Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction

Chem, Год журнала: 2023, Номер 9(7), С. 1768 - 1827

Опубликована: Июнь 21, 2023

Язык: Английский

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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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Pulsed electroreduction of low-concentration nitrate to ammonia

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 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.

Язык: Английский

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Atomic coordination environment engineering of bimetallic alloy nanostructures for efficient ammonia electrosynthesis from nitrate

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(32)

Опубликована: Июль 31, 2023

Electrochemical nitrate reduction reaction (NO 3 RR) to ammonia has been regarded as a promising strategy balance the global nitrogen cycle. However, it still suffers from poor Faradaic efficiency (FE) and limited yield rate for production on heterogeneous electrocatalysts, especially in neutral solutions. Herein, we report one-pot synthesis of ultrathin nanosheet-assembled RuFe nanoflowers with low-coordinated Ru sites enhance NO RR performances electrolyte. Significantly, exhibit outstanding FE 92.9% 38.68 mg h −1 cat (64.47 ) at −0.30 −0.65 V (vs. reversible hydrogen electrode), respectively. Experimental studies theoretical calculations reveal that are highly electroactive an increased d-band center guarantee efficient electron transfer, leading low energy barriers reduction. The demonstration rechargeable zinc-nitrate batteries large-specific capacity using indicates their great potential next-generation electrochemical systems.

Язык: 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, Год журнала: 2024, Номер 146(11), С. 7779 - 7790

Опубликована: Март 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.

Язык: 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, Год журнала: 2023, Номер 62(43)

Опубликована: Сен. 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

Язык: 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, Год журнала: 2023, Номер 35(48)

Опубликована: Сен. 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.

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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Crystal Phase Engineering of Ultrathin Alloy Nanostructures for Highly Efficient Electroreduction of Nitrate to Ammonia

Advanced Materials, Год журнала: 2024, Номер 36(14)

Опубликована: Янв. 26, 2024

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) toward ammonia synthesis is recognized as a sustainable strategy to balance the global nitrogen cycle. However, it still remains great challenge achieve highly efficient production due complex proton‐coupled electron transfer process in NO RR. Here, controlled of RuMo alloy nanoflowers (NFs) with unconventional face‐centered cubic (fcc) phase and hexagonal close‐packed/fcc heterophase for RR reported. Significantly, fcc NFs demonstrate high Faradaic efficiency 95.2% large yield rate 32.7 mg h −1 cat at 0 −0.1 V (vs reversible hydrogen electrode), respectively. In situ characterizations theoretical calculations have unraveled that possess highest d‐band center superior electroactivity, which originates from strong Ru─Mo interactions intrinsic activity phase. The optimal electronic structures supply adsorption key intermediates suppression competitive evolution, further determines remarkable performance. successful demonstration high‐performance zinc‐nitrate batteries suggests their substantial application potential electrochemical energy systems.

Язык: Английский

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Optimizing Intermediate Adsorption via Heteroatom Ensemble Effect over RuFe Bimetallic Alloy for Enhanced Nitrate Electroreduction to Ammonia

Advanced Energy Materials, Год журнала: 2023, Номер 13(31)

Опубликована: Июнь 30, 2023

Abstract The electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach for removal and NH synthesis at ambient conditions. As complex eight‐electron/nine‐proton transfer process, its performance relies heavily on the adsorption ability of intermediates catalyst surface, which determined by geometric electronic configurations active sites. In this work, heteroatom ensemble effect deliberately triggered over RuFe bimetallic alloy to optimize intermediate NO RR. A record‐high yield rate 118.8 mg h −1 high Faradaic efficiency 92.2% are achieved −1.4 V vs reversible hydrogen electrode, ranking top state‐of‐the‐art. Experimental computational results reveal that characteristics induced play crucial roles. Both Ru Fe display continuous state throughout Fermi level, suggesting electron density benefits whole result, facilitated − , efficient stabilization key intermediates, as well timely desorption simultaneously achieved, thus significantly promoting direct .

Язык: Английский

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