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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Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction

Chem, Journal Year: 2023, Volume and Issue: 9(7), P. 1768 - 1827

Published: June 21, 2023

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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Unveiling Cutting‐Edge Developments in Electrocatalytic Nitrate‐to‐Ammonia Conversion

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(16)

Published: Jan. 11, 2024

The excessive enrichment of nitrate in the environment can be converted into ammonia (NH

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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Recent Advances in Electrocatalysts for Efficient Nitrate Reduction to Ammonia

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(43)

Published: June 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.

Language: Английский

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High-Efficiency Electrochemical Nitrate Reduction to Ammonia on a Co₃O₄ Nanoarray Catalyst with Cobalt Vacancies

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(41), P. 46595 - 46602

Published: Oct. 5, 2022

Electrocatalytic nitrate reduction reaction (NO3RR) affords a bifunctional character in the carbon-free ammonia synthesis and remission of pollution water. Here, we fabricated Co3O4 nanosheet array with cobalt vacancies on carbon cloth (vCo-Co3O4/CC) by situ etching aluminum-doped Co3O4/CC, which exhibits an excellent Faradaic efficiency 97.2% large NH3 yield as high 517.5 μmol h-1 cm-2, better than pristine Co3O4/CC. Theoretical calculative results imply that can tune local electronic environment around Co sites Co3O4, increasing charge reducing electron cloud density sites, is thus conducive to adsorption NO3- for greatly enhanced reduction. Furthermore, vCo-Co3O4 (311) facet presents NO3RR activity low energy barrier about 0.63 eV potential-determining step, much smaller (1.3 eV).

Language: Английский

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Recent progress and strategies on the design of catalysts for electrochemical ammonia synthesis from nitrate reduction

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3489 - 3514

Published: Jan. 1, 2023

Ammonia (NH3) is an essential raw material in the production of fertilizers and a promising carbon-free energy carrier, however, its synthesis still depends on energy- capital-intensive Haber–Bosch process. Recently, electrochemical N2 reduction reaction has attracted significant interest as emerging method for NH3 under ambient conditions. However, limited solubility aqueous electrolyte strong NN bonds result low yield rate, inferior faradaic efficiency unsatisfactory selectivity, impeding further practical application. Considering high water nitrate (NO3−), NO3− (NO3−RR) become fascinating route achieving sustainable NH3, enormous progress been made this field. As consequence, review discusses mechanism systematically summarizes recent development electrocatalysts NO3−RR, including noble-metal-based materials, single-atom metal catalysts, transition-metal-based catalysts. Diverse design strategies catalysts to boost NO3−RR performance, such defect engineering, rational structure design, strain engineering constructing heterostructures, are discussed. This followed by illustration how robust understanding optimization affords fundamental insights into efficiency, selectivity electrocatalysts. Finally, we conclude with future perspectives critical issues, challenges research directions high-efficiency selective NH3.

Language: Английский

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Advances in the Electrocatalytic Hydrogen Evolution Reaction by Metal Nanoclusters‐based Materials

Small, Journal Year: 2022, Volume and Issue: 18(52)

Published: Oct. 26, 2022

Abstract With the development of renewable energy systems, clean hydrogen is burgeoning as an optimal alternative to fossil fuels, in which its application promising retarding global and environmental crisis. The evolution reaction (HER), capable producing high‐purity rapidly electrocatalytic water splitting, has received much attention. Abundant research about HER been done, focusing on advanced electrocatalyst design with high efficiency robust stability. As potential catalysts, metal nanoclusters (MNCs) have studied extensively. They are composed several a hundred atoms, sizes being comparable Fermi wavelength electrons, that is, < 2.0 nm. Different from atoms/nanoparticles, they exhibit unique catalytic properties due their quantum size effect low‐coordination environment. In this review, activity‐enhancing approaches MNCs applied electrocatalysis mainly summarized. Furthermore, recent progress classified different stabilization strategies, freestanding MNCs, organic, carbon supports, introduced. Finally, current challenges deficiencies these for prospected.

Language: Английский

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