Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(...Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.展开更多
Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been construc...Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been constructed hydrothermally at 160℃ using H_(3)tpta([1,1':3',1″-terphenyl]-4,4',5'-tricarboxylic acid),py(pyridine),H_(2)biim(2,2'-biimidazole),dpe(1,2-di(4-pyridyl)ethylene),and zinc,nickel and cadmium chlorides,resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy,element analysis,thermogravimetric analysis,as well as structural analyses conducted via single-crystal X-ray diffraction.The findings from these single-crystal Xray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P2_(1)/c space group(1)or triclinic system P1 space group(2 and 3),and possess 1D,0D,and 3D structures,respectively.Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions.In addition,complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.CCDC:2449810,1;2449811,2;2449812,3.展开更多
Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits ...Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits in the future.However,designing catalysts that simultaneously exhibit high activity and long-term stability remains a significant challenge.Tuning the catalyst’s structure and electronic properties is an effective strategy for enhancing the reaction performance.In this work,a series of NixZr/ZSM-5 catalysts were prepared using the incipient wetness impregnation method,and the effect of Zr loadings on catalyst properties and performance was systematically investigated.The calcined and reduced catalysts were characterized by low-temperature N_(2)adsorption-desorption,XRD,SEM,H_(2)-TPR and XPS.The results showed that the addition of Zr significantly increased the specific surface area of the catalyst and reduced the metal particle size.Smaller NiO particles were found to enter the pores of the HZSM-5 support,and electronic interactions between NiO and ZrO_(2)markedly enhanced the metal-support interaction.The catalyst exhibited optimal catalytic performance at a Zr loading of 5%,achieving a maximum methane conversion of 68%at 625℃,maintaining activity for 900 min,and delivering a carbon yield of 1927%.Further increasing the Zr loading yielded only limited improvements in catalytic performance.Characterization of the spent catalysts and carbon products via TEM,Raman spectroscopy,and TGA revealed that the introduction of ZrO_(2)reduced metal sintering and promoted a shift in carbon nanofibers growth mode from tip-growth to base-growth.The mechanism of base-growth enabled the catalyst to maintain reaction activity for an extended period.展开更多
To address the kinetic constraints inherent in the catalytic combustion of pulverized coal injection under low heating-rate conditions within conventional air atmospheres,a drop tube furnace was utilized to simulate t...To address the kinetic constraints inherent in the catalytic combustion of pulverized coal injection under low heating-rate conditions within conventional air atmospheres,a drop tube furnace was utilized to simulate the catalytic combustion of pulverized coal(PC).The effects of gas composition,oxygen concentration,the type,and the content of catalysts on the combustion reactivity were systematically analyzed.Furthermore,the structural changes of unburned pulverized coal were also examined.Experimental results indicate that as the oxygen concentration increased from 21%to 79%,compared with the O_(2)/N_(2)condition,the increment in the burnout rate of PC under the O_(2)/CO_(2)condition increased from 3%to 23%.After the addition of catalysts,including hematite,metallurgical oil sludge,and light-burnt dolomite(LBD),under the condition of 21%oxygen concentration,the effects of the three catalysts under the O_(2)/CO_(2)condition were superior to those under the O_(2)/N_(2)condition.This trend was reversed under the conditions of 38%and 79%oxygen concentrations.In all atmospheres,the three catalysts can enhance the burnout rate of PC.Among them,LBD exhibits the most favorable effect,and there exists an optimal dosage.Mechanistic analysis through scanning electron microscopy,X-ray diffraction,and N_(2)adsorption-desorption reveals that under 21%O_(2)/79%CO_(2)conditions,high-concentration CO_(2)leads to the formation of pores,and additives accelerate the oxidation of C and the gasification of CO_(2)through oxygen transfer,thereby enhancing the burnout rate of PC.展开更多
Background:The bacterial biofilm poses a significant challenge to traditional antibiotic therapy.There is a great need to develop novel antibiofilm agents combined with biofilm disrupting and bacteria-killing without ...Background:The bacterial biofilm poses a significant challenge to traditional antibiotic therapy.There is a great need to develop novel antibiofilm agents combined with biofilm disrupting and bacteria-killing without the dependence of antibiotic.Methods:Herein,we prepared ultrasound/magnetic field-responsive ferroferric oxide nanoparticles(Fe_(3)O_(4))/glucose oxidase microbubbles(FGMB)to form a cascade catalytic system for effective removing methicillin-resistant Staphylococcus aureus biofilms.FGMB were prepared through interfacial self-assembly of Fe_(3)O_(4) nanoparticles(NPs)and glucose oxidase(GOx)at the gas-liquid interface stabilized by surfactants.Under ultrasound/magnetic field stimulation,FGMB disrupted biofilm architecture through microbubble collapse-induced microjets and magnetically driven displacement.Simultaneously,ultrasound-triggered rupture of FGMB released GOx and Fe_(3)O_(4) NPs.Glucose can be oxidized by GOx to generate gluconic acid and hydrogen peroxide which was subsequently catalyzed into hydroxyl radicals by Fe_(3)O_(4) NPs,enabling chemical eradication of biofilm-embedded bacteria.Results:Optical microscopy images demonstrated that FGMB have spherical structure with average size of approximately 17μm.FGMB showed a 65.4%decrease in methicillin-resistant Staphylococcus aureus biofilm biomass and 1.1 log bacterial inactivation efficiency(91.2%),suggesting effective biofilm elimination.In vitro experimental results also indicate that FGMB have good biocompatibility.Conclusion:This antibiofilm strategy integrated dual modes of physical biofilm disruption with chemical bacteria-killing shows great potential as a versatile,non-resistant strategy for bacterial biofilm elimination.展开更多
Regenerative catalytic oxidizers(RCO)are widely used to remove volatile organic compounds(VOCs)due to their energy-saving and stability.In this study,a multi-component catalytic reaction model was constructed to numer...Regenerative catalytic oxidizers(RCO)are widely used to remove volatile organic compounds(VOCs)due to their energy-saving and stability.In this study,a multi-component catalytic reaction model was constructed to numerically investigate the reaction process of hydrocarbon-containing VOCs in RCO using computational fluid dynamics(CFD)simulation.To obtain the conversion characteristics of multi-component hydrocarbons,the effects of intake load,equivalence ratio,and the composition of multi-component hydrocarbons on the flow,heat transfer,and conversion rate of the reactor were analyzed.A feasibility study plan targeting the hard-to-convert components was also proposed.The results indicated that as the load increases,the conversion rates of the various components decrease,while the reaction rates increase.Moreover,increasing the flow velocity intensifies turbulence and enhances the collision frequency between the gas and the wall surfaces.This,in turn,amplifies the resistance effect of the porous medium.As the equivalence ratio of VOCs to oxygen increases,the oxygen-deficient condition leads to a decrease in the molecular weight of the hydrocarbons involved in the reaction.The reaction temperature also shows a downward trend.A comparative analysis of the catalytic combustion characteristics of multi-component VOCs and single-component gases reveals that adding ethane and propane can facilitate methane oxidation.展开更多
The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps...The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps conducted under harsh reaction conditions.Herein,we report a cyclic catalytic process for the production of NH_(3) by directly utilizing earth-abundant CH_(4) as a hydrogen source for N_(2) hydrogenation while simultaneously co-producing H_(2) over an alumina-supported iron catalyst(Fe/Al_(2)O_(3)).It achieves exceptional productivities of 2300μmol g^(-1)h^(-1)for NH_(3) and 400 mmol g^(-1)h^(-1)for H_(2) at700℃.By eliminating the coke that results from CH_(4) pyrolysis through a reaction with the greenhouse gas CO_(2) to produce valuable CO,we establish an atom-economic cyclic catalytic process while producing a CO stream intrinsically separated in the regeneration step.Mechanistic investigations indicate that the iron species in Fe/Al_(2) O_(3) serve as tri-functional active sites for CH_(4) pyrolysis,N_(2) hydrogenation,and coke elimination to produce CO,thus enabling an efficient and environmentally friendly cyclic catalytic process.展开更多
The Ru-based catalysts with different preparation methods or supports were achieved and applied in efficientlycatalytic elimination of 1,2-dichloroethane(1,2-DCE).It wasfirstly found that the redox ability and chlorine...The Ru-based catalysts with different preparation methods or supports were achieved and applied in efficientlycatalytic elimination of 1,2-dichloroethane(1,2-DCE).It wasfirstly found that the redox ability and chlorine re-sistance of the catalyst could be improved by regulating the interaction between Ru and supports.Compared withother supports and conventionally impregnated methods,the Ru@ZSM-5 catalyst synthesized by the in-situ en-capsulation strategy exhibited an excellent low-temperature catalytic performance(T50=262°C,T90=327℃),superior stability in long-term test as well as ideal target products.The acidity,specific surface area,and in-teraction with precious metals of the supports have significant influences on the catalytic activity,and the Ruclusters inside the pore structures are more closely bound to the framework Al species,which promotes theoxidation behavior.The encapsulation strategy also significantly improves the Ru dispersion thereby facilitatesoxygen activation as well as Cl-containing volatile organic compounds(CVOCs)deep oxidation,and preserveslarge amounts of Brønsted acid sites to optimize the hydrolysis mechanism for purification of CVOCs.Subse-quently,the synergistic effect between metal redox and acidity is greatly optimized,thus extremely promotingthe catalytic efficiency of 1,2-DCE oxidation.展开更多
Among various advanced oxidation processes(AOPs),heterogeneous catalytic ozonation has garnered extensive attention in wastewater treatment owing to its broad pH range applicability and the elimination of the need for...Among various advanced oxidation processes(AOPs),heterogeneous catalytic ozonation has garnered extensive attention in wastewater treatment owing to its broad pH range applicability and the elimination of the need for additional energy input.Enhancing catalyst activity by introducing oxygen vacancies has been used extensively in heterogeneous catalytic ozonation.This paper reviews prevalent methods for the construction and characterization of oxygen vacancies.Based on a thorough examination of existing research,the role of oxygen vacancies is categorized according to their primary mechanisms of action in heterogeneous catalytic ozonation.For example,modulation of the catalyst electronic structure to enhance electron transfer;participation in the reaction as an active site to generate radicals and non-radicals;and exposure of more metal sites to enhance the reaction.Lastly,the paper delineates the limitations and future research directions concerning the role of oxygen vacancies in catalytic ozonation.This review addresses the gap in existing literature concerning the role of oxygen vacancies in catalytic ozone systems,establishes a comprehensive theoretical framework to aid in the design of efficient ozone catalysts,and delves into the functionality of oxygen vacancies in heterogeneous catalytic ozone reactions.展开更多
Traditional nanofiltration membranes face challenges such as membrane fouling and difficulties in achieving precise separation of small organic molecules.A promising solution to these issues is the preparation of thin...Traditional nanofiltration membranes face challenges such as membrane fouling and difficulties in achieving precise separation of small organic molecules.A promising solution to these issues is the preparation of thin-film nanocomposite membranes.In this study,Cu and Ag bimetals were incorporated into covalent organic frameworks to fabricate thin-film nanocomposite membranes.The hydrophilic monomer 1,3,5-tris(4-aminophenyl)benzene of covalent organic frameworks was introduced as a water phase monomer during interfacial polymerization to enhance the organic-inorganic compatibility.The incorporated covalent organic frameworks within the thin-film nanocomposite membrane loosened the selective layer,resulting in an enhanced permeability of 24.6 LMH bar^(-1).The membrane exhibited a rejection rate over 99.0%for Congo Red,Xylene Brilliant Cyanine G,and Reactive Blue,while exhibiting relatively low rejection rates of MgCl_(2) and NaCl.Moreover,the outstanding catalytic capability of the incorporated bimetals led to a 4-nitrophenol conversion rate of 84.38%,enabling simultaneous conversion and separation.The integration of covalent organic frameworks and bimetals also imparted robust antibacterial properties,significantly enhancing operational stability.In conclusion,the covalent organic framework-Cu/Ag-based thin-film nanocomposite membrane demonstrated superior catalytic and separation capabilities,presenting a promising alternative for advanced filtration applications.展开更多
Methyl mercaptan(CH_(3)SH)is notorious for global air pollution owing to its odorous characteristics and adverse health effects.Although CeO_(2) is currently regarded as a promising catalyst for CH_(3)SH decomposition...Methyl mercaptan(CH_(3)SH)is notorious for global air pollution owing to its odorous characteristics and adverse health effects.Although CeO_(2) is currently regarded as a promising catalyst for CH_(3)SH decomposition,the high conversion temperature followed by high energy consumption is still a bottleneck.Herein,the cobalt-doped CeO_(2) catalyst was synthesized by a facile one-pot preparation strategy and successfully reduces the decomposition temperature from 450 to 250℃.Further studies demonstrate that the excellent low-temperature catalytic activity of Co_(0.6)Ce_(0.4)O_(2-σ)is attributed to its abundant oxygen vacancies and reactive oxygen species.Oxygen vacancies promote the adsorption and dissociation of CH_(3)SH,while reactive oxygen species facilitate the decomposition of CH_(3)SH.Moreover,Co acts as a sacrificial agent for the adsorption of sulfur species in CH_(3)SH,while Ce is responsible for the adsorption and activation of CH_(3)SH as the active metal phase.Furthermore,the migration and transformation mechanism of CH_(3)SH on the surface of Co_(0.6)Ce_(0.4)O_(2-δ)was determined via in situ diffuse reflectance infrared Fourier transform spectra(in situ-DRIFTS).This work provides a new strategy to synthesize highperformance catalysts for decomposing sulfur-containing volatile organic compounds(VOCs)at low temperatures,which is beneficial to decreasing the energy consumption.展开更多
Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespr...Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.展开更多
Ce and its oxide(CeO_(2))have garnered extensive research attention in catalytic elimination of various air pollutants owing to their superior redox performance and oxygen storage capacity,which might originate from t...Ce and its oxide(CeO_(2))have garnered extensive research attention in catalytic elimination of various air pollutants owing to their superior redox performance and oxygen storage capacity,which might originate from the overlap of Ce 4f-5d atomic orbitals,as depicted in Cotton atomic orbital energy level diagram.To further tap the potential of CeO_(2),strategic integration with diverse transition metals and noble metals has been implemented.The distinctive nature of Cu in forming strong interactions with CeO_(2),coupled with its economic viability,has propelled substantial investigations into CuO-CeO_(2)composite catalysts for air pollutant removal.In this review,starting from a discussion on the classical dispersion model of Cu on CeO_(2),the current development in the synthesis and characterization of CuOCeO_(2) catalysts is systematically summarized.Subsequently,the application of CuO-CeO_(2) catalysts in several common air pollutant elimination-related reactions(e.g.,CO oxidation,NO reduction by CO,NH_(3)-SCR and NH_(3)-SCO)is discussed in depth.The review can provide significant guidance for the rational engineering of high-efficiency CuO-CeO_(2) catalysts.展开更多
4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass ...4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass transfer constraints and metal leaching,necessitating the development of stable and efficient catalysts.Herein,BCn-H/MS,the derivative of Bi(Ce)-MOF,was prepared by in situ incorporation,thermal decomposition and acid etching.The resulting materials were characterized and employed in catalytic ozonation for the reduction of 4-NP.Under the specific experimental conditions of the O_(3)+BC0.3-H/MS system,the total organic carbon(TOC)and chemical oxygen demand(COD)removal rates of 4-NP were observed to reach 94.6%and 91.8%within 30 min,respectively.These two parameters were improved by raising the initial pH,reducing the pollutant concentration and increasing the catalyst dosage.The abundant oxygen vacancies(OVs)were regarded as the pivotal catalytic site of BC0.3-H/MS,which was conducive to the adsorption of O_(3) and the acceleration of the formation of reactive oxygen species(ROS).The regular hollow square structure effectively boosted the specific surface area,increased OVs exposure and accelerated the adsorption and mass transfer process.The electron paramagnetic resonance(EPR)results demonstrated that the primary ROS engaged in the degradation reaction were⋅OH and⋅O_(2)−.BC0.3-H/MS demonstrated excellent stability and reusability in cyclic experiments.Toxicity analysis revealed that the O_(3)+BC0.3-H/MS system exhibited an effective detoxification effect.Ultimately,the primary degradation pathway of 4-NP was proposed through liquid chromatography-mass spectroscopy(LC-MS)and in-situ diffuse reflectance infrared fourier-transform spectroscopy(DRIFTS)analyses at varying reaction times.展开更多
Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin f...Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin first”strategy,corn straw is converted to valuable chemicals including lignin monomers,furfural and 5-methoxymethylfurfural via a two steps process.The key of this research lies in the development of a green and low-cost catalytic process utilizing magnetic Raney Ni catalyst and high boiling point ethylene glycol.The utilization of neat ethylene glycol as the sole slovent under atmospheric conditions obviates the need for additional additives,thereby facilitating the entire process to be conducted in glass flasks and rendering it highly convenient for scaling up.In the initial step,depolymerization of corn straw lignin resulted in a monomer yield of 18.1 wt%.Subsequently,in a dimethyl carbonate system,the carbohydrate component underwent complete conversion in a one-pot process,yielding furfural and 5-methoxymethylfurfural as the primary products with an impressive yield of 47.7%.展开更多
Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor...Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor often fails to create a suitable structure for sodium-ion storage.Molecular-level control of graphitization with open channels for Na^(+)ions is crucial for high-performance hard carbon,whereas closed pores play a key role in improving the low-voltage(<0.1 V)plateau capacity of hard carbon anodes for SIBs.However,creation of these closed pores presents significant challenges.This work proposes a zinc gluconate-assisted catalytic carbonization strategy to regulate graphitization and create numerous nanopores simultaneously.As the temperature increases,trace amounts of zinc remain as single atoms in the hard carbon,featuring a uniform coordination structure.This mitigates the risk of electrochemically irreversible sites and enhances sodium-ion transport rates.The resulting hard carbon shows an excellent reversible capacity of 348.5 mAh g^(-1) at 30 mA g^(-1) and a high ICE of 92.84%.Furthermore,a sodium storage mechanism involving“adsorption-intercalation-pore filling”is elucidated,providing insights into the pore structure and dynamic pore-filling process.展开更多
Catalytic destruction is an ascendant technology for the abatement of volatile organic compounds(VOCs)originating fromsolvent-based industrial processes.The varied composition tends to influence each VOC’s catalytic ...Catalytic destruction is an ascendant technology for the abatement of volatile organic compounds(VOCs)originating fromsolvent-based industrial processes.The varied composition tends to influence each VOC’s catalytic behavior in the reaction mixture.We investigated the catalytic destruction of multi-component VOCs including dichloromethane(DCM)and ethyl acetate(EA),as representatives from pharmaceutical waste gases,over co-supported HxPO_(4)-RuOx/CeO_(2) catalyst.A mutual inhibitory effect relating to concentrations because of competitive adsorption was verified in the binary VOCs oxidation and EA posed a more negative effect on DCM oxidation owing to EA’s superior adsorption capacity.Preferential adsorption of EA on acidic sites(HxPO_(4)/CeO_(2))promoted DCM activation on basic sites(O^(2−))and the dominating EA oxidation blocked DCM’s access to oxidation centers(RuOx/CeO_(2)),resulting in boosted monochloromethane yield and increased chlorine deposition for DCM oxidation.The impaired redox ability of Ru species owing to chlorine deposition in turn jeopardized deep oxidation of EA and its by-products,leading to increased gaseous by-products such as acetic acid originating fromEA pyrolysis.Notably,DCM at low concentration slightly promoted EA conversion at low temperatures with or without water,consistent with the enhanced EA adsorption in co-adsorption analyses.This was mainly due to that DCM impeded the shielding effect of hydrolysate deposition from rapid EA hydrolysis depending on the decreased acidity.Moreover,water benefited EA hydrolysis but decreased CO_(2) selectivity while the generated water derived from EA was likely to affect DCM transformation.This work may provide theoretical guidance for the promotion of applied catalysts toward industrial applications.展开更多
BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degradi...BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degrading Rhodamine B(RhB)unde mechanical vibrations,they exhibit superior activity compared to pure ZnO.The 40wt%ZnO/BiVO_(4)heterojunction composite displayed the highest activity,along with good stability and recyclability.The enhanced piezoelectric catalytic activity can be attributed to the form ation of an I-scheme heterojunction structure,which can effectively inhibit the electron-hole recombination.Furthermore,hole(h+)and superoxide radical(·O_(2)^(-))are proved to be the primary active species.Therefore,ZnO/BiVO_(4)stands as an efficient and stable piezoelectric catalyst with broad potential application in the field of environmental water pollution treatment.展开更多
The integration of surface filtration and catalytic decomposition functions in catalytic bags enables the synergistic removal of multiple pollutants(such as dust,nitrogen oxide,acid gases,and dioxins)in a single react...The integration of surface filtration and catalytic decomposition functions in catalytic bags enables the synergistic removal of multiple pollutants(such as dust,nitrogen oxide,acid gases,and dioxins)in a single reactor,thus effectively reducing the cost and operational difficulties associated with flue gas treatment.In this study,Mn-Ce-Sm-Sn(MCSS)catalysts were prepared and loaded onto hightemperature resistant polyimide(P84)filter through ultrasonic impregnation to create composite catalytic filter.The results demonstrate that the NO conversion rates of the composite catalytic filter consistently achieve above 95%within the temperature range of 160-260℃,with a chlorobenzene T_(90)value of 230℃.The ultrasonic impregnation method effectively loaded the catalyst onto the filter,ensuring high dispersion both on the surface and inside the filter.This increased exposure of catalyst active sites enhances the catalytic activity of the composite catalytic filter.Additionally,increasing the catalyst loading leads to a gradual decrease in permeability,an increase in pressure drops and the long residence time of the flue gas,thereby improving catalytic activity.Compared to ordinary impregnation methods,ultrasonic impregnation improves the bonding strength between the catalyst and filter,as well as the permeability of the composite catalytic filter under the same loading conditions.Overall,this study presents a novel approach to prepare composite catalytic filter for the simultaneous removal of NO and chlorobenzene at low temperatures.展开更多
Multidimensional confined structure systems are proposed and demonstrated by using MoO_(2)@MO_(2)C(MMC)to enhance the photothermal catalytic performance of the metal sulfides-multidimensional confined structure(TMs-MD...Multidimensional confined structure systems are proposed and demonstrated by using MoO_(2)@MO_(2)C(MMC)to enhance the photothermal catalytic performance of the metal sulfides-multidimensional confined structure(TMs-MDCS).Specifically,the MMC nanoparticles confined to the surface of the ZnIn_(2)S_(4)hollow tube-shell(MMC/HT-ZIS)achieve a hydrogen evolution rate of 9.72 mmol g^(-1)h^(-1),which is 11.2 times higher than that of pure HT-ZIS.Meanwhile,the MnCdS(MCS)nanoparticles are encapsulated within the two-dimensional MMC(2D MMC/MCS)through precise regulation of size and morphology.The 10-MMC/MCS lamellar network demonstrates the highest hydrogen evolution rate of 8.19 mmol g^(-1)-h^(-1).The obtained MMC/TMs-MDCS catalysts exhibit an enhanced photocatalytic hydrogen evolution rate,which can be attributed to the strong synergistic interaction between the multidimensional confinement and the photothermal effects.The confinement space and the strong interfacial relationship within the MMC/TMs-MDCS create abundant channels and active sites that facilitate electron migration and transport.Furthermore,the construction of a confined environment positions these materials as promising candidates for achieving exceptional photothermal catalytic performance,as MMC/TMs-MDCS enhance light absorption through light scattering and reflecting effects.Additionally,the capacity of MMC/TMsMDCS to convert solar light into thermal energy significantly reduces the activation energy of the reaction,thereby facilitating reaction kinetics and accelerating the separation and transport of photogenerated carriers.This work provides valuable insights for the development of highly efficient photothermal catalytic water-splitting systems for hydrogen production using multidimensional confined catalysts.展开更多
文摘Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.
文摘Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been constructed hydrothermally at 160℃ using H_(3)tpta([1,1':3',1″-terphenyl]-4,4',5'-tricarboxylic acid),py(pyridine),H_(2)biim(2,2'-biimidazole),dpe(1,2-di(4-pyridyl)ethylene),and zinc,nickel and cadmium chlorides,resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy,element analysis,thermogravimetric analysis,as well as structural analyses conducted via single-crystal X-ray diffraction.The findings from these single-crystal Xray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P2_(1)/c space group(1)or triclinic system P1 space group(2 and 3),and possess 1D,0D,and 3D structures,respectively.Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions.In addition,complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.CCDC:2449810,1;2449811,2;2449812,3.
基金Supported by Innovative Research Groups of the National Natural Science Foundation of China(22021004)。
文摘Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits in the future.However,designing catalysts that simultaneously exhibit high activity and long-term stability remains a significant challenge.Tuning the catalyst’s structure and electronic properties is an effective strategy for enhancing the reaction performance.In this work,a series of NixZr/ZSM-5 catalysts were prepared using the incipient wetness impregnation method,and the effect of Zr loadings on catalyst properties and performance was systematically investigated.The calcined and reduced catalysts were characterized by low-temperature N_(2)adsorption-desorption,XRD,SEM,H_(2)-TPR and XPS.The results showed that the addition of Zr significantly increased the specific surface area of the catalyst and reduced the metal particle size.Smaller NiO particles were found to enter the pores of the HZSM-5 support,and electronic interactions between NiO and ZrO_(2)markedly enhanced the metal-support interaction.The catalyst exhibited optimal catalytic performance at a Zr loading of 5%,achieving a maximum methane conversion of 68%at 625℃,maintaining activity for 900 min,and delivering a carbon yield of 1927%.Further increasing the Zr loading yielded only limited improvements in catalytic performance.Characterization of the spent catalysts and carbon products via TEM,Raman spectroscopy,and TGA revealed that the introduction of ZrO_(2)reduced metal sintering and promoted a shift in carbon nanofibers growth mode from tip-growth to base-growth.The mechanism of base-growth enabled the catalyst to maintain reaction activity for an extended period.
基金the National Natural Science Foundation of China(No.52374347)Yulin Science and Technology Program Project(No.2024-SF-227)Key Research and Development Program of Shaanxi(No.2021GY-128).
文摘To address the kinetic constraints inherent in the catalytic combustion of pulverized coal injection under low heating-rate conditions within conventional air atmospheres,a drop tube furnace was utilized to simulate the catalytic combustion of pulverized coal(PC).The effects of gas composition,oxygen concentration,the type,and the content of catalysts on the combustion reactivity were systematically analyzed.Furthermore,the structural changes of unburned pulverized coal were also examined.Experimental results indicate that as the oxygen concentration increased from 21%to 79%,compared with the O_(2)/N_(2)condition,the increment in the burnout rate of PC under the O_(2)/CO_(2)condition increased from 3%to 23%.After the addition of catalysts,including hematite,metallurgical oil sludge,and light-burnt dolomite(LBD),under the condition of 21%oxygen concentration,the effects of the three catalysts under the O_(2)/CO_(2)condition were superior to those under the O_(2)/N_(2)condition.This trend was reversed under the conditions of 38%and 79%oxygen concentrations.In all atmospheres,the three catalysts can enhance the burnout rate of PC.Among them,LBD exhibits the most favorable effect,and there exists an optimal dosage.Mechanistic analysis through scanning electron microscopy,X-ray diffraction,and N_(2)adsorption-desorption reveals that under 21%O_(2)/79%CO_(2)conditions,high-concentration CO_(2)leads to the formation of pores,and additives accelerate the oxidation of C and the gasification of CO_(2)through oxygen transfer,thereby enhancing the burnout rate of PC.
基金supported by the National Natural Science Foundation of China(22375101)the Natural Science of Colleges and Universities in Jiangsu Province(24KJB430027).
文摘Background:The bacterial biofilm poses a significant challenge to traditional antibiotic therapy.There is a great need to develop novel antibiofilm agents combined with biofilm disrupting and bacteria-killing without the dependence of antibiotic.Methods:Herein,we prepared ultrasound/magnetic field-responsive ferroferric oxide nanoparticles(Fe_(3)O_(4))/glucose oxidase microbubbles(FGMB)to form a cascade catalytic system for effective removing methicillin-resistant Staphylococcus aureus biofilms.FGMB were prepared through interfacial self-assembly of Fe_(3)O_(4) nanoparticles(NPs)and glucose oxidase(GOx)at the gas-liquid interface stabilized by surfactants.Under ultrasound/magnetic field stimulation,FGMB disrupted biofilm architecture through microbubble collapse-induced microjets and magnetically driven displacement.Simultaneously,ultrasound-triggered rupture of FGMB released GOx and Fe_(3)O_(4) NPs.Glucose can be oxidized by GOx to generate gluconic acid and hydrogen peroxide which was subsequently catalyzed into hydroxyl radicals by Fe_(3)O_(4) NPs,enabling chemical eradication of biofilm-embedded bacteria.Results:Optical microscopy images demonstrated that FGMB have spherical structure with average size of approximately 17μm.FGMB showed a 65.4%decrease in methicillin-resistant Staphylococcus aureus biofilm biomass and 1.1 log bacterial inactivation efficiency(91.2%),suggesting effective biofilm elimination.In vitro experimental results also indicate that FGMB have good biocompatibility.Conclusion:This antibiofilm strategy integrated dual modes of physical biofilm disruption with chemical bacteria-killing shows great potential as a versatile,non-resistant strategy for bacterial biofilm elimination.
基金supported by National Key Research&Development Program of China(2022YFB4101500).
文摘Regenerative catalytic oxidizers(RCO)are widely used to remove volatile organic compounds(VOCs)due to their energy-saving and stability.In this study,a multi-component catalytic reaction model was constructed to numerically investigate the reaction process of hydrocarbon-containing VOCs in RCO using computational fluid dynamics(CFD)simulation.To obtain the conversion characteristics of multi-component hydrocarbons,the effects of intake load,equivalence ratio,and the composition of multi-component hydrocarbons on the flow,heat transfer,and conversion rate of the reactor were analyzed.A feasibility study plan targeting the hard-to-convert components was also proposed.The results indicated that as the load increases,the conversion rates of the various components decrease,while the reaction rates increase.Moreover,increasing the flow velocity intensifies turbulence and enhances the collision frequency between the gas and the wall surfaces.This,in turn,amplifies the resistance effect of the porous medium.As the equivalence ratio of VOCs to oxygen increases,the oxygen-deficient condition leads to a decrease in the molecular weight of the hydrocarbons involved in the reaction.The reaction temperature also shows a downward trend.A comparative analysis of the catalytic combustion characteristics of multi-component VOCs and single-component gases reveals that adding ethane and propane can facilitate methane oxidation.
基金financial support from the National Key R&D Program of China(2022YFA1504500 and 2023YFA1506300)the National Natural Science Foundation of China(22588201,22225204,and 22472169)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0600100)Liaoning Binhai Laboratory(LBLG-2024-03)。
文摘The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps conducted under harsh reaction conditions.Herein,we report a cyclic catalytic process for the production of NH_(3) by directly utilizing earth-abundant CH_(4) as a hydrogen source for N_(2) hydrogenation while simultaneously co-producing H_(2) over an alumina-supported iron catalyst(Fe/Al_(2)O_(3)).It achieves exceptional productivities of 2300μmol g^(-1)h^(-1)for NH_(3) and 400 mmol g^(-1)h^(-1)for H_(2) at700℃.By eliminating the coke that results from CH_(4) pyrolysis through a reaction with the greenhouse gas CO_(2) to produce valuable CO,we establish an atom-economic cyclic catalytic process while producing a CO stream intrinsically separated in the regeneration step.Mechanistic investigations indicate that the iron species in Fe/Al_(2) O_(3) serve as tri-functional active sites for CH_(4) pyrolysis,N_(2) hydrogenation,and coke elimination to produce CO,thus enabling an efficient and environmentally friendly cyclic catalytic process.
基金supported by the National Key Research and Development Program of China(No.2023YFC3905400)the National Natural Science Foundation of China(No.22176010).
文摘The Ru-based catalysts with different preparation methods or supports were achieved and applied in efficientlycatalytic elimination of 1,2-dichloroethane(1,2-DCE).It wasfirstly found that the redox ability and chlorine re-sistance of the catalyst could be improved by regulating the interaction between Ru and supports.Compared withother supports and conventionally impregnated methods,the Ru@ZSM-5 catalyst synthesized by the in-situ en-capsulation strategy exhibited an excellent low-temperature catalytic performance(T50=262°C,T90=327℃),superior stability in long-term test as well as ideal target products.The acidity,specific surface area,and in-teraction with precious metals of the supports have significant influences on the catalytic activity,and the Ruclusters inside the pore structures are more closely bound to the framework Al species,which promotes theoxidation behavior.The encapsulation strategy also significantly improves the Ru dispersion thereby facilitatesoxygen activation as well as Cl-containing volatile organic compounds(CVOCs)deep oxidation,and preserveslarge amounts of Brønsted acid sites to optimize the hydrolysis mechanism for purification of CVOCs.Subse-quently,the synergistic effect between metal redox and acidity is greatly optimized,thus extremely promotingthe catalytic efficiency of 1,2-DCE oxidation.
基金support from the Key R&D Program of Zhejiang province(No.2024C03136).
文摘Among various advanced oxidation processes(AOPs),heterogeneous catalytic ozonation has garnered extensive attention in wastewater treatment owing to its broad pH range applicability and the elimination of the need for additional energy input.Enhancing catalyst activity by introducing oxygen vacancies has been used extensively in heterogeneous catalytic ozonation.This paper reviews prevalent methods for the construction and characterization of oxygen vacancies.Based on a thorough examination of existing research,the role of oxygen vacancies is categorized according to their primary mechanisms of action in heterogeneous catalytic ozonation.For example,modulation of the catalyst electronic structure to enhance electron transfer;participation in the reaction as an active site to generate radicals and non-radicals;and exposure of more metal sites to enhance the reaction.Lastly,the paper delineates the limitations and future research directions concerning the role of oxygen vacancies in catalytic ozonation.This review addresses the gap in existing literature concerning the role of oxygen vacancies in catalytic ozone systems,establishes a comprehensive theoretical framework to aid in the design of efficient ozone catalysts,and delves into the functionality of oxygen vacancies in heterogeneous catalytic ozone reactions.
基金sponsored by the National Natural Science Foundation of China(Grant No.NSFC-22378160 and U23A20688).
文摘Traditional nanofiltration membranes face challenges such as membrane fouling and difficulties in achieving precise separation of small organic molecules.A promising solution to these issues is the preparation of thin-film nanocomposite membranes.In this study,Cu and Ag bimetals were incorporated into covalent organic frameworks to fabricate thin-film nanocomposite membranes.The hydrophilic monomer 1,3,5-tris(4-aminophenyl)benzene of covalent organic frameworks was introduced as a water phase monomer during interfacial polymerization to enhance the organic-inorganic compatibility.The incorporated covalent organic frameworks within the thin-film nanocomposite membrane loosened the selective layer,resulting in an enhanced permeability of 24.6 LMH bar^(-1).The membrane exhibited a rejection rate over 99.0%for Congo Red,Xylene Brilliant Cyanine G,and Reactive Blue,while exhibiting relatively low rejection rates of MgCl_(2) and NaCl.Moreover,the outstanding catalytic capability of the incorporated bimetals led to a 4-nitrophenol conversion rate of 84.38%,enabling simultaneous conversion and separation.The integration of covalent organic frameworks and bimetals also imparted robust antibacterial properties,significantly enhancing operational stability.In conclusion,the covalent organic framework-Cu/Ag-based thin-film nanocomposite membrane demonstrated superior catalytic and separation capabilities,presenting a promising alternative for advanced filtration applications.
基金Project supported by the National Natural Science Foundation of China(22306081,42030712,42477109,21966018 and 22106055)National Key R&D Program of China(2023YFB3810800)Yunnan Major Scientific and Technological Projects(202302AG050002)。
文摘Methyl mercaptan(CH_(3)SH)is notorious for global air pollution owing to its odorous characteristics and adverse health effects.Although CeO_(2) is currently regarded as a promising catalyst for CH_(3)SH decomposition,the high conversion temperature followed by high energy consumption is still a bottleneck.Herein,the cobalt-doped CeO_(2) catalyst was synthesized by a facile one-pot preparation strategy and successfully reduces the decomposition temperature from 450 to 250℃.Further studies demonstrate that the excellent low-temperature catalytic activity of Co_(0.6)Ce_(0.4)O_(2-σ)is attributed to its abundant oxygen vacancies and reactive oxygen species.Oxygen vacancies promote the adsorption and dissociation of CH_(3)SH,while reactive oxygen species facilitate the decomposition of CH_(3)SH.Moreover,Co acts as a sacrificial agent for the adsorption of sulfur species in CH_(3)SH,while Ce is responsible for the adsorption and activation of CH_(3)SH as the active metal phase.Furthermore,the migration and transformation mechanism of CH_(3)SH on the surface of Co_(0.6)Ce_(0.4)O_(2-δ)was determined via in situ diffuse reflectance infrared Fourier transform spectra(in situ-DRIFTS).This work provides a new strategy to synthesize highperformance catalysts for decomposing sulfur-containing volatile organic compounds(VOCs)at low temperatures,which is beneficial to decreasing the energy consumption.
基金supports from the National Natural Science Foundation of China(Grant Nos.12305372 and 22376217)the National Key Research&Development Program of China(Grant Nos.2022YFA1603802 and 2022YFB3504100)+1 种基金the projects of the key laboratory of advanced energy materials chemistry,ministry of education(Nankai University)key laboratory of Jiangxi Province for persistent pollutants prevention control and resource reuse(2023SSY02061)are gratefully acknowledged.
文摘Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.
基金Project supported by the National Natural Science Foundation of China(22306090,22272077,22402027)the Natural Science Foundation of Jiangsu Province(BK20230773,BK20231513)+1 种基金the Young Elite Scientists Sponsorship Program by CAST(YESS20230298)the Sinopec Group(H25007)。
文摘Ce and its oxide(CeO_(2))have garnered extensive research attention in catalytic elimination of various air pollutants owing to their superior redox performance and oxygen storage capacity,which might originate from the overlap of Ce 4f-5d atomic orbitals,as depicted in Cotton atomic orbital energy level diagram.To further tap the potential of CeO_(2),strategic integration with diverse transition metals and noble metals has been implemented.The distinctive nature of Cu in forming strong interactions with CeO_(2),coupled with its economic viability,has propelled substantial investigations into CuO-CeO_(2)composite catalysts for air pollutant removal.In this review,starting from a discussion on the classical dispersion model of Cu on CeO_(2),the current development in the synthesis and characterization of CuOCeO_(2) catalysts is systematically summarized.Subsequently,the application of CuO-CeO_(2) catalysts in several common air pollutant elimination-related reactions(e.g.,CO oxidation,NO reduction by CO,NH_(3)-SCR and NH_(3)-SCO)is discussed in depth.The review can provide significant guidance for the rational engineering of high-efficiency CuO-CeO_(2) catalysts.
基金supported by the National Natural Science Foundation of China(Regional Fund)(No.51868054)the Natural Science Foundation of Inner Mongolia of China(General Program)(No.2022MS05052).
文摘4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass transfer constraints and metal leaching,necessitating the development of stable and efficient catalysts.Herein,BCn-H/MS,the derivative of Bi(Ce)-MOF,was prepared by in situ incorporation,thermal decomposition and acid etching.The resulting materials were characterized and employed in catalytic ozonation for the reduction of 4-NP.Under the specific experimental conditions of the O_(3)+BC0.3-H/MS system,the total organic carbon(TOC)and chemical oxygen demand(COD)removal rates of 4-NP were observed to reach 94.6%and 91.8%within 30 min,respectively.These two parameters were improved by raising the initial pH,reducing the pollutant concentration and increasing the catalyst dosage.The abundant oxygen vacancies(OVs)were regarded as the pivotal catalytic site of BC0.3-H/MS,which was conducive to the adsorption of O_(3) and the acceleration of the formation of reactive oxygen species(ROS).The regular hollow square structure effectively boosted the specific surface area,increased OVs exposure and accelerated the adsorption and mass transfer process.The electron paramagnetic resonance(EPR)results demonstrated that the primary ROS engaged in the degradation reaction were⋅OH and⋅O_(2)−.BC0.3-H/MS demonstrated excellent stability and reusability in cyclic experiments.Toxicity analysis revealed that the O_(3)+BC0.3-H/MS system exhibited an effective detoxification effect.Ultimately,the primary degradation pathway of 4-NP was proposed through liquid chromatography-mass spectroscopy(LC-MS)and in-situ diffuse reflectance infrared fourier-transform spectroscopy(DRIFTS)analyses at varying reaction times.
基金supported by the Fundamental Research Funds for the Central Universities(QNTD202302)National Natural Science Foundation of China(22378024)the Foreign expert program(G2022109001L).
文摘Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin first”strategy,corn straw is converted to valuable chemicals including lignin monomers,furfural and 5-methoxymethylfurfural via a two steps process.The key of this research lies in the development of a green and low-cost catalytic process utilizing magnetic Raney Ni catalyst and high boiling point ethylene glycol.The utilization of neat ethylene glycol as the sole slovent under atmospheric conditions obviates the need for additional additives,thereby facilitating the entire process to be conducted in glass flasks and rendering it highly convenient for scaling up.In the initial step,depolymerization of corn straw lignin resulted in a monomer yield of 18.1 wt%.Subsequently,in a dimethyl carbonate system,the carbohydrate component underwent complete conversion in a one-pot process,yielding furfural and 5-methoxymethylfurfural as the primary products with an impressive yield of 47.7%.
基金supported by the National Natural Science Foundation of China(22209103)Science and Technology Commission of Shanghai Municipality(22010500400)Australian Research Council(FT180100705)。
文摘Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor often fails to create a suitable structure for sodium-ion storage.Molecular-level control of graphitization with open channels for Na^(+)ions is crucial for high-performance hard carbon,whereas closed pores play a key role in improving the low-voltage(<0.1 V)plateau capacity of hard carbon anodes for SIBs.However,creation of these closed pores presents significant challenges.This work proposes a zinc gluconate-assisted catalytic carbonization strategy to regulate graphitization and create numerous nanopores simultaneously.As the temperature increases,trace amounts of zinc remain as single atoms in the hard carbon,featuring a uniform coordination structure.This mitigates the risk of electrochemically irreversible sites and enhances sodium-ion transport rates.The resulting hard carbon shows an excellent reversible capacity of 348.5 mAh g^(-1) at 30 mA g^(-1) and a high ICE of 92.84%.Furthermore,a sodium storage mechanism involving“adsorption-intercalation-pore filling”is elucidated,providing insights into the pore structure and dynamic pore-filling process.
基金supported by the National Natural Science Foundation of China (Nos.21906087 and 52070168)the Key R&D Plan of Zhejiang Province (No.2023C03127)the Fundamental Research Funds for the Central Universities (No.226-2022-00150).
文摘Catalytic destruction is an ascendant technology for the abatement of volatile organic compounds(VOCs)originating fromsolvent-based industrial processes.The varied composition tends to influence each VOC’s catalytic behavior in the reaction mixture.We investigated the catalytic destruction of multi-component VOCs including dichloromethane(DCM)and ethyl acetate(EA),as representatives from pharmaceutical waste gases,over co-supported HxPO_(4)-RuOx/CeO_(2) catalyst.A mutual inhibitory effect relating to concentrations because of competitive adsorption was verified in the binary VOCs oxidation and EA posed a more negative effect on DCM oxidation owing to EA’s superior adsorption capacity.Preferential adsorption of EA on acidic sites(HxPO_(4)/CeO_(2))promoted DCM activation on basic sites(O^(2−))and the dominating EA oxidation blocked DCM’s access to oxidation centers(RuOx/CeO_(2)),resulting in boosted monochloromethane yield and increased chlorine deposition for DCM oxidation.The impaired redox ability of Ru species owing to chlorine deposition in turn jeopardized deep oxidation of EA and its by-products,leading to increased gaseous by-products such as acetic acid originating fromEA pyrolysis.Notably,DCM at low concentration slightly promoted EA conversion at low temperatures with or without water,consistent with the enhanced EA adsorption in co-adsorption analyses.This was mainly due to that DCM impeded the shielding effect of hydrolysate deposition from rapid EA hydrolysis depending on the decreased acidity.Moreover,water benefited EA hydrolysis but decreased CO_(2) selectivity while the generated water derived from EA was likely to affect DCM transformation.This work may provide theoretical guidance for the promotion of applied catalysts toward industrial applications.
基金financially supported by the National Natural Science Foundation of China(No.22272151)Public Welfare Technology Application Research Project of Jinhua City,China(No.2023-4-022)。
文摘BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degrading Rhodamine B(RhB)unde mechanical vibrations,they exhibit superior activity compared to pure ZnO.The 40wt%ZnO/BiVO_(4)heterojunction composite displayed the highest activity,along with good stability and recyclability.The enhanced piezoelectric catalytic activity can be attributed to the form ation of an I-scheme heterojunction structure,which can effectively inhibit the electron-hole recombination.Furthermore,hole(h+)and superoxide radical(·O_(2)^(-))are proved to be the primary active species.Therefore,ZnO/BiVO_(4)stands as an efficient and stable piezoelectric catalyst with broad potential application in the field of environmental water pollution treatment.
基金Project supported by the National Key Research and Development Program of China(2021YFB3500600,2021YFB3500605)Natural Science Foundation of Jiangsu Province(BK20220365)+5 种基金Key R&D Program of Jiangsu Province(BE2022142)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB610002)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_1419)Science and Technology Plan of Yangzhou(YZ2022030,YZ2023020)the State Key Laboratory of Clean and Efficient Coal-fired Power Generation and Pollution Control(D2022FK098)。
文摘The integration of surface filtration and catalytic decomposition functions in catalytic bags enables the synergistic removal of multiple pollutants(such as dust,nitrogen oxide,acid gases,and dioxins)in a single reactor,thus effectively reducing the cost and operational difficulties associated with flue gas treatment.In this study,Mn-Ce-Sm-Sn(MCSS)catalysts were prepared and loaded onto hightemperature resistant polyimide(P84)filter through ultrasonic impregnation to create composite catalytic filter.The results demonstrate that the NO conversion rates of the composite catalytic filter consistently achieve above 95%within the temperature range of 160-260℃,with a chlorobenzene T_(90)value of 230℃.The ultrasonic impregnation method effectively loaded the catalyst onto the filter,ensuring high dispersion both on the surface and inside the filter.This increased exposure of catalyst active sites enhances the catalytic activity of the composite catalytic filter.Additionally,increasing the catalyst loading leads to a gradual decrease in permeability,an increase in pressure drops and the long residence time of the flue gas,thereby improving catalytic activity.Compared to ordinary impregnation methods,ultrasonic impregnation improves the bonding strength between the catalyst and filter,as well as the permeability of the composite catalytic filter under the same loading conditions.Overall,this study presents a novel approach to prepare composite catalytic filter for the simultaneous removal of NO and chlorobenzene at low temperatures.
基金supported by the Postgraduate Education Reform Project of Shandong Province(SDYAL2023032)the National Key Research and Development Program(2021YFB3500102)。
文摘Multidimensional confined structure systems are proposed and demonstrated by using MoO_(2)@MO_(2)C(MMC)to enhance the photothermal catalytic performance of the metal sulfides-multidimensional confined structure(TMs-MDCS).Specifically,the MMC nanoparticles confined to the surface of the ZnIn_(2)S_(4)hollow tube-shell(MMC/HT-ZIS)achieve a hydrogen evolution rate of 9.72 mmol g^(-1)h^(-1),which is 11.2 times higher than that of pure HT-ZIS.Meanwhile,the MnCdS(MCS)nanoparticles are encapsulated within the two-dimensional MMC(2D MMC/MCS)through precise regulation of size and morphology.The 10-MMC/MCS lamellar network demonstrates the highest hydrogen evolution rate of 8.19 mmol g^(-1)-h^(-1).The obtained MMC/TMs-MDCS catalysts exhibit an enhanced photocatalytic hydrogen evolution rate,which can be attributed to the strong synergistic interaction between the multidimensional confinement and the photothermal effects.The confinement space and the strong interfacial relationship within the MMC/TMs-MDCS create abundant channels and active sites that facilitate electron migration and transport.Furthermore,the construction of a confined environment positions these materials as promising candidates for achieving exceptional photothermal catalytic performance,as MMC/TMs-MDCS enhance light absorption through light scattering and reflecting effects.Additionally,the capacity of MMC/TMsMDCS to convert solar light into thermal energy significantly reduces the activation energy of the reaction,thereby facilitating reaction kinetics and accelerating the separation and transport of photogenerated carriers.This work provides valuable insights for the development of highly efficient photothermal catalytic water-splitting systems for hydrogen production using multidimensional confined catalysts.
