Tandem Electrocatalytic Nitrate Reduction to Ammonia on MBenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(13)

Published: Feb. 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.

Language: Английский

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Unveiling the Synergy of O‐Vacancy and Heterostructure over MoO_3‐x/MXene for N₂ Electroreduction to NH₃

Advanced Energy Materials, Journal Year: 2021, Volume and Issue: 12(3)

Published: Dec. 21, 2021

Abstract The electrochemical N 2 reduction reaction (NRR) offers a promising approach for sustainable NH 3 production, and modulating the structural/electronic configurations of catalyst materials with optimized electrocatalytic properties is pivotal achieving high‐efficiency NRR electrocatalysis. Herein, vacancy heterostructure engineering are rationally integrated to explore O‐vacancy‐rich MoO 3‐ x anchored on Ti C T ‐MXene (MoO /MXene) as highly active selective electrocatalyst, an exceptional activity yield 95.8 µg h −1 mg (−0.4 V) Faradaic efficiency 22.3% (−0.3 V). A combination in situ spectroscopy, molecular dynamics simulations density functional theory computations employed unveil synergistic effect O‐vacancies heterostructures NRR, which demonstrates that serve sites chemisorption activation, while MXene substrate can further regulate O‐vacancy break scaling relation effectively stabilize *N /*N H destabilizing *NH /*NH , resulting more binding affinity intermediates toward reduced energy barriers enhanced /MXene.

Language: Английский

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

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(12)

Published: Jan. 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.

Language: Английский

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

ACS Nano, Journal Year: 2023, Volume and Issue: 17(2), P. 1081 - 1090

Published: Jan. 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.

Language: Английский

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“Capture-Backdonation-Recapture” Mechanism for Promoting N₂ Reduction by Heteronuclear Metal-Free Double-Atom Catalysts

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(21), P. 9344 - 9353

Published: May 20, 2022

Facing the increasingly serious energy and environmental crisis, development of heteronuclear metal-free double-atom catalysts is a potential strategy to realize efficient catalytic nitrogen reduction with low consumption no pollution because it could combine advantages flexible active sites in while also being pollution-free have high Faraday efficiency simultaneously. However, according existing mechanism, finite orbits other nonmetallic atoms, except boron atom, reduce possibility catalysis hinder catalysts. Herein, we propose new "capture-backdonation-recapture" which skillfully uses electron capture-backdonation-recapture between boron, substrate, elements solve above problems. Based on this by means first-principle calculations, material structure, adsorption energy, activity, selectivity 36 are systematically investigated evaluate their performance. B-Si@BP1 B-Si@BP3 selected for good performance limiting potentials -0.14 -0.10 V, respectively. Meanwhile, mechanism verified analyzing results transfer. Our work broadens ideas lays theoretical foundation future.

Language: Английский

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Regulating surface oxygen species on copper (I) oxides via plasma treatment for effective reduction of nitrate to ammonia

Applied Catalysis B Environment and Energy, Journal Year: 2021, Volume and Issue: 305, P. 121021 - 121021

Published: Dec. 18, 2021

Language: Английский

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

ACS Nano, Journal Year: 2022, Volume and Issue: 16(5), P. 7915 - 7925

Published: April 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.

Language: Английский

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Lewis Acid Fe‐V Pairs Promote Nitrate Electroreduction to Ammonia

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(13)

Published: Jan. 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.

Language: Английский

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Sulfur-deficient Bi2S3−x synergistically coupling Ti3C2Tx-MXene for boosting electrocatalytic N2 reduction

Nano Research, Journal Year: 2022, Volume and Issue: 15(5), P. 3991 - 3999

Published: Feb. 8, 2022

Language: Английский

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

Nano Research, Journal Year: 2023, Volume and Issue: 16(7), P. 8737 - 8742

Published: March 8, 2023

Language: Английский

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