Tandem Electrocatalytic Nitrate Reduction to Ammonia on MBenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(13)

Опубликована: Фев. 3, 2023

We demonstrate the great feasibility of MBenes as a new class tandem catalysts for electrocatalytic nitrate reduction to ammonia (NO3 RR). As proof concept, FeB2 is first employed model MBene catalyst NO3 RR, showing maximum NH3 -Faradaic efficiency 96.8 % with corresponding yield 25.5 mg h-1 cm-2 at -0.6 V vs. RHE. Mechanistic studies reveal that exceptional RR activity arises from catalysis mechanism, is, B sites activate NO3- form intermediates, while Fe dissociate H2 O and increase *H supply on promote intermediate hydrogenation enhance -to-NH3 conversion.

Язык: Английский

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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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Recent Advances in Electrocatalysts for Efficient Nitrate Reduction to Ammonia

Advanced Functional Materials, Год журнала: 2023, Номер 33(43)

Опубликована: Июнь 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.

Язык: Английский

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Iridium single-atom catalyst for highly efficient NO electroreduction to NH3

Nano Research, Год журнала: 2023, Номер 16(7), С. 8737 - 8742

Опубликована: Март 8, 2023

Язык: Английский

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Urea Electrosynthesis from Nitrate and CO₂ on Diatomic Alloys

Advanced Materials, Год журнала: 2024, Номер 36(30)

Опубликована: Июнь 14, 2024

Abstract Urea electrosynthesis from co–electrolysis of NO 3 − and CO 2 (UENC) offers a promising technology for achieving sustainable efficient urea production. Herein, diatomic alloy catalyst (CuPd 1 Rh –DAA), with mutually isolated Pd atoms alloyed on Cu substrate, is theoretically designed experimentally confirmed to be highly active selective UENC catalyst. Combining theoretical computations operando spectroscopic characterizations reveals the synergistic effect –Cu sites promote via tandem catalysis mechanism, where site triggers early C–N coupling promotes *CO –to–*CO NH steps, while facilitates subsequent protonation step *COOHNH toward formation. Impressively, CuPd –DAA assembled in flow cell presents highest Faradaic efficiency 72.1% yield rate 53.2 mmol h −1 g cat at −0.5 V versus RHE, representing nearly performance among all reported catalysts.

Язык: Английский

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Self-Tandem Electrocatalytic NO Reduction to NH₃ on a W Single-Atom Catalyst

Nano Letters, Год журнала: 2023, Номер 23(5), С. 1735 - 1742

Опубликована: Фев. 14, 2023

We design single-atom W confined in MoO3-x amorphous nanosheets (W1/MoO3-x) comprising W1-O5 motifs as a highly active and durable NORR catalyst. Theoretical operando spectroscopic investigations reveal the dual functions of to (1) facilitate activation protonation NO molecules (2) promote H2O dissociation while suppressing *H dimerization increase proton supply, eventually resulting self-tandem mechanism W1/MoO3-x greatly accelerate energetics NO-to-NH3 pathway. As result, exhibits highest NH3-Faradaic efficiency 91.2% NH3 yield rate 308.6 μmol h-1 cm-2, surpassing that most previously reported catalysts.

Язык: Английский

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Linear Adsorption Enables NO Selective Electroreduction to Hydroxylamine on Single Co Sites

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Май 2, 2023

Hydroxylamine (NH2 OH), a vital industrial feedstock, is presently synthesized under harsh conditions with serious environmental and energy concerns. Electrocatalytic nitric oxide (NO) reduction attractive for the production of hydroxylamine ambient conditions. However, selectivity limited by competitive reaction ammonia production. Herein, we regulate adsorption configuration NO adjusting atomic structure catalysts to control product selectivity. Co single-atom show state-of-the-art NH2 OH from electroreduction neutral (FE NH2OH${{_{{\rm NH}{_{2}}{\rm OH}}}}$ : 81.3 %), while nanoparticles are inclined generate NH3${{_{{\rm NH}{_{3}}}}}$ 92.3 %). A series in situ characterizations theoretical simulations unveil that linear on isolated sites enables formation bridge adjacent induces ammonia.

Язык: Английский

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Pd₁Cu Single-Atom Alloys for High-Current-Density and Durable NO-to-NH₃ Electroreduction

Nano Letters, Год журнала: 2024, Номер 24(2), С. 541 - 548

Опубликована: Янв. 8, 2024

Electrochemical reduction of NO to NH3 (NORR) offers a prospective method for efficient electrosynthesis. Herein, we first design single-atom Pd-alloyed Cu (Pd1Cu) as an and robust NORR catalyst at industrial-level current densities (>0.2 A cm–2). Operando spectroscopic characterizations theoretical computations unveil that Pd1 strongly electronically couples its adjacent two atoms (Pd1Cu2) enhance the activation while promoting NO-to-NH3 protonation energetics suppressing competitive hydrogen evolution. Consequently, flow cell assembled with Pd1Cu exhibits unprecedented yield rate 1341.3 μmol h–1 cm–2 NH3–Faradaic efficiency 85.5% density 210.3 mA cm–2, together excellent long-term durability 200 h electrolysis, representing one highest performances on record.

Язык: Английский

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Tandem Electrocatalytic Nitrate Reduction to Ammonia on MBenes

Angewandte Chemie, Год журнала: 2023, Номер 135(13)

Опубликована: Фев. 3, 2023

Abstract We demonstrate the great feasibility of MBenes as a new class tandem catalysts for electrocatalytic nitrate reduction to ammonia (NO 3 RR). As proof concept, FeB 2 is first employed model MBene catalyst NO RR, showing maximum NH ‐Faradaic efficiency 96.8 % with corresponding yield 25.5 mg h −1 cm −2 at −0.6 V vs. RHE. Mechanistic studies reveal that exceptional RR activity arises from catalysis mechanism, is, B sites activate − form intermediates, while Fe dissociate H O and increase *H supply on promote intermediate hydrogenation enhance ‐to‐NH conversion.

Язык: Английский

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