Insights into the photocatalytic mechanism of the C4N/MoS2 heterostructure: A first-principle study

Constructing heterostructures by combining COFs and TMD is a new strategy to design efficient photocatalysts for CO2 reduction reaction(CO2RR) due to their good stability,tunable band gaps and efficient charge separation.Based on the synthesis of completely novel C4N-COF in our previous re ported work,a new C4N/MoS2 heterostructure was constructed and then the related structural,electronic and optical properties were also studied using first principle calculations.The interlayer coupling effect and charge transfer between the C4N and MoS2 layer are systematically illuminated.The reduced band gap of the C4N/MoS2 heterostructure is beneficial to absorb more visible light.For the formation of type-Ⅱ band alignment,a built-in electric field appears which separates the photogene rated electrons and holes into different layers efficiently and produces redox active sites.The band alignment of the heterostructure ensures its photocatalytic activities of the whole CO2 reduction reaction.Furthermore,the charge density difference and charge carrier mobility confirm the existence of the built-in electric field at the interface of the C4N/MoS2 heterostructure directly.Finally,the high optical absorption indicates it is an efficient visible light harvesting photocatalyst.Therefore,this wo rk could provide strong insights into the internal mechanism and high photocatalytic activity of the C4N/MoS2 heterostructure and offer guiding of designing and synthesizing COF/TMD heterostructure photocatalysts.

Two Dimension C_3N_4/MoS_2 Nanocomposites with Enhanced Photocatalytic Hydrogen Evolution under Visible Light Irradiation

MoS_2-decorated C_3N_4(C_3N_4/MoS_2) nanosheets hybrid photocatalysts were prepared by a simple sonication-impregnation method. Face-to-face lamellar heterojunctions were well established between two dimension(2D) C_3N_4 and MoS_2 nanosheets. The effects of MoS_2 content on the light absorption, charge transfer and photocatalytic activity of the hybrid samples were investigated. Characterization results show that MoS_2 nanosheets are well anchored on the face of C_3N_4 nanosheets and the composites have well dispersed layered morphology. After loading with MoS_2, the light absorption of composites was much improved, especially in visible-light region. The photocatalytic activities of C_3N_4/MoS_2 samples were evaluated based on the H_2 evolution under visible light irradiation(λ > 400 nm). When the loading amount of MoS_2 was increased to 5 wt%, the highest H_2 evolution rate(274 μmol·g^(-1)·h^(-1)) was obtained. Compared with samples obtained from direct impregnation method, sonication pretreatment is favorable for the formation of 2D layered heterojuctions and thus improve the photocatalytic activity. Slightly deactivation of C_3N_4/MoS_2 composites could be observed when recycled due to the mild photocorrosion of MoS_2. Based on the band alignments of C_3N_4 and MoS_2, a possible photocatalytic mechanism was discussed, where MoS_2 could efficiently promote the separation of the photogenerated carriers of C_3N_4.