Adjusting Surface Oxidized Layer of CoTe on PCN via In Situ N-Doping Strategy to Promote Charge Separation of Z-Scheme Heterojunction for Propelling Photocatalytic CO2 Reduction.

It has been a challenging issue to profoundly actuate the transfer and separation of photoinduced charge carriers by controlling the interface structure inside the heterojunction, owing to the molecular/subnanometric level interface region. Herein, a unique one-dimensional/two-dimensional (1D/2D) CoTe/PCN Z-scheme heterojunction is fabricated through the self-assembly of CoTe nanorods on the surface of polymeric carbon nitride (PCN) nanosheets. Significantly, in situ N-doping in the molecular/subnanometric surface oxidized layer of CoTe nanorods is achieved, effectively adjusting its chemical structure and element chemical states. Moreover, this N-doped surface oxidized layer can serve as a recombination region of photogenerated electrons from PCN and photogenerated holes from CoTe to increase the overall carrier separation efficiency in the Z-scheme heterojunction actuated by the built-in electric field. As a result, the photocatalytic CO2 reduction (CO2R) performance is enhanced dramatically, in which the yield of CO generated over the optimal 1D/2D CoTe/PCN heterojunction reaches up to triple than that over PCN. This unique contribution provides an emblematic paradigm for adjusting the interfacial structure of heterojunction and has a profound insight into the interfacial adjusting mechanism to improve the charge separation efficiency in the photocatalytic reaction.

3D/2D Heterojunction Fabricated from RuS2 Nanospheres Encapsulated in Polymeric Carbon Nitride Nanosheets for Selective Photocatalytic CO2 Reduction to CO.

Micro/nanostructure control of heterostructures is still a challenge for achieving high efficiency and selectivity of photocatalytic CO2 conversion. In this work, a new three-dimensiona/two-dimensional (3D/2D) heterostructure is fabricated by encapsulating RuS2 nanospheres in the interlayer of mesoporous polymeric carbon nitride (PCN) nanosheets based on an in situ growth and polymerization strategy. The unique microstructure of the obtained 3D/2D RuS2/PCN heterojunction can effectively improve the transfer and separation efficiency of photogenerated charge carriers, reduce the mass transfer resistance of CO2 toward active sites, and provide a confined reaction space, thus propelling the photocatalytic CO2 reduction to CO with high selectivity. The CO yield over the optimal 5%-RuS2/PCN sample reaches 4.2 and 2.8 times as high as that of single PCN and RuS2 within 4 h, respectively. Furthermore, the plausible charge transfer mechanism and CO2 reduction path are revealed by time-dependent in situ Fourier transform infrared (FT-IR) spectra combined with photophysical, electrochemical, and photoelectrochemical techniques and density functional theory (DFT) calculations. This work develops the microstructural engineering design strategy of PCN-based heterojunctions for selective photocatalytic CO2 fuel conversion.