Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction

Chem, Journal Year: 2023, Volume and Issue: 9(7), P. 1768 - 1827

Published: June 21, 2023

Language: Английский

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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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Recent Advances in Electrocatalysts for Efficient Nitrate Reduction to Ammonia

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(43)

Published: June 25, 2023

Abstract Ammonia as an irreplaceable chemical has been widely demanded to keep the sustainable development of modern society. However, its industrial production consumes huge energy and releases extraordinary green‐house gases, leading various environmental issues. To achieve green ammonia is a great challenge that extensively pursued recently. In review, most promising strategy, electrochemical nitrate reduction reaction (e‐NO 3 RR) for purpose comprehensively investigated give full understanding mechanism provide guidance future directions. Particularly, electrocatalysts focused realize high yield rate Faraday efficiency applications. The recent‐developed catalysts, including noble metallic materials, alloys, metal compounds, single‐metal‐atom metal‐free are systematically discussed review effects factors on catalytic performance in e‐NO RR. Accordingly, strategies, defects engineering, coordination environment modulating, surface controlling, hybridization, carefully improve performance, such intrinsic activity selectivity. Finally, perspectives challenges given out. This shall insightful advanced systems efficiently industry.

Language: Английский

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Laser-controlled tandem catalytic sites of CuNi alloys with ampere-level electrocatalytic nitrate-to-ammonia reduction activities for Zn–nitrate batteries

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(7), P. 2991 - 3001

Published: Jan. 1, 2023

Laser-constructed CuNi alloy electrodes with tandem sites of Ni provide H* and Cu for NO 3 − reduction, achieving ampere-level reduction high-performance Zn–NO batteries.

Language: Английский

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Boosting Electrocatalytic Nitrate‐to‐Ammonia via Tuning of N‐Intermediate Adsorption on a Zn−Cu Catalyst

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(43)

Published: Sept. 4, 2023

The renewable-energy-powered electroreduction of nitrate (NO3- ) to ammonia (NH3 has garnered significant interest as an eco-friendly and promising substitute for the Haber-Bosch process. However, sluggish kinetics hinders its application at a large scale. Herein, we first calculated N-containing species (*NO3 *NO2 binding energy free hydrogen evolution reaction over Cu with different metal dopants, it was shown that Zn candidate. Based on theoretical study, designed synthesized Zn-doped nanosheets, as-prepared catalysts demonstrated excellent performance in NO3- -to-NH3 . maximum Faradaic efficiency (FE) NH3 could reach 98.4 % outstanding yield rate 5.8 mol g-1 h-1 , which is among best results up date. catalyst also had cycling stability. Meanwhile, presented FE exceeding 90 across wide potential range concentration range. Detailed experimental studies revealed doping modulate intermediates adsorption strength, enhance NO2- conversion, change *NO configuration bridge adsorption, decrease barrier, leading catalytic

Language: Английский

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In Situ Construction of Metal–Organic Frameworks as Smart Channels for the Effective Electrocatalytic Reduction of Nitrate at Ultralow Concentrations to Ammonia

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 9125 - 9135

Published: June 26, 2023

Electrochemical conversion of nitrate, a widespread water pollutant, into high-value-added ammonia is renewable and delocalized route to restore the globally perturbed nitrogen cycle. However, premature desorption catalytic intermediates competitive reaction hydrogen evolution make current performance still far from suitable for practical applications. In this work, Zr-based metal–organic framework (MOF) in situ constructed at interface serve as smart channel highly selective electrocatalytic reduction nitrate ammonia. The secondary coordination interaction introduced by pendant Brønsted acidic groups MOF not only effectively stabilize facilitate overall process but also certainly increase proton activation barrier suppress competing reaction. When coupled with nanocluster active center, proof-of-concept system achieves simultaneous improvement three critical parameters, rate 97.6%, an selectivity 95.2%, Faradaic efficiency 91.4% −1.0 V (vs RHE) under ultralow concentration conditions. This strategy provides interesting application MOFs paves way removal its

Language: Английский

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Unveiling the Reaction Mechanism of Nitrate Reduction to Ammonia Over Cobalt-Based Electrocatalysts

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 12976 - 12983

Published: April 3, 2024

Electrocatalytic reduction of nitrate to ammonia (NRA) has emerged as an alternative strategy for sewage treatment and generation. Despite excellent performances having been achieved over cobalt-based electrocatalysts, the reaction mechanism well veritable active species across a wide potential range are still full controversy. Here, we adopt CoP, Co, Co3O4 model materials solve these issues. CoP evolves into core@shell structured CoP@Co before NRA. For Co catalysts, three-step relay is carried out superficial dynamical Coδ+ under low overpotential, while continuous hydrogenation from unveiled high overpotential. In comparison, stable steadily catalyze range. As result, exhibit much higher NRA activity than especially Moreover, performance although they experience same mechanism. A series characterizations clarify reason enhancement highlighting that core donates abundant electrons species, leading generation more hydrogen nitrogen-containing intermediates.

Language: Английский

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Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 1, 2024

Abstract Nitrate can be electrochemically degraded to produce ammonia while treating sewage it remains grand challenge simultaneously realize high Faradaic efficiency and production rate over wide-range concentrations in real wastewater. Herein, we report the defect-rich Cu nanowire array electrode generated by in-situ electrochemical reduction, exhibiting superior performance nitrate reduction reaction benefitting from triple synergistic modulation. Notably, delivers current density ranging 50 1100 mA cm −2 across wide (1–100 mM) with 90%. Operando Synchrotron radiation Fourier Transform Infrared Spectroscopy theoretical calculations revealed that defective sites enhance adsorption, promote water dissociation suppress hydrogen evolution. A two-electrode system integrating industrial wastewater glycerol oxidation achieves of 550 at −1.4 V 99.9% selectivity conversion 100 h stability, demonstrating outstanding practicability.

Language: Английский

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Intermediates Regulation via Electron‐Deficient Cu Sites for Selective Nitrate‐to‐Ammonia Electroreduction

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

Published: Sept. 21, 2023

Ammonia (NH3 ), known as one of the fundamental raw materials for manufacturing commodities such chemical fertilizers, dyes, ammunitions, pharmaceuticals, and textiles, exhibits a high hydrogen storage capacity ≈17.75%. Electrochemical nitrate reduction (NO3 RR) to valuable ammonia at ambient conditions is promising strategy facilitate artificial nitrogen cycle. Herein, copper-doped cobalt selenide nanosheets with selenium vacancies are reported robust highly efficient electrocatalyst ammonia, exhibiting maximum Faradaic efficiency ≈93.5% an yield rate 2360 µg h-1 cm-2 -0.60 V versus reversible electrode. The in situ spectroscopical theoretical study demonstrates that incorporation Cu dopants Se into efficiently enhances electron transfer from Co atoms via bridging atoms, forming electron-deficient structure sites accelerate NO3- dissociation stabilize *NO2 intermediates, eventually achieving selective catalysis entire NO3 RR process produce efficiently.

Language: Английский

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Modulating Metal‐Nitrogen Coupling in Anti‐Perovskite Nitride via Cation Doping for Efficient Reduction of Nitrate to Ammonia

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: Aug. 1, 2023

The complexes of metal center and nitrogen ligands are the most representative systems for catalyzing hydrogenation reactions in small molecule conversion. Developing heterogeneous catalysts with similar active metal-nitrogen functional centers, nevertheless, still remains challenging. In this work, we demonstrate that coupling anti-perovskite Co4 N can be effective modulated by Cu doping to form Co3 CuN, leading strongly promoted process during electrochemical reduction nitrate (NO3- RR) ammonia. combination advanced spectroscopic techniques density theory calculations reveal dopants strengthen Co-N bond upshifted d-band towards Fermi level, promoting adsorption NO3- *H facilitating transition from *NO2 /*NO H/*NOH. Consequently, CuN delivers noticeably better RR activity than pristine N, optimal Faradaic efficiency 97 % ammonia yield 455.3 mmol h-1 cm-2 at -0.3 V vs. RHE. This work provides an strategy developing high-performance catalyst synthesis.

Language: Английский

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