Maurin Antoine, Ng Chi-On, Chen Lingjing, Lau Tai-Chu, Robert Marc, Ko Chi-Chiu
Université Paris Diderot, Sorbonne Paris Cité, Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université-CNRS no. 7591, Bâtiment Lavoisier, 15 rue Jean de Baïf, 75205 Paris Cedex 13, France.
Dalton Trans. 2016 Oct 7;45(37):14524-9. doi: 10.1039/c6dt01686c. Epub 2016 Jun 13.
The electrochemical and photochemical catalytic reductions of CO2 using N,O and N,S-NHC-containing dicarbonyl rhenium(i) bipyridine complexes have been investigated. By replacing the carbonyl ligand in tricarbonyl rhenium(i) complexes with a weaker π-accepting ligand, the characteristic MLCT transitions shifted to lower energy. This makes photocatalysts capable of harvesting low-energy visible light for catalyzing CO2 reduction. A detailed study revealed that these dicarbonyl rhenium(i) complexes are also highly selective for photocatalysis of CO2 to CO with a good quantum efficiency (10%), similar to that of the tricarbonyl rhenium(i) complex analogues. From the electrochemical study, it was observed that the catalysts efficiently produce CO from CO2 with high turnover frequency and good stability over time.
已对使用含N、O和N、S-NHC的二羰基铼（I）联吡啶配合物进行的二氧化碳电化学和光化学催化还原反应进行了研究。通过用较弱的π-受体配体取代三羰基铼（I）配合物中的羰基配体，特征性的MLCT跃迁移向更低能量。这使得光催化剂能够捕获低能量可见光以催化二氧化碳还原。一项详细研究表明，这些二羰基铼（I）配合物在光催化二氧化碳生成一氧化碳方面也具有高度选择性，量子效率良好（10%），与三羰基铼（I）配合物类似物相当。从电化学研究中观察到，这些催化剂能以高周转频率并随时间保持良好稳定性地从二氧化碳高效生成一氧化碳。
