Boosting photocatalytic NO oxidation mediated by high redox charge carriers from visible light-driven C3N4/UiO-67 S-scheme heterojunction photocatalyst.

The construction of CN/UiO-67 (CNU) S-scheme heterojunction composites through in situ formation of UiO-67 on carbon nitride (C3N4) helps to address the limitations of carbon nitride (CN) in photocatalytic NO elimination. The optimized CNU3 demonstrates superior photocatalytic efficiency, which is attributed to electronic channels constructed by Zr-N bonds and S-scheme electron transport mechanism, effectively promoting the efficient separation of photogenerated charge carriers with high redox potentials. Density Functional Theory (DFT) calculations reveal redistributed electronic orbitals in CNU3, with progressive and continuous energy levels near the Fermi level, which bolsters electronic conduction. Comprehensive quenching experiments, Electron Paramagnetic Resonance (EPR), and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) analyses highlight a synergistic interplay of electrons, holes, and superoxide radicals in CNU3, inhibiting the generation of toxic nitrogen oxide intermediates and culminating in highly efficient photocatalytic NO oxidation. This study not only elucidates the mechanisms underpinning the enhanced performance of CNU3 heterojunctions but also offers new perspectives on the preparation and interfacial charge separation of heterojunction photocatalysts.

Switching on photocatalytic NO oxidation and proton reduction of NH2-MIL-125(Ti) by convenient linker defect engineering.

Photocatalysis technology has been widely adopted to abate typical air pollutants. Nevertheless, developing photocatalysts aimed at improving photocatalytic efficiency is a challenge. Herein, the linker-defect NH2-MIL-125(Ti) photocatalyst was synthesized through a convenient one-step heating-stirring method (just adjusting multiple temperatures) to firstly realize efficient photocatalytic performances of NO removal and hydrogen evolution. The optimal sample (named 65-NMIL) with a linker-defect content of 32.08% exhibited a NO removal ratio of 65.49%, which was 37.57% higher than that of pristine NH2-MIL-125(Ti), and displayed better H2-production activity. Through ESR, it was confirmed that 65-NMIL can generate more •O2- and •OH under visible light, and the radical trapping experiment further proved that •O2- played a more important role in photocatalytic activity. Moreover, the photocatalytic NO oxidation process was also monitored by in situ DRIFTS, it was found that the defective samples could promote the oxidation of NO and intermediates to the final product (NO3-). On the basis of the above-mentioned photocatalytic experimental results and characterization, a possible mechanism or pathway was proposed and illustrated. This work can provide a new strategy for the subsequent defect engineering for photocatalytic MOFs materials to further solve environmental and energy crises.