Herein, we employed a molecular Ru(II) catalyst immobilized onto TiO 2 particulates of (4,4′-Y 2 -bpy)Ru II (CO) 2 Cl 2 (RuP; Y = CH 2 PO(OH) 2 ), as a hybrid catalyst system to secure the efficient and steady catalytic activity of a molecular bipyridyl Ru(II)-complex-based photocatalytic system for CO 2 reduction. From a series of operando FTIR spectrochemical analyses, it was found that the TiO 2 -fixed molecular Ru(II) complex leads to efficient stabilization of the key monomeric intermediate, Ru IIhydride (LRu II (H)(CO) 2 Cl), and suppresses the formation of polymeric Ru(II) complex (−(L(CO) 2 Ru−Ru(CO) 2 L) n −), which is a major deactivation product produced during photoreaction via the Ru−Ru dimeric route. Active promotion of the monomeric catalytic route in a hetero-binary system (IrPS + TiO 2 /RuP) that uses TiO 2 -bound Ru(II) complex as reduction catalyst led to highly increased activity as well as durability of photocatalytic behavior with respect to the homogeneous catalysis of free Ru(II) catalyst (IrPS + Ru(II) catalyst). This catalytic strategy produced maximal turnover numbers (TONs) of >4816 and >2228, respectively, for CO and HCOO − production in CO 2 -saturated N,Ndimethylformamide (DMF)/TEOA (16.7 vol % TEOA) solution containing a 0.1 M sacrificial electron donor.

While the incorporation of pendant Brønsted acid/base sites in the secondary coordination sphere is a promising and effective strategy to increase the catalytic performance and product selectivity in organometallic catalysis for CO 2 reduction, the control of product selectivity still faces a great challenge. Herein, we report two new trans(Cl)-[Ru(6-X-bpy)(CO) 2 Cl 2 ] complexes functionalized with a saturated ethylene-linked functional group (bpy = 2,2′-bipyridine; X = −(CH 2 ) 2 −OH or −(CH 2 ) 2 −N(CH 3 ) 2 ) at the ortho(6)-position of bpy ligand, which are named Ru-bpy OH and Ru-bpy diMeN , respectively. In the series of photolysis experiments, compared to nontethered case, the asymmetric attachment of tethering ligand to the bpy ligand led to less efficient but more selective formate production with inactivation of CO 2 -to-CO conversion route during photoreaction. From a series of in situ FTIR analyses, it was found that the Ru−formate intermediates are stabilized by a highly probable hydrogen bonding between pendent proton donors (−diMeN + H or −OH) and the oxygen atom of metal-bound formate (Ru I −OCHO•••H−E−(CH 2 ) 2 −, E = O or diMeN + ). Under such conformation, the liberation of formate from the stabilized Ru I −formate becomes less efficient compared to the nontethered case, consequently lowering the CO 2 -to-formate conversion activities during photoreaction. At the same time, such stabilization of Ru−formate species prevents the dehydration reaction route (η 1 -OCHO → η 1 -COOH on Ru metal) which leads toward the generation of Ru−CO species (key intermediate for CO production), eventually leading to the reduction of CO 2to-CO conversion activity.