ReS₂ Nanosheets with In Situ Formed Sulfur Vacancies for Efficient and Highly Selective Photocatalytic CO₂ Reduction

Abstract

Artificial photosynthesis can provide valuable fuels and positively impact greenhouse effects, via transforming carbon dioxide (CO2) and water (H2O) into hydrocarbons using semiconductor‐based photocatalysts. However, the inefficient charge‐carrier dissociation and transportation as well as the lack of surface active sites are two major drawbacks to boosting their activity and selectivity in photocatalytic CO2 reduction. Recently, ReS2 has received tremendous attention in the photocatalysis area due to its intriguing physicochemical properties. Nevertheless, the application of ReS2 in photocatalytic CO2 reduction is scarcely covered. Herein, a heterojunction formed between ReS2 nanosheets and CdS nanoparticles is reported, achieving an apparently raised CO production of 7.1 μmol g−1 and high selectivity of 93.4%. The as‐prepared ReS2/CdS heterojunction exhibits strengthened visible‐light absorption, high‐efficiency electron–hole pair separation/transfer, and increased adsorption/activation/reduction of CO2 on in situ created sulfur vacancies of ReS2, thus all favoring CO2 photoreduction. These are corroborated by advanced characterization techniques, e.g., synchrotron‐based X‐ray absorption near‐edge structure, and density functional theory–based computations. The findings will be of broad interest in practical design and fabrication of surface active sites and semiconductor heterojunctions for applications in catalysis, electronics, and optoelectronics.

Binary Atomically Dispersed Metal‐Site Catalysts with Core−Shell Nanostructures for O2 and CO2 Reduction Reactions

“…X-ray photoelectron spectroscopy (XPS) elucidated the composition and chemical state of the elements in the surface layers. [51] Figure 3d and S6ÀS8, Supporting Information, show the N 1s and other XPS peaks. Tables S1ÀS3, Supporting Information, summarize the surface elemental composition of different catalysts.…”

Atomically Dispersed High‐Density Al–N4 Sites in Porous Carbon for Efficient Photodriven CO2 Cycloaddition

“…Despite the adverse effects of CO 2 , as a nontoxic, abundant and renewable C 1 resource, CO 2 can be fixated into various value‐added chemical products, such as methanol, amides and cyclic carbonates, etc. [ 4–18 ] The cycloaddition of CO 2 with epoxides to produce cyclic carbonates attracts extensive attentions owing to its 100% atomic utilization and the diverse usage of products. So far, various types of homogeneous catalysts (e.g., Schiff bases, [ 19,20 ] metal salts, [ 21 ] metal complexes, [ 22,23 ] and ionic liquids [ 24,25 ] ) have been developed for the CO 2 cycloaddition reaction.…”

Challenges and prospects in the selective photoreduction of CO2 to C1 and C2 products with nanostructured materials: a review

“…The product selectivity was ascribed to the conduction band value of the Ni/TiO 2 [oxygen vacancy] [−1.3 V vs. NHE] rather than Ni/TiO 2 [−1.16 V vs. NHE] and matched with the onset reduction potential of CO 2 . Jingrun Ran and Shi-Zhang Qiao proposed a sulphide-based heterojunction semiconductor between ReS 2 nanosheets and CdS nanoparticles for the photoreduction of CO 2 to CO. 166 The higher CO 2 photoreduction activity was ascribed to the in situ generation of sulphur vacancies on the ReS 2 sites upon light irradiation. The in situ formed sulphur vacancies provided effective adsorption and activation of CO 2 molecules, the separation/migration of photogenerated charge carriers, and the reduction of CO 2 to CO.…”