Unraveling the pyridinic nitrogen vacancy in carbon nitride for photo-self Fenton-like purification of organic contaminants.

This work reports a carbon nitride with pyridinic nitrogen-vacancy (N2CV-CN), which purifies organic contaminants via an in-situ photo-self Fenton-like reaction. Experiments and calculations demonstrated that the nitrogen-vacancy induces lone-paired (LP) and symmetry-unpaired electrons, promoting the formation of low-energy LP-π hybridized orbitals and helping to overcome the pairing energy required for oxygen to accept electrons. Furthermore, the nitrogen-vacancy accelerates film and intra-particle diffusion rates of organic contaminants on N2CV-CN, creating beneficial conditions for reactive oxide species to mineralize organic contaminants. Under sunlight and atmospheric oxygen, a photo-self Fenton-like reaction involving proton-coupled electron transfer occurred on the surface of N2CV-CN. Furthermore, by integrating photocatalysis with flocculation, about 99.1 % suspended substance, 45.5 % chemical oxygen demand, and 38.4 % biological oxygen demand were reduced from polluted river-water. Constructing N2CV-CN and understanding its crucial role offer theoretical and methodological insights into the in-situ purification of contaminated water bodies.

The "4 + 1" strategy fabrication of iron single-atom catalysts with selective high-valent iron-oxo species generation.

Single-atom catalysts (SACs) with atomic dispersion active sites have exhibited huge potentials in peroxymonosulfate (PMS)-based Fenton-like chemistry in water purification. However, four-N coordination metal (MN4) moieties often suffer from such problems as low selectivity and narrow workable pH. How to construct SACs in a controllable strategy with optimized electronic structures is of great challenge. Herein, an innovative strategy (i.e., the "4 + 1" fabrication) was devised to precisely modulate the first-shell coordinated microenvironment of FeN4 SAC using an additional N (SA-FeN5). This leads to almost 100% selective formation of high-valent iron-oxo [Fe(IV)═O] (steady-state concentration: 2.00 × 10-8 M) in the SA-FeN5/PMS system. In-depth theoretical calculations unveil that FeN5 configuration optimizes the electron distribution of monatomic Fe sites, which thus fosters PMS adsorption and reduces the energy barrier for Fe(IV)═O generation. SA-FeN5 was then attached to polyvinylidene difluoride membrane for a continuous flow device, showing long-term abatement of the microcontaminant. This work furnishes a general strategy for effective PMS activation and selective high-valent metal-oxo species generation by high N-coordination number regulation in SACs, which would provide guidance in the rational design of superior environmental catalysts for water purification.

Selective electrophilic attack towards organic micropollutants with superior Fenton-like activity by biochar-supported cobalt single-atom catalyst.

The global shortage of freshwater and inadequate supply of clean water have necessitated the implementation of robust technologies for wastewater purification, and Fenton-like chemistry is a highly-promising approach. However, realizing the rapid Fenton-like chemistry for high-efficiency degradation of organic micropollutants (OMs) remains challenging. Herein, one novel system was constructed by a Co single-atom catalyst activating peroxymonosulfate (PMS), and the optimal system (SA-Co-NBC-0.2/PMS) achieved unprecedented catalytic performance towards a model OM [Iohexol (IOH)], i.e., almost 100% decay ratio in only 10 min (the observed rate constant: 0.444 min-1) with high electrophilic species 1O2 (singlet oxygen) generation. Theoretical calculations unveiled that Co-N4 sites preferred to adsorb the terminal-O of PMS (more negative adsorption energy than other O sites: -32.67 kcal/mol), promoting the oxidation of PMS to generate 1O2. Iodine (I)23 (0.1097), I24 (0.1154) and I25 (0.0898) on IOH with higher f- electrophilic values were thus identified as the main attack sites. Furthermore, 16S ribosomal RNA high-throughput sequencing and quantitative structure-activity relationship analysis illustrated the environmentally-benign property of the SA-Co-NBC-0.2 and the tapering ecological risk during IOH degradation process. Significantly, this work comprehensively checked the competence of the SA-Co-NBC-0.2/PMS system for organics abatement in practical wastewater.

Efficient and Stable Photocatalytic Hydrogen Evolution Activity of Multi-Heterojunction Composite Photocatalysts: CdS and NiS2 Co-modified NaNbO3 Nanocubes.

In this study, a NaNbO3/CdS/NiS2 ternary composite photocatalyst containing no precious metals was successfully prepared by a simple hydrothermal method. The prepared ternary photocatalyst has a significant improvement in photocatalytic performance of hydrogen production from water splitting under visible light irradiation. The best sample NCN40% hydrogen production rate is 4.698 mmol g-1 h-1, which is about 24.7 times that of pure CdS sample. In addition, the stability of the composite catalyst in the long-term photocatalytic hydrogen production cycle is also improved. The reason for the enhanced hydrogen production performance may be the optimization of the microstructure of the catalyst and the reduction of photogenerated electron-hole recombination. The construction of multi-heterojunctions (NaNbO3-CdS, CdS-NiS2, and NaNbO3-NiS2) helps to reduce the recombination of carriers. Furthermore, the in-situ-formed NiS2 nanoparticles can serve as active sites for hydrogen evolution. All of these factors induced the improved photocatalytic activity of the as-prepared ternary photocatalyst.