Pulsed electroreduction of low-concentration nitrate to ammonia DOI Creative Commons
Yanmei Huang, Caihong He, Chuanqi Cheng

et al.

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

Published: Nov. 14, 2023

Electrocatalytic nitrate (NO3-) reduction to ammonia (NRA) has emerged as an alternative strategy for effluent treatment and production. Despite significant advancements that have been achieved in this field, the efficient conversion of low-concentration at low overpotential remains a formidable challenge. This challenge stems from sluggish reaction kinetics caused by limited distribution negatively charged NO3- vicinity working electrode competing side reactions. Here, pulsed potential approach is introduced overcome these issues. A good NRA performance (Faradaic efficiency: 97.6%, yield rate: 2.7 mmol-1 h-1 mgRu-1, 96.4%) (≤10 mM) reduction, obviously exceeding potentiostatic test 65.8%, 1.1 54.1%). The combined results situ characterizations finite element analysis unveil enhancement mechanism periodic appearance anodic can significantly optimize adsorption configuration key *NO intermediate increase local concentration. Furthermore, our research implies effective rational design precise manipulation processes, potentially extending its applicability broader range catalytic applications.

Language: Английский

Splicing the active phases of copper/cobalt-based catalysts achieves high-rate tandem electroreduction of nitrate to ammonia DOI Creative Commons
Wenhui He, Jian Zhang, Stefan Dieckhöfer

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: March 2, 2022

Electrocatalytic recycling of waste nitrate (NO3-) to valuable ammonia (NH3) at ambient conditions is a green and appealing alternative the Haber-Bosch process. However, reaction requires multi-step electron proton transfer, making it grand challenge drive high-rate NH3 synthesis in an energy-efficient way. Herein, we present design concept tandem catalysts, which involves coupling intermediate phases different transition metals, existing low applied overpotentials, as cooperative active sites that enable cascade NO3--to-NH3 conversion, turn avoiding generally encountered scaling relations. We implement by electrochemical transformation Cu-Co binary sulfides into potential-dependent core-shell Cu/CuOx Co/CoO phases. Electrochemical evaluation, kinetic studies, in-situ Raman spectra reveal inner preferentially catalyze NO3- reduction NO2-, rapidly reduced nearby shell. This unique catalyst system leads Faradaic efficiency 93.3 ± 2.1% wide range concentrations pH 13, high yield rate 1.17 mmol cm-2 h-1 0.1 M -0.175 V vs. RHE, half-cell energy ~36%, surpassing most previous reports.

Language: Английский

Citations

553
Ultralow overpotential nitrate reduction to ammonia via a three-step relay mechanism DOI
Shuhe Han, Hongjiao Li, Tieliang Li

et al.

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(5), P. 402 - 414

Published: April 20, 2023

Language: Английский

Citations

487
Efficient Electrochemical Nitrate Reduction to Ammonia with Copper‐Supported Rhodium Cluster and Single‐Atom Catalysts DOI

Huimin Liu,

Xiuyao Lang, Chao Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(23)

Published: March 17, 2022

The electrochemical nitrate reduction reaction (NITRR) provides a promising solution for restoring the imbalance in global nitrogen cycle while enabling sustainable and decentralized route to source ammonia. Here, we demonstrate novel electrocatalyst NITRR consisting of Rh clusters single-atoms dispersed onto Cu nanowires (NWs), which delivers partial current density 162 mA cm-2 NH3 production Faradaic efficiency (FE) 93 % at -0.2 V vs. RHE. highest ammonia yield rate reached record value 1.27 mmol h-1 . Detailed investigations by electron paramagnetic resonance, situ infrared spectroscopy, differential mass spectrometry functional theory modeling suggest that high activity originates from synergistic catalytic cooperation between sites, whereby adsorbed hydrogen on site transfers vicinal *NO intermediate species promoting hydrogenation formation.

Language: Английский

Citations

408
Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis DOI Creative Commons
Jie Liang, Qian Liu, Abdulmohsen Ali Alshehri

et al.

Deleted Journal, Journal Year: 2022, Volume and Issue: 1, P. e9120010 - e9120010

Published: May 30, 2022

To restore the natural nitrogen cycle (N-cycle), artificial N-cycle electrocatalysis with flexibility, sustainability, and compatibility can convert intermittent renewable energy (e.g., wind) to harmful or value-added chemicals minimal carbon emissions. The background of such N-cycles, as fixation, ammonia oxidation, nitrate reduction, is briefly introduced here. discussion emerging nanostructures in various conversion reactions focused on architecture/compositional design, electrochemical performances, reaction mechanisms, instructive tests. Energy device advancements for achieving more functions well in situ/operando characterizations toward understanding key steps are also highlighted. Furthermore, some recently proposed less discussed C–N coupling summarized. We classify inorganic sources that each other under an applied voltage into three types, namely, abundant nitrogen, toxic (nitrite), oxides, useful compounds ammonia, hydrazine, hydroxylamine, goal providing critical insights strategies facilitate development our circular economy.

Language: Английский

Citations

350
Elucidating the activity, mechanism and application of selective electrosynthesis of ammonia from nitrate on cobalt phosphide DOI
Shenghua Ye, Zhida Chen,

Guikai Zhang

et al.

Energy & Environmental Science, Journal Year: 2021, Volume and Issue: 15(2), P. 760 - 770

Published: Dec. 17, 2021

Cobalt phosphide is an effective electrocatalyst for NO 3 − electroreduction into NH . Phosphorus crucial stabilizing the active phase and optimizing energy barriers, Co 4p orbitals directly participate in nitrate reduction.

Language: Английский

Citations

267
Efficient Ammonia Electrosynthesis and Energy Conversion through a Zn‐Nitrate Battery by Iron Doping Engineered Nickel Phosphide Catalyst DOI
Rong Zhang, Ying Guo, Shaoce Zhang

et al.

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(13)

Published: Feb. 9, 2022

Abstract The electrocatalytic nitrate reduction reaction (NO 3 ‐RR) to ammonia (NH ) offers a promising alternative approach for NH production and nitrate‐based voltaic cells which can deliver both electricity as products, are also highly attractive. However, nitrate‐to‐NH conversion involves proton‐assisted multiple‐electron transfer process with considerable kinetic barrier, underlying the need efficient catalysts NO – RR. A Zn‐nitrate battery is reported enable “killing three birds one stone” strategy energy supply, removal of pollutants iron doped nickel phosphide (Fe/Ni 2 P) RR catalyst electrode. Iron doping induces downshift d‐band center Ni atoms Fermi level, allowing optimization Gibbs free energies intermediates. Fe/Ni P exhibits 94.3% Faradaic efficiency (FE) nearly 100% at –0.4 V vs. reversible hydrogen electrode (RHE). Further applying this electrocatalyst cathode material, novel power density 3.25 mW cm –2 FE 85.0% production. This work enriches application Zn‐based batteries in field electrocatalysis highlights promise bimetal

Language: Английский

Citations

243
Structurally Disordered RuO2 Nanosheets with Rich Oxygen Vacancies for Enhanced Nitrate Electroreduction to Ammonia DOI
Yuting Wang, Hongjiao Li, Wei Zhou

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(19)

Published: March 1, 2022

Electrochemical reduction of nitrate pollutants to ammonia has emerged as an attractive alternative for synthesis. Currently, many strategies have been developed enhancing (NRA) efficiency, but the influence degree structural disorder is still unexplored. Here, carbon-supported RuO2 nanosheets with adjustable crystallinity are synthesized by a facile molten salt method. The as-synthesized amorphous displays high Faradaic efficiency (97.46 %) and selectivity (96.42 %), greatly outperforming crystalline counterparts. disordered structure abundant oxygen vacancies revealed modulate d-band center hydrogen affinity, thus lowering energy potential-determining step (NH2 *→NH3 *).

Language: Английский

Citations

242
Main-group elements boost electrochemical nitrogen fixation DOI Creative Commons
Laiquan Li, Cheng Tang, Huanyu Jin

et al.

Chem, Journal Year: 2021, Volume and Issue: 7(12), P. 3232 - 3255

Published: Nov. 9, 2021

Language: Английский

Citations

202
Enabled Efficient Ammonia Synthesis and Energy Supply in a Zinc–Nitrate Battery System by Separating Nitrate Reduction Process into Two Stages DOI Creative Commons
Haifeng Jiang, Gao‐Feng Chen, Aleksandr Savateev

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(13)

Published: Feb. 2, 2023

The aqueous electrocatalytic reduction of NO3- into NH3 (NitrRR) presents a sustainable route applicable to production and potentially energy storage. However, the NitrRR involves directly eight-electron transfer process generally required large overpotential (<-0.2 V versus reversible hydrogen electrode (vs. RHE)) reach optimal efficiency. Here, inspired by biological nitrate respiration, was separated two stages along [2+6]-electron pathway alleviate kinetic barrier. system employed Cu nanowire catalyst produces NO2- with current efficiencies 91.5 % 100 %, respectively at lower overpotentials (>+0.1 vs. RHE). high efficiency for such further explored in zinc-nitrate battery. This battery could be specified output voltage 0.70 V, an average density 566.7 Wh L-1 10 mA cm-2 power 14.1 mW , which is well beyond all previously reported similar concepts.

Language: Английский

Citations

171
Recent development of electrochemical nitrate reduction to ammonia: A mini review DOI Creative Commons
Xingmei Lü, Haoqiang Song, Jinmeng Cai

et al.

Electrochemistry Communications, Journal Year: 2021, Volume and Issue: 129, P. 107094 - 107094

Published: July 17, 2021

Nitrate (NO3-) pollution has become increasingly prominent due to industry and agriculture. Electrochemical reduction can convert NO3- into high value-added ammonia (NH3) remove pollution. This review focuses on the latest research progress in field of electrochemical nitrate reaction (NO3-RR) NH3. The mechanism NO3-RR is briefly discussed. Catalysts, as well qualitative quantitative methods for detection NH3 are also summarized. Finally, challenges prospects this We hope mini aids researchers design development advanced strategies NO3--to-NH3 processes.

Language: Английский

Citations

170