Coverage-sensitive mechanism of electrochemical NO reduction on the SrTiO3(001) surface: a DFT investigation.

Due to its adverse environmental and human health hazards, addressing the elimination of nitric oxide (NO) has become a pressing concern for modern society. Currently, electrochemical NO reduction provides a new alternative to traditional selective catalytic reduction technology under mild reaction conditions. However, the complexity and variability of products make the coverage of NO an influencing factor that needs to be investigated. Hence, this study delves into the coverage-sensitive mechanism of electrochemical NO reduction on cost-effective perovskite catalysts, using SrTiO3 as an example, through density functional theory calculations. Phase diagrams analysis reveals that the coverage range from 0.25 to 1.00 monolayer (ML) coverage is favorable for NO adsorption. Gibbs free energy results indicate that the selectivity is significantly influenced by NO coverage. NH3 is likely to be generated at low coverage, while N2O and N2 are more likely to be produced at high coverage through a dimer mechanism. Charge analysis suggests that the charge transfer and Ti-O bond strength between reactants and catalysts are crucial factors. This work not only provides deep insights into coverage-sensitive reaction mechanisms but also is a guideline towards further rational design of high-performance perovskite catalysts.

Fabrication of p-n Heterostructured Photocatalysts with Triazine-Based Covalent Organic Framework and CuInS2 for High-Efficiency CO2 Reduction.

The application of covalent organic frameworks (COFs) for the photocatalytic reduction of CO2 is mostly limited by severe charge recombination and low sunlight utilization. Herein, a triazine-based COF with an electron-rich and large π-conjugated system (TCOF) was employed as a building block and integrated with CuInS2 (CIS) to construct a noble-metal-free and high-efficiency photocatalyst for CO2 reduction. The in situ growth of CIS nanosheets on TCOF creates a p-n heterojunction, named CIS@TCOF. Compared with TCOF, the CIS@TCOF heterostructure exhibits a dramatically boosted photocatalytic performance in the reduction of CO2. The produced HCOOH yield over 10 wt % CIS@TCOF can be up to 171.2 µmol g-1 h-1 under visible light irradiation with good reproducibility, which is about 3 times as high as that over TCOF. Further in-depth studies indicate that the introduction of CIS not only enhances the visible light utilization but also restrains the recombination of photogenerated electron-hole pairs efficiently and facilitates the photoinduced charge transfer via the p-n heterojunction system due to the unique structural and compositional features. This research shows the great potential of COFs as efficient photocatalytic carbon fixation materials and provides a versatile route to construct semiconductor-COF heterostructures for photocatalysis.