Relay Catalysis of Fe and Co with Multi‐Active Sites for Specialized Division of Labor in Electrocatalytic Nitrate Reduction Reaction

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

Published: April 8, 2024

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) driven by renewable energy is a promising technology for the removal of nitrate‐containing wastewater. However, sluggish kinetics resulted from complex proton‐coupled electron transfer and various intermediates remain key barriers large‐scale application NO RR. Herein, tactic reported to raise rate RR increase selectivity N 2 using bimetal catalyst: Co inclined act on steps needed in process, rate‐determining step (RDS: *NO , asterisk means intermediates) subsequent *N hydrogenation as well Fe exhibits efficient activity selectivity‐ determining (SDS: then ) via relay catalysis mechanism. A efficiency 78.5% an ultra‐long cycle stability 60 cycles (12 h per cycle) are achieved FeCo alloy confined with nitrogen‐doped porous carbon nanofibers (FeCo‐NPCNFs). DFT calculations unveil that introduction active site not only regulates d‐band center alloy, optimizes adsorption intermediates, but also has strong capacity supply hydrogen species. Clearly, this study elucidates effects bimetallic performance electrocatalytic offers avenues designing Fe‐based catalysts realize nitrogen‐neutral cycle.

Language: Английский

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Molten salts etching strategy construct alloy/MXene heterostructures for efficient ammonia synthesis and energy supply via Zn-nitrite battery

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 348, P. 123862 - 123862

Published: April 24, 2024

Language: Английский

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Screening of Intermetallic Compounds Based on Intermediate Adsorption Equilibrium for Electrocatalytic Nitrate Reduction to Ammonia

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20069 - 20079

Published: July 10, 2024

Electrocatalytic nitrate (NO

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Synergistic Effect of Ni/Ni(OH)₂ Core‐Shell Catalyst Boosts Tandem Nitrate Reduction for Ampere‐Level Ammonia Production

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 23, 2024

Electrocatalytic reduction of nitrate to ammonia provides a green alternate the Haber-Bosch method, yet it suffers from sluggish kinetics and low yield rate. The follows tandem reaction nitrite subsequent hydrogenation generate ammonia, Faraday efficiency (FE) is limited by competitive hydrogen evolution reaction. Herein, we design heterostructure catalyst remedy above issues, which consists Ni nanosphere core Ni(OH)

Language: Английский

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Optimizing Intermediate Adsorption over PdM (M=Fe, Co, Ni, Cu) Bimetallene for Boosted Nitrate Electroreduction to Ammonia

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: March 7, 2024

Electrochemical reduction of nitrate to ammonia (NO

Language: Английский

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Modulating the Electrolyte Microenvironment in Electrical Double Layer for Boosting Electrocatalytic Nitrate Reduction to Ammonia

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 29, 2024

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to achieve remediation of nitrate‐polluted wastewater and sustainable production ammonia. However, it still restricted by the low activity, selectivity Faraday efficiency for ammonia synthesis. Herein, we propose an effective strategy modulate electrolyte microenvironment in electrical double layer (EDL) mediating alkali metal cations enhance NO RR performance. Taking bulk Cu as model catalyst, experimental study reveals that − ‐to‐NH performance different electrolytes follows trend Li + <Cs <Na <K . Theoretical studies illustrate proton transport rate activity rate‐determining step 2 ) increase order The cation effects are also general two typical nanostructured catalysts including copper/cuprous oxide nickel phosphides, achieving near‐100 % Faradaic over 99 conversion NH Furthermore, demonstrate can be converted high‐purity 4 Cl catalyst K ‐containing electrolyte.

Language: Английский

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Synthesis of Hydroxylamine via Ketone-Mediated Nitrate Electroreduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10934 - 10942

Published: April 6, 2024

Hydroxylamine (HA, NH2OH) is a critical feedstock in the production of various chemicals and materials, its efficient sustainable synthesis great importance. Electroreduction nitrate on Cu-based catalysts has emerged as promising approach for green ammonia (NH3) production, but electrosynthesis HA remains challenging due to overreduction NH3. Herein, we report first work ketone-mediated using water. A metal–organic-framework-derived Cu catalyst was developed catalyze reaction. Cyclopentanone (CP) used capture situ form CP oxime (CP-O) with C═N bonds, which prone hydrolysis. could be released easily after electrolysis, regenerated. It demonstrated that CP-O formed an excellent Faradaic efficiency 47.8%, corresponding formation rate 34.9 mg h–1 cm–2, remarkable carbon selectivity >99.9%. The hydrolysis release regeneration also optimized, resulting 96.1 mmol L–1 stabilized solution, significantly higher than direct reduction. Detailed characterizations, control experiments, theoretical calculations revealed surface reconstruction reaction mechanism, showed coexistence Cu0 Cu+ facilitated protonation reduction *NO2 *NH2OH desorption, leading enhancement production.

Language: Английский

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Sustainable Electrosynthesis of Cyclohexanone Oxime through Nitrate Reduction on a Zn–Cu Alloy Catalyst

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3287 - 3297

Published: Feb. 15, 2024

Cyclohexanone oxime is an important precursor for Nylon-6 and typically synthesized via the nucleophilic addition–elimination of hydroxylamine with cyclohexanone. Current technologies production are, however, not environment-friendly due to requirement harsh reaction conditions. Here, we report electrochemical method one-pot synthesis cyclohexanone under ambient conditions aqueous nitrate as nitrogen source. A series Zn–Cu alloy catalysts are developed drive reduction nitrate, where intermediate formed in electroreduction process can undergo a chemical present electrolyte produce corresponding oxime. The best performance achieved on Zn93Cu7 electrocatalyst 97% yield 27% Faradaic efficiency at 100 mA/cm2. By analyzing catalytic activities/selectivities different alloys conducting in-depth mechanistic studies situ Raman spectroscopy theoretical calculations, demonstrate that adsorption species plays central role performance. Overall, this work provides attractive strategy build C–N bond organic through reduction, while highlighting importance controlling surface product selectivity electrosynthesis.

Language: Английский

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The synergistic catalysis effect on electrochemical nitrate reduction at the dual-function active sites of the heterostructure

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(13), P. 4582 - 4593

Published: Jan. 1, 2024

The synergistic catalysis effect based on CoP and Cu 3 P dual-function active sites is proposed to understand the mechanism of hydrogen (*H) adsorbed intermediates (*NO x ) during water-splitting nitrate reduction.

Language: Английский

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Nitrogenous Intermediates in NO_x‐involved Electrocatalytic Reactions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 16, 2024

Abstract Chemical manufacturing utilizing renewable sources and energy emerges as a promising path towards sustainability carbon neutrality. The electrocatalytic reactions involving nitrogen oxides (NO x ) offered potential strategy for synthesizing various nitrogenous chemicals. However, it is currently hindered by low selectivity/efficiency limited reaction pathways, mainly due to the difficulties in controllable generation utilization of intermediates. In this minireview, focusing on intermediates NO ‐involved reactions, we discuss newly developed methodologies studying controlling generation, conversion, intermediates, which enable recent developments that yield products, including ammonia (NH 3 ), organonitrogen molecules, compounds exhibiting unconventional oxidation states. Furthermore, also make an outlook highlight future directions emerging field reactions.

Language: Английский

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