Photoelectrothermocatalytic reduction of CO2 to glycol via Cu2S/MoS2-Vs octahedral heterostructure with synergistic mechanism.

The defects and interface engineering are efficient approaches to adjust the physical and chemical properties of nanomaterials to enhance catalytic performance. In this study, we report a new MOFs-driven porous Cu2S/MoS2-Vs octahedral semiconductor with heterostructure and photothermal effect. The introduction of sulfur vacancies directly improves the adsorption performance of CO2, and the formation of heterostructure significantly increases the charge transfer rate. The C-penetrating material obtained from MOFs not only acts as an octahedral skeleton support, but also gives photothermal effects under photoelectric conditions. The formation rate of sole C2 products in photoelectrocatalytic CO2 reduction by using Cu2S/MoS2-Vs heterostructure is up to 52 µM·h-1·cm-2 equal to the total electron transfer rate of 541 µM·h-1·cm-2. The carbene mechanism and reaction pathways were proposed and verified by 13CO2 isotopic labelling and operando Fourier transform infrared (FT-IR) spectra. The important intermediates of *CO2-, *CO, *CHO and *CHO-CHO were identified by operando FT-IR spectra. In the comparative experiments, the photothermal electrons are beneficial to C2 products. DFT calculations indicate that the presence of S vacancies (Vs) reduces the energy barrier for product generation.

Leaf-like MSX/TiN heterojunction photocathodes mimicking plant cell - An effective strategy to enhance photoelectrocatalytic carbon dioxide reduction and systematic mechanism investigation.

Semiconductors, such as metal oxides and metal sulfides (MSX), are widely investigated as effectively catalytic materials to convert carbon dioxide (CO2) and water into chemicals under simulated solar light. These valuable investigations might address both the energy crisis and climate change in our modern society. Herein, a novel strategy to construct leaf-like heterojunctions of VS-ZnIn2S4/TiN-x is reported. The new semiconductor heterojunctions were then applied to photoelectrocatalytic CO2 reduction, achieving excellent performance (formate formation rate of 1173.2 µM h-1 cm-2) attributed to the plant cell-like morphology and enhanced electron mobility from the heterojunction interfaces to the active sites on the surface. Our findings suggest that titanium nitride (TiN) with good conductivity can improve the photoelectrocatalytic ability of MSX through heterojunction construction. The photocathode VS-ZnIn2S4/TiN-3 exhibits 81.0 % selectivity toward C2 products by optimizing the material structure and reaction conditions. According to the systematic investigation of operando Fourier transform infrared (FTIR) spectra, common intermediates such as *COO-, *COOH, *CO, *CHO, *COCHO, and *COCH3 reported in the literature were carefully verified. Among these, the carbene specie serve as the key intermediate responsible for generating other intermediates and resulting in all products.