Photocatalytic CO<SUB>2</SUB>-to-CO/Formate Conversion by Cationic Half-metallocene Ru(II)(<EM>η</EM>6-<EM>p</EM>-Cymene) Complex and Its Mechanistic Investigation
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This study details the photocatalytic CO2-to-CO or formate conversion activities of two different photocatalytic systems (IrPE + (p-Cym)RuPE and IrP/TiO2/(p-Cym)RuP) to evaluate the catalytic behavior of homogeneous and heterogenized (p-Cym)Ru(II) catalyst, respectively. A single run photolysis of the mixed homogeneous system (IrPE + (p-Cym)RuPE) in the presence of 16.7 vol % TEOA exhibited a maximal turnover number (TON) of ~800 for 48 h with a high product selectivity of formate (＞79%), while the ternary hybrid system with TiO2-immobilized (p-Cym)RuP showed the relatively higher and steady CO2-to-CO and CO2-to-formate conversion activities (a TON of ＞1660 for 100 h), reflecting the CO2 reduction route bisected by heterogenization of (p-Cym)RuP.