The catalytic abatement of volatile organic compounds (VOCs) has always faced challenges of low activity and water poisoning, requiring high-performance catalysts. Waste slag, primarily composed of CaTiO3, possesses tunable electronic structure, strong stability, and sintering resistance, making it an ideal support. Herein we innovatively construct MnCe dual sites on waste slag (MnCe/CTO) to improve VOCs degradation. Doped Mn single atom replaces Ti and efficiently activates lattice oxygen as reactive oxygen species. Mn single atom also promotes VOCs adsorption and activation through strong electronic coupling between Mn 3d orbital and C 2p orbital, enhancing catalytic activity. Ce3+ species, generated via the interaction between co-doped Mn and Ce, dissociate water into hydroxyl radicals with a lower energy barrier, solving water poisoning. Following Mars-van Krevelen (MvK) mechanism, MnCe/CTO achieves complete toluene conversion (100%) at 375 degrees C, whereas pristine waste slag exhibits negligible activity. MnCe/CTO maintains similar to 90% stability after 24 h of continuous operation under 27.7% relative humidity. Similarly, MnCe/CTO demonstrates outstanding degradation performance for benzene and styrene. Such dual-site engineering provides a novel approach to simultaneously address low activity and water poisoning in VOCs degradation, while recycling inert waste slag to realize higher value, establishing an ideal model for "treating pollutants with waste".

Manganese oxides (MnOx) are promising catalysts for HCHO oxidation owing to their favorable redox properties. However, their performance is often constrained by structural instability and limited low-temperature activity. Herein, we present a flexible and robust catalytic membrane composed of K and C co-doped MnOx (K-MnOx/C) anchored on PDDA-cationized poly(ethylene terephthalate) nanofibers (PETP). In this system, K incorporation weakens Mn-O bonds, promotes in-plane lattice vibrations, and enhances lattice oxygen reactivity, while interstitial C doping promotes charge migration. This dual metal-nonmetal doping strategy synergistically modulates the electronic structure of MnOx, suppresses structural distortion, enhancing the structure stability of MnOx. Consequently, the K-MnOx/C/PETP membrane achieves 90.6% HCHO removal within 15 min at 25 degrees C and maintains 96.5% efficiency even at 8 degrees C, outperforming most noble-metal-free catalysts. HCHO oxidation proceeds via a Mars-van Krevelen (MVK) mechanism, in which lattice oxygen oxidizes HCHO to formate and DOM intermediates that are readily converted to CO2. Furthermore, the flexible membrane demonstrates outstanding structural integrity, retaining its catalytic performance under mechanical deformation, airflow erosion, and water washing. This work provides a rational co-doping strategy for catalyst design and introduces a practical, energy-efficient material for indoor air purification.

The direct oxidation of methane to liquid oxygenates is challenging due to the high C-H bond activation barrier. While metal sites in zeolites are typically considered the primary active centers, this study reveals that Brønsted acid sites (BAS) are indispensable for CH4 activation. Atomic-level incorporation of Cu and Zn into ZSM-5 tunes Brønsted acid strength and stabilizes the framework, creating a cooperative acid-metal environment that enables a remarkable C1 oxygenates productivity of 41651 μmol gcat.-1 h-1 with nearly 90% selectivity at 70 °C. Through CH4-DRIFTS, in situ EPR, and DFT calculations, we demonstrate that BAS induce polarization of CH4, while Cu and Zn activate H2O2 to generate •OH and •OOH radicals. The •OH radicals cleave polarized CH4 to form •CH3 radicals, which selectively couple with reactive oxygen species to yield CH3OH and HCOOH. This work highlights the critical acid-metal synergy in metal-zeolite catalysts for efficient CH4 valorization under mild conditions.

Sustainable and efficient catalytic oxidation of chlorinated volatile organic compounds (CVOCs) poses an enduring challenge. This bottleneck arises from the limited catalytic activity of redox reactions and chlorine desorption, causing catalyst deactivation and secondary pollution. Herein, our sound strategy involves Ru-loaded facet-engineered {201}-TiO2 with tuned defects, thereby boosting its reactivity. Comprehensive characterizations and DFT calculation manifested that Ru/{201}-TiO2, with abundant oxygen vacancies, Ti3+ defects, and robust metal-support interaction, enabled flexible electron transfer to activate O-2 and the dissociation of H2O, thus facilitating the continuous generation of reactive oxygen species (ROS), such as center dot O-2(-) and hydroxyl species. These ROS effectively enhance chlorine desorption and chlorobenzene deep oxidation. Ru/{201}-TiO2 exhibited superior reactivity for chlorobenzene degradation, with an apparent activation energy (Ea) of 31.0 KJ/mol and 100 % chlorobenzene conversion in a 1000-min stability test, even with H2O introduction. Ru/{201}-TiO2 produced 2.2-3.1 times fewer small-molecule chlorinated byproducts than Ru/{101}-TiO2, with no polychlorinated benzenes detected.

Boron-based catalysts typically promote the oxidative dehydrogenation of propane through a gas-phase radical mechanism, achieving high propylene selectivity but limited propane conversion. In this study, palladium is incorporated into B/Al2O3 to construct a bifunctional Pd-B/Al2O3 catalyst that shifts the reaction pathway from a radical-dominated route to a surface-catalyzed Langmuir-Hinshelwood mechanism. This cooperative effect increases propane conversion while maintaining the propylene selectivity. Quantitative analysis of both gaseous and surface H2O2 indicates a likely shift in the reaction mechanism from a gas-phase radical pathway to a surface-catalyzed process. Combined in situ EPR, DRIFT, and XPS analyses, along with DFT calculations, reveal that Pd sites promote propane adsorption and substantially lower the dehydrogenation barrier of C3H7, while adjacent BOx(OH)3-x species selectively oxidize hydrogen to H2O, mitigating over-oxidation. The presence of surface B-OH groups further improves performance, increasing propylene selectivity by approximately 5% under humidified conditions. These findings highlight a new strategy for designing efficient ODHP catalysts by harnessing bifunctional active sites to promote surface-mediated reaction pathways.

Palladium is incorporated into B/Al 2 O 3 , creating a bifunctional catalyst that shifts the pathway from a radical-dominated to a surface-catalyzed process.

Reconstruction of catalysts, widely acknowledged in electrocatalysis, has rarely been explored in thermal catalysis. This study demonstrates a dynamic favorable reconstruction of BiVO4 in thermal selective oxidation of benzylic C-H of toluene using in situ techniques. BiVO4 undergoes reconstruction during high-temperature H-2 reduction, wherein Bi dissolves and aggregates into metallic Bi particle to form Bi/BiVO4. Bi/BiVO4 undergoes secondary reconstruction through high-temperature O-2 oxidation in thermal catalysis, wherein Bi migrates toward metallic Bi particle to form Bi2O3/BiVO4. Bi2O3/BiVO4 exhibits good adsorption performance on toluene and O-2, and promotes charge transport to generate more abundant active species. Therefore, a toluene conversion of 26,300.00 mu molg(cat)(-1)h(-1) and product yield of 410.00 mmolg(cat)(-1) were achieved, giving the highest reported product yield for thermal selective oxidation of the benzylic C-H bond of toluene. Based on this, Bi2O3/BiVO4 catalysts with high-performance can be synthesized by a one-step hydrothermal method, opening up new avenues for thermal catalyst design.

Hexachlorobutadiene (HCBD), an increasingly threatening persistent organic pollutant, has few mineralization disposal methods due to its high chlorination, thus demanding urgent development of efficient and cost-effective catalytic systems. Herein, LaMn1-xNixO3-Nano perovskite catalysts were rationally engineered through a dual-strategy combining nanocasting with B-site doping, which exhibited superior oxidation activity toward HCBD. At 250°C and 10 vol% H2O, the CO2 yield of LaMn0.7Ni0.3O3-Nano reached 637.89 μg within 90 min, representing a 7.51-fold increase compared to pure LaMnO3. Notably, this enhancement surpassed the sum of two single-strategy catalysts, including Ni-doped LaMn0.7Ni0.3O3 (1.05-fold increase) and nanocasted LaMnO3-Nano (4.90-fold increase), demonstrating synergistically enhanced (1 + 1 > 2) HCBD mineralization, along with the best cost-effectiveness (62.43 μg•CO2/dollar). Comprehensive characterizations revealed that Ni doping induced lattice distortions in MnO6 octahedra, boosting Mn4+ /Mn3+ active sites to generate reactive oxygen species and increasing acidic sites. Simultaneously, nanocasting significantly enlarged the specific surface area, facilitating catalysts' adsorption capacity and exposure to active sites. The synergy strengthened redox ability and pollutants dissociation, endowing LaMn0.7Ni0.3O3-Nano with efficient HCBD mineralization and lowest small molecule CVOCs generation. HCBD mineralization mechanism was proposed via qualitative and quantitative analysis of intermediates. Insights from this study provide valuable guidance for recalcitrant pollutants disposal and promising catalyst design.

Phenol photocatalytic degradation typically relies on the consumption of oxidative species such as H2O2. In this study, we found the persistent H2O2 generation promoted by the phenol photocatalytic degradation process over flower-like ZnIn2S4 under visible light. The H2O2 generation efficiency achieved 626 mu molg(-1)h(-1), which was 5.35 times higher than in pure water, whereas the phenol degradation efficiency was 97.34%. Experimental and theoretical analysis showed that H2O2 was generated via a two-electron O-2 reduction reaction over ZnIn2S4. Meanwhile, phenol was attacked by the photogenerated holes which facilitated H2O2 production. More interestingly, phenol degradation process can also promote the H2O2 generation, in which hydroquinone (HQ), as the key intermediate, played an important role in promoting the persistent generation of H2O2. This work provided new insights into the in-situ production of H2O2 accompanied with the purification of contaminated water.

The sustainable and affordable environmental application of Pd catalysis needs further improvement of Pd mass activity. Besides the well-recognized importance of physical utilization efficiency-the ratio of surface atoms forming reactant-accessible reactive sites-a lesser-known fact is that the congestion of these reactive sites, which we term as the chemical utilization efficiency, also influences the mass activity. Herein, by leveraging the 100% physical utilization efficiency of a fully exposed Pd cluster (Pd n ) and the hydrogenation activity of TiNiN, we developed Pd n /TiNiN as a high physical and chemical utilization efficiency catalyst. During the catalytic hydrodechlorination of 4-chlorophenol and the subsequent hydrogenation of phenol, Pd n focuses on H2 dissociation and C-Cl cleavage, while TiNiN facilitates the subsequent hydrogenation of phenol into less toxic cyclohexanone via H-spillover. This synergy results in a 20-40-fold increase in the hydrodechlorination rate. The enhanced chemical utilization efficiency of Pd informs the design of Pd n /TiNiN microspheres for the conversion of halogenated organics from pharmaceutical wastewater and the design of a fixed-bed reactor to transfer trace amounts of 4-CP from river water. Ultimately, this approach decentralizes the use of Pd in environmental catalysis and reduction processes.

Recently intensified oil exploitation has resulted in the discharge of large amounts of wastewater containing high concentrations of organic matter and nutrients into the receiving aquatic and soil environments; however, the effects of oilfield-produced water on the soil microbiota are poorly understood. In this study, we conducted a comprehensive analysis to reveal the composition and diversity of the microbial community at horizontal and vertical scales in a typical arid soil receiving oilfield-produced water in Northwest China. Oilfield-produced water caused an increase in microbial diversity at the horizontal scale, and the communities in the topsoil were more variable than those in the subsoil. Additionally, the microbial taxonomic composition differed significantly between the near- and far-producing water soils, with Proteobacteria and Halobacterota dominating the water-affected and reference soil communities, respectively. Soil property analysis revealed that pH, salt, and total organic content influenced the bacterial communities. Furthermore, the oil-produced water promoted the complexity and modularity of distance-associated microbial networks, indicating positive interactions for soil ecosystem function, but not for irrigation or livestock watering. This is the first detailed examination of the microbial communities in soil receiving oilfield-produced water, providing new insights for understanding the microbial spatial distributions in receiving arid soils.

It remains challenging to obtain a single product in the gas-solid photocatalytic reduction of CO2 because CO and CH4 are usually produced simultaneously. This study presents the design of the I-type nested heterojunction TiO2/BiVO4 with controllable electron transport by modulating the TiO2 component. This study demonstrates that slowing electron transport could enable TiO2/BiVO4-4 to generate CO with 100% selectivity. In addition, modifying TiO2/BiVO4-4 by loading a Cu single atom further increased the CO product yield by 3.83 times (17.33 μmol·gcat-1·h-1), while maintaining 100% selectivity for CO. Characterization and density functional theory (DFT) calculations revealed that the selectivity was mainly determined by the electron transport of the support, whereas CO2 was efficiently adsorbed and activated by the Cu single atom. Such a two-step regulation strategy of combining heterojunction with single atom enhances the possibility of simultaneously obtaining high selectivity and high yield in the photocatalytic reduction of CO2.

Selective oxidation of toluene is a key reaction to produce high value-added products but remains a big challenge. In this study, we introduce a nitrogen-doped TiO2 (N-TiO2) catalyst to create more Ti3+ and oxygen vacancy (OV), which act as active sites for selective oxidation of toluene via activating O2 to superoxide radical (•O2-). Interestingly, the resulting N-TiO2-2 exhibited an outstanding photo-assisted thermal performance with a product yield of 209.6 mmol·gcat-1 and a toluene conversion of 10960.0 μmol·gcat-1·h-1, which are 1.6 and 1.8 times greater than those obtained under thermal catalysis. We showed that the enhanced performance under photo-assisted thermal catalysis was attributed to more active species generation by making full use of photogenerated carriers. Our work suggests a viewpoint to apply a noble-metal-free TiO2 system in the selective oxidation of toluene under solvent-free conditions.

Bisphenol A (BPA) and its analogs are endocrine-disrupting chemicals that are frequently detected in environmental and human samples. However, the effective removal of BPA and its analogs has not yet been extensively studied. Herein, we introduce a novel enzyme reactor for the degradation of BPA and its analogs in water. The influence of pore size on the degradation efficiency of immobilized laccase in the spatial nanopores of hydrogel was investigated using BPA as a representative compound. This showed that nanopores enhance the activity of immobilized laccases in a pore size-dependent manner and increase their stability. Compared with the same amount of free laccase, the 50 mg/L BPA degradation performance of laccase immobilized in 76 nm nanopores increased to 300 %. Taking advantage of magnetic separation, this immobilized laccase can be reused, and its degradation capacity was maintained at over 73.7 % after ten reactions. Moreover, the degradation of seven BPA analogs was 1.03-5.88 times higher using laccase immobilized in nanopores compared with free laccase. Also, the biocatalyst could efficiently degrade BPA analogs in real water matrix. This study opens up a new avenue for the removal of BPA and its analogs by immobilizing laccase in nanopores, overcoming the key limitations introduced by the short enzyme life span and non-reusability.

It is challenging to achieve high selectivity over Pt-metal-oxide catalysts widely used in many selective oxidation reactions because Pt is prone to over-oxidize substrates. Herein, our sound strategy for enhancing the selectivity is to saturate the under-coordinated single Pt atoms with Cl- ligands. In this system, the weak electronic metal-support interactions between Pt atoms and reduced TiO2 cause electron extraction from Pt to Cl- ligands, resulting in strong Pt-Cl bonds. Therefore, the two-coordinate single Pt atoms adopt a four-coordinate configuration and thus inactivated, thereby inhibiting the over-oxidation of toluene over Pt sites. The selectivity for the primary C-H bond oxidation products of toluene was increased from 50.1 to 100%. Meanwhile, the abundant active Ti3+ sites were stabilized in reduced TiO2 by Pt atoms, leading to a rising yield of the primary C-H oxidation products of 249.8 mmol gcat-1. The reported strategy holds great promise for selective oxidation with enhanced selectivity.

Bacterial infections have become a great threat to public health in recent years. A primary lysozyme is a natural antimicrobial protein; however, its widespread application is limited by its instability. Here, we present a poly (N-isopropylacrylamide) hydrogel inverse opal particle (PHIOP) as a microcarrier of lysozyme to prolong and enhance the efficiency against bacteria. This PHIOP-based lysozyme (PHIOP-Lys) formulation is temperature-responsive and exhibits long-term sustained release of lysozyme for up to 16 days. It shows a potent antibacterial effect toward both Escherichia coli and Staphylococcus aureus, which is even higher than that of free lysozyme in solution at the same concentration. PHIOPs-Lys were demonstrated to effectively inhibit bacterial infections and enhance wound healing in a full-thickness skin wound rat model. This study provides a novel pathway for prolonging the enzymatic activity and antibacterial effects of lysozyme.

Endocrine disruptors such as bisphenol A(BPA)adversely affect the environment and hu-man health.Laccases are used for the efficient biodegradation of various persistent or-ganic pollutants in an environmentally safe manner.However,the direct application of free laccases is generally hindered by short enzyme lifetimes,non-reusability,and the high cost of a single use.In this study,laccases were immobilized on a novel magnetic three-dimensional poly(ethylene glycol)diacrylate(PEGDA)-chitosan(CS)inverse opal hydrogel(LAC@MPEGDA@CS@IOH).The immobilized laccase showed significant improvement in the BPA degradation performance and superior storage stability compared with the free lac-case.91.1％of 100 mg/L BPA was removed by the LAC@MPEGDA@CS@IOH in 3 hr,whereas only 50.6％of BPA was removed by the same amount of the free laccase.Compared with the laccase,the outstanding BPA degradation efficiency of the LAC@MPEGDA@CS@IOH was maintained over a wider range of pH values and temperatures.Moreover,its relative activity of was maintained at 70.4％after 10 cycles,and the system performed well in actual water matrices.This efficient method for preparing immobilized laccases is simple and green,and it can be used to further develop ecofriendly biocatalysts to remove organic pollutants from wastewater.

Microplastics (MPs) are ubiquitous in environmental compartments and consumer products. Although liver is frequently reported to be a target organ of MP accumulation in mammals, few studies have focused on MP hepatoxicity in humans. In this study, we used normal human liver cells, THLE-2, to assess the acute and chronic toxicity of polystyrene (PS) MPs with sizes of 0.1 and 1 μm. The results showed that after 48 h of exposure, both kinds of PS MPs could enter THLE-2 cells and cause no obviously acute cytotoxicity at <20 μg/mL. In contrast, metabolomic analysis revealed that 90 days of PS MPs exposure at environmentally relevant dose (0.2 μg/mL) could significantly alter the metabolic profiles of the cells, especially the nanosized MPs. KEGG pathway analysis showed that the ATP-binding cassette (ABC) transporter pathway was the most significantly changed pathway. Cell functional tests confirmed that chronic PS MP treatment could inhibit the activity of the ABC efflux transporter and further increase the cytotoxicity of arsenic, indicating that the PS MPs had a chemosensitizing effect. These findings underline the chronic risk of MPs to human liver.

The La-based perovskite (LaBO 3 ) exhibits excellent optical properties. However, its valence band (VB) potential is not sufficiently positive to reach the oxidation potential required for the cleavage of chemical bonds (such as benzylic C–H), limiting its application in photocatalysis. Herein, we report the unconventional effects of heat activation on the reduction of the dissociation energy of benzylic C–H and aqueous H–O, thereby triggering the photocatalytic activity of La 2 Co x Mn 2-x O 6 perovskites. Additionally, we demonstrate that photocatalysis is the main contributor to substrate conversion in the selective oxidation of toluene and reduction of CO 2 . Particularly, La 2 Co 1.5 Mn 0.5 O 6 shows excellent performance with a product yield of 550.00 mmol g cat −1 and a toluene conversion of 22,866.67 μmol g cat −1 h −1 . To the best of our knowledge, this is the highest reported product yield for the selective oxidation of benzylic C–H bond of toluene. Our findings provide insight into the specific role of heat activation in photocatalysis, which is crucial for breaking and overcoming the VB barrier to realize challenging reactions.

The La-based perovskite (LaBO3) exhibits excellent optical properties. However, its valence band (VB) potential is not sufficiently positive to reach the oxidation potential required for the cleavage of chemical bonds (such as benzylic C-H), limiting its application in photocatalysis. Herein, we report the unconventional effects of heat activation on the reduction of the dissociation energy of benzylic C-H and aqueous H-O, thereby triggering the photocatalytic activity of La2CoxMn2-xO6 perovskites. Additionally, we demonstrate that photocatalysis is the main contributor to substrate conversion in the selective oxidation of toluene and reduction of CO2. Particularly, La2Co1.5Mn0.5O6 shows excellent performance with a product yield of 550.00 mmol gcat-1 and a toluene conversion of 22,866.67 μmol gcat-1 h-1. To the best of our knowledge, this is the highest reported product yield for the selective oxidation of benzylic C-H bond of toluene. Our findings provide insight into the specific role of heat activation in photocatalysis, which is crucial for breaking and overcoming the VB barrier to realize challenging reactions.