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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Single‐Atom Bi Alloyed Pd Metallene for Nitrate Electroreduction to Ammonia

Advanced Functional Materials, Год журнала: 2023, Номер 33(12)

Опубликована: Янв. 15, 2023

Abstract Electrochemical reduction of nitrate to ammonia (NO 3 RR) holds a great promise for attaining both NH electrosynthesis and wastewater purification. Herein, single‐atom Bi alloyed Pd metallene (Bi 1 Pd) is reported as highly effective NO RR catalyst, showing near 100% ‐Faradaic efficiency with the corresponding yield 33.8 mg h −1 cm −2 at −0.6 V versus RHE, surpassing those almost all ever catalysts. In‐depth theoretical operando spectroscopic investigations unveil that electronically couples its neighboring atoms synergistically activate − destabilize *NO on Pd, leading reduced energy barrier potential‐determining step (*NO→*NOH) enhanced protonation energetics ‐to‐NH pathway.

Язык: Английский

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Sub-nm RuO_x Clusters on Pd Metallene for Synergistically Enhanced Nitrate Electroreduction to Ammonia

ACS Nano, Год журнала: 2023, Номер 17(2), С. 1081 - 1090

Опубликована: Янв. 11, 2023

The electrochemical nitrate reduction to ammonia reaction (NO3RR) has emerged as an appealing route for achieving both wastewater treatment and production. Herein, sub-nm RuOx clusters anchored on a Pd metallene (RuOx/Pd) are reported highly effective NO3RR catalyst, delivering maximum NH3-Faradaic efficiency of 98.6% with corresponding NH3 yield rate 23.5 mg h–1 cm–2 partial current density 296.3 mA at −0.5 V vs RHE. Operando spectroscopic characterizations combined theoretical computations unveil the synergy enhance energetics through mechanism hydrogen spillover hydrogen-bond interactions. In detail, activates NO3– form intermediates, while dissociates H2O generate *H, which spontaneously migrates RuOx/Pd interface via process. Further interactions between spillovered *H intermediates makes desorb from participate in intermediate hydrogenation, contributing enhanced activity NO3–-to-NH3 conversion.

Язык: Английский

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High-Efficiency N₂ Electroreduction Enabled by Se-Vacancy-Rich WSe_2–x in Water-in-Salt Electrolytes

ACS Nano, Год журнала: 2022, Номер 16(5), С. 7915 - 7925

Опубликована: Апрель 22, 2022

Electrocatalytic nitrogen reduction reaction (NRR) is a promising approach for renewable NH3 production, while developing the NRR electrocatalysis systems with both high activity and selectivity remains significant challenge. Herein, we combine catalyst electrolyte engineering to achieve high-efficiency enabled by Se-vacancy-rich WSe2-x in water-in-salt (WISE). Extensive characterizations, theoretical calculations, situ X-ray photoelectron/Raman spectroscopy reveal that WISE ensures suppressed H2 evolution, improved N2 affinity on surface, as well an enhanced π-back-donation ability of active sites, thereby promoting NRR. As result, excellent faradaic efficiency 62.5% yield 181.3 μg h-1 mg-1 achieved 12 m LiClO4, which among highest performances reported date.

Язык: Английский

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Lewis Acid Fe‐V Pairs Promote Nitrate Electroreduction to Ammonia

Advanced Functional Materials, Год журнала: 2023, Номер 33(13)

Опубликована: Янв. 18, 2023

Abstract Electrochemical reduction of nitrate to ammonia (NO 3 RR) has been recognized as an appealing approach realize both sustainable NH production and waste removal. Herein, from the perspective Lewis acid‐base interaction, a single‐atom Fe‐doped V 2 O 5 (Fe‐V ) catalyst enriched is designed with acid sites, which present maximum ‐Faradaic efficiency 97.1% corresponding yield 12.5 mg h −1 cm −2 at –0.7 versus RHE. Mechanistic studies based on theoretical calculations operando spectroscopic characterizations identify creation Fe‐V pairs , can synergetically activate NO − promote hydrogenation energetics, restrain hydrogen evolution, leading enhanced RR activity selectivity.

Язык: Английский

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Recent progress in electrocatalytic nitrogen reduction to ammonia (NRR)

Coordination Chemistry Reviews, Год журнала: 2022, Номер 478, С. 214981 - 214981

Опубликована: Дек. 25, 2022

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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p-Block Antimony Single-Atom Catalysts for Nitric Oxide Electroreduction to Ammonia

ACS Energy Letters, Год журнала: 2023, Номер 8(3), С. 1281 - 1288

Опубликована: Фев. 3, 2023

Electrocatalytic NO reduction to NH3 (NORR) offers a prospective approach attain both harmful removal and efficient electrosynthesis. Main-group p-block metals are promising NORR candidates but still lack adequate exploration. Herein, Sb single atoms confined in amorphous MoO3 (Sb1/a-MoO3) designed as an catalyst, exhibiting the highest yield rate of 273.5 μmol h–1 cm–2 NO-to-NH3 Faradaic efficiency 91.7% at −0.6 V vs RHE. In situ spectroscopic characterizations theoretical computations reason that outstanding performance Sb1/a-MoO3 arises from isolated Sb1 sites, which can optimize adsorption *NO/*NHO lower reaction energy barriers simultaneously exhibit higher affinity than H2O/H species. Moreover, our strategy be extended prepare Bi1/a-MoO3, showing high property, demonstrating immense potential metal single-atom catalysts toward high-performing electrocatalysis.

Язык: Английский

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Electronic Modulation of Metal–Organic Frameworks by Interfacial Bridging for Efficient pH‐Universal Hydrogen Evolution

Advanced Functional Materials, Год журнала: 2022, Номер 33(1)

Опубликована: Окт. 26, 2022

Abstract Designing well‐defined interfacial chemical bond bridges is an effective strategy to optimize the catalytic activity of metal–organic frameworks (MOFs), but it remains challenging. Herein, a facile in situ growth reported for synthesis tightly connected 2D/2D heterostructures by coupling MXene with CoBDC nanosheets. The multifunctional nanosheets high conductivity and ideal hydrophilicity as bridging carriers can ensure structural stability sufficient exposure active sites. Moreover, Co–O–Ti formed at interface effectively triggers charge transfer modulates electronic structure Co‐active site, which enhances reaction kinetics. As result, optimized CoBDC/MXene exhibits superior hydrogen evolution (HER) low overpotentials 29, 41, 76 mV 10 mA cm −2 alkaline, acidic, neutral electrolytes, respectively, comparable commercial Pt/C. Theoretical calculation demonstrates that bridging‐induced electron redistribution optimizes free energy water dissociation adsorption, resulting improved evolution. This study not only provides novel electrocatalyst efficient HER all pH conditions also opens up new avenue designing highly systems.

Язык: Английский

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Ultra-efficient N2 electroreduction achieved over a rhodium single-atom catalyst (Rh1/MnO2) in water-in-salt electrolyte

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 316, С. 121651 - 121651

Опубликована: Июнь 21, 2022

Язык: Английский

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