Emerging p-Block-Element-Based Electrocatalysts for Sustainable Nitrogen Conversion DOI
Chade Lv, Jiawei Liu, Carmen Lee

et al.

ACS Nano, Journal Year: 2022, Volume and Issue: 16(10), P. 15512 - 15527

Published: Oct. 14, 2022

Artificial nitrogen conversion reactions, such as the production of ammonia via dinitrogen or nitrate reduction and synthesis organonitrogen compounds C–N coupling, play a pivotal role in modern life. As alternatives to traditional industrial processes that are energy- carbon-emission-intensive, electrocatalytic reactions under mild conditions have attracted significant research interests. However, electrosynthesis process still suffers from low product yield Faradaic efficiency, which highlight importance developing efficient catalysts. In contrast transition-metal-based catalysts been widely studied, p-block-element-based recently shown promising performance because their intriguing physiochemical properties intrinsically poor hydrogen adsorption ability. this Perspective, we summarize latest breakthroughs development electrocatalysts toward applications, including N2 urea using nitrogen-containing feedstocks carbon dioxide. The catalyst design strategies underlying reaction mechanisms discussed. Finally, major challenges opportunities future directions also proposed.

Language: Английский

Tandem Electrocatalytic Nitrate Reduction to Ammonia on MBenes DOI
Guike Zhang, Xiaotian Li, Kai Chen

et al.

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

Citations

293
Single‐Atom Bi Alloyed Pd Metallene for Nitrate Electroreduction to Ammonia DOI
Kai Chen,

Ziyu Ma,

Xingchuan Li

et al.

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

Citations

231
Sub-nm RuOx Clusters on Pd Metallene for Synergistically Enhanced Nitrate Electroreduction to Ammonia DOI
Xiaotian Li, Peng Shen, Xingchuan Li

et al.

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

Citations

226
High-Efficiency N2 Electroreduction Enabled by Se-Vacancy-Rich WSe2–x in Water-in-Salt Electrolytes DOI
Peng Shen, Xingchuan Li, Yaojing Luo

et al.

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

Citations

171
Lewis Acid Fe‐V Pairs Promote Nitrate Electroreduction to Ammonia DOI
Nana Zhang, Guike Zhang, Peng Shen

et al.

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

Citations

146
Recent progress in electrocatalytic nitrogen reduction to ammonia (NRR) DOI
Zanling Huang, Madiha Rafiq, Abebe Reda Woldu

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 478, P. 214981 - 214981

Published: Dec. 25, 2022

Language: Английский

Citations

132
Iridium single-atom catalyst for highly efficient NO electroreduction to NH3 DOI
Kai Chen, Guohui Wang, Yali Guo

et al.

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

Published: March 8, 2023

Language: Английский

Citations

120
p-Block Antimony Single-Atom Catalysts for Nitric Oxide Electroreduction to Ammonia DOI
Kai Chen, Ying Zhang,

Jiaqi Xiang

et al.

ACS Energy Letters, Journal Year: 2023, Volume and Issue: 8(3), P. 1281 - 1288

Published: Feb. 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.

Language: Английский

Citations

116
Electronic Modulation of Metal–Organic Frameworks by Interfacial Bridging for Efficient pH‐Universal Hydrogen Evolution DOI
Luqi Wang, Li Song, Zhenyu Yang

et al.

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 33(1)

Published: Oct. 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.

Language: Английский

Citations

114
Ultra-efficient N2 electroreduction achieved over a rhodium single-atom catalyst (Rh1/MnO2) in water-in-salt electrolyte DOI
Peng Shen, Xiaotian Li, Yaojing Luo

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 316, P. 121651 - 121651

Published: June 21, 2022

Language: Английский

Citations

108