Plastic waste valorization offers significant potential for advancing the circular economy, and photocatalysis presents a sustainable strategy for this purpose. In this work, we report the defect engineering of graphitic carbon nitride (g-CN) for improving its performance in the photocatalytic reforming of polystyrene (PS). Specifically, two distinct vacancy defects are constructed for overcoming the limits in the activity of pristine g-CN. And it is found that the catalyst with carbon vacancies engineered (CV-CN) achieves a remarkable PS conversion rate of 2.02 mmolCarbon & sdot;gcat-1 & sdot;h-1, doubling that of pristine g-CN. Meanwhile, it also maintains a well selectivity of around 80% toward valuable organic products like benzoic acid (BA). In contrast, the nitrogen-vacancy-rich catalyst (NV-CN) favor deep oxidation, reducing organics selectivity. Mechanistic investigations reveal that both vacancies-engineered samples facilitate photogenerated charge generation and transport, while their distinct electronic environments bring about divergent reactive oxygen species (ROS) evolution pathways, which are closed related to the product selectivity. CV-CN selectively enriches singlet oxygen (1O2), which is closed associated with BA formation, and also facilitates BA desorption, thereby improving BA selectivity and inhibiting the over-oxidation. Conversely, NV-CN, with its strong O2 adsorption affinity, generates substantial superoxide (O2 center dot-) and hydroxyl (center dot OH) radicals, favoring products over-oxidation and COx accumulation. This work establishes a clear structure-performances relationship, correlating vacancy identity with ROS and product distribution, providing a useful guidance for developing advanced photocatalysts towards plastics upcycling.

Catalytic oxidation of H2 S at room temperature has been regarded as a promising method for removing malodorous H2 S pollution. However, most of the existing research has primarily focused on developing catalysts with high sulfur capacity, i.e. , high elemental sulfur selectivity, which was unfavored for the catalyst regeneration. The present work prioritizes efficient water wash regeneration as a key objective. A series of activated carbon fibers (ACFs) was synthesized using a synergistic strategy of "nitrogen dopingplasma defect engineering". The certain amount of nitrogen species ensured a certain level of sulfur capacity. The plasma defect engineering can result in the enhancement of surface acidity and defect density, which worked together to make the catalyst with high sulfate selectivity. The O2 -plasma modified NH3 ACF-O10 cat alyst achieved the best catalytic performance with appropriate sulfur capacity (0.21 g/g) and highest sulfate selectivity (85.40 %). Importantly, it can be easily regenerated by water wash, and almost 83.33 % sulfur capacity can be recovered. Besides, superoxide radicals (O2 center dot - ) were identified as the primary reactive oxygen species for the reaction. And the reaction obeyed a Langmuir-Hinshelwood (L-H) like mechanism, i.e. , the reaction was proceeded via chemisorbed H2 S and O2 center dot - , which was adsorbed and activated by defect. (c) 2026 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

In this study, a series of V2O5-MoO3/TiO2 (VMo/Ti) catalysts were prepared using TiO2 supports with varying specific surface area for selective catalytic reduction of NOx by ammonia (NH3-SCR). The activity tests revealed that the NO conversion of different samples showed a volcano-type variation with surface area rising, where the VMo/Ti-S3 catalyst with moderate surface area possessed the best SCR activity (>80% NO conversion at 250 °C). Meanwhile, the SO2 oxidation ratio decreased at an elevated surface area. At 350 °C, the SO2 oxidation ratio of VMo/Ti-S1 catalyst with lowest surface area was about 4.4%, which was around 4 times that of VMo/Ti-S4 sample with highest surface area. Characterization results indicated that, as the surface area increased, both the redox capacity and surface acidity were enhanced. And the vanadium oxides became less polymeric with a gradual increased ratio in dimeric vanadium species and finally more monomer VOx formation, corresponding to the highest SCR activity of VMo/Ti-S3 catalyst. Additionally, the characterization results indicated that the chemisorption of SO2 was inhibited on high-surface-area catalysts, which was consistent with DFT results. And DFT simulations also confirmed an increased energy barrier for SO2 oxidation to generate SO3 process on less polymeric vanadium species. Both the results above indicated the critical role of vanadium polymerization state in SCR activity and SO2 oxidation. This work offers new insights into the development of efficient SCR catalysts with low SO2 oxidation rates for industrial applications.

ABSTRACT The direct conversion of methane into value‐added chemicals under mild conditions offers a sustainable pathway to utilize this abundant hydrocarbon feedstock and mitigate greenhouse gas emissions. However, the thermodynamic stability of the C─H bond and the propensity for product overoxidation pose formidable scientific challenges. This review systematically summarizes recent breakthroughs in electrocatalytic, photocatalytic, and photoelectrocatalytic strategies for methane valorization. We critically examine fundamental activation mechanisms, structure‐property relationships in catalyst design, and strategies to tune product selectivity toward liquid oxygenates and coupled hydrocarbons. Beyond material innovation, this review places particular emphasis on reactor engineering, elaborating on the evolution from conventional batch systems to advanced continuous flow architectures, such as gas convection electrodes and hierarchical triphase diffusion architectures, to overcome mass transfer limitations. Finally, we provide forward looking perspectives on emerging frontiers, including data‐driven catalyst discovery and integrated system design, to guide the transition from laboratory research to industrial implementation.

Layered double hydroxides (LDHs), with their atomically tunable layer composition, abundant surface coordination sites, and modifiable two-dimensional confined interlayer space, offer an ideal ‘atomic canvas’ for the precise design and in situ modulation of single-atom catalysts. The review elaborates on this core concept, systematically presenting synthesis strategies for the precise construction of single-atom sites on LDHs, including in situ growth, post-synthetic anchoring, and topological transformation pathways. Furthermore, the article focuses on leveraging the dynamic properties and synergistic effects of the LDH supports. Multi-dimensional strategies, such as electronic modulation, coordination engineering, interfacial synergy, and reaction pathway reconstruction, are discussed for the rational enhancement of catalytic performance and functional expansion. Despite rapid progress, challenges remain, including the stability of single atoms under high loading, elucidation of dynamic catalytic mechanisms, and scalable fabrication. Future research should integrate advanced characterization and theoretical calculations to clarify the dynamic interactions between the ‘canvas’ and single atoms, and promote the practical application of these high-performance catalysts in energy conversion and green synthesis.

In this study, the promotional effect of Ce and Nb doping on Cu/TiO2 catalyst for diethylamine catalytic degradation was investigated. The activity tests reveal that the Ce and Nb modification can facilitate the rising of mineralization rate and N2 selectivity during diethylamine degradation, achieving over 90% mineralization rate at 250-450 degrees C, along with N2 selectivity exceeding 80% within 300-400 degrees C. Characterization results show that the co-addition of Ce and Nb induces strong interactions with Cu species and increases surface Br & oslash;nsted acid sites. Crucially, the enhanced redox capability derived from interactions guarantees good catalytic activity and mineralization rate. Additionally, the increased Br & oslash;nsted acidity from Nb doping can suppress the formation of NCO(a) species, resulting in less generation of NOx from NCO(a) oxidation. Moreover, the enhanced Br & oslash;nsted acidity can promote the internal SCR reaction, which also reduces the NOx emission. This work could offer valuable insights for designing catalysts with superior catalytic performance for amine-like volatile organic compounds (VOCs) degradation. (c) 2024 Chinese Society of Rare Earths. Published by Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

The electrocatalytic reduction of CO2 into C2+ products using Cu-based catalysts offers a promising strategy for CO2 utilization. However, unsatisfactory catalytic selectivity for C2+ products and complex catalyst synthesis hinder its practical application. Herein, we report a rapid, cost-effective, and efficient electrodeposition method to synthesize Cu0/Cu1 heterointerfaces. The optimal catalyst, Cu/CP-ed-5, achieves a high C2+ faradaic efficiency of 61.2% (15.3 mA/cm2) at-0.88 V in an H-cell and 62.02% (188.13 mA/cm2) at-1.26 V in a flow cell, together with reasonable stability. Based on the operando Raman spectroscopy and DFT calculations, the enriched Cu0/Cu1 heterointerfaces of Cu/CP-ed-5 sample would facilitate the CO2 activation, *CO coverage and *CO-*CO coupling, thereby promoting the C2+ productivity. Furthermore, the lower Cu0/Cul ratio of Cu/CP-ed-5 sample allowed more efficient CO2 reduction to C2+ products on Cu0/Cu1 heterointerfaces. This work provided a facile synthesis method to modulate Cu electronic structure for directing CO2 reduction pathways.

Directly burning methane for energy production wastes chemical potential and exacerbates CO2 emissions, while catalytic conversion into high-value fuel/chemicals provides economic and environmental sustainability. Photocatalytic CH4 conversion has emerged as a transformative technology, enabling selective oxidation under ambient conditions to directly synthesize value-added organic compounds. This addresses the dual challenges of climate mitigation and sustainable energy conversion. This review systematically examines the development of photocatalytic CH4 conversion, with three key dimensions. Firstly, we elucidate fundamental reaction mechanisms governing CH4 activation, emphasizing critical steps such as C–H bond scission via charge transfer, intermediate stabilization, and product desorption kinetics. Subsequently, we classify emerging photocatalytic pathways (partial oxidation, coupling, and reforming) and analyze material innovations. Finally, the challenges of the current photocatalytic CH4 conversion system and catalyst development were discussed, and perspectives were presented. The overarching objective of this work is to provide a comprehensive roadmap for the development of solar-driven CH4 conversion systems that are aligned with global carbon neutrality goals.

The efficient capture of elemental mercury (Hg-0) from high-SO2 flue gas in non-ferrous smelting remains a key environmental challenge. In this study, a mixed-valence copper sulfide adsorbent (Cu1.8S) was rationally designed via a facile hydrothermal method using CTAB and hexamethylenetetramine as structure-directing agents, which integrates Cu+ and Cu2+ sites into a synergistic redox cycle, enabling exceptional Hg-0 uptake capacity and strong SO2 resistance. Compared with CuS and Cu2S, Cu1.8S achieves virtually complete Hg-0 removal (>99%) over 120 min at 50-100 degrees C and retains > 95% efficiency even under 3000 ppm SO2, surpassing most reported metal-sulfide sorbents. Comprehensive characterization (XRD, SEM, XPS, EPR, Hg-TPD, et al) reveals that the dynamic Cu+ <-> Cu2+ interconversion facilitates continuous electron transfer, regenerates more active sites, and stabilizes reactive sulfur species (S2-, S-x(2-)). This cyclic mechanism not only promotes Hg-0 oxidation and immobilization as HgS but also mitigates SO2-induced deactivation by preserving the active surface. Kinetic and thermodynamic analyses confirm Hg-0 adsorption of Cu1.8S is jointly governed by interfacial diffusion and chemical adsorption, with a high Hg-binding energy of 31.95 kJ mol(-1), reflecting robust chemisorption. The work demonstrates a novel valence-engineering strategy to design sulfur-tolerant mercury adsorbents, offering a practical and efficient solution for Hg-0 abatement in high-SO2 industrial flue gases.

Ammonia (NH3) has emerged as a promising zero‑carbon energy source for energy and transportation. However, its utilization leads to the emission of NH3, which contributes to PM2.5 formation and disrupts the global nitrogen cycle. Selective catalytic oxidation (SCO) represents a mainstream technology for NH3 treatment, yet achieving both sufficient activity and high N2 selectivity across a broad temperature window remains challenging. Here, a core-shell Pt@Cu-ZSM-5 catalyst was employed for NH3 catalytic abatement by encapsulating metallic Pt clusters (Pt0) inside the channels of Cu ion-exchanged ZSM-5. The optimal sample achieved a complete NH3 conversion below 250 °C and maintained over 92% N2 selectivity from 250 to 500 °C due to the synergism between the Pt-Cu dual sites. Mechanistic studies revealed that NH3 oxidation preferentially occurred on Pt0 sites with excellent redox capacity to produce N2O and NOx at relatively low and high temperatures, respectively. And the presence of Cu ions (Cuδ+) could efficiently both inhibit the formation of N2O on Pt0 sites and reduce NOx emission, thereby improving the N2 selectivity. At relatively low temperatures, NH3-solvated Cu+(NH3)2 could migrate to the adjacent Pt sites and reduce the adsorbed NO* species from NH3 oxidation, damping the formation of N2O. At high temperatures, the NO and NO2 emitted from Pt0 sites could be reduced on Cuδ+ sites via a typical selective catalytic reduction. This study provides new insights into the rational design of bifunctional SCO catalysts and offers a comprehensive understanding of the synergistic effects in Pt-Cu dual-site systems.

Preventing postoperative infection is the key to ensuring the long-term survival of biological implants. However, polyetheretherketone (PEEK) widely used at present, due to its insufficient antibacterial performance, is difficult to meet the strict requirements of clinical practice for the anti-infection ability of implant materials. Herein, S-nitrosoglutathione (GSNO) loaded polydopamine (PDA) coatings were fabricated on sulfonated PEEK (SPEEK) surfaces to construct the SPEEK-PDA-GSNO platform. Upon 808 nm near-infrared (NIR) laser irradiation, the hyperthermia generated by PDA accelerates release of nitric oxide (NO). The combination of photothermal therapy (PTT) and NO can effectively eradicate bacteria and disrupt bacterial biofilms. In vivo evaluation further confirmed the NIR-responsive antibacterial efficacy of SPEEK-PDA-GSNO. This work presents a dual-mode synergistic antibacterial strategy to enhance the antimicrobial performance of PEEK implants.

In this work, S-scheme Ti-MOF/Cs2AgBiBr6 heterojunction photocatalysts were developed via an in situ self-assembly strategy, achieving satisfactory interfacial contact, matched band alignment, enhanced charge separation, and redox activity. The optimized Ti-MOF/Cs2AgBiBr6 composite exhibited remarkable photocatalytic performance toward benzyl alcohol oxidation under visible light, achieving > 99 % conversion and selectivity without external oxidants and sacrificial agents. It represents a fourfold enhancement over individual components, while maintaining broad substrate applicability and excellent cycling stability. The S-scheme configuration ensures sufficient oxidation potential compared with conventional Type-II systems. This work addresses challenges of limited bandgap tunability and inefficient carrier transport in selective aromatic alcohol oxidation, establishing a promising strategy for designing efficient lead-free perovskite photocatalysts toward sustainable organic transformations.

In this study, CePO4 supported Cu-Ce catalysts with different spatial distributions of active sites were developed to investigate the simultaneous catalytic removal of NOx and CO. The physically mixed CuCe-P-10 catalyst exhibits outstanding performance, achieving over 90% NO conversion and complete CO conversion within 250–400 °C. This performance far surpasses that of the wet-impregnation prepared CuCe/P-10 catalyst, which delivers only above 80% NO conversion along with incomplete CO oxidation. Characterization results reveal that the engineered distribution of active sites in CuCe-P-10 preserves strong Cu-Ce interactions while integrating acidic CePO4, thereby enhancing redox capacity and maintaining sufficient surface acidity to enable efficient activation of both CO and selective catalytic reduction (SCR) reactants. In contrast, the interactions formed between Cu/Ce species and CePO4 support in CuCe/P-10 restrain the activation ability of Cu active sites toward CO oxidation. Moreover, a new phenomenon is observed in which CO conversion is inhibited by the presence of NO, owing to the competitive chemisorption between CO and NO on active sites at the catalyst surface. This study provides new insights into the design of efficient multifunctional catalysts for simultaneous abatement of NOx and CO in industrial flue gases.

Room temperature catalytic oxidation of hydrogen sulfide (H2S) was considered as an efficient approach for malodorous H2S pollution control. The nitrogen-doped carbon catalysts have been the most extensively studied catalyst for the reaction. However, the role of doped nitrogen species, a form of extrinsic defects, was still somewhat unclear with the role of intrinsic defects receiving comparatively little attention. In the presented work, a facile NH3-programmed temperature calcination strategy was employed to prepare bamboo-based carbon materials with high density intrinsic defects and well-developed mesopore structure. It was revealed that the residual nitrogen species can function as basic sites, facilitating H2S adsorption, while the intrinsic defect can be regarded as the active site for both oxygen activation and H2S adsorption. The chemisorbed oxygen and superoxide radicals were identified as the primary active oxygen species for the reaction. Additionally, the well-developed mesopore structure can significantly enhance the sulfur capacity as well by improving mass transfer, facilitating elemental sulfur formation, and offering sufficient storage space. NBAC-950 catalyst was among the catalysts exhibiting the best catalytic activity, achieving a high saturated sulfur capacity of 1.66 gH2S/g catalyst. Besides, the catalysts can still maintain robust performance in complex atmospheres, with saturated capacities of 0.94 gH2S/g catalyst and 0.09 g methyl mercaptan (MT)/g catalyst. These findings can provide a strategic foundation for the rational design of highly efficient H2S removal catalysts via defect engineering.

In this study, novel CePO4 supported Cr catalyst was applied to eliminate slipping NH3 from stationary sources in the presence of SO2. Experimental results revealed that over 85 % NH3 conversion and well N2 selectivity could be achieved on Cr/CePO4 catalyst within 300-450 degrees C after 20 h reaction running in the presence of SO2. Importantly, superior SCO activity (about 95 %) could be maintained during the stability test. Characterization results indicated that active Cr sites could form strong interactions with acidic CePO4 support on Cr/CePO4 catalyst, which slightly suppressed reactivity of active Cr species but showed enhanced surface acidity. Importantly, the existed strong interactions and enhanced surface acidity significantly impeded the adsorption and oxidation process of SO2, which weakened the deposition and thermal stability of sulfate species and retained more active sites to participate in SCO reactions, thereby enhancing sulfur tolerance of Cr/CePO4 catalyst. Such findings could pave a new way for development of highly efficient SCO catalysts with well sulfur tolerance for real application. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

To effectively remove mercury from sulfur-rich flue gas in nonferrous metal smelting, this study systematically evaluated the effects of different defect structures on the adsorption performance of mercury in sulfur-rich flue gas from nonferrous metal smelting by preparing defect-free (CuS), single sulfur-deficient (CuS1-x), and doubledeficient (Cu1-yS1-x) copper sulfide materials. The experimental results demonstrate that the Cu1-yS1-x material with a double-defect structure exhibits optimal mercury adsorption properties. At 100 degrees C, it maintained 100 % Hg0 removal efficiency after 120 min of continuous operation and showed minimal efficiency loss under high SO2 concentrations (3000-10,000 ppm), confirming excellent sulfur resistance. A comprehensive characterization and mechanistic analysis revealed that Cu1-yS1-x exposed more active sites (Cu2+, S22-, Sx2-) that enhance mercury capture. The relevant reaction mechanism studies indicated that S22-, Sx2- and Cu2+ in the adsorbent play a crucial role for Hg0 capture, which reacted with Hg0(ads) to form HgS. This study provides a new idea for the Hg0 removal from the flue gas in the process of nonferrous metal smelting, and a new strategy for the design and preparation of specific Hg adsorption materials.

Propargylic alcohol cyclizing carboxylation with CO2 at atmospheric pressure was catalyzed by a nanocluster, Cu(I)4(histidinyl)4Ga(I)I. excess His, abbreviated Cu-Ga, at 50°C, providing α-alkylidene cyclic carbonates in good yields. The nanocluster Cu-Ga supported in ZIF-8, noted Cu-Ga/ZIF-8, heterogeneously catalyzed this cyclizing carboxylation of various terminal propargyl alcohols and was recycled five time without significant yield decrease.

Utilizing waste to develop advanced materials for pollutant removal is an innovative and promising strategy for effective environmental management. In this article, a novel bifunctional adsorbent/Fenton-like catalyst, Na4Ti5O12/Na0.23TiO2@carbon (NTC), is prepared using waste polyethylene terephthalate (PET) and commercially available TiO2 through a simple and low-cost molten salt treatment method. This agent exhibits excellent adsorption and catalytic activity for the removal of organic dyes from aqueous solutions across a wide pH range, due to its high surface area (621.0 m2/g) and total pore volume (0.32 cm3/g), as well as the presence of abundant oxygen vacancies and graphene layers derived from waste PET. In the presence of H2O2 at concentrations as low as 0.3 g/L, the degradation efficiency of CV exceeds 99 % within 60 min, due to the formation of center dot OH, center dot O2- and 1O2 reactive oxygen species (ROS) as the key reactive agents, with 1O2 as the major ROS. The reaction rate constant increases by a factor of six to 9.48 x 10-2 min-1 upon increasing temperature from 20 to 40 degrees C. In the absence of H2O2, NTC exhibits a CV adsorption capacity of 165.8 mg/g, which is significantly higher than that of the initial TiO2 (13.2 mg/g). In the presence of low concentrations of H2O2, the rate of combined adsorption and Fenton-like reaction is 3.5 to 6.6 times faster than adsorption alone, with total activation energies of 38.3 and 51.0 kJ mol-1, respectively. NTC effectively removes cationic dyes, leveraging its negatively charged surface to preferentially adsorb such dye species.

Integrating the principles of "carbon neutrality" and "zero pollution" into the removal processes of emerging contaminants (ECs) is essential for their effective elimination from the global supply chain. In this study, a green titanium-based composite material, BC-TNM, was developed using agricultural and forestry waste, corn stalks, as the raw material for biochar. The synergistic adsorption and photocatalytic removal performance of BC-TNM for ciprofloxacin (CIP) in water environment were systematically studied. The optimal removal efficiency of 10 mg center dot L- 1 CIP was achieved at pH = 6 and BC-TNM dosage of 0.2 g center dot L- 1, reaching 96.89 %. After 4 cycles, it remained at 93.52 %. Density functional theory (DFT) calculations and liquid chromatography-mass spectrometry (LC-MS) revealed multiple degradation pathways of CIP, including the opening of the piperazine and quinolone rings. The T.E.S.T method indicated a significant reduction in the toxicity of degradation intermediates. Total organic carbon (TOC) analysis confirmed a mineralization rate of 95.04 %, demonstrating that most of the CIP was converted into inorganic substances. This study provides valuable insights into the development of green photocatalytic materials for efficient degradation of ECs, contributing to environmentally sustainable strategies for pollution control and the ecological assessment of degradation products.

Nanoconfinement strategy that overcomes the defects of conventional heterogeneous catalysts in electron and mass transport provides a new outlet to enhance REDOX processes. Nonetheless, limitations in the activity and selectivity of effective catalytic sites are still the drawbacks of nanoconfined catalysts. In this study, a B-doped carbon nanotubes-confined-FexOy catalyst (B500Fe200@CNTs-L) coupled with a dielectric barrier discharge (DBD) plasma system (DBD/B500Fe200@CNTs-L) was developed for Cu-EDTA removal. The DBD/B500Fe200@CNTs-L system realized 100% Cu-EDTA decomplexation within 3 min, which was 3.6 times kinetically faster than without B doping. The system emphasized extensive pH adaptability, maintaining 100% Cu-EDTA removal at a pH of 3-9. B doping increased the selectivity to O3 and promoted active species generation, in which •OH and O2•- prominently contributed to Cu-EDTA decomplexation, as well as FeIV=O. The strong electronic activity induced by BC3 conformation enhanced charge transfer, regulating the positive charge and d-band center of central Fe atoms to decline the energy barriers of H2O2 and O3 adsorption and active species formation. Moreover, this system emphasized the superior catalytic stability under different matrix water (Cl⁻, CO₃²⁻, NO₃⁻, SO₄²⁻, and PO₄³⁻).