Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: June 9, 2023

Natural nitrogen cycle has been severely disrupted by anthropogenic activities. The overuse of N-containing fertilizers induces the increase nitrate level in surface and ground waters, substantial emission oxides causes heavy air pollution. Nitrogen gas, as main component air, used for mass ammonia production over a century, providing enough nutrition agriculture to support world population increase. In last decade, researchers have made great efforts develop processes under ambient conditions combat intensive energy consumption high carbon associated with Haber-Bosch process. Among different techniques, electrochemical reduction reaction (NO

Language: Английский

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Pulsed Nitrate-to-Ammonia Electroreduction Facilitated by Tandem Catalysis of Nitrite Intermediates

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6471 - 6479

Published: March 10, 2023

Electroreduction of nitrate to ammonia offers a promising pathway for nutrient recycling and recovery from wastewater with energy environmental sustainability. There have been considerable efforts on the regulation reaction pathways facilitate nitrate-to-ammonia conversion over competing hydrogen evolution but only limited success. Here, we report Cu single-atom gel (Cu SAG) electrocatalyst that produces NH3 both nitrite under neutral conditions. Given unique mechanism NO2- activation SAGs spatial confinement strengthened kinetics, pulse electrolysis strategy is presented cascade accumulation intermediates during NO3- reduction prohibited competition reaction, thus substantially enhancing Faradaic efficiency yield rate production compared constant potential electrolysis. This work underlines cooperative approach three-dimensional (3D) framework structures highly efficient enabled by tandem catalysis unfavorable intermediates.

Language: Английский

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Emerging Applications, Developments, Prospects, and Challenges of Electrochemical Nitrate‐to‐Ammonia Conversion

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(29)

Published: April 23, 2023

Abstract Ammonia is not only an important feedstock for chemical industry but also a carbon‐free energy carrier and safe storage media hydrogen. Due to the advantages compared Haber–Bosch process, electrochemical NO 3 − ‐to‐NH conversion via nitrate reduction reaction (NO RR) received attention. Recently, “green hydrogen” generated from water electrolysis shows promise become future limited by safety of transportation. This review proposes can store renewable electric into NH , which potential solution solving puzzle Moreover, theoretical insights RR electrocatalyst design are discussed. Finally, challenges opportunities in this field elucidated. provides novel perspective accelerates development effective electrocatalysts conversion.

Language: Английский

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Recent progress and strategies on the design of catalysts for electrochemical ammonia synthesis from nitrate reduction

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3489 - 3514

Published: Jan. 1, 2023

Ammonia (NH3) is an essential raw material in the production of fertilizers and a promising carbon-free energy carrier, however, its synthesis still depends on energy- capital-intensive Haber–Bosch process. Recently, electrochemical N2 reduction reaction has attracted significant interest as emerging method for NH3 under ambient conditions. However, limited solubility aqueous electrolyte strong NN bonds result low yield rate, inferior faradaic efficiency unsatisfactory selectivity, impeding further practical application. Considering high water nitrate (NO3−), NO3− (NO3−RR) become fascinating route achieving sustainable NH3, enormous progress been made this field. As consequence, review discusses mechanism systematically summarizes recent development electrocatalysts NO3−RR, including noble-metal-based materials, single-atom metal catalysts, transition-metal-based catalysts. Diverse design strategies catalysts to boost NO3−RR performance, such defect engineering, rational structure design, strain engineering constructing heterostructures, are discussed. This followed by illustration how robust understanding optimization affords fundamental insights into efficiency, selectivity electrocatalysts. Finally, we conclude with future perspectives critical issues, challenges research directions high-efficiency selective NH3.

Language: Английский

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Metastable Phase Cu with Optimized Local Electronic State for Efficient Electrocatalytic Production of Ammonia from Nitrate

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 33(6)

Published: Nov. 28, 2022

Abstract Electrocatalytic nitrate (NO 3 − ) reduction reaction (NITRR) is an inspiring route for ammonia (NH synthesis at ambient condition. The metallic Cu‐based material with low cost and high activity one of the most promising electrocatalysts NITRR. However, due to weaker atomic H * ‐providing capacity, produced intermediate—nitrite tends accumulate on its surface, leading unsatisfactory NH selectivity Faradic efficiency (FE). Herein, a novel facile O 2 /Ar plasma oxidation subsequent electro‐reduction strategy developed synthesize kind metastable phase Cu. Excitingly, Cu demonstrates superior NITRR performance conventional 4 + (97.8%) FE (99.8%). Density function theory (DFT) calculations reveal that upshift d ‐band center near Fermi level in contributes enhanced activity, while relatively strong adsorption facilitates conversion from NO /NO NOOH /NOH thus ensures FE. Furthermore, when evaluated as cathode Zn‐NO battery, power density (7.56 mW cm −2 yield (76 µmol h −1 are achieved by battery.

Language: Английский

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Thermally Enhanced Relay Electrocatalysis of Nitrate-to-Ammonia Reduction over Single-Atom-Alloy Oxides

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7779 - 7790

Published: March 11, 2024

The electrochemical nitrate reduction reaction (NO3RR) holds promise for converting nitrogenous pollutants to valuable ammonia products. However, conventional electrocatalysis faces challenges in effectively driving the complex eight-electron and nine-proton transfer process of NO3RR while also competing with hydrogen evolution reaction. In this study, we present thermally enhanced nitrate-to-ammonia conversion over nickel-modified copper oxide single-atom alloy nanowires. catalyst demonstrates improved production performance a Faradaic efficiency approximately 80% yield rate 9.7 mg h–1 cm–2 at +0.1 V versus reversible electrode elevated cell temperatures. addition, system displays impressive stability, interference resistance, favorable energy consumption greenhouse gas emissions simulated industrial wastewater treatment. Complementary situ analyses confirm that significantly superior relay active species formed Ni sites facilitates thermal-field-coupled Cu surface-adsorbed *NOx hydrogenation. Theoretical calculations further support thermodynamic kinetic feasibility catalysis mechanism Ni1Cu model catalyst. This study introduces conceptual thermal-electrochemistry approach synergistic regulation catalytic processes, highlighting potential multifield-coupled advance sustainable-energy-powered chemical synthesis technologies.

Language: Английский

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A Bi‐Co Corridor Construction Effectively Improving the Selectivity of Electrocatalytic Nitrate Reduction toward Ammonia by Nearly 100%

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(48)

Published: Sept. 22, 2023

Improving the selective ammonia production capacity of electrocatalytic nitrate reduction reaction (NO3 RR) at ambient conditions is critical to future development and industrial application electrosynthesis ammonia. However, involves multi-proton electron transfer as well desorption underutilization intermediates, posing a challenge selectivity NO3 RR. Here electrodeposition site Co modulated by depositing Bi bottom catalyst, thus obtaining Co+Bi@Cu NW catalyst with Bi-Co corridor structure. In 50 mm NO3- , exhibits highest Faraday efficiency ≈100% (99.51%), an yield rate 1858.2 µg h-1 cm-2 high repeatability -0.6 V versus reversible hydrogen electrode. Moreover, change NO2- concentration on surface observed in situ reflection absorption imaging intermediates RR process detected electrochemical Raman spectroscopy together verify trapping effect It believed that measure modulating deposition loading element easy-to-implement general method for improving NH3 corresponding scientific research applications.

Language: Английский

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Understanding the Atomic and Defective Interface Effect on Ruthenium Clusters for the Hydrogen Evolution Reaction

ACS Catalysis, Journal Year: 2022, Volume and Issue: 13(1), P. 49 - 59

Published: Dec. 12, 2022

Water electrolysis powered by renewable electric energy is a promising technology for green hydrogen production without carbon emissions, while highly efficient and cost-effective electrocatalysts with long durability are urgently needed. Here, we demonstrate oxygen-coordinated single-atom iron sites (Fe–O4) decorated nanotubes abundant vacancies as the substrate stabilizing Ru clusters (CNT–V–Fe–Ru). The catalyst shows high performance evolution reaction (HER) in both acidic alkaline media, respectively. HER kinetics analysis demonstrates that defective single-atomic could significantly improve intrinsic activity of species. Theoretical calculations also support superior behavior CNT–V–Fe–Ru fundamental insights into metal–substrate interactions. present study highlights unique feature catalysts serving advanced supporting materials, which offers tremendous opportunities to adequately regulate electronic structures interfaces at atomic level.

Language: Английский

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Electrochemical Co-Production of Ammonia and Biodegradable Polymer Monomer Glycolic Acid via the Co-Electrolysis of Nitrate Wastewater and Waste Plastic

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(15), P. 10394 - 10404

Published: July 25, 2023

Electrochemical reformation of nitrate wastewater and poly(ethylene terephthalate) (PET) plastic waste into ammonia (NH3) fine chemicals is a sustainable strategy for resource utilization. Herein, co-production system glycolic acid (GA, degradable polymer monomer) constructed by coupling reduction ethylene glycol (EG, in PET hydrolysate) oxidation. Low-crystalline CoOOH (LC-CoOOH/CF) Pd nanothorns (Pd NTs/NF) grown situ on the metal foam substrates are employed as cathode anode, respectively. The high density amorphous regions LC-CoOOH/CF enables enhanced adsorption provides abundant active sites, ultimately leading to an Faradic efficiency (FE) 97.38 ± 1.0% at −0.25 V vs reversible hydrogen electrode (RHE). Meanwhile, unique nanothorn morphology endows NTs/NF with high-curvature tip, triggering tip effect (TE) promote highly selective oxidation EG GA. Furthermore, two-electrode system, NH3 GA operated low energy consumption (onset voltage: 0.5 V), much lower than traditional electrolysis process (1.4 V). This study method utilization co-produce value-added chemicals.

Language: Английский

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A multifunctional copper single-atom electrocatalyst aerogel for smart sensing and producing ammonia from nitrate

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(26)

Published: June 20, 2023

Despite modern chemistry's success in providing affordable fertilizers for feeding the population and supporting ammonia industry, ineffective nitrogen management has led to pollution of water resources air, contributing climate change. Here, we report a multifunctional copper single-atom electrocatalyst-based aerogel (Cu SAA) that integrates multiscale structure coordinated single-atomic sites 3D channel frameworks. The Cu SAA demonstrates an impressive faradaic efficiency 87% NH3 synthesis, as well remarkable sensing performance with detection limits 0.15 ppm NO3- 1.19 NH4+. These features enable precise control conversion nitrate catalytic process, facilitating accurate regulation ammonium ratios fertilizers. We thus designed into smart sustainable fertilizing system (SSFS), prototype device on-site automatic recycling nutrients precisely controlled nitrate/ammonium concentrations. SSFS represents forward step toward nutrient/waste recycling, permitting efficient utilization crops mitigating pollutant emissions. This contribution exemplifies how electrocatalysis nanotechnology can be potentially leveraged agriculture.

Language: Английский

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