Enhanced photocatalytic activity by regulating charge transferring: Unveiling the decisive role of cerium oxide crystal-facet engineering over heterojunction.

Heterojunctions have been verified to be effective for separation of photogenerated electrons and holes, therefore improving the photocatalytic efficiency. Meanwhile, cerium oxide (CeO2) is an ideal semiconductor for studying the influence of different exposed crystal facets on regulation of electron transport pathways over heterojunctions. Herein, various kinds of crystal facet-dependent CeO2/g-C3N4 (graphitic carbon nitride) heterojunctions have been successfully engineered as representative model catalysts, and their critical role in regulating charge transfer pathways has been confirmed by systemic characterizations. It was found that facet-dependent heterojunctions followed different charge transport pathways, leading to different H2 evolution activities. In detail, heterojunctions with (100) and (110) exposed surfaces followed the Z-scheme transport pathways, while heterojunction with (111) exposed surface followed the type-II pathway. The H2 evolution rates via these three kinds of heterojunctions were determined to be 3.084, 1.925, and 1.128 mmol·g-1·h-1, respectively, which were 13.3, 7.9, 4.2 times that of bare g-C3N4. It's revealed that the different exposed crystal facets of CeO2 with different Fermi levels determine the transport pathways of photogenerated carriers. This work shows an example of controlling photocatalytic activity by facet-dependent heterojunctions and reveals the importance role of crystal-facet engineering toward heterojunction construction, which is expected to provide an important guidance for the design of new photocatalytic systems.

Significantly enhanced photothermal catalytic hydrogen evolution over Cu2O-rGO/TiO2 composite with full spectrum solar light.

Reduced graphene oxide (rGO) has conspicuous photothermal characteristics in photothermal applications. Thus in our previous work, we used reduced graphene oxide (rGO) supported titanium dioxide (TiO2) nanocomposite (rGO/TiO2) to absorb the ultraviolet and infrared light in the photothermal hydrogen evolution process. In order to make use of the full spectrum solar energy into other clear energy, the visible light should be also considered in following research. Herein, we report a cuprous oxide (Cu2O) decorated reduced graphene oxide (rGO) supported titanium dioxide (TiO2) (Cu2O-rGO/TiO2) catalysts, which can absorb full spectrum solar light in an innovative way. The Cu2O-rGO/TiO2 catalyst is synthesized through a one-step hydrothermal method. The rates of hydrogen evolution are 17800 µmol·g-1h-1 under photothermal condition (90°C), 3800 µmol·g-1h-1 under photocatalysis condition only (25°C) and 0 µmol·g-1h-1 under thermal catalysis condition only. The result of photothermal catalytic hydrogen evolution rate is about 4.7 times that of the sum of the photocatalytic and thermal reactions. The photothermal synergetic effect promotes the photo-generated electron-holes separation through the rGO due to the temperature rising, and accelerates the reaction rates on the catalyst surface in hydrogen evolution process simultaneously. This work could provide us a new promising way for the conversion of full spectrum solar energy to hydrogen energy.