Сибирский федеральный университет

Тип публикации: статья из журнала

Год издания: 2021

Идентификатор DOI: 10.1016/j.apmt.2021.101206

Ключевые слова: synthetic ammonia, electrocatalysis, nitrate reduction, nitrate removal, single-atom cu

Аннотация: Electrochemical methods have been proven to effectively eliminate nitrates in sewage and convert them into high value-added ammonia products. Here, after annealing treatment of metal boron cluster organic polymers formed by the combination of 1,10-phenanthroline, Cu2+ and closo-[B12H12](2)(-), a Cu single-atom doped BCN (B-doped CN) with a diamond-shaped nanosheet structure was obtained. In the electrochem-ical reduction reaction of nitrate, BCN-Cu exhibits excellent catalytic activity, specifically: 1) the ammonia yield rate reached as high as 498.85 mu g h(-1) cm(-2), 1047.14 mu g h(-1) cm(-2), 1900.07 mu g h(-1) cm(-2) and 3358.74 mu g h(-1) cm(-2) at -0.3 V, -0.4 V, -0.5 V and -0.6 V vs reversible hydrogen electrode, respectively, and Faradaic efficiency is 95.90%, 97.28%, 98.23% and 97.37%; 2) after repeated use of BCN-Cu 10 times or continuous operation for 16 h, the activity against electrochemical reduction reaction of nitrate anions is almost unchanged. The (NO3-)-N-15 isotopic labeling experiment proved that the detected NH3 comes from the reduction of NO3- on BCN-Cu. Control experiments show that the presence of Cu determines whether BCN-Cu has the possibility of catalyzing electrochemical reduction reactions of nitrate, and the presence of the B element enhances the catalytic activity of BCN-Cu. Density functional calculations indicate that in the water phase the process of reducing NO3- to NH3 on Cu-0 is an exothermic reaction, and that the adsorption process of NO3- on Cu-0 is the rate-determining step. (C) 2021 Elsevier Ltd. All rights reserved. Electrochemical methods have been proven to effectively eliminate nitrates in sewage and convert them into high value-added ammonia products. Here, after annealing treatment of metal boron cluster organic polymers formed by the combination of 1,10-phenanthroline, Cu2+ and closo-[B12H12]2-, a Cu single-atom doped BCN (B-doped CN) with a diamond-shaped nanosheet structure was obtained. In the electrochemical reduction reaction of nitrate, BCN-Cu exhibits excellent catalytic activity, specifically: 1) the ammonia yield rate reached as high as 498.85 μg h−1 cm−2, 1047.14 μg h−1 cm−2, 1900.07 μg h−1 cm−2 and 3358.74 μg h−1 cm−2 at -0.3 V, -0.4 V, -0.5 V and -0.6 V vs reversible hydrogen electrode, respectively, and Faradaic efficiency is 95.90%, 97.28%, 98.23% and 97.37%; 2) after repeated use of BCN-Cu 10 times or continuous operation for 16 h, the activity against electrochemical reduction reaction of nitrate anions is almost unchanged. The 15NO3− isotopic labeling experiment proved that the detected NH3 comes from the reduction of NO3− on BCN-Cu. Control experiments show that the presence of Cu determines whether BCN-Cu has the possibility of catalyzing electrochemical reduction reactions of nitrate, and the presence of the B element enhances the catalytic activity of BCN-Cu. Density functional calculations indicate that in the water phase the process of reducing NO3− to NH3 on Cu0 is an exothermic reaction, and that the adsorption process of NO3− on Cu0 is the rate-determining step. © 2021 Elsevier Ltd

Журнал: APPLIED MATERIALS TODAY

Выпуск журнала: Vol. 25

Номера страниц: 101206

ISSN журнала: 23529407

Место издания: AMSTERDAM

Издатель: ELSEVIER

• Zhao Xue (Yunnan Univ, Sch Ecol & Environm Sci, Inst Ecol Res & Pollut Control Plateau Lakes, Kunming 650504, Yunnan, Peoples R China; Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Peoples R China)
• Jia Xiuxiu (Yunnan Univ, Sch Ecol & Environm Sci, Inst Ecol Res & Pollut Control Plateau Lakes, Kunming 650504, Yunnan, Peoples R China)
• He Yingnan (Yunnan Univ, Sch Ecol & Environm Sci, Inst Ecol Res & Pollut Control Plateau Lakes, Kunming 650504, Yunnan, Peoples R China)
• Zhang Haibo (Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Peoples R China)
• Zhou Xiaohai (Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Peoples R China)
• Zhang Hucai (Yunnan Univ, Sch Ecol & Environm Sci, Inst Ecol Res & Pollut Control Plateau Lakes, Kunming 650504, Yunnan, Peoples R China)
• Zhang Shusheng (Zhengzhou Univ, Coll Chem & Mol Engn, Zhengzhou 450000, Peoples R China)
• Dong Yemin (Chinese Acad Sci, Shanghai Inst Microsyst & Informat Technol, State Key Lab Funct Mat Informat, Shanghai 200050, Peoples R China)
• Hu Xun (Univ Jinan, Sch Mat Sci & Engn, Jinan 250022, Peoples R China)
• Kuklin Artem (Siberian Fed Univ, Int Res Ctr Spect & Quantum Chem IRC SQC, 79 Svobodny Pr, Krasnoyarsk 660041, Russia; Uppsala Univ, Dept Phys & Astron, Box 516, SE-75120 Uppsala, Sweden)
• Baryshnikov Glib (Linkoping Univ, Lab Organ Elect, ITN, S-60174 Norrkoping, Sweden)
• Agren Hans (Uppsala Univ, Dept Phys & Astron, Box 516, SE-75120 Uppsala, Sweden)
• Hu Guangzhi (Yunnan Univ, Sch Ecol & Environm Sci, Inst Ecol Res & Pollut Control Plateau Lakes, Kunming 650504, Yunnan, Peoples R China)

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