Assemblies of MXene and Metal–Organic Polyhedra with Post-Functionalized Re(I) Sites for Selective CO2 Photoreduction
Purna K. Boruah, Duc Manh Nguyen, Rupjyoti Dutta, Nidhi Sharma, Manash R. Das, Ryo Ohtani, Maya Marinova, Yuki Tomita, Hironobu Ozawa, Ken Sakai, Vitaly Ordomsky, Benjamin Le Ouay, Masaaki OhbaAbstract
Metal–organic polyhedra (MOPs) are promising building blocks for porous materials, but their use in association with 2D materials is still largely unexplored. Here, we have synthesized novel microporous MOPs-MXene assemblies by simply mixing cationic Zr-based MOP with negatively charged, surface-functionalized MXenes. The composite MOP-MXene was further functionalized with Re(I) (designated as ZrMOP(Re)-MXene) to enable the selective photocatalytic reduction of CO2. ZrMOP(Re)-MXene showed good performance as a heterogeneous photocatalyst without the addition of an external photosensitizer, achieving a turnover number (TON) of 51 and an excellent selectivity of 93% for CO. The integration with MXene serves as an efficient electron transport mediator within the assembly, resulting in TONs being 4.5 and 7 times higher than those of the homogeneous controls of ZrMOP(Re) and [Re(bpy)(CO)3Cl], respectively.