Elucidating Relay Catalysis on Copper Clusters With Satellite Single Atoms for Enhanced Urea Electrosynthesis DOI Open Access
Xinyue Ma, Baoguang Mao, Zhong‐Zhen Yu

et al.

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

Published: March 10, 2025

Relay catalysis represents significant efficacy in alleviating competition among different reactants during coupling reactions. However, a comprehensive understanding of the reaction mechanism underlying relay for urea electrosynthesis remains challenging. Herein, we have developed catalyst (CuAC-CuSA@NC) comprising Cu atomic clusters (CuAC) with satellite Cu─N4 single atoms (CuSA) sites on nitrogen-doped porous interconnected carbon skeleton (NC), enabling elucidation process co-reduction CO2 and NO3 -. The designed CuAC-CuSA@NC exhibits an approximately threefold higher yield rate compared to that CuSA@NC at -1.3 V versus RHE. Ex-situ experimental results in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy analysis reveal formation sequence between *NH2 *NH2CO species increasing reduction potential. combination theoretical calculations further elucidates pathway involves "CuAC" facilitating conversion *NO3 *NOx, followed by hydrogenation form *H from water dissociation promoted "CuSA" sites, which subsequently couples *CO2 produce urea. This work provides novel insights into investigation reactions, but not limit to, synthesis.

Language: Английский

Enhancing Compatibility of Two‐Step Tandem Catalytic Nitrate Reduction to Ammonia Over P‐Cu/Co(OH)2 DOI

Qiuyu Yan,

Rundong Zhao, Lihong Yu

et al.

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

Published: Sept. 11, 2024

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to realize ammonia generation and wastewater treatment. However, the transformation from NO − NH involves multiple proton‐coupled electron transfer processes by‐products 2 , H etc.), making high selectivity challenge. Herein, two‐phase nanoflower P‐Cu/Co(OH) electrocatalyst consisting of P‐Cu clusters P‐Co(OH) nanosheets designed match two‐step tandem process ) more compatible, avoiding excessive accumulation optimizing whole reaction. Focusing on initial 2e process, inhibited * desorption Cu sites in gives rise appropriate released electrolyte. Subsequently, exhibits superior capacity for trapping transforming desorbed during latter 6e due thermodynamic advantage contributions active hydrogen. In 1 m KOH + 0.1 leads yield rate 42.63 mg h cm Faradaic efficiency 97.04% at −0.4 V versus reversible hydrogen electrode. Such well‐matched achieves remarkable synthesis performance perspective catalytic reaction, offering novel guideline design RR electrocatalysts.

Language: Английский

Citations

20
Ammonia electrosynthesis from nitrate using a stable amorphous/crystalline dual-phase Cu catalyst DOI Creative Commons
Yi Wang, Shuo Wang,

Yunfan Fu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 21, 2025

Renewable energy-driven electrocatalytic nitrate reduction reaction presents a low-carbon and sustainable route for ammonia synthesis under mild conditions. Yet, the practical application of this process is currently hindered by unsatisfactory activity long-term stability. Herein we achieve high-rate electrosynthesis using stable amorphous/crystalline dual-phase Cu catalyst. The partial current density formation rate reach 3.33 ± 0.005 A cm-2 15.5 0.02 mmol h-1 at low cell voltage 2.6 0.01 V, respectively. Remarkably, catalyst can maintain production with Faradaic efficiency around 90% high 1.5 up to 300 h. scale-up demonstration an electrode size 100 cm2 achieves as 11.9 0.5 g total 160 A. impressive performance ascribed presence amorphous domains which promote adsorption hydrogenation nitrogen-containing intermediates, thus improving kinetics formation. This work underscores importance stabilizing metastable structures reactivity

Language: Английский

Citations

3
Interfacial Water Regulation for Nitrate Electroreduction to Ammonia at Ultralow Overpotentials DOI Open Access
Yuchi Wan,

Maojun Pei,

Yalu Tang

et al.

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

Citations

2
Unveiling Ionized Interfacial Water‐Induced Localized H* Enrichment for Electrocatalytic Nitrate Reduction DOI
Sujun Zheng, Xiaoyu Dong, Hong Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 4, 2024

Electrocatalytic nitrate reduction reaction (NO

Language: Английский

Citations

15
Regioselective Doping into Atomically Aligned Core–Shell Structures for Electrocatalytic Reduction of Nitrate to Ammonia DOI Open Access
Ying Zhang, Tianyi Gao, Fei Zhang

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(46)

Published: Aug. 26, 2024

Abstract The electrochemical nitrate reduction reaction (NO 3 − RR) presents an environmentally friendly approach for efficient NO pollutant removal and ammonia (NH ) production, compared to the conventional Haber–Bosch approach. While core/shell engineering has demonstrated its potential in enhancing RR performance, significant synthetic challenges limited shell layer modification capabilities impede exploration of high‐performance catalysts. Herein, CuCoO/Co(OH) 2 structure via situ activation is synthesized. catalyst delivers a maximum NH Faradaic efficiency (FE) 94.7% at −0.5 V RHE with excellent durability selectivity over wide range potentials RR, surpassing electrocatalytic performance both undoped core components. outstanding Cu─CoO/Co(OH) ascribed enhanced charge transfer, stabilization key intermediates, regulation hydrogen adsorption Cu‐doped structure. Furthermore, assembled Zn−NO battery device attains peak current density exceeding 32 mA cm −2 yield up 145.4 µmol h −1 . work offers novel strategy sheds light on doping effects synthesis.

Language: Английский

Citations

13
Hydration‐effect Boosted Active Hydrogen Facilitates Neutral Ammonia Electrosynthesis from Nitrate Reduction DOI
Meng Zhang,

Xuetao Cheng,

Yun Duan

et al.

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

Published: Oct. 8, 2024

Abstract Electrocatalytic nitrate reduction to ammonia (NO 3 RR) in a neutral medium is green and effective strategy for treating pollution meanwhile producing ammonia. However, the insufficient active hydrogen (H * ) on catalyst surface resulting from sluggish Volmer step 2 O → H + OH − ), competitive evolution reaction (HER) caused by coupling severely restrict enhancement of NO RR activity. Herein, hydration‐effect boosted ‐rich facilitating electrosynthesis proposed. The introduction hydration‐effect‐promoting element aluminum into copper‐based forming CuAlO , which adjusts electron density distribution system, significantly promotes generation medium. Moreover, rapid charge transfer at CuO/CuAlO interface facilitates kinetics diffusion. More importantly, Al weakens overly strong adsorption intermediates CuO, thereby accelerating hydrogenation process suppressing HER. Thus, under conditions, reached Faradaic efficiency an yield as high 97.81 ± 1.94% 10.21 0.64 mg h −1 cm −2 −1.0 V versus RHE toward RR.

Language: Английский

Citations

9
Engineering Nickel Dopants in Atomically Thin Molybdenum Disulfide for Highly Efficient Nitrate Reduction to Ammonia DOI

Jiangnan Lv,

Xiaoting Sun, Fang Wang

et al.

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

Published: Sept. 16, 2024

Abstract The electrocatalytic nitrate reduction reaction (NO 3 − RR) presents a promising pathway for achieving both ammonia (NH ) electrosynthesis and water pollutant removal simultaneously. Among various electrocatalysts explored, 2D materials have emerged as candidates due to their ability regulate electronic states active sites through doping. However, the impact of doping effects in on mechanism NO RR remains relatively unexplored. Here, Ni‐doped MoS 2 (Ni‐MoS nanosheets are investigated model system, demonstrating enhanced performance compared undoped counterparts. By controlling concentration, Ni‐MoS achieve remarkable faradic efficiency (FE) 92.3% NH at −0.3 V RHE with excellent stability. mechanistic studies reveal that elevation performances originates from generation more hydrogen acceleration nitrite facilitated by Ni Combining experimental observations theoretical calculations it is revealed appropriate level can enhance *NO adsorption strength, thereby facilitating subsequent steps. Together demonstration Zn−NO battery devices, work provides new insights into design regulation material catalysts efficient RR.

Language: Английский

Citations

8
Identifying Upper d-Band Edge as Activity Descriptor for Ammonia Oxidation on PtCo Alloys in Low-Temperature Direct Ammonia Fuel Cells DOI
Fei Fang,

Qiyang Cheng,

Mengfan Wang

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Low-temperature direct ammonia fuel cell (DAFC) stands out as a more secure technology than the hydrogen system, while there is still lack of elegant bottom-up synthesis procedures for efficient oxidation reaction (AOR) electrocatalysts. The widely accepted d-band center, even with consideration width, usually fails to describe variations in AOR reactivity many practical conditions, and accurate activity descriptor necessary less empirical path. Herein, upper edge, εu, derived from model, identified an effective accurately establishing descriptor–activity relationship. Using PtCo alloy varying atomic composition example, εu value succeeds reflecting corresponding trends activity, showing striking linear correlation coefficient determination (R2) high 0.90. effectiveness established relationship verified experimentally. optimum electrocatalyst delivers excellent peak current density 74.04 A g–1 at 5 mV s–1, assembled DAFC generates power density, outperforming majority extensively reported systems. This work brings fundamental insights into between chemical electronic structure benefits rational optimization next-generation low-temperature DAFC.

Language: Английский

Citations

1
Co-Doped CuO Nanoarrays for Enhanced Electrocatalytic Nitrate Reduction to Ammonia via Active Hydrogen Regulation DOI

Zhexuan Li,

Yaxuan Li,

Song Cheng

et al.

ACS Applied Nano Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

Language: Английский

Citations

1
Electro‐Reconstructed Transition Metal Electrodes for Coupled‐Upgrading of Nitrate Pollution and Waste Poly(Ethylene Terephthalate) Plastics DOI Open Access
Haoye Wang, Bowen Yang, Richard L. Smith

et al.

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

Published: Jan. 28, 2025

Abstract Two unrelated forms of pollution, nitrate‐containing wastewater and waste poly(ethylene terephthalate) (PET) plastics, can be converted into high‐value chemicals by electrochemical reduction oxidation reactions. Herein, coupled electrocatalysis is used for the co‐production ammonia (NH 3 ) formic acid (FA) with a cathode formed reconstructing Co on copper foam (R‐Co/CF) as catalyst nitrate reaction (NO RR) an anode NiCo nickel (R‐NiCo/NF) ethylene glycol (EGOR). The Faraday efficiency R‐Co/CF 96.2% that R‐NiCo/NF catalysts 98.2%. By coupling NO RR PET hydrolysate reaction, cell voltage required at current density 50 mA cm −2 202 mV lower than traditional electrolytic system, indicating electrocatalytic upcycling plastics energy‐saving cost‐effective strategy producing value‐added chemicals. Techno‐economic analysis indicates compared RR//OER RR//PET system save 2.8 × 10 kW h −1 in electricity generate ≈6 900 USD revenue per tonne NH .

Language: Английский

Citations

1