Switching the Oxygen Evolution Mechanism on Atomically Dispersed Ru for Enhanced Acidic Reaction Kinetics

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(43), P. 23659 - 23669

Published: Oct. 23, 2023

Designing stable single-atom electrocatalysts with lower energy barriers is urgent for the acidic oxygen evolution reaction. In particular, atomic catalysts are highly dependent on kinetically sluggish acid-base mechanism, limiting reaction paths of intermediates. Herein, we successfully manipulate steric localization Ru single atoms at Co3O4 surface to improve by precise control anchor sites. The delicate structure design can switch mechanism from lattice (LOM) optimized adsorbate (AEM). embedded into cation vacancies reveal an that activates proton donor-acceptor function (PDAM), demonstrating a new catalytic pathway circumvent classic scaling relationship. Steric interactions intermediates anchored Ru-O-Co interface played primary role in optimizing intermediates' conformation and reducing barrier. As comparison, confined sites exhibit process. result, atom spatial position presents 100-fold increase mass activity 36.96 A gRu(ads)-1 4012.11 gRu(anc)-1 1.50 V. These findings offer insights behavior.

Language: Английский

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Microenvironment Engineering of Single/Dual‐Atom Catalysts for Electrocatalytic Application

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(31)

Published: Feb. 23, 2023

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric electronic uncovering structure-property relationships of single/dual-metal confront with grand challenges. Herein, this review summarizes latest progress in microenvironment engineering single/dual-atom sites via a comprehensive comparison single-atom catalyst (SACs) dual-atom catalysts (DACs) term design principles, modulation strategy, theoretical understanding structure-performance correlations. Subsequently, recent advances several typical electrocatalysis process are discussed to get general reaction mechanisms finely-tuned SACs DACs. Finally, full-scaled summaries challenges prospects given for This will provide new inspiration development atomically dispersed electrocatalytic application.

Language: Английский

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Comprehensive overview of polyoxometalates for electrocatalytic hydrogen evolution reaction

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 482, P. 215058 - 215058

Published: Feb. 22, 2023

Language: Английский

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Facilitating alkaline hydrogen evolution reaction on the hetero-interfaced Ru/RuO2 through Pt single atoms doping

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 16, 2024

Abstract Exploring an active and cost-effective electrocatalyst alternative to carbon-supported platinum nanoparticles for alkaline hydrogen evolution reaction (HER) have remained elusive date. Here, we report a catalyst based on single atoms (SAs) doped into the hetero-interfaced Ru/RuO 2 support (referred as Pt-Ru/RuO ), which features low HER overpotential, excellent stability distinctly enhanced cost-based activity compared commercial Pt/C Ru/C in 1 M KOH. Advanced physico-chemical characterizations disclose that sluggish water dissociation is accelerated by RuO while Pt SAs metallic Ru facilitate subsequent H* combination. Theoretical calculations correlate with experimental findings. Furthermore, only requires 1.90 V reach A cm −2 delivers high price anion exchange membrane electrolyzer, outperforming benchmark Pt/C. This research offers feasible guidance developing noble metal-based catalysts performance cost toward practical H production.

Language: Английский

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Microwave Synthesis of Pt Clusters on Black TiO₂ with Abundant Oxygen Vacancies for Efficient Acidic Electrocatalytic Hydrogen Evolution

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 9, 2023

Oxygen vacancies-enriched black TiO2 is one promising support for enhancing hydrogen evolution reaction (HER). Herein, oxygen vacancies enriched supported sub-nanometer Pt clusters (Pt/TiO2 -OV ) with metal interactions designed through solvent-free microwave and following low-temperature electroless approach the first time. High-temperature strong reductants are not required then can avoid aggregation of decorated species. Experimental theoretical calculation verify that created exhibit synergistic effects optimizing kinetics. Based on it, Pt/TiO2 presents remarkable electrocatalytic performance 18 mV to achieve 10 mA cm-2 coupled small Tafel slope 12 dec-1 . This work provides quick synthetic strategy preparing titanium dioxide based nanomaterials.

Language: Английский

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Stabilizing Low‐Valence Single Atoms by Constructing Metalloid Tungsten Carbide Supports for Efficient Hydrogen Oxidation and Evolution

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Sept. 2, 2023

Abstract Designing novel single‐atom catalysts (SACs) supports to modulate the electronic structure is crucial optimize catalytic activity, but rather challenging. Herein, a general strategy proposed utilize metalloid properties of trap and stabilize single‐atoms with low‐valence states. A series supported on surface tungsten carbide (M‐WC x , M=Ru, Ir, Pd) are rationally developed through facile pyrolysis method. Benefiting from WC exhibit weak coordination W C atoms, resulting in formation active centers similar metals. The unique metal‐metal interaction effectively stabilizes single atoms improves orbital energy level distribution sites. As expected, representative Ru‐WC exhibits superior mass activities 7.84 62.52 mg Ru −1 for hydrogen oxidation evolution reactions (HOR/HER), respectively. In‐depth mechanistic analysis demonstrates that an ideal dual‐sites cooperative mechanism achieves suitable adsorption balance H ad OH energetically favorable Volmer step. This work offers new guidance precise construction highly SACs.

Language: Английский

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Swinging Hydrogen Evolution to Nitrate Reduction Activity in Molybdenum Carbide by Ruthenium Doping

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(24), P. 15045 - 15055

Published: Nov. 28, 2022

A common challenge for electrochemical ammonia synthesis in an aqueous phase is the consumption of Faradaic charge by competing hydrogen evolution reaction (HER), which reduces efficiency desired conversion, i.e., nitrate reduction (NO3RR) to ammonium. This problem particularly severe when a single-phase catalyst operated at high current limits, thus cocatalyst system that works synergistically acquisition and deoxygenation needed promote NO3RR over HER. Herein, we select well-known HER Mo2C investigate how metal doping can switch its kinetics from HER-dominated NO3RR-dominated pathways. At 3.8 wt % Ru Mo2C, 75% single pass conversion (0.1 M) ammonium 16 cm2 flow electrolyzer was achieved, corresponding yield rate 9.07 mmol h–1 full cell voltage 2 V. As confirmed DFT calculations kinetic isotope experiments, ruthenium dopants matrix serve as sink point adsorbed during cooperative *NO3 *NO2 on Ru–Mo cocatalytic site. Our study suggests optimizing reactions systems effective strategy synthesis.

Language: Английский

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Low-Pt supported on MOF-derived Ni(OH)2 with highly-efficiently electrocatalytic seawater splitting at high current density

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 331, P. 122703 - 122703

Published: March 31, 2023

Language: Английский

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Regulating Hydrogen/Oxygen Species Adsorption via Built‐in Electric Field ‐Driven Electron Transfer Behavior at the Heterointerface for Efficient Water Splitting

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 29, 2024

Abstract Alkaline water electrolysis (AWE) plays a crucial role in the realization of hydrogen economy. The design and development efficient stable bifunctional catalysts for both evolution reaction (HER) oxygen (OER) are pivotal to achieving high‐efficiency AWE. Herein, WC 1‐x /Mo 2 C nanoparticle‐embedded carbon nanofiber (WC C@CNF) with abundant interfaces is successfully designed synthesized. Benefiting from electron transfer behavior Mo , electrocatalysts C@CNF exhibit superior HER OER performance. Furthermore, when employed as anode cathode membrane electrode assembly devices, catalyst exhibits enhanced catalytic activity remarkable stability 100 hours at high current density 200 mA cm −2 towards overall splitting. experimental characterizations theoretical simulation reveal that modulation d‐band center C@CNF, achieved through asymmetric charge distribution resulting built‐in electric field induced by work function, enables optimization adsorption strength hydrogen/oxygen intermediates, thereby promoting kinetics This provides promising strategies designing highly active energy conversion fields.

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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