Electrocatalytic CO<sub>2</sub> Reduction and H<sub>2</sub> Evolution by a Copper (II) Complex with Redox-Active Ligand
The process of electrocatalytic CO<sub>2</sub> reduction and H<sub>2</sub> evolution from water, regarding renewable energy, has become one of the global solutions to problems related to energy consumption and environmental degradation. In order to promote the electrocatalyti...
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| Format: | Article |
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MDPI AG
2022-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/4/1399 |
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| author | Jingjing Li Shifu Zhang Jinmiao Wang Xiaomeng Yin Zhenxing Han Guobo Chen Dongmei Zhang Mei Wang |
| author_facet | Jingjing Li Shifu Zhang Jinmiao Wang Xiaomeng Yin Zhenxing Han Guobo Chen Dongmei Zhang Mei Wang |
| author_sort | Jingjing Li |
| collection | DOAJ |
| description | The process of electrocatalytic CO<sub>2</sub> reduction and H<sub>2</sub> evolution from water, regarding renewable energy, has become one of the global solutions to problems related to energy consumption and environmental degradation. In order to promote the electrocatalytic reactivity, the study of the role of ligands in catalysis has attracted more and more attention. Herein, we have developed a copper (II) complex with redox-active ligand [Cu(<b>L<sup>1</sup></b>)<sub>2</sub>NO<sub>3</sub>]NO<sub>3</sub> (<b>1</b>, <b>L<sup>1</sup></b> = 2-(6-methoxypyridin-2-yl)-6-nitro-1h-benzo [D] imidazole). X-ray crystallography reveals that the Cu ion in cation of complex <b>1</b> is coordinated by two redox ligands <b>L<sup>1</sup></b> and one labile nitrate ligand, which could assist the metal center for catalysis. The longer Cu-O bond between the metal center and the labile nitrate ligand would break to provide an open coordination site for the binding of the substrate during the catalytic process. The electrocatalytic investigation combined with DFT calculations demonstrate that the copper (II) complex could homogeneously catalyze CO<sub>2</sub> reduction towards CO and H<sub>2</sub> evolution, and this could occur with great performance due to the cooperative effect between the central Cu (II) ion and the redox- active ligand <b>L<sup>1</sup></b>. Further, we discovered that the added proton source H<sub>2</sub>O and TsOH·H<sub>2</sub>O (p-Toluenesulfonic acid) could greatly enhance its electrocatalytic activity for CO<sub>2</sub> reduction and H<sub>2</sub> evolution, respectively. |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T21:20:21Z |
| publishDate | 2022-02-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj.art-f61879ebb30a44359b251a819af1a5e02023-11-23T21:23:24ZengMDPI AGMolecules1420-30492022-02-01274139910.3390/molecules27041399Electrocatalytic CO<sub>2</sub> Reduction and H<sub>2</sub> Evolution by a Copper (II) Complex with Redox-Active LigandJingjing Li0Shifu Zhang1Jinmiao Wang2Xiaomeng Yin3Zhenxing Han4Guobo Chen5Dongmei Zhang6Mei Wang7Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, ChinaKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, ChinaKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, ChinaKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, ChinaKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, ChinaKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, ChinaKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, ChinaKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, ChinaThe process of electrocatalytic CO<sub>2</sub> reduction and H<sub>2</sub> evolution from water, regarding renewable energy, has become one of the global solutions to problems related to energy consumption and environmental degradation. In order to promote the electrocatalytic reactivity, the study of the role of ligands in catalysis has attracted more and more attention. Herein, we have developed a copper (II) complex with redox-active ligand [Cu(<b>L<sup>1</sup></b>)<sub>2</sub>NO<sub>3</sub>]NO<sub>3</sub> (<b>1</b>, <b>L<sup>1</sup></b> = 2-(6-methoxypyridin-2-yl)-6-nitro-1h-benzo [D] imidazole). X-ray crystallography reveals that the Cu ion in cation of complex <b>1</b> is coordinated by two redox ligands <b>L<sup>1</sup></b> and one labile nitrate ligand, which could assist the metal center for catalysis. The longer Cu-O bond between the metal center and the labile nitrate ligand would break to provide an open coordination site for the binding of the substrate during the catalytic process. The electrocatalytic investigation combined with DFT calculations demonstrate that the copper (II) complex could homogeneously catalyze CO<sub>2</sub> reduction towards CO and H<sub>2</sub> evolution, and this could occur with great performance due to the cooperative effect between the central Cu (II) ion and the redox- active ligand <b>L<sup>1</sup></b>. Further, we discovered that the added proton source H<sub>2</sub>O and TsOH·H<sub>2</sub>O (p-Toluenesulfonic acid) could greatly enhance its electrocatalytic activity for CO<sub>2</sub> reduction and H<sub>2</sub> evolution, respectively.https://www.mdpi.com/1420-3049/27/4/1399copper (II) complexredox-active ligandelectrocatalysisCO<sub>2</sub> reductionH<sub>2</sub> evolution |
| spellingShingle | Jingjing Li Shifu Zhang Jinmiao Wang Xiaomeng Yin Zhenxing Han Guobo Chen Dongmei Zhang Mei Wang Electrocatalytic CO<sub>2</sub> Reduction and H<sub>2</sub> Evolution by a Copper (II) Complex with Redox-Active Ligand Molecules copper (II) complex redox-active ligand electrocatalysis CO<sub>2</sub> reduction H<sub>2</sub> evolution |
| title | Electrocatalytic CO<sub>2</sub> Reduction and H<sub>2</sub> Evolution by a Copper (II) Complex with Redox-Active Ligand |
| title_full | Electrocatalytic CO<sub>2</sub> Reduction and H<sub>2</sub> Evolution by a Copper (II) Complex with Redox-Active Ligand |
| title_fullStr | Electrocatalytic CO<sub>2</sub> Reduction and H<sub>2</sub> Evolution by a Copper (II) Complex with Redox-Active Ligand |
| title_full_unstemmed | Electrocatalytic CO<sub>2</sub> Reduction and H<sub>2</sub> Evolution by a Copper (II) Complex with Redox-Active Ligand |
| title_short | Electrocatalytic CO<sub>2</sub> Reduction and H<sub>2</sub> Evolution by a Copper (II) Complex with Redox-Active Ligand |
| title_sort | electrocatalytic co sub 2 sub reduction and h sub 2 sub evolution by a copper ii complex with redox active ligand |
| topic | copper (II) complex redox-active ligand electrocatalysis CO<sub>2</sub> reduction H<sub>2</sub> evolution |
| url | https://www.mdpi.com/1420-3049/27/4/1399 |
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