Construction of a heterojunction with fast charge transport channels for photocatalytic hydrogen evolution via a synergistic strategy of Co-doping and crystal plane modulation.

Carrier spatial separation efficiency and active electron density are the key factors affecting photocatalytic hydrogen evolution activity. Heterojunction catalysts with fast charge separation and directed electron transport systems were successfully prepared by a synergistic modification strategy of transition metal (Co) doping and crystal plane modulation. The optimized electronic structure and enhanced reaction kinetics enabled unidirectional electron transfer. Photocatalytic results show that CdS(002)/Co-C3N4 exhibits remarkable hydrogen evolution activity (991.2 µmol h-1 g-1) in the absence of a co-catalyst, which is 37.0 and 3.4 times higher than that of C3N4 (26.8 µmol h-1 g-1) and Co-C3N4 (294.6 µmol h-1 g-1), respectively. Density functional theory (DFT) calculations indicate that the enhanced catalytic activity of CdS(002)/Co-C3N4 is attributed to the reduced electron-hole recombination rate and the increased electron density at the active site. This work provides a new idea for the design of photocatalysts with directed charge transport channels from the perspective of re-optimizing heterojunctions.

A MXene-based multiple catalyst for highly efficient photocatalytic removal of nitrate.

Photocatalytic removal of nitrate in wastewater has attracted wide attention because of its simple operation and environmental protection. However, the preparation of photocatalysts with high efficiency and high nitrogen selectivity is still a challenge. In this paper, TiO2 is grown in situ on Ti3C2 MXene by a simple calcination method and modified with silver particles. The presence of Ti3C2 reduces the recombination rate of photogenerated electrons and generates more photogenerated electrons. At the same time, the silver particles also increase the photoelectron density and further improve the carrier separation of the catalyst. Due to its unique structure and optical properties, the prepared photocatalyst shows an excellent nitrate removal rate under a high-pressure mercury lamp. At 500 mgN/L, the nitrate removal rate reaches 96.1%, and the nitrogen selectivity reaches 92.6%. Even after 5 cycles, the prepared photocatalyst still maintains a high nitrate photocatalytic removal efficiency (89%). The electron transfer path is verified by density functional theory calculations.

Fe-based MOFs@Pd@COFs with spatial confinement effect and electron transfer synergy of highly dispersed Pd nanoparticles for Suzuki-Miyaura coupling reaction.

Controlling the spatial confinement effect and highly dispersed Pd nanoparticles (NPs) can help to improve applicability in catalysis, energy conversion, and separation. However, the nonspatial confinement effect, agglomeration of Pd NPs of catalyst and harsh reaction conditions have become the urgent problems to be solved in Suzuki-Miyaura cross-coupling reaction. Herein, we report the first application of a new MOFs@COFs by using core with metal organic frameworks (MOFs) NH2-MIL-101(Fe) and shell with covalent organic frameworks (COFs) for loading Pd NPs. The quickly formation of a transition state, the highly dispersed Pd NPs and the advancedly spatial confinement effect were achieved by coupling Fe base synergistic active components, electron-oriented anchoring with controlling pore scale, respectively. Most notably, as a proof-of-concept application, the high catalytic activity of NH2-MIL-101(Fe)@Pd@COFs(3 + 3) in catalysis is elucidated for Suzuki-Miyaura coupling reaction by the broad scope of the reactants and the preeminent yields of the products, together with excellent stability and recoverability. With this strategy, the mechanism of Suzuki-Miyaura coupling reaction was verified by examining the catalytic activity. We hope that our approach can further facilitate the study of the design and use of functional MOFs@Pd@COFs materials.