Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

Advanced Materials, Год журнала: 2023, Номер 36(17)

Опубликована: Июнь 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

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(19), С. 12976 - 12983

Опубликована: Апрель 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.

Язык: Английский

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Atomic Co─P Catalytic Pair Drives Efficient Electrochemical Nitrate Reduction to Ammonia

Advanced Energy Materials, Год журнала: 2024, Номер 14(28)

Опубликована: Март 3, 2024

Abstract Electrochemically reducing nitrate (NO 3 − ), a common water pollutant, to valuable ammonia (NH ) offers green, sustainable, and decentralized route for synthesis. Electrochemical reduction reaction RR) involves two crucial steps: deoxygenation followed by nitrite hydrogenation; in particular, the hydrogenation is rate‐determining step (RDS) NO RR. In this work, an atomically dispersed cobalt‐phosphorus (Co─P) catalytic pair (CP) with strong electronic coupling reported. The Co site Co─P CP effectively activates , while P facilitates dissociation release H + synergistically enhancing thermodynamic kinetic performance of electrochemical ammonia.

Язык: Английский

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Phase Engineering of High‐Entropy Alloy for Enhanced Electrocatalytic Nitrate Reduction to Ammonia

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Май 4, 2024

Abstract Directly electrochemical conversion of nitrate (NO 3 − ) is an efficient and environmentally friendly technology for ammonia (NH production but challenged by highly selective electrocatalysts. High‐entropy alloys (HEAs) with unique properties are attractive materials in catalysis, particularly multi‐step reactions. Herein, we first reported the application HEA (FeCoNiAlTi) electrocatalytic NO reduction to NH (NRA). The bulk active NRA limited unsatisfied yield 0.36 mg h −1 cm −2 Faradaic efficiency (FE) 82.66 %. Through effective phase engineering strategy, uniform intermetallic nanoparticles introduced on increase surface area charge transfer efficiency. resulting nanostructured (n‐HEA) delivers enhanced performance terms (0.52 FE (95.23 %). Further experimental theoretical investigations reveal that multi‐active sites (Fe, Co, Ni) dominated electrocatalysis over n‐HEA. Notably, typical Co exhibit lowest energy barrier *NH 2 as rate‐determining step.

Язык: Английский

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Interfacial Assembly of Nanocrystals on Nanofibers with Strong Interaction for Electrocatalytic Nitrate Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Авг. 8, 2023

One-dimensional fiber architecture serves as an excellent catalyst support. The orderly arrangement of active materials on such a substrate can enhance catalytic performance by exposing more sites and facilitating mass diffusion; however, this remains challenge. We developed interfacial assembly strategy for the distribution metal nanocrystals different substrates to optimize their electrocatalytic performance. Using electrochemical nitrate reduction reaction (NO3- RR) representative reaction, iron-based nanofibers (Fe/NFs) structure achieved removal capacity 2317 mg N/g Fe N2 selectivity up 97.2 %. This could promote rational design synthesis fiber-based electrocatalysts.

Язык: Английский

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Relay Catalysis of Fe and Co with Multi‐Active Sites for Specialized Division of Labor in Electrocatalytic Nitrate Reduction Reaction

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Апрель 8, 2024

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) driven by renewable energy is a promising technology for the removal of nitrate‐containing wastewater. However, sluggish kinetics resulted from complex proton‐coupled electron transfer and various intermediates remain key barriers large‐scale application NO RR. Herein, tactic reported to raise rate RR increase selectivity N 2 using bimetal catalyst: Co inclined act on steps needed in process, rate‐determining step (RDS: *NO , asterisk means intermediates) subsequent *N hydrogenation as well Fe exhibits efficient activity selectivity‐ determining (SDS: then ) via relay catalysis mechanism. A efficiency 78.5% an ultra‐long cycle stability 60 cycles (12 h per cycle) are achieved FeCo alloy confined with nitrogen‐doped porous carbon nanofibers (FeCo‐NPCNFs). DFT calculations unveil that introduction active site not only regulates d‐band center alloy, optimizes adsorption intermediates, but also has strong capacity supply hydrogen species. Clearly, this study elucidates effects bimetallic performance electrocatalytic offers avenues designing Fe‐based catalysts realize nitrogen‐neutral cycle.

Язык: Английский

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Electron-deficient cobalt nanocrystals for promoted nitrate electrocatalytic reduction to synthesize ammonia

Nano Energy, Год журнала: 2023, Номер 117, С. 108901 - 108901

Опубликована: Сен. 13, 2023

Язык: Английский

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Palladium-Copper bimetallic catalysts for electroreduction of CO2 and nitrogenous species

Coordination Chemistry Reviews, Год журнала: 2024, Номер 509, С. 215802 - 215802

Опубликована: Март 26, 2024

Язык: Английский

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Critical review in electrocatalytic nitrate reduction to ammonia towards a sustainable nitrogen utilization

Chemical Engineering Journal, Год журнала: 2024, Номер 483, С. 148952 - 148952

Опубликована: Янв. 22, 2024

Язык: Английский

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Optimizing Intermediate Adsorption over PdM (M=Fe, Co, Ni, Cu) Bimetallene for Boosted Nitrate Electroreduction to Ammonia

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Март 7, 2024

Electrochemical reduction of nitrate to ammonia (NO

Язык: Английский

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