Xiaochao Zhang

In this study, organic‐inorganic hybrid photocatalysts consisting of BiOCl and soybean polysaccharide (SP) were successfully fabricated through a hydrothermal route. The effects of SP content on the crystal structure, optical properties, and charge transport behavior of BiOCl were systematically investigated. Benefiting from Bi─O─C interfacial coordination interaction and the boosted separation efficiency of photogenerated electron‑hole pairs, coupled with improved adsorption ability, the BiOCl‐SP composites delivered remarkable dual‐functional photocatalytic performance in ciprofloxacin (CIP) degradation and hydrogen peroxide (H ₂ O ₂ ) production. Among the as‐synthesized samples, BiOCl‐SP0.2 exhibited the highest photocatalytic activity, with the CIP degradation rate and H ₂ O ₂ yield nearly 1.2 and 1.1 times higher than those of pure BiOCl, respectively, accompanied by favorable stability. Radical trapping tests verified that holes (h ⁺ ) and hydroxyl radicals (•OH) acted as the main reactive species, whereas the contribution of superoxide radicals (•O ₂ ⁻ ) was relatively weak. This work not only offers a simple and effective strategy for designing high‐performance photocatalysts but also provides a new vision for the application of natural polysaccharides in environmental remediation and photocatalytic H ₂ O ₂ production.

Rapid recombination of photogenerated charge carriers, sluggish interfacial charge transport and insufficient surface active sites severely limit the photocatalytic efficiency of narrow-bandgap semiconductors. Herein, an interface-engineered CNT/g-C3N4/Cu (CNT/CN/Cu) nanocomposite was constructed to establish a dual-channel charge transfer network to synergistically enhance redox kinetics. In this architecture, highly conductive one-dimensional Carbon nanotubes (CNT) serve as oriented conductive channels rapidly shuttling photogenerated electrons from g-C3N4 to Cu co-catalysts anchored along the CNT backbone for reduction reactions. In parallel, plasmonic Cu nanoparticles intimately contacted with CN form a Schottky junction, which facilitates charge separation, extends visible-light harvesting via the localized surface plasmon resonance (LSPR) effect, and provides abundant active sites. Benefiting from the dual-channel facilitated charge transfer and LSPR-enhanced light harvesting, this architecture effectively suppresses electron–hole recombination, accelerates interfacial charge transport, and maximizes photon utilization and active-site accessibility, thereby significantly boosting the overall photocatalytic redox efficiency. Under simulated solar irradiation, the CNT/CN/Cu nanocomposite achieves 99.49% RhB degradation and 99.44% Cr(VI) reduction within 20 min, with apparent rate constants 3.18 and 2.92 times higher than those of pristine g-C3N4, respectively. This work proposes a universal interface engineering strategy for high-performance photocatalysts toward environmental remediation

Photocatalytic CO2 hydrogenation to methanol offers a sustainable pathway for carbon resource recycling and low-carbon fuel production, yet the insufficient methanol selectivity, sluggish multi-electron reduction kinetics, and ambiguous structure-activity relationship severely restrict practical development. Copper-based catalysts are uniquely suitable for methanol-oriented CO2 photoreduction, but the distinct roles of multivalent Cu species (Cu0, Cu+, and Cu2+) remain poorly understood. In this work, nitrogen-rich porous carbon spheres derived from potassium acetate activation were adopted as high-conductivity and defect-enriched supports to fabricate a series of Cu-based photocatalysts with precisely regulated valence distribution and controllable metal loading via impregnation and controlled thermal treatment. Comprehensive characterizations and photoelectrochemical tests confirm that the Cu+-dominated catalyst exhibits optimized interfacial coupling, strengthened metal-support interaction, and promoted photogenerated charge separation efficiency. Profiting from the synergistic coupling between anchored Cu+ centers and intrinsic nitrogen active sites within the porous carbon framework, the optimized catalyst achieves a prominent methanol yield of 49.90 μmol·g-1·h-1, along with excellent liquid-product selectivity and long-term cycling stability. In-depth mechanistic analysis reveals that the robust electronic interaction of Cu+-N moieties effectively promotes CO2 adsorption and inert C=O bond activation, accelerates interfacial charge transfer, and preferentially stabilizes the key CH3O* intermediate. Such favorable modulation substantially facilitates the multi-electron hydrogenation pathway toward methanol, while Cu0 and Cu2+ sites are less favorable for stabilizing critical intermediates and readily induce competitive side reactions. This study offers a rational strategy for construction of high-selectivity and high-efficiency non-noble metal photocatalysts toward CO2 green conversion.

Photoelectrocatalytic (PEC) CO ₂ reduction offers a sustainable route to address energy and environmental challenges. Herein, we designed a photoanode–cathode cooperative strategy by coupling d‐band center‐regulated BiVO ₄ photoanodes (t/m‐BiVO ₄ , m‐BiVO _4, and m‐BiVO ₄ /Bi) with a BiCu cathode to elucidate bilateral synergy in PEC CO ₂ reduction. Among the evaluated photoanodes, the m‐BiVO ₄ /Bi delivers superior photoelectrochemical performance, achieving 98.84% Faradaic efficiency toward quantified liquid products, an applied‐bias photon‐to‐current efficiency of 1.67% at 0.6 V versus reversible hydrogen electrode (RHE), and a photocurrent density of 5.59 mA·cm ⁻² at 1.23 V versus RHE. More importantly, the CO ₂ reduction pathways are tunable. In particular, the m‐BiVO ₄ /Bi‖BiCu favors the C ₂ pathway (HCOOH → C ₂ H ₅ OH) over −0.7 to −1.1 V versus RHE. The improved performance is attributed to an optimized photoanode electronic structure that facilitates hole injection to accelerate water‐oxidation kinetics, thereby supplying an optimal proton–electron flux to the cathode, boosting overall PEC activity, and creating favorable conditions conducive to C─C coupling. This work highlights photoanode electronic‐structure engineering as an effective lever to modulate the product selectivity and interfacial reaction dynamics in PEC CO ₂ reduction.

Photo-electrocatalysis has been proven to be one of the most effective methods for CO2 conversion to formic acid. Although the in-situ preparation of bismuth nanofilm electrode solves the problem of efficient Bi catalyst immobilization, the poor conductivity and high overpotentials are still key bottlenecks restricting improvement of CO2 reduction efficiency. To overcome these bottlenecks, this study introduces transition metals (M = Co, Ni, or Cu) onto Bi nanofilms via electrochemical deposition to create a series of Bi-M-t catalysts. The effect of varying the electrodeposition time (t = 5 to 30 minutes) on CO2 reduction performance was investigated.Results indicate that an optimal deposition time of 10 minutes yields the highest formate selectivity. Notably, the Bi-Cu-10 nanofilm achieved an outstanding formate Faradaic efficiency of 92.19% at -0.9 V vs. RHE. Furthermore, the catalyst demonstrated excellent stability, maintaining steady catalytic activity over 12 hours of continuous reaction.This enhanced performance is attributed to the transition metal modifications, which generate new active sites (Bi-O-M and M-O), boost electron transport capabilities, and improve resistance to photocorrosion. Ultimately, this work outlines the reaction mechanism and successfully resolves the limitations of Bi-based nanofilms, offering a promising new strategy for designing efficient in-situ modified catalysts.

The development of efficient, stable, and cost-effective metal-free photocatalysts is highly urgent for practical CO2 photoreduction, yet conventional photocatalysts typically suffer from insufficient active sites, poor mass transfer, and rapid charge recombination. Herein, self-nitrogen-functionalized hierarchical porous carbon spheres (PACs) were rationally synthesized via one-step suspension polymerization followed by mild potassium salt-assisted activation, using acrylonitrile as the sole carbon and nitrogen precursor. The pore structure engineering strategy effectively optimized the spatial distribution and accessibility of nitrogen-doped sites, enabling the synergistic integration of hierarchical porosity, large specific surface area, and high nitrogen content within a single carbon framework. As a result, the PACs prepared at 700°C with potassium acetate activation exhibited outstanding photocatalytic CO2-to-CO conversion activity and exceptional cycling durability. The CO yield reached 18.74 μmol g-1, remarkably higher than the pristine counterpart (10.63 μmol g-1), and 96.74% of the initial activity was preserved even after 20 consecutive cycles. Systematic characterizations revealed that the hierarchical porous architecture not only exposed abundant accessible nitrogen active sites but also strengthened CO2 adsorption and diffusion kinetics. Meanwhile, surface nitrogen species promoted interfacial charge separation and suppressed photogenerated electron-hole recombination. The synergistic effect between engineered porous structure and tunable nitrogen doping verified the crucial role of bidirectional “pore-nitrogen” regulation in boosting photocatalytic performance. This work provides a facile and mild activation route for constructing high-performance nitrogen-doped carbon-based metal-free photocatalysts, offering a promising paradigm for efficient and stable CO2 photoreduction.

Direct synthesis of dimethyl carbonate (DMC) from CO2 as a carbon source is considered as an extremely attractive CO2 valorization route. However, it is still limited by the thermodynamic inertness of CO2 and the intrinsic limitations associated with the synergistic activation and efficient coupling of methanol molecules. To address these challenges, this study employs crystallite boundary engineering. A kind of new CeO2 nanorod catalyst enriched with crystallite boundaries (CeO2-NR-GB) is constructed through solvothermal method, which creates a reaction interface with spatially proximal multiple active sites. Structural and electronic characterizations indicate that the crystallite boundary regions are enriched with Ce3+ species and oxygen vacancies (OV), providing a favorable microenvironment for the co-activation of CO2 and methanol. Under mild conditions of 1 MPa CO2 and 120°C, the CeO2-NR-GB catalyst achieves a DMC yield of 7.37 mmol/gcat., which is significantly superior to the control samples. In situ infrared spectroscopy confirms that the crystallite boundaries accelerate the key coupling steps between the activated methoxy species and CO2 species, thereby promoting the formation of the monomethyl carbonate (MMC) intermediate. This work elucidates the atomic-scale role of crystallite boundaries as reaction interfaces in regulating the CO2/CH3OH conversion behavior over CeO2, offering new insights for the interface-structure design of Ce-based catalysts.