Inorganic nanoparticles/metal organic framework hybrid membrane reactors for efficient photocatalytic conversion of CO2

Photocatalytic conversion of carbon dioxide (CO2) to useful products has potential to address the adverse environmental impact of global warming. However, most photocatalysts used to date exhibit limited catalytic performance, due to poor CO2 adsorption capacity, inability to efficiently generate photoexcited electrons, and/or poor transfer of the photogenerated electrons to CO2 molecules adsorbed on the catalyst surface. The integration of inorganic semiconductor nanoparticles across metal organic framework (MOF) materials has potential to yield new hybrid materials, combining the high CO2 adsorption capacity of MOF and the ability of the semiconductor nanoparticles to generate photoexcited electrons. Herein, controlled encapsulation of TiO2 and Cu-TiO2 nanoparticles within zeolitic imidazolate framework (ZIF-8) membranes was successfully accomplished, using rapid thermal deposition (RTD), and their photocatalytic efficiency toward CO2 conversion was investigated under UV irradiation. Methanol and carbon monoxide (CO) were found to be the only products of the CO2 reduction, with yields strongly dependent upon the content and composition of the dopant semiconductor particles. CuTiO2 nanoparticle doped membranes exhibited the best photocatalytic performance, with 7 μg of the semiconductor nanoparticle enhancing CO yield of the pristine ZIF-8 membrane by 233%, and methanol yield by 70%. This work opens new routes for the fabrication of hybrid membranes containing inorganic nanoparticles and MOFs, with potential application not only in catalysis but also in electrochemical, separation, and sensing applications.