The pollution of phenol wastewater is becoming worse. In this paper, a 2D/2D nanosheet-like ZnTiO₃/Bi₂WO₆ S-Scheme heterojunction was synthesized for the first time through a two-step calcination method and a hydrothermal method. In order to improve the separation efficiency of photogenerated carriers, the S-Scheme heterojunction charge-transfer path was designed and constructed, the photoelectrocatalytic effect of the applied electric field was utilized, and the photoelectric coupling catalytic degradation performance was greatly enhanced. When the applied voltage was +0.5 V, the ZnTiO₃/Bi₂WO₆ molar ratio of 1.5:1 had highest degradation rate under visible light: the degradation rate was 93%, and the kinetic rate was 3.6 times higher than that of pure Bi₂WO₆. Moreover, the stability of the composite photoelectrocatalyst was excellent: the photoelectrocatalytic degradation rate of the photoelectrocatalyst remained above 90% after five cycles. In addition, through electrochemical analysis, XRD, XPS, TEM, radical trapping experiments, and valence band spectroscopy, we found that the S-scheme heterojunction was constructed between the two semiconductors, which effectively retained the redox ability of the two semiconductors. This provides new insights for the construction of a two-component direct S-scheme heterojunction as well as a feasible new solution for the treatment of phenol wastewater pollution.

With the development of the global economy, large amounts of fossil fuels are being burned, causing a severe energy crisis and climate change. Photocatalytic CO₂ reduction is a clean and environmentally friendly method to convert CO₂ into hydrocarbon fuel, providing a feasible solution to the global energy crisis and climate problems. Photocatalytic CO₂ reduction has three key steps: solar energy absorption, electron transfer, and CO₂ catalytic reduction. The previous literature has obtained many significant results around the first two steps, while in the third step, there are few results due to the need to add a co-catalyst. In general, the co-catalysts have three essential roles: (1) promoting the separation of photoexcited electron–hole pairs, (2) inhibiting side reactions, and (3) improving the selectivity of target products. This paper summarizes different types of photocatalysts for photocatalytic CO₂ reduction, the reaction mechanisms are illustrated, and the application prospects are prospected.

Two-dimensional carbon materials and their derivatives are widely applied as promising electrocatalysts and supports of single-atom sites. Theoretical investigations of 2D carbon materials are usually based on planar models, yet ignore local curvature brought on by possible surface distortion, which can be significant to the exact catalytic performance as has been realized in latest research. In this work, the curvature-influenced electrocatalytic nitrogen reduction reaction (NRR) reactivity of heme-like FeN₄ single-atom site was predicted by a first-principle study, with FeN₄-CNT(m,m) (m = 5~10) models adopted as local curvature models. The results showed that a larger local curvature is favored for NRR, with a lower limiting potential and higher N₂ adsorption affinity, while a smaller local curvature shows lower NH₃ desorption energy and is beneficial for catalyst recovery. Using electronic structures and logarithm fitting, we also found that FeN₄-CNT(5,5) shows an intermediate-spin state, which is different from the high-spin state exhibited by other FeN₄-CNT(m,m) (m = 6~10) models with a smaller local curvature.

Quercetin 2,4-dioxygenase (QueD) with various transition metal ion co-factors shows great differences, but the internal reasons have not been illustrated in detail. In order to explore the effects of metal ion centers on the catalytic reactivity of QueD, we calculated and compared the minimum energy crossing point (MECP) of dioxygen from the relatively stable triplet state to the active singlet state under different conditions by using the DFT method. It was found that the metal ions play a more important role in the activation of dioxygen compared with the substrate and the protein environment. Simultaneously, the catalytic reactions of the bacterial QueDs containing six different transition metal ions were studied by the QM/MM approach, and we finally obtained the reactivity sequence of metal ions, Ni²⁺ > Co²⁺ > Zn²⁺ > Mn²⁺ > Fe²⁺ > Cu²⁺, which is basically consistent with the previous experimental results. Our calculation results indicate that metal ions act as Lewis acids in the reaction to stabilize the substrate anion and the subsequent superoxo and peroxo species in the reaction, and promote the proton coupled electron transfer (PCET) process. Furthermore, the coordination tendencies of transition metal ion centers also have important effects on the catalytic cycle. These findings have general implications on metalloenzymes, which can expand our understanding on how various metal ions play their key role in modulating catalytic reactivity.