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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Ambient Electrosynthesis of Urea with Nitrate and Carbon Dioxide over Iron‐Based Dual‐Sites

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(6)

Published: Oct. 20, 2022

The development of efficient electrocatalysts to generate key *NH2 and *CO intermediates is crucial for ambient urea electrosynthesis with nitrate (NO3- ) carbon dioxide (CO2 ). Here we report a liquid-phase laser irradiation method fabricate symbiotic graphitic encapsulated amorphous iron oxide nanoparticles on nanotubes (Fe(a)@C-Fe3 O4 /CNTs). Fe(a)@C-Fe3 /CNTs exhibits superior electrocatalytic activity toward synthesis using NO3- CO2 , affording yield 1341.3±112.6 μg h-1 mgcat-1 faradic efficiency 16.5±6.1 % at conditions. Both experimental theoretical results indicate that the formed Fe(a)@C Fe3 CNTs provide dual active sites adsorption activation thus generating lower energy barriers formation. This work would be helpful design high-efficiency dual-site synthesis.

Language: Английский

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Electrochemical C–N coupling of CO₂and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(6), P. 2193 - 2237

Published: Jan. 1, 2023

Electrochemical C–N coupling reaction by renewable electricity for the electrosynthesis of organonitrogen compounds with abundant CO 2 and nitrogenous small molecules as carbon nitrogen sources, respectively, is a promising sustainable synthetic strategy.

Language: Английский

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Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu–W bimetallic C–N coupling sites

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

Published: July 26, 2023

Electrocatalytic urea synthesis is an emerging alternative technology to the traditional energy-intensive industrial protocol. Novel strategies are urgently needed promote electrocatalytic C-N coupling process and inhibit side reactions. Here, we report a CuWO4 catalyst with native bimetallic sites that achieves high production rate (98.5 ± 3.2 μg h-1 mg-1cat) for co-reduction of CO2 NO3- Faradaic efficiency (70.1 2.4%) at -0.2 V versus reversible hydrogen electrode. Mechanistic studies demonstrated combination stable intermediates *NO2 *CO increases probability reduces potential barrier, resulting in low overpotential. This study provides new perspective on achieving efficient electrosynthesis by stabilizing key reaction intermediates, which may guide design other electrochemical systems high-value bond-containing chemicals.

Language: Английский

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Review on Electrocatalytic Coreduction of Carbon Dioxide and Nitrogenous Species for Urea Synthesis

ACS Nano, Journal Year: 2023, Volume and Issue: 17(4), P. 3209 - 3224

Published: Feb. 14, 2023

The electrochemical coreduction of carbon dioxide (CO2) and nitrogenous species (such as NO3–, NO2–, N2, NO) for urea synthesis under ambient conditions provides a promising solution to realize carbon/nitrogen neutrality mitigate environmental pollution. Although an increasing number studies have made some breakthroughs in synthesis, the unsatisfactory Faradaic efficiency, low yield rate, ambiguous C–N coupling reaction mechanisms remain major obstacles its large-scale applications. In this review, we present recent progress on based CO2 aqueous solutions conditions, providing useful guidance discussion rational design metal nanocatalyst, understanding mechanism, existing challenges prospects synthesis. We hope that review can stimulate more insights inspiration toward development electrocatalytic technology.

Language: Английский

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Recent advances on electrocatalytic CO2 reduction to resources: Target products, reaction pathways and typical catalysts

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 453, P. 139663 - 139663

Published: Oct. 8, 2022

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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Turning Waste into Wealth: Sustainable Production of High-Value-Added Chemicals from Catalytic Coupling of Carbon Dioxide and Nitrogenous Small Molecules

ACS Nano, Journal Year: 2022, Volume and Issue: 16(11), P. 17911 - 17930

Published: Oct. 31, 2022

Carbon neutrality is one of the central topics not only scientific community but also majority human society. The development highly efficient carbon dioxide (CO2) capture and utilization (CCU) techniques expected to stimulate routes concepts go beyond fossil fuels provide more economic benefits for a carbon-neutral economy. While various single-carbon (C1) multi-carbon (C2+) products have been selectively produced date, scope CCU can be further expanded valuable chemicals simple species by integration nitrogenous reactants into CO2 reduction. In this Review, research progress toward sustainable production high-value-added (urea, methylamine, ethylamine, formamide, acetamide, glycine) from catalytic coupling small molecules (NH3, N2, NO3–, NO2–) highlighted. C–N bond formation key mechanistic step in N-integrated reduction, so we focus on possible pathways starting reduction processes as well attributes that enable coupling. We propose directions prospects field, aiming inspire future investigations achieve comprehensive improvement performance product systems.

Language: Английский

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Synergy of dual-atom catalysts deviated from the scaling relationship for oxygen evolution reaction

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

Published: July 24, 2023

Dual-atom catalysts, particularly those with heteronuclear active sites, have the potential to outperform well-established single-atom catalysts for oxygen evolution reaction, but underlying mechanistic understanding is still lacking. Herein, a large-scale density functional theory employed explore feasibility of *O-*O coupling mechanism, which can circumvent scaling relationship improving catalytic performance N-doped graphene supported Fe-, Co-, Ni-, and Cu-containing dual-atom namely, M'M@NC. Based on constructed activity maps, rationally designed descriptor be obtained predict homonuclear catalysts. Seven four possess high activities that minimum theoretical overpotential. The chemical structural origin in favor mechanism thus leading enhanced reaction been revealed. This work not only provides additional insights into fundamental mechanisms, also offers guideline accelerated discovery efficient

Language: Английский

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Kinetically matched C–N coupling toward efficient urea electrosynthesis enabled on copper single-atom alloy

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

Published: Nov. 1, 2023

Chemical C-N coupling from CO2 and NO3-, driven by renewable electricity, toward urea synthesis is an appealing alternative for Bosch-Meiser production. However, the unmatched kinetics in NO3- reduction reactions complexity of C- N-species involved co-reduction render challenge coupling, leading to low yield rate Faradaic efficiency. Here, we report a single-atom copper-alloyed Pd catalyst (Pd4Cu1) that can achieve highly efficient electrosynthesis. The regulated matched steering Cu doping level Pd4Cu1/FeNi(OH)2 interface. Charge-polarized Pdδ--Cuδ+ dual-sites stabilize key *CO *NH2 intermediates promote coupling. synthesized Pd4Cu1-FeNi(OH)2 composite achieves 436.9 mmol gcat.-1 h-1 efficiency 66.4%, as well long cycling stability 1000 h. In-situ spectroscopic results theoretical calculation reveal atomically dispersed lattice promotes deep *NH2, Pd-Cu lower energy barrier pivotal between *CO.

Language: Английский

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