Strategies, and Challenges

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

Published: June 11, 2024

Abstract The electrochemical carbon dioxide reduction reaction (CO 2 RR) is a promising approach for reducing atmospheric ) emissions, allowing harmful CO to be converted into more valuable carbon‐based products. On one hand, single (C 1 products have been obtained with high efficiency and show great promise industrial capture. However, multi‐carbon 2+ possess market value demonstrated significant as potential RR. Due RR's multiple pathways similar equilibrium potentials, the extended mechanisms necessary form C continue reduce overall selectivity of ‐to‐C electroconversion. Meanwhile, RR whole faces many challenges relating system optimization, owing an intolerance low surface pH, systemic stability utilization issues, competing side in H evolution (HER). Ethylene 4 remains incredibly within chemical industry; however, current established method producing ethylene (steam cracking) contributes emission atmosphere. Thus, strategies significantly increase this technology are essential. This review will discuss vital factors influencing forming summarize recent advancements electrosynthesis.

Language: Английский

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Elucidating Relay Catalysis on Copper Clusters With Satellite Single Atoms for Enhanced Urea Electrosynthesis

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Relay catalysis represents significant efficacy in alleviating competition among different reactants during coupling reactions. However, a comprehensive understanding of the reaction mechanism underlying relay for urea electrosynthesis remains challenging. Herein, we have developed catalyst (CuAC-CuSA@NC) comprising Cu atomic clusters (CuAC) with satellite Cu─N4 single atoms (CuSA) sites on nitrogen-doped porous interconnected carbon skeleton (NC), enabling elucidation process co-reduction CO2 and NO3 -. The designed CuAC-CuSA@NC exhibits an approximately threefold higher yield rate compared to that CuSA@NC at -1.3 V versus RHE. Ex-situ experimental results in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy analysis reveal formation sequence between *NH2 *NH2CO species increasing reduction potential. combination theoretical calculations further elucidates pathway involves "CuAC" facilitating conversion *NO3 *NOx, followed by hydrogenation form *H from water dissociation promoted "CuSA" sites, which subsequently couples *CO2 produce urea. This work provides novel insights into investigation reactions, but not limit to, synthesis.

Language: Английский

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Leveraging Atomic-Scale Synergy for Selective CO₂ Electrocatalysis to CO over CuNi Dual-Atom Catalysts

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 16224 - 16233

Published: Oct. 18, 2024

Revealing the synergistic catalytic mechanism involving multiple active centers is crucial for understanding multiphase catalysis. However, complex structures of catalysts and interfacial environments pose a challenge in thoroughly exploring experimental evidence. This study reports utilization CuNi dual-atom catalyst (Cu/Ni–NC) electrochemical reduction CO2. It demonstrates high Faradaic efficiency CO exceeding 99%, remarkable reaction activity with partial current density surpassing –300 mA cm–2, prolonged stability more than 5 days at –200 mA·cm–2. Operando characterization techniques functional theory calculations reveal that Ni atoms function as sites activation hydrogenation CO2, while Cu serve dissociation H2O, supplying protons subsequent process. Moreover, electronic interactions between facilitate formation *COOH illustrating CO2 sites.

Language: Английский

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Regulating Spin Polarization via Axial Nitrogen Traction at Fe‐N5 Sites Enhanced Electrocatalytic CO2 Reduction for Zn‐CO2 Batteries

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(43)

Published: July 18, 2024

Abstract Single Fe sites have been explored as promising catalysts for the CO 2 reduction reaction to value‐added CO. Herein, we introduce a novel molten salt synthesis strategy developing axial nitrogen‐coordinated Fe‐N 5 on ultrathin defect‐rich carbon nanosheets, aiming modulate pathway precisely. This distinctive architecture weakens spin polarization at sites, promoting dynamic equilibrium of activated intermediates and facilitating balance between *COOH formation *CO desorption active site. Notably, synthesized FeN , supported in nitrogen‐doped (FeN @DNC), exhibits superior performance RR, achieving Faraday efficiency 99 % production (−0.4 V vs. RHE) an H‐cell, maintaining 98 current density 270 mA cm −2 (−1.0 flow cell. Furthermore, @DNC catalyst is assembled reversible Zn−CO battery with cycle durability 24 hours. In situ IR spectroscopy functional theory (DFT) calculations reveal that N coordination traction induces transformation crystal field local symmetry, therefore weakening central atom lowering energy barrier desorption.

Language: Английский

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Selenic Acid Etching Assisted Atomic Engineering for Designing Metal-Semimetal Dual Single-Atom Catalysts for Enhanced CO₂ Electroreduction

ACS Nano, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

Single-atom catalysts are promising for electrocatalytic CO2 conversion but face challenges in controllable syntheses. Herein, a facile selenic acid etching-assisted strategy has been developed to fabricate hybrid metal-semimetal dual single-atom catalyst reduction. This enables the simultaneous generation of monodisperse active sites and hierarchical morphologies with hollow nanostructures. The as-obtained Fe–Se supported by porous nitrogen-doped carbon (FeSe-NC) shows exceptional catalytic activity CO selectivity, delivering Faradaic efficiency (FE) >97% industrially comparable jCO, superior Fe catalyst. Moreover, FeSe-NC-based rechargeable Zn-CO2 battery delivers high power density (2.01 mW cm–2) outstanding FECO (>90%), as well excellent cycling stability. Experimental results together theoretical calculations reveal that etching-induced defects Se-modulated centers asymmetrical polarized charge distributions synergistically facilitate key intermediate *CO desorption thus accelerate CO2-to-CO conversion.

Language: Английский

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Coupling [Bmim]PF₆ and Pd NPs Modulated MOF-Based Material for Synergetic Regulating Electrocatalytic CO₂ Reduction

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 17, 2024

Metal-organic frameworks (MOFs) with a large number of active sites and high porosity are considered to be good platforms for the carbon dioxide electroreduction reaction (CO

Language: Английский

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