Unraveling the Common Nature of O and S Doping in Improving Electrochemical O₂ Reduction Reaction Performance of FeN₄C

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4039 - 4050

Published: Feb. 20, 2025

Heteroatom-doped Fe-N-C catalysts have emerged as promising alternatives to noble metals for the oxygen reduction reaction (ORR) due their lower cost. However, underlying mechanisms responsible enhanced performance, particularly electrochemical stability, remain a subject of debate. This study leverages density functional theory calculations coupled with constant potential and implicit solvent model investigate stabilities activities pyridinic (PD-) pyrrolic FeN4C (PL-FeN4C) catalysts. Our findings reveal that hydrogenation susceptibility coordinating nitrogen atoms is critical determinant stability within Moreover, we demonstrate sulfur doping exerts similar effects on enhancing overall ORR performance PD-FeN4C catalysts: (1) by reducing p-band center nitrogen, thereby improving resistance hydrogenation, (2) increasing valence electrons iron, leading stronger adsorption intermediates consequently activity. Finally, our predictions suggest O/S-doped PL-FeN4C could achieve significantly improved superior in both acidic alkaline environments. These insights contribute deeper understanding microenvironment engineering single-atom (SACs) offer valuable guidelines development unprecedented M-N-C

Language: Английский

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Computational and Experimental Elucidation of the Charge‐Dependent Acid‐Etching Dynamics and Electrocatalytic Performance of Au₂₅(SR)₁₈^q(q = −1, 0, +1) Nanoclusters

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

Published: Feb. 24, 2025

Abstract Using thiolate‐protected Au 25 (SR) 18 nanocluster (NC) with different charge states as the test candidate, how effect affects etching dynamics of thiolate ligands in acid and electrocatalytic performance is explored. The ab initio molecular (AIMD) simulations revealed charge‐dependent reaction kinetics acid, where anionic neutral (SCH 3 ) q (q = −1, 0) favorably react partially remove via two‐step proton attack, while cationic + NC acid‐resistant no tendency for ‐SR removal. Density functional theory (DFT) calculations further predict that dethiolated sites exhibit enhanced catalytic activity CO 2 electroreduction to CO, − showing significantly superior activity. Acid experiments confirmed partial removal 0), NCs electroreduction, particularly exhibiting better than 0 . This work an interesting state‐mediated interface behaviors NCs, which can be applied modulate properties other atomically precise metal nanoclusters.

Language: Английский

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Efficient Electrocatalytic Semi‐Hydrogenation of Alkynes by Interfacial Engineering of Atomically Precise Silver Nanoclusters

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

Published: March 6, 2025

Owing to its green energy and hydrogen sources, electrocatalytic semi-hydrogenation of alkynes is an attractive alternative for industrial alkene production. However, broad application hindered by low selectivity Faradaic efficiency (FE) due side reactions like over-hydrogenation alkanes. Here, we demonstrate that atomically precise Ag25(MHA)18 nanoclusters (NCs) can electrocatalyze alkyne with 98 % conversion, 99 selectivity, 85 FE, in a substrate pool. This achieved engineering the local environment at catalytically active sites. We leverage amphiphilic MHA (6-mercaptohexanoic acid) ligands pre-concentrate water molecules near ligand-layer/Ag25 interface. Long-chain disrupt hydrogen-bond network interface, high negative charge Ag25 attract weakly hydrogen-bonded through counterions promote generation (H*), while enzyme-like catalytic pockets on surface NCs facilitate adsorption terminal via σ-bonding Ag atoms. Density functional theory calculations confirmed preference model further revealed facile release product alkene. work not only exemplifies interface strategy control sites optimized activity selectivity.

Language: Английский

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Electrochemical Dechlorination Promotes Syngas Production in N-Heterocyclic Carbene Protected Au₁₃ Nanoclusters

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Surface ligands play an important role in dictating the structure and catalytic properties of metal nanoclusters. Recently, a novel class Au clusters protected by N-heterocyclic carbenes (NHCs) halogens has been synthesized; however, dynamic stability Au-NHCs/Au-halogen interface real electrochemical environments as well influence ligand layer on process remains obscure. Herein, we combined first-principles simulations with experiments to investigate metal-ligand interaction classical [Au13(NHCMe)9Cl3]2+ cluster its unique potential promote electrocatalytic CO2 reduction syngas. Our revealed facile shedding chlorine from surface Au13 core upon biasing, more negative applied potential, faster kinetics Au-Cl bond cleavage. By contrast, Au-NHC is highly stable, indicating greater Au-C bonds over under conditions. Interestingly, exposed icosahedral dechlorinated [Au13(NHCMe)9Cl2]3+ capable efficiently catalyzing generate CO H2 comparable barriers wide range, showcasing strong for syngas formation. predictions are further corroborated experimental data, where X-ray photoelectron spectroscopy (XPS) verified halogen stripping acid or neutral media, activated demonstrated enhanced efficacy formation : ratio approximately 0.8 1.2 across broad range -0.50 -1.20 V. This work reveals exciting frontier understanding etching dynamics NHC-protected nanoclusters, particularly, preference production first time gold-based which distinctive previously reported nanoclusters that mainly produce CO.

Language: Английский

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Recent Progress on the Electrocatalytic Applications of Thiolate-protected Metal Nanoclusters

Nanoscale Horizons, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The latest developments in thiolate-protected metal nanoclusters important electrocatalytic applications, such as hydrogen evolution, oxygen reduction and CO 2 reactions, are briefly reviewed this work.

Language: Английский

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