The development of high-efficiency photocatalysts is of great importance to realize robust solar-driven CO2 conversion; however, the low carrier separation efficiency and poor light absorption ability usually limit the performance of the photocatalysts. Herein, a hollow In2S3/polymeric carbon nitride (IS/CN) heterojunction was prepared via electrostatic self-assembly and in situ sulfidation under solvothermal conditions. The intimate interfacial contact between the IS and CN facilitates the construction of an effective heterojunction, as demonstrated by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The optimized IS/CN-5 sample exhibits a high CO evolution rate of 483.4 μmol g–1 h–1, which is 99 and 6 times as high as that of IS and CN, respectively. The improved charge separation and transfer efficiency, the hollow nanotube structure, and the enhanced CO2 adsorption ability are the reasons for the excellent photocatalytic activity. Besides, a possible photocatalytic mechanism of CO2 reduction by the IS/CN heterojunction was proposed on the basis of the band structures. This work provides an effective and facile strategy to construct hollow semiconductor heterojunctions for photocatalytic applications.

Realizing high-efficiency solar-driven CO2 reduction to chemicals and fuels requires high-performance photocatalysts with high utilization efficiency of solar light, efficient charge separation and transfer, and robust adsorption capacity for CO2. In this work, a tubular In2O3–C/CdIn2S4 (IOC/CIS) ternary heterojunction with an intimate interfacial contact was fabricated by pyrolysis of In-MIL-68 and subsequent solvothermal synthesis of CdIn2S4. The construction of a heterojunction promotes the separation and transfer efficiency of photogenerated carriers. The introduction of carbon not only accelerates the interfacial charge migration but also enhances light absorption and CO2 adsorption. The resulting 5IOC/CIS sample presents a remarkably improved photocatalytic CO2 reduction activity with a CO generation rate of 2432 μmol g–1 h–1, much higher than that of the In2O3/CdIn2S4 (IO/CIS) heterojunction (1906 μmol g–1 h–1). Furthermore, the type II charge transfer mechanism of the heterojunction was confirmed by the electron paramagnetic resonance characterization. This work provides new insight into the design and preparation of a highly efficient hollow heterojunction for photocatalytic applications.