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
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
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
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
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
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
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
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
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
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
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
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
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
Production of green hydrogen through water electrolysis powered by renewable energy sources has garnered increasing attention as an attractive strategy for the storage of clean and sustainable energy.Among various ele...Production of green hydrogen through water electrolysis powered by renewable energy sources has garnered increasing attention as an attractive strategy for the storage of clean and sustainable energy.Among various electrolysis technologies,the emerging anion exchange membrane water electrolyser(AEMWE)exhibits the most potential for green hydrogen production,offering a potentially costeffective and sustainable approach that combines the advantages of high current density and fast start from proton exchange membrane water electrolyser(PEMWE)and low-cost catalyst from traditional alkaline water electrolyser(AWE)systems.Due to its relatively recent emergence over the past decade,a series of efforts are dedicated to improving the electrochemical reaction performance to accelerate the development and commercialization of AEMWE technology.A catalytic electrode comprising a gas diffusion layer(GDL)and a catalyst layer(CL)is usually called a gas diffusion electrode(GDE)that serves as a fundamental component within AEMWE,and also plays a core role in enhancing mass transfer during the electrolysis process.Inside the GDEs,bubbles nucleate and grow within the CL and then are transported through the GDL before eventually detaching to enter the electrolyte in the flow field.The transfer processes of water,gas bubbles,charges,and ions are intricately influenced by bubbles.This phenomenon is referred to as bubble-associated mass transfer.Like water management in fuel cells,effective bubble management is crucial in electrolysers,as its failure can result in various overpotential losses,such as activation losses,ohmic losses,and mass transfer losses,ultimately degrading the AEMWE performance.Despite significant advancements in the development of new materials and techniques in AEMWE,there is an urgent need for a comprehensive discussion focused on GDEs,with a particular emphasis on bubbleassociated mass transfer phenomena.This review aims to highlight recent findings regarding mass transfer in GDEs,particularly the impacts of bubble accumulation;and presents the latest advancements in designing CLs and GDLs to mitigate bubble-related issues.It is worth noting that a series of innovative bubble-free-GDE designs for water electrolysis are also emphasized in this review.This review is expected to be a valuable reference for gaining a deeper understanding of bubble-related mass transfer,especially the complex bubble behavior associated with GDEs,and for developing innovative practical strategies to advance AEMWE for green hydrogen production.展开更多
Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,t...Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.展开更多
MnCeO_(x)/P84 catalytic filters with spherical,flower-like,cubic and rod-like catalytic interfaces were synthesized respectively,and their catalytic activities in the NH_(3)-SCR reaction were investigated.The MnCeO_(x...MnCeO_(x)/P84 catalytic filters with spherical,flower-like,cubic and rod-like catalytic interfaces were synthesized respectively,and their catalytic activities in the NH_(3)-SCR reaction were investigated.The MnCeO_(x)/P84 catalytic filter with spherical catalytic interfaces(recorded as S-MnCeO_(x)/P84)exhibits the best catalytic denitration performance.The NO_(x)removal efficiency of S-MnCeO_(x)/P84 reaches the highest value of 98.6%at 160℃when the catalyst loading is 100 g/m^(2).At the same time,S-MnCeO_(x)/P84 exhibits good SO_(2)resistance and stability,achieving a NO_(x)removal rate of 83%at 190℃with 30 ppm SO_(2).The characterization results illustrate that the MnCeO_x active component in S-MnCeO_(x)/P84 is present in weak crystalline states,tightly wrapped around the surface of the filter fiber,and uniformly dispersed,and the mesopore is the main pore structure of the S-MnCeO_(x)/P84,which can provide a channel for the catalytic reaction to proceed.At the same time,transmission electron microscopy(TEM)characterization shows that y-MnO_(2)is the main form of MnO_(2)in the S-MnCeO_(x)/P84.Further analysis of H_(2)temperature programmed reduction(H_(2)-TPR).NH_(3)temperature programmed desorption(NH_(3)-TPD)and in-situ diffuse reflectance infrared spectra(DRIFTS)show that S-MnCeO_(x)/P84 has good redox ability at 100-200℃and has abundant Lewis acid sites and Bronsteds acid sites,which provides an important guarantee for its superior low-temperature NH_(3)-SCR denitration performance.展开更多
China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technolo...China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technology can address certain technical,environmental,and cost problems during the extraction process,the catalysts often suffer from poor stability and low catalytic efficiency.In this study,a green and simple room-temperature stirring method was employed to synthesize a class of highly efficient and stable 2D MOF catalysts,which possess the capability to conduct in-situ catalytic pyrolysis of heavy oil and reduce the viscosity.Under the condition of 160℃,a catalyst concentration of 0.5 wt%,and a hydrogen donor(tetralin)concentration of 2 wt%,the viscosity-reduction rate of Fe-MOF is as high as 89.09%,and it can decrease the asphaltene content by 8.42%.In addition,through the structural identification and analysis of crude oil asphaltenes,the causes for the high viscosity of heavy oil are explained at the molecular level.Through the analysis of catalytic products and molecular dynamics simulation,the catalytic mechanism is studied.It is discovered that Fe-MOF can interact with heavy oil macromolecules via coordination and pore-channel effects,facilitating their cracking and dispersal.Furthermore,synergistic interactions between Fe-MOF and the hydrogen donor facilitates hydrogenation reactions and enhances the viscosity-reducing effect.This study provides a novel strategy for boosting heavy oil recovery and underscores the potential of 2D MOFs in catalytic pyrolysis applications.展开更多
Quantitatively mapping enzyme sequence-catalysis landscapes remains a critical challenge in understanding enzyme function,evolution,and design.In this study,we leveraged emerging microfluidic technology to measure cat...Quantitatively mapping enzyme sequence-catalysis landscapes remains a critical challenge in understanding enzyme function,evolution,and design.In this study,we leveraged emerging microfluidic technology to measure catalytic constants-kcat and KM-for hundreds of diverse orthologs and mutants of adenylate kinase(ADK).We dissected this sequence-catalysis landscape's topology,navigability,and mechanistic underpinnings,revealing catalytically heterogeneous neighborhoods organized by domain architecture.展开更多
Developing heterojunction photocatalyst with well-matched interfaces andmultiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal,but still remains a great c...Developing heterojunction photocatalyst with well-matched interfaces andmultiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal,but still remains a great challenge.In present work,a new strategy of chloride anion intercalation in Bi_(2)O_(3)via one-pot hydrothermal process is proposed.The as-prepared Ta-BiOCl/Bi_(24)O_(31)Cl_(10)(TBB)heterojunctions are featured with Ta-Bi_(24)O_(31)Cl_(10)and Ta-BiOCl lined shoulder-by-shouleder via semi-coherent interfaces.In this TBB heterojunctions,the well-matched semi-coherent interfaces and shoulder-by-shoulder structures provide fast electron transfer andmultiple transfer paths,respectively,leading to enhanced visible light response and improved photogenerated charge separation.Meanwhile,a type-II heterojunction for photocharge separation has been obtained,in which photogenerated electrons are drove from the CB(conduction band)of Ta-Bi_(24)O_(31)Cl_(10)to the both of bilateral empty CB of Ta-BiOCl and gathered on the CB of Ta-BiOCl,while the photogenerated holes are left on the VB(valence band)of Ta-Bi_(24)O_(31)Cl_(10),effectively hindering the recombination of photogenerated electron-hole pairs.Furthermore,the separated electrons can effectively activate dissolved oxygen for the generation of reactive oxygen species(·O_(2)^(−)).Such TBB heterojunctions exhibit remarkably superior photocatalytic degradation activity for tetracycline hydrochloride(TCH)solution to Bi_(2)O_(3),Ta-BiOCl and Ta-Bi_(24)O_(31)Cl_(10).This work not only proposes a Ta-BiOCl/Bi_(24)O_(31)Cl_(10)shoulder-by-shoulder micro-ribbon architectures with semi-coherent interfaces and successive type-Ⅱheterojunction for highly efficient photocatalytic activity,but offers a new insight into the design of highly efficient heterojunction through phasestructure synergistic transformation strategy.展开更多
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.
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.
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(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support from the National Natural Science Foundation of China(Grant No.52006029)the Promotion Foundation for Young Science and Technology Talents in Jilin Province(Grant No.QT202113)+2 种基金the Special Foundation of Industrial Innovation in Jilin Province(Grant No.2019C056-2)the Special Foundation for Outstanding Young Talents Training in Jilin(Grant No.20200104107)the UK EPSRC(EP/W03784X/1)。
文摘Production of green hydrogen through water electrolysis powered by renewable energy sources has garnered increasing attention as an attractive strategy for the storage of clean and sustainable energy.Among various electrolysis technologies,the emerging anion exchange membrane water electrolyser(AEMWE)exhibits the most potential for green hydrogen production,offering a potentially costeffective and sustainable approach that combines the advantages of high current density and fast start from proton exchange membrane water electrolyser(PEMWE)and low-cost catalyst from traditional alkaline water electrolyser(AWE)systems.Due to its relatively recent emergence over the past decade,a series of efforts are dedicated to improving the electrochemical reaction performance to accelerate the development and commercialization of AEMWE technology.A catalytic electrode comprising a gas diffusion layer(GDL)and a catalyst layer(CL)is usually called a gas diffusion electrode(GDE)that serves as a fundamental component within AEMWE,and also plays a core role in enhancing mass transfer during the electrolysis process.Inside the GDEs,bubbles nucleate and grow within the CL and then are transported through the GDL before eventually detaching to enter the electrolyte in the flow field.The transfer processes of water,gas bubbles,charges,and ions are intricately influenced by bubbles.This phenomenon is referred to as bubble-associated mass transfer.Like water management in fuel cells,effective bubble management is crucial in electrolysers,as its failure can result in various overpotential losses,such as activation losses,ohmic losses,and mass transfer losses,ultimately degrading the AEMWE performance.Despite significant advancements in the development of new materials and techniques in AEMWE,there is an urgent need for a comprehensive discussion focused on GDEs,with a particular emphasis on bubbleassociated mass transfer phenomena.This review aims to highlight recent findings regarding mass transfer in GDEs,particularly the impacts of bubble accumulation;and presents the latest advancements in designing CLs and GDLs to mitigate bubble-related issues.It is worth noting that a series of innovative bubble-free-GDE designs for water electrolysis are also emphasized in this review.This review is expected to be a valuable reference for gaining a deeper understanding of bubble-related mass transfer,especially the complex bubble behavior associated with GDEs,and for developing innovative practical strategies to advance AEMWE for green hydrogen production.
文摘Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.
基金Project supported by the National Natural Science Foundation of China(51902166)the Natural Science Foundation of Jiangsu Province(BK20190786)+1 种基金Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology(CICAEET)Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control。
文摘MnCeO_(x)/P84 catalytic filters with spherical,flower-like,cubic and rod-like catalytic interfaces were synthesized respectively,and their catalytic activities in the NH_(3)-SCR reaction were investigated.The MnCeO_(x)/P84 catalytic filter with spherical catalytic interfaces(recorded as S-MnCeO_(x)/P84)exhibits the best catalytic denitration performance.The NO_(x)removal efficiency of S-MnCeO_(x)/P84 reaches the highest value of 98.6%at 160℃when the catalyst loading is 100 g/m^(2).At the same time,S-MnCeO_(x)/P84 exhibits good SO_(2)resistance and stability,achieving a NO_(x)removal rate of 83%at 190℃with 30 ppm SO_(2).The characterization results illustrate that the MnCeO_x active component in S-MnCeO_(x)/P84 is present in weak crystalline states,tightly wrapped around the surface of the filter fiber,and uniformly dispersed,and the mesopore is the main pore structure of the S-MnCeO_(x)/P84,which can provide a channel for the catalytic reaction to proceed.At the same time,transmission electron microscopy(TEM)characterization shows that y-MnO_(2)is the main form of MnO_(2)in the S-MnCeO_(x)/P84.Further analysis of H_(2)temperature programmed reduction(H_(2)-TPR).NH_(3)temperature programmed desorption(NH_(3)-TPD)and in-situ diffuse reflectance infrared spectra(DRIFTS)show that S-MnCeO_(x)/P84 has good redox ability at 100-200℃and has abundant Lewis acid sites and Bronsteds acid sites,which provides an important guarantee for its superior low-temperature NH_(3)-SCR denitration performance.
基金supported by the National Natural Science Foundation of China(52174047)Sinopec Project(No.P23138).
文摘China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technology can address certain technical,environmental,and cost problems during the extraction process,the catalysts often suffer from poor stability and low catalytic efficiency.In this study,a green and simple room-temperature stirring method was employed to synthesize a class of highly efficient and stable 2D MOF catalysts,which possess the capability to conduct in-situ catalytic pyrolysis of heavy oil and reduce the viscosity.Under the condition of 160℃,a catalyst concentration of 0.5 wt%,and a hydrogen donor(tetralin)concentration of 2 wt%,the viscosity-reduction rate of Fe-MOF is as high as 89.09%,and it can decrease the asphaltene content by 8.42%.In addition,through the structural identification and analysis of crude oil asphaltenes,the causes for the high viscosity of heavy oil are explained at the molecular level.Through the analysis of catalytic products and molecular dynamics simulation,the catalytic mechanism is studied.It is discovered that Fe-MOF can interact with heavy oil macromolecules via coordination and pore-channel effects,facilitating their cracking and dispersal.Furthermore,synergistic interactions between Fe-MOF and the hydrogen donor facilitates hydrogenation reactions and enhances the viscosity-reducing effect.This study provides a novel strategy for boosting heavy oil recovery and underscores the potential of 2D MOFs in catalytic pyrolysis applications.
文摘Quantitatively mapping enzyme sequence-catalysis landscapes remains a critical challenge in understanding enzyme function,evolution,and design.In this study,we leveraged emerging microfluidic technology to measure catalytic constants-kcat and KM-for hundreds of diverse orthologs and mutants of adenylate kinase(ADK).We dissected this sequence-catalysis landscape's topology,navigability,and mechanistic underpinnings,revealing catalytically heterogeneous neighborhoods organized by domain architecture.
基金supported by the National Natural Science Foundation of China(Nos.22208262,52271228,52202298,52201279,51834009,and 51801151)the Natural Science Foundation of Shaanxi Province(Nos.2021JQ-468,2020JZ-47)+3 种基金the Natural Science Foundation of Shaanxi Provincial Department of Education(No.21JP086)the Postdoctoral Research Foundation of China(Nos.2020M683528 and 2018M633643XB)the Young Talent Fund of Association for Science and Technology in Shaanxi,China(No.20230625)the Hundred Talent Program of Shaanxi Province.
文摘Developing heterojunction photocatalyst with well-matched interfaces andmultiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal,but still remains a great challenge.In present work,a new strategy of chloride anion intercalation in Bi_(2)O_(3)via one-pot hydrothermal process is proposed.The as-prepared Ta-BiOCl/Bi_(24)O_(31)Cl_(10)(TBB)heterojunctions are featured with Ta-Bi_(24)O_(31)Cl_(10)and Ta-BiOCl lined shoulder-by-shouleder via semi-coherent interfaces.In this TBB heterojunctions,the well-matched semi-coherent interfaces and shoulder-by-shoulder structures provide fast electron transfer andmultiple transfer paths,respectively,leading to enhanced visible light response and improved photogenerated charge separation.Meanwhile,a type-II heterojunction for photocharge separation has been obtained,in which photogenerated electrons are drove from the CB(conduction band)of Ta-Bi_(24)O_(31)Cl_(10)to the both of bilateral empty CB of Ta-BiOCl and gathered on the CB of Ta-BiOCl,while the photogenerated holes are left on the VB(valence band)of Ta-Bi_(24)O_(31)Cl_(10),effectively hindering the recombination of photogenerated electron-hole pairs.Furthermore,the separated electrons can effectively activate dissolved oxygen for the generation of reactive oxygen species(·O_(2)^(−)).Such TBB heterojunctions exhibit remarkably superior photocatalytic degradation activity for tetracycline hydrochloride(TCH)solution to Bi_(2)O_(3),Ta-BiOCl and Ta-Bi_(24)O_(31)Cl_(10).This work not only proposes a Ta-BiOCl/Bi_(24)O_(31)Cl_(10)shoulder-by-shoulder micro-ribbon architectures with semi-coherent interfaces and successive type-Ⅱheterojunction for highly efficient photocatalytic activity,but offers a new insight into the design of highly efficient heterojunction through phasestructure synergistic transformation strategy.
