Constructing heterojunctions between two semiconductors with matched band structure is an effective strategy to acquire high-efficiency photocatalysts. The S-scheme heterojunction system has shown great potential in facilitating separation and transfer of photogenerated carriers, as well as acquiring strong photoredox ability. Herein, a 0D/2D S-Scheme heterojunction material involving CeO2 quantum dots and polymeric carbon nitride (CeO2 /PCN) is designed and constructed by in situ wet chemistry with subsequent heat treatment. This S-scheme heterojunction material shows high-efficiency photocatalytic sterilization rate (88.1 %) towards Staphylococcus aureus (S. aureus) under visible-light irradiation (λ≥420 nm), which is 2.7 and 8.2 times that of pure CeO2 (32.2 %) and PCN (10.7 %), respectively. Strong evidence of S-scheme charge transfer path is verified by theoretical calculations, in situ irradiated X-ray photoelectron spectroscopy, and electron paramagnetic resonance.

Designing a 0D/2D S-Scheme Heterojunction over Polymeric Carbon Nitride for Visible-Light Photocatalytic Inactivation of Bacteria.

The development of efficient photocatalysts for the production of hydrogen peroxide (H2O2) is a promising strategy to realize solar-to-chemical energy conversion. Graphitic carbon nitride (g-C3N4) presents giant potential for photocatalytic H2O2 production, but the sluggish charge separation depresses its photocatalytic performance. Herein, an interfacial Schottky junction composed of Ti3C2 nanosheets and porous g-C3N4 nanosheets (TC/pCN) is constructed by a facile electrostatic self-assembly route to significantly boost the spatial charge separation to promote the activation of molecular oxygen for H2O2 production. As the optimal sample, TC/pCN-2 possesses the highest H2O2 production rate (2.20 μmol L−1 min−1) under visible light irradiation (λ > 420 nm), which is about 2.1 times than that of the porous g-C3N4. The results of superoxide radical detection and rotating disk electrode measurement suggest that the two-step single-electron reduction of oxygen is the predominant reaction step during this photocatalytic H2O2 production process. The enhanced photocatalytic performance is ascribed to the formation of Schottky junction and subsequent built-in electric field at their interface, which accelerate the spatial charge separation and restrain the charge recombination. This work provides an in-depth understanding of the mechanism of photocatalytic H2O2 production, and gives ideas for the design of highly active materials for photocatalytic H2O2 production.

Ti3C2 Mxene/porous g-C3N4 interfacial Schottky junction for boosting spatial charge separation in photocatalytic H2O2 production

Advanced oxidation has great promise in the degradation of organic pollutants, but the high preparation requirements, adjustment difficulty, high cost, potential hazard, and low repeatability of catalysts limit the practical applications of this technology. In this study, a metal-free biochar-based catalyst derived from biomass fiber was prepared assisted by graphitization and nitrogen incorporation (PGBF-N). The heterogeneous catalysis of peroxymonosulfate (PMS) was triggered by PGBF-N with degradation rate 7 times higher than that of pristine biochar. The high catalytic efficiency was attributed to the accelerated electron transfer originated from the high degree of graphitization and nitrogen functionalization of PGBF-N, in which the non-radical pathways containing carbon-bridge and singlet oxygen-mediated oxidation were elucidated as the predominant pathways for tetracycline degradation, instead of the dominant role of radical pathway in pristine biochar. Vacancies and defective edges formed on sp2-hybridized carbon framework as well as the nitrogen doping sites and ketonic group of PGNF-N were considered as possible active sites. The excellent degradation rate in actual water indicated that the PGBF-N/PMS system dominated by non-radical pathway exhibited a high anti-interference ability to surrounding organic or inorganic compounds. This study provides a facile protocol for converting biomass fiber into functional catalyst and enables underlying insight in mediating dominated degradation mechanism of heterogeneous catalysis by biochar fiber.

Nitrogen-doped biochar fiber with graphitization from Boehmeria nivea for promoted peroxymonosulfate activation and non-radical degradation pathways with enhancing electron transfer

Transforming CO2 into fuels by utilizing sunlight is promising to synchronously overcome global warming and energy-supply issues. It is crucial to design efficient photocatalysts with intriguing features such as robust light-harvesting ability, strong redox potential, high charge-separation, and excellent durability. Hitherto, a single-component photocatalyst is incapable to simultaneously meet all these criteria. Inspired by natural photosynthesis, constructing artificial Z-scheme photocatalysts provides a facile way to conquer these bottlenecks. In this review, we firstly introduce the fundamentals of photocatalytic CO2 reduction and Z-scheme systems. Thereafter we discuss state-of-the-art Z-scheme photocatalytic CO2 reduction, whereby special attention is placed on the predominant factors that affect photoactivity. Additionally, further modifications that are important for efficient photocatalysis are reviewed.

Z-Scheme Photocatalytic Systems for Carbon Dioxide Reduction: Where Are We Now?

Emerging single atom catalysts (SACs), especially carbon-based SACs are appealing materials in environmental catalysis because of their ultrahigh performances, environmental friendliness, structural/chemical robustness, and the maximum utilization of active metal sites. The metal centres, carbon matrixes, and coordination characteristics collectively determine the electronic features of carbon-based SACs, and their behaviours in catalysing peroxide activation and efficiencies in advanced oxidation processes (AOPs). However, there is lack of a comprehensive and critical review reporting the successful marriage of carbon-based SACs in AOP-based remediation technologies. It is particularly necessary to systematically compare and reveal the catalytic sites and the associated mechanisms of carbon-based SACs in diverse AOP systems. In this review, we highlight the synthetic strategies, characterisation, and computation of carbon-based SACs, and for the first time, showcase their innovative applications in AOP technologies. We unveil the origins of versatile catalytic oxidation pathways in different AOP systems and the mechanisms of micropollutant degradation over carbon-based SACs, distinguished from the upsized counterparts (metals/oxides and carbon substrates). We also provide directions to the rational design of on-demand SACs for green chemistry and environmental sustainability. Also, we suggest a designated and integrated experimental/theoretical protocol for revealing the structure-catalysis relations of SACs in AOP applications, and propose the prospects for future opportunities and challenges.

Single-atom catalysis in advanced oxidation processes for environmental remediation.

Artificial Z-scheme photocatalytic system: What have been done and where to go?

Facile construction of hierarchical flower-like Z-scheme AgBr/Bi2WO6 photocatalysts for effective removal of tetracycline: Degradation pathways and mechanism

Assembly of AgI nanoparticles and ultrathin g-C3N4 nanosheets codecorated Bi2WO6 direct dual Z-scheme photocatalyst: An efficient, sustainable and heterogeneous catalyst with enhanced photocatalytic performance

In-situ synthesis of facet-dependent BiVO4/Ag3PO4/PANI photocatalyst with enhanced visible-light-induced photocatalytic degradation performance: Synergism of interfacial coupling and hole-transfer

Jing Li

Papers

Artificial Z-scheme photocatalytic system: What have been done and where to go?

Facile construction of hierarchical flower-like Z-scheme AgBr/Bi2WO6 photocatalysts for effective removal of tetracycline: Degradation pathways and mechanism

Assembly of AgI nanoparticles and ultrathin g-C3N4 nanosheets codecorated Bi2WO6 direct dual Z-scheme photocatalyst: An efficient, sustainable and heterogeneous catalyst with enhanced photocatalytic performance

In-situ synthesis of facet-dependent BiVO4/Ag3PO4/PANI photocatalyst with enhanced visible-light-induced photocatalytic degradation performance: Synergism of interfacial coupling and hole-transfer

Mn doped magnetic biochar as persulfate activator for the degradation of tetracycline