Metal Organic Framework-Assisted Copper-Modified Titania (cu/tio2) with Abundant Exposed Active Sites and Highly Accessible Pore Channels for an Enhanced Photo-Generation of Hydrogen

Metal-doping is a common strategy for establishing active sites on photocatalyst, but appropriately exposing them for maximized atomic utilization remains a great challenge in photocatalytic research. Herein, we propose a metal organic framework (MOF)-assisted approach to synthesis copper-modified titania (Cu-TiO2/Cu) photocatalyst with homogenously distributed and highly accessible active sites in its matrix. Significantly, an MOF precursor, namely NH2-MIL-125, with co-chelation of titania (Ti) and copper (Cu) was subjected to mild calcination, subsequently results in Cu-modified TiO2 with highly accessible channels to its inner surface. These channels provide not only a large reactive surface (>400 m(2) g(-1)); they also enable facile modifying route for the pre-deposited Cu in prior to photoreaction. Specifically, NH3 treatment was applied to partially reduce deposited Cu ions (Cu+ and Cu2+) into Cu nanoparticles, where their interplays realize improved optical properties and charge separation during photoreactions. Furthermore, the NH3-induced Cu nanoparticles could also serve as the adsorptive site for H+, thereby enabling 5629 mu mol h(-1) g(-1) H-2 generation over the optimum photocatalyst of Cu-20/TiO2/Cu-500. Such performance is associated to 35.44 and 1.71-fold improvements compared to pure TiO2 (Cu-0/TiO2) and untreated Cu-ion modified TiO2 (Cu-20/TiO2), respectively. This work offers a new synthetic strategy for obtaining photocatalyst with evenly distributed and highly accessible active sites, thus improving the commensurability of photocatalytic H-2 generation from the industrial perspective.