Abstract

Two new supramolecular photocatalysts containing Ru(II) polypyridine units as light-harvesting photosensitizers and Re(I) polypyridine subunits as catalytic centers have been prepared. The new species, RuRe2A and Ru2ReA, contain catalytic Re(I) subunits coordinated by the preformed CO2TEOA adduct (known to be the effective catalytic subunits; TEOA is triethanolamine) and exhibit quite efficient and selective photoreduction of CO2 to CO, with outstanding TONs of 2368 and 2695 and a selectivity of 99.9% and 98.9%, respectively. Such photocatalytic properties are significantly improved with respect to those of previously studied RuRe2 and Ru2Re parent compounds, containing chloride ligands instead of the CO2TEOA adduct. Comparison between photocatalytic performance of the new species and their parent compounds allows to investigate the effect of the CO2TEOA insertion process as well as the eventual effect of the presence of chloride ions in solution on the photocatalytic processes. The improved photocatalytic properties of RuRe2A and Ru2ReA compared with their parent species are attributed to a combined effect of different distribution of the one-electron reduced form of the supramolecular photocatalysts on the Ru-subunit(s) (leading to decreased CO formation due to a poisoning ligand loss process) and on the Re-subunit(s) and to the presence of chloride ions in solution for RuRe2 and Ru2Re, which could interfere with the CO2TEOA adduct formation, a needed requisite for CO forming catalysis. These results strongly indicate the utility of preparing supramolecular photocatalysts containing preformed adducts.

Details

Title
Photocatalyzed CO2 reduction to CO by supramolecular photocatalysts made of Ru(II) photosensitizers and Re(I) catalytic subunits containing preformed CO2TEOA adducts
Author
Santoro, Antonio 1 ; Cancelliere, Ambra M. 1 ; Kamogawa, Kei 2 ; Serroni, Scolastica 1 ; Puntoriero, Fausto 1 ; Tamaki, Yusuke 3 ; Campagna, Sebastiano 1 ; Ishitani, Osamu 4 

 University of Messina, and Interuniversitary Research Center for Artificial Photosynthesis (Solar Chem, Messina Node), Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, Messina, Italy (GRID:grid.10438.3e) (ISNI:0000 0001 2178 8421) 
 Tokyo Institute of Technology, Department of Chemistry, School of Science, Meguro-Ku, Japan (GRID:grid.32197.3e) (ISNI:0000 0001 2179 2105) 
 National Institute of Advanced Industrial Science and Technology (AIST), Research Institute for Chemical Process Technology, Department of Materials and Chemistry, Sendai, Japan (GRID:grid.208504.b) (ISNI:0000 0001 2230 7538) 
 Tokyo Institute of Technology, Department of Chemistry, School of Science, Meguro-Ku, Japan (GRID:grid.32197.3e) (ISNI:0000 0001 2179 2105); Hiroshima University, Department of Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima, Japan (GRID:grid.257022.0) (ISNI:0000 0000 8711 3200) 
Pages
11320
Publication year
2023
Publication date
2023
Publisher
Nature Publishing Group
e-ISSN
20452322
Source type
Scholarly Journal
Language of publication
English
ProQuest document ID
2836681491
Copyright
© The Author(s) 2023. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.