Revealing the role of interfacial water and key intermediates at ruthenium surfaces in the alkaline hydrogen evolution reaction

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 30, 2023

Ruthenium exhibits comparable or even better alkaline hydrogen evolution reaction activity than platinum, however, the mechanistic aspects are yet to be settled, which elucidated by combining in situ Raman spectroscopy and theoretical calculations herein. We simultaneously capture dynamic spectral evidence of Ru surfaces, interfacial water, *H *OH intermediates. surfaces exist different valence states potential range, dissociating water differently generating two distinct *H, resulting activities. The local cation tuning effect hydrated Na+ ion large work function high-valence Ru(n+) promote dissociation. Moreover, compared low-valence Ru(0) have more moderate adsorption energies for *OH. They, therefore, facilitate activity. Our findings demonstrate regulation state on intermediates, finally catalytic activity, provide guidelines rational design high-efficiency catalysts.

Language: Английский

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Amorphous nickel hydroxide shell tailors local chemical environment on platinum surface for alkaline hydrogen evolution reaction

Nature Materials, Journal Year: 2023, Volume and Issue: 22(8), P. 1022 - 1029

Published: June 22, 2023

Language: Английский

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Ce‐Induced Differentiated Regulation of Co Sites via Gradient Orbital Coupling for Bifunctional Water‐Splitting Reactions

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(30)

Published: June 22, 2023

Abstract Rare‐earth (RE) elements have emerged as crucial promoters to regulate the electrocatalysis of transition metals (TM), but knowledge about RE‐enhanced mechanism TM in is limited. Herein, an array‐like Ce‐CoP catalyst constructed explore origin and distinction Ce‐induced enhanced Co sites both hydrogen evolution reaction (HER) oxygen (OER). Compared with individual CoP, developed exhibits superior bifunctional electrocatalytic activity overpotentials 81 240 mV at 10 mA cm −2 , respectively for HER OER, excellent stability. Theoretical calculations show that unique 4 f valence electron structure Ce endows differentiated regulation OER through f‐p‐d gradient orbital coupling. In HER, retained Ce‐4 state induces spin parallelism surrounding sites, promoting adsorption *H intermediates. While band acts sacrificing protect from overoxidation Ce‐O‐Co chain optimized Co‐3 d state, providing additional coupling These findings provide new insights into comprehending present valuable design guidelines development efficient multi‐functional electrocatalysts.

Language: Английский

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Understanding Cation Effects on the Hydrogen Evolution Reaction

ACS Energy Letters, Journal Year: 2022, Volume and Issue: 8(1), P. 657 - 665

Published: Dec. 21, 2022

The hydrogen evolution reaction (HER) is known to be influenced by the identity of alkali metal cations in electrolyte. But a clear understanding this behavior has not been developed. Here, we present results experimental and theoretical studies that describe how influence HER acidic basic electrolytes. Alkali are shown have no systematic effect on rates acid. In alkaline media, decrease with increasing cation size over Ir, Pd, Pt (Li+ > Na+ K+ Cs+) increase Cu, Ag, Au < Cs+). We argue interfacial lower activation barrier for water dissociation, an elementary step unique media. limited but Pt, explaining inverted activity trend. Based ab initio molecular dynamics simulations, suggest trends attributable greater willingness large, weakly solvated approach electrode surface.

Language: Английский

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Optimizing Pt-Based Alloy Electrocatalysts for Improved Hydrogen Evolution Performance in Alkaline Electrolytes: A Comprehensive Review

ACS Nano, Journal Year: 2023, Volume and Issue: 17(21), P. 20804 - 20824

Published: Nov. 3, 2023

The splitting of water through electrocatalysis offers a sustainable method for the production hydrogen. In alkaline electrolytes, lack protons forces dissociation to occur before hydrogen evolution reaction (HER). While pure Pt is gold standard electrocatalyst in acidic since 5d orbital nearly fully occupied, when it overlaps with molecular water, generates Pauli repulsion. As result, formation Pt–H* bond an environment difficult, which slows HER and negates benefits using catalyst. To overcome this limitation, can be alloyed transition metals, such as Fe, Co, Ni. This approach has potential not only enhance performance but also increase dispersion decrease its usage, thus overall improving catalyst's cost-effectiveness. excellent adsorption ability metals contributes generation proton-rich local near Pt-based alloy that promotes HER. Significant progress been achieved comprehending mechanism manipulation structure composition electrocatalysts based on alloy. objective review analyze condense latest developments It focuses modified alloys clarifies design principles catalytic catalysts from both experimental theoretical perspective. highlights some difficulties encountered during opportunities increasing performance. Finally, guidance development more efficient provided.

Language: Английский

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Local reaction environment in electrocatalysis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(4), P. 2022 - 2055

Published: Jan. 1, 2024

Beyond conventional electrocatalyst engineering, recent studies have unveiled the effectiveness of manipulating local reaction environment in enhancing performance electrocatalytic reactions. The general principles and strategies environmental engineering for different processes been extensively investigated. This review provides a critical appraisal advancements aiming to comprehensively assess this emerging field. It presents interactions among surface structure, ions distribution electric field relation environment. Useful protocols such as interfacial reactant concentration, mass transport rate, adsorption/desorption behaviors, binding energy are in-depth discussed toward modifying Meanwhile, electrode physical structures cell configurations viable optimization methods environments. In combination with

Language: Английский

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Coupled and decoupled electrochemical water splitting for boosting hydrogen evolution: A review and perspective

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 510, P. 215837 - 215837

Published: April 9, 2024

Language: Английский

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Pulsed co-electrolysis of carbon dioxide and nitrate for sustainable urea synthesis

Nature Sustainability, Journal Year: 2024, Volume and Issue: 7(4), P. 442 - 451

Published: Feb. 26, 2024

Language: Английский

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Ordering‐Dependent Hydrogen Evolution and Oxygen Reduction Electrocatalysis of High‐Entropy Intermetallic Pt₄FeCoCuNi

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(28)

Published: May 11, 2023

Abstract Disordered solid‐solution high‐entropy alloys have attracted wide research attention as robust electrocatalysts. In comparison, ordered intermetallics been hardly explored and the effects of degree chemical ordering on catalytic activity remain unknown. this study, a series multicomponent intermetallic Pt 4 FeCoCuNi nanoparticles with tunable degrees is fabricated. The transformation mechanism from disordered structure into revealed at single‐particle level, it agrees macroscopic analysis by selected‐area electron diffraction X‐ray diffraction. electrocatalytic performance correlates well their crystal electronic structure. It found that increasing promotes performance. highly achieves highest mass activities toward both acidic oxygen reduction reaction (ORR) alkaline hydrogen evolution (HER) which are 18.9‐fold 5.6‐fold higher than those commercial Pt/C, respectively. experiment also shows catalyst demonstrates better long‐term stability partially Pt/C when subject to HER ORR. This ordering‐dependent structure–property relationship provides insight rational design catalysts stimulates exploration many other alloys.

Language: Английский

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Unveiling the Electrolyte Cations Dependent Kinetics on CoOOH‐Catalyzed Oxygen Evolution Reaction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 21, 2023

The electrolyte cations-dependent kinetics have been widely observed in many fields of electrocatalysis, however, the exact mechanism influence on catalytic performance is still a controversial topic considerable discussion. Herein, combined with operando X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), we verify that cations could intercalate into layer pristine CoOOH catalyst during oxygen evolution reaction (OER) process, while bigger lead to enlarged interlayer spacing increased OER activity, following order Cs+ >K+ >Na+ >Li+ . absorption spectroscopy (XAS), situ Raman, Ultraviolet-visible (UV/Vis) spectroscopy, XAS cyclic voltammetry (CV), theoretical calculations reveal intercalation efficiently modify oxidation states Co by enlarging Co-O bonds, which turn enhance d-band center Co, optimize adsorption strength intermediates, facilitate formation active Co(IV) species, reduce energy barrier rate-determing step (RDS), thereby enhancing activity. This work not only provides an informative picture understand complicated dependence cations, but also sheds light understanding other cation-targeted electrocatalysis.

Language: Английский

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