Highly Efficient Photothermocatalytic CO_(2) Reduction in Ni/Mg-Doped Al_(2)O_(3) with High Fuel Production Rate, Large Light-to-Fuel Efficiency, and Good Durability

A novel nanocomposite of Ni nanoparticles loaded on Mg-doped Al_(2)O_(3)(Ni/Mg-Al_(2)O_(3))was prepared.By photothermocatalytic CO_(2) reduction with methane(CRM)merely using focused UV-vis-IR illumination on Ni/Mg-Al_(2)O_(3),high production rates of H_(2)(r_(H2),69.71 mmol min^(−1) g^(−1))and CO(rCO,74.57 mmol min^(−1) g^(−1))and an extremely large light-to-fuel efficiency(η,32.9%)are acquired.High rH2 and rCO(51.07 and 59.66 mmol min^(−1) g^(−1))and a largeη(32.5%)are acquired even by using focusedλ>560 nm vis-IR illumination.Ni/Mg-Al_(2)O_(3) shows good durability for photothermocatalytic CRM due to the side reaction of carbon deposition being enormously inhibited in comparison with a reference catalyst of Ni nanoparticles loaded on Al_(2)O_(3).The enormous carbon deposition inhibition is ascribed to the presence of a fence of CO_(2) molecules(strongly adsorbed on Mg-doped Al_(2)O_(3))around Ni nanoparticles,which block the polymerization and growth of carbon species to nanofibers by promoting the oxidation of carbon species formed by CH_(4) dissociation.The high photothermocatalytic activity of Ni/Mg-Al_(2)O_(3) arises from efficient light-driven thermocatalytic CRM.A photoactivation is found to considerably raise the photothermocatalytic activity of Ni/Mg-Al_(2)O_(3) because of the apparent activation energy(Ea)being substantially decreased upon focused illumination.The Ea reduction is associated with the rate-determining steps of CRM(e.g.,CH_(4) dissociation and the oxidation of carbon species)being accelerated upon focused illumination.