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Copper confined in vesicle-like BCN cavities promotes electrochemical reduction of nitrate to ammonia in water
Wuhan Univ, Peoples R China; Yunnan Univ, Peoples R China.
Yunnan Univ, Peoples R China; Zhengzhou Univ, Peoples R China.
Yunnan Univ, Peoples R China.
Zhengzhou Univ, Peoples R China.
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2021 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 9, no 41, p. 23675-23686Article in journal (Refereed) Published
Abstract [en]

Electrochemical methods to convert high-concentration nitrates present in sewage into high-value-added ammonia do not just alleviate the problem of environmental pollution but also provide less energy-intensive alternatives to the Haber-Bosch process. In this work, a metal-boron organic polymer precursor was annealed at high temperature to obtain copper nanoparticles encapsulated in a vesicle-like BCN matrix (BCN@Cu). In the electrochemical reduction of nitrate (E-NIRR), this species exhibited excellent catalytic activity. Specifically, the ammonia yields of BCN@Cu under applied potentials of -0.3 V, -0.4 V, -0.5 V, and -0.6 V versus the reversible hydrogen electrode were 271.1 mu mol h(-1) mg(cat.)(-1), 354.8 mu mol h(-1) mg(cat.)(-1), 435.6 mu mol h(-1) mg(cat.)(-1), and 576.2 mu mol h(-1) mg(cat.)(-1), respectively, and the corresponding Faraday efficiencies were 86.3%, 88.0%, 89.3%, and 88.9%. Isotope labeling experiments with (NO3-)-N-15 confirmed that the detected ammonia had originated from the electrochemical reduction of NO3- on the catalyst surface. Moreover, the E-NIRR activity of BCN@Cu remained high even after using it ten consecutive times or 20 h of continuous operation, suggesting the practicality of the industrial application of BCN@Cu. The presence of copper was key in determining BCN@Cus E-NIRR activity, while the presence of boron greatly improved its catalytic performance. Furthermore, density functional theory calculations indicated that BCN does not itself promote the reaction but rather assists the dispersion of Cu nanoparticles, thereby expanding the catalysts active surface area.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY , 2021. Vol. 9, no 41, p. 23675-23686
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URN: urn:nbn:se:liu:diva-180531DOI: 10.1039/d1ta05718aISI: 000706764200001OAI: oai:DiVA.org:liu-180531DiVA, id: diva2:1605792
Note

Funding Agencies|National Key R&D Program of China [2019YFC1804400]; National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [U2002213, 22179100, 21677171]; Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University [2019FY003025]; Double First Class University Construction Project [C176220100042]; Science and Technology Innovation Program of Hunan Province [2020RC5026, 2020GK4040]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [2020-04600, 2020/3-29]

Available from: 2021-10-25 Created: 2021-10-25 Last updated: 2022-04-13

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