Tandem Active Sites in Cu/Mo‐WO₃ Electrocatalysts for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

Abstract Electrocatalytic NO 3 − reduction to NH is a promising technique for both ammonia synthesis and nitrate wastewater treatment. However, this conversion involves tandem processes of H 2 O dissociation hydrogenation, leading inferior Faraday efficiency (FE) yield rate. Herein, catalyst by anchoring atomically dispersed Cu species on Mo‐doped WO (Cu 5 /Mo 0.6 ‐WO ) the RR constructed, which achieves superior FE N 98.6% rate 26.25 mg h −1 cat at −0.7 V (vs RHE) in alkaline media, greatly exceeding performance Mo /WO counterparts. Systematic electrochemical measurement results reveal that promoted activation sites, accompanying accelerated water producing active hydrogens are responsible performance. In situ infrared spectroscopy theoretical calculation further demonstrate sites accelerate , dopant activates adjacent resulting decreased energy barrier * stepwise hydrogenation processes, making thermodynamically favorable. This work demonstrates critical role atomic level enhancing electrocatalytic paving feasible avenue developing high‐performance electrocatalysts.

Language: Английский

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Interfacial Water Regulation for Nitrate Electroreduction to Ammonia at Ultralow Overpotentials

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Abstract Nitrate electroreduction is promising for achieving effluent waste‐water treatment and ammonia production with respect to the global nitrogen balance. However, due impeded hydrogenation process, high overpotentials need be surmounted during nitrate electroreduction, causing intensive energy consumption. Herein, a hydroxide regulation strategy developed optimize interfacial H 2 O behavior accelerating conversion of at ultralow overpotentials. The well‐designed Ru─Ni(OH) electrocatalyst shows remarkable efficiency 44.6% +0.1 V versus RHE nearly 100% Faradaic NH 3 synthesis 0 RHE. In situ characterizations theoretical calculations indicate that Ni(OH) can regulate structure promoted dissociation process contribute spontaneous hydrogen spillover boosting NO − Ru sites. Furthermore, assembled rechargeable Zn‐NO /ethanol battery system exhibits an outstanding long‐term cycling stability charge–discharge tests high‐value‐added ammonium acetate, showing great potential simultaneously removal, conversion, chemical synthesis. This work not only provide guidance in extensive reactions but also inspire design novel hybrid flow multiple functions.

Language: Английский

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A Copper–Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 8012 - 8023

Published: Feb. 18, 2025

The electrocatalytic nitrite reduction (NO2RR) converts nitrogen-containing pollutants to high-value ammonia (NH3) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead low activity NH3 selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper-zinc cyanamide (Cu0.8Zn0.2NCN) with localized structure distortion tailored surface electrostatic potential, allowing asymmetric binding of NO2-. It exhibits outstanding NO2RR performance Faradaic efficiency ∼100% an yield 22 mg h-1 cm-2, among best such process. Theoretical calculations in situ spectroscopic measurements demonstrate that Cu-Zn sites coordinated linear polarized [NCN]2- could transform symmetric [Cu-O-N-O-Cu] CuNCN-NO2- [Cu-N-O-Zn] configuration Cu0.8Zn0.2NCN-NO2-, thus enhancing adsorption bond cleavage. A paired electro-refinery Cu0.8Zn0.2NCN cathode reaches 2000 mA cm-2 at 2.36 V remains fully operational industrial-level 400 >140 h production rate ∼30 mgNH3 cm-2. Our work opens new avenue tailoring potentials using strategy advanced electrocatalysis.

Language: Английский

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FeIr Alloy Optimizes the Trade‐Off Between Nitrate Reduction and Active Hydrogen Generation for Efficient Electro‐Synthesis of Ammonia in Neutral Media

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

Abstract Electrochemically promoted nitrate reduction reaction (NITRR) holds great potential for the “green” synthesis of ammonia (NH 3 ). However, NITRR in neutral media, though close to practical scenario, is often limited by an insufficient supply active hydrogen (*H) due sluggish water cleavage. In this work, it demonstrated that a bimetallic alloy FeIr can optimize trade‐off between and *H formation media. As result, exhibits excellent catalytic performance toward with Faradaic efficiency NH up 97.3% high yield rate 11.67 mg h −1 cm −2 at low working −0.6 V (versus reversible electrode (RHE)), surpassing monometallic catalysts as well majority Fe‐based state‐of‐the‐art. It also found displays remarkable electron rearrangement hetero‐atoms their significant orbital hybridization, which benefits not only but process. Moreover, coupling FeIr‐based methanol oxidation (MOR) results sustainable productions formate combined FE nearly 200% cell‐voltage 2 V. This work thus demonstrates promising strategy designing efficient NITRR.

Language: Английский

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Breaking symmetry for better catalysis: insights into single-atom catalyst design

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review examines the strategies of symmetry breaking (charge/coordination/geometric) in single-atom catalysts to regulate active site electronic structures, greatly enhancing catalytic performance.

Language: Английский

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Nano‐High Entropy Materials in Electrocatalysis

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

Published: Sept. 19, 2024

Abstract High entropy materials (HEMs) compositing of at least five elements have gained widespread attention in the field electrocatalysis due to their tunable activities and high stability. These intrinsic properties can be further highlighted when size HEMs comes nanoscale. In nanostructured HEMs, fascinating including large composition space, multi‐element synergy, configuration are expected endow nano‐HEMs with excellent catalytic activity stability, thus providing greater potential for design advanced electrocatalysts. this review, differentiated detail dimensions common synthesis methods summarized. Additionally, from perspective complex nanostructure‐performance relationship, applications systems, water‐splitting (hydrogen evolution reaction (HER), oxygen (OER)), hydrogen oxidation (HOR), reduction (ORR), carbon dioxide (CO 2 RR), nitrogen (NRR) alcohol (AOR) discussed. Finally, main challenges faced by underscored. This review is provide more insights into understanding developing efficient electrocatalytic practical applications.

Language: Английский

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Heterostructure Engineering in High‐Entropy Alloy Catalysts

SusMat, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

ABSTRACT Confronting the limitation of traditional homogeneous high‐entropy alloys (HEAs) with randomly distributed elements and active sites, heterostructured HEAs were developed to further amplify catalytic activity stability. This perspective dissects genesis heterogeneity within HEAs, highlighting how their expansive compositional space facilitates customization heterogeneity. By manipulating key factors, such as chemical affinity, standard redox potentials, oxidation potential, researchers are tapping into unprecedented attributes. Strategies like acid leaching, galvanic replacement, additive deposition broadening structural repertoire steering development catalysts. synthesizes current discoveries, introduces provocative concepts, provides a roadmap for engineering in HEA catalysts, particularly harnessing elevate efficiency. The confluence theoretical practical advancements is anticipated lead way evolution endowing them exceptional capabilities.

Language: Английский

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A Review of the Mechanisms of Single-Atom-Based Advanced Oxidation Processes for the Degradation of Persistent Organic Pollutants in Water Environments

ACS ES&T Water, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 22, 2024

Language: Английский

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Embedding Pure‐Phase Fe₃C Functional Sites Into Biochar Matrix for Multi‐Scenario Electrocatalytic Ammonia Synthesis and Energy Conversion Utilization

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

Abstract The rational design and development of application‐oriented advanced functional catalysts is crucial for facilitating the conversion nitrogen oxides into high‐value ammonia. Herein, biomass derived from pomelo peel, which rich in metal complex groups exhibits a metallic foam‐like framework, utilized as precursor. Iron carbide (Fe 3 C) active sites are incorporated locally 2D, globally 3D biochar structure, enabling multi‐scenario green synthesis ammonia integrated energy utilization. As catalyst, Fe C‐BC achieved an yield rate up to 102120.53 µg h⁻¹ mg cat ⁻¹, with maximum selectivity 100%. A flow‐based electrolysis system featuring not only facilitated continuous but also enhanced solar harvesting. Additionally, nitrate battery employing anode exhibited high output enabled self‐driven synthesis, offering novel insights operational solutions future production. Density‐functional‐theory calculations confirmed that C actively reduces barrier key steps eNitRR process while accelerating water dissociation promote sustained proton supply. These findings collectively provide promising foundation advancing ammonia, emphasizing both efficient catalytic performance sustainable integration.

Language: Английский

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Sustainable ammonia synthesis: opportunities for electrocatalytic nitrate reduction

Journal of Energy Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 1, 2025

Language: Английский

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