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
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
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
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
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
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
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
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
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
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
Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully...Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene.The CuMn_(2)O_(4)sample exhibited the best catalytic performance,the conversion of benzene reached 100%at 350℃,and toluene conversion reached 100%at 250℃.XRD,N_(2)adsorption-desorption,HRTEM-EDS,ED-XRF,Raman spectroscopy,H_(2)-TPR,NH_(3)-TPD,O_(2)-TPD and XPS were used to characterize the physical and chemical properties of MMn_(2)O_(4)catalysts.The excellent redox properties,high concentration of surface Mn4+,and adsorption of oxygen species over the CuMn_(2)O_(4)sample facilitated the simultaneous and efficient removal of benzene and toluene.Additionally,in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene.Notably,as an effective catalytic material,spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene,providing some insight for the development of efficient multicomponent VOC catalysts.展开更多
Catalyst-aided regeneration is a promising method for reducing the high regeneration energy consumption of amine-based CO_(2)capture technologies.However,the intrinsic relationship between the properties of the acidic...Catalyst-aided regeneration is a promising method for reducing the high regeneration energy consumption of amine-based CO_(2)capture technologies.However,the intrinsic relationship between the properties of the acidic sites and their catalytic activity is controversial.In this study,a series of W-based catalysts supported by ZrTiO_(x)were synthesised,and the effects of the intensity,distribution,and type of acid sites were systematically investigated by quantitatively regulating the acidic site properties.The results indicate stronger acidic sites play a more important role in the catalytic reaction.Moreover,the catalysts showed excellent performance only if the Br?nsted acid sites(BASs)and Lewis acid sites(LASs)coexisted.During the catalytic reaction,the BASs facilitated deprotonation,and the LASs promoted the decomposition of carbamates.The ratio of BASs to LASs(B/L)was a critical factor for catalytic activity,wherein optimal performance was achieved when the B/L ratio was close to 1.The 10%HPW/ZrTiO_(x)composite performed better than WO_(3)/ZrTiO_(x)and HSiW/ZrTiO_(x)because it had a stronger acid intensity and a suitable B/L ratio.As a result,the relative heat duty was reduced by 47%compared to 30%aqueous MEA,and the maximum CO_(2)desorption rate was increased by 83%.The Bader charge indicated that the W atoms of HPW/ZrTiO_(x)lost more electrons(0.18)than those of WO_(3)/ZrTiO_(x),which can weaken the O±H bond energy.Consequently,the calculated deprotonation energy is as low as 257 kJ mol^(-1)for HPW/ZrTiO_(x).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
Although solar steam generation strategy is efficient in desalinating seawater,it is still challenging to achieve continuous solar-thermal desalination of seawater and catalytic degradation of organic pollutants.Herei...Although solar steam generation strategy is efficient in desalinating seawater,it is still challenging to achieve continuous solar-thermal desalination of seawater and catalytic degradation of organic pollutants.Herein,dynamic regulations of hydrogen bonding networks and solvation structures are realized by designing an asymmetric bilayer membrane consisting of a bacterial cellulose/carbon nanotube/Co_(2)(OH)_(2)CO_(3)nanorod top layer and a bacterial cellulose/Co_(2)(OH)_(2)CO_(3)nanorod(BCH)bottom layer.Crucially,the hydrogen bonding networks inside the membrane can be tuned by the rich surface–OH groups of the bacterial cellulose and Co_(2)(OH)_(2)CO_(3)as well as the ions and radicals in situ generated during the catalysis process.Moreover,both SO_(4)^(2−)and HSO_(5)−can regulate the solvation structure of Na^(+)and be adsorbed more preferentially on the evaporation surface than Cl^(−),thus hindering the de-solvation of the solvated Na^(+)and subsequent nucleation/growth of NaCl.Furthermore,the heat generated by the solar-thermal energy conversion can accelerate the reaction kinetics and enhance the catalytic degradation efficiency.This work provides a flow-bed water purification system with an asymmetric solar-thermal and catalytic membrane for synergistic solar thermal desalination of seawater/brine and catalytic degradation of organic pollutants.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.
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.
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.
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 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supported by the National Natural Science Foundation of China(Nos.22206146,22006079,and U21A20524)the Fundamental Research Funds for the Central Universities,the Youth Innovation Promotion Association of Chinese Academy of Sciences,the Fundamental Research Program of Shanxi Province(No.202103021223280)+1 种基金the Special Fund for Science and Technology Innovation Teams of Shanxi Province(No.202204051002026)the Natural Science Foundation of Shandong Province(No.ZR2021QB133).
文摘Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene.The CuMn_(2)O_(4)sample exhibited the best catalytic performance,the conversion of benzene reached 100%at 350℃,and toluene conversion reached 100%at 250℃.XRD,N_(2)adsorption-desorption,HRTEM-EDS,ED-XRF,Raman spectroscopy,H_(2)-TPR,NH_(3)-TPD,O_(2)-TPD and XPS were used to characterize the physical and chemical properties of MMn_(2)O_(4)catalysts.The excellent redox properties,high concentration of surface Mn4+,and adsorption of oxygen species over the CuMn_(2)O_(4)sample facilitated the simultaneous and efficient removal of benzene and toluene.Additionally,in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene.Notably,as an effective catalytic material,spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene,providing some insight for the development of efficient multicomponent VOC catalysts.
基金supported by the National Natural Science Foundation of China(No.52100133,No.52222005)the Key R&D Program of Yunnan Province(No.202303AC100008)。
文摘Catalyst-aided regeneration is a promising method for reducing the high regeneration energy consumption of amine-based CO_(2)capture technologies.However,the intrinsic relationship between the properties of the acidic sites and their catalytic activity is controversial.In this study,a series of W-based catalysts supported by ZrTiO_(x)were synthesised,and the effects of the intensity,distribution,and type of acid sites were systematically investigated by quantitatively regulating the acidic site properties.The results indicate stronger acidic sites play a more important role in the catalytic reaction.Moreover,the catalysts showed excellent performance only if the Br?nsted acid sites(BASs)and Lewis acid sites(LASs)coexisted.During the catalytic reaction,the BASs facilitated deprotonation,and the LASs promoted the decomposition of carbamates.The ratio of BASs to LASs(B/L)was a critical factor for catalytic activity,wherein optimal performance was achieved when the B/L ratio was close to 1.The 10%HPW/ZrTiO_(x)composite performed better than WO_(3)/ZrTiO_(x)and HSiW/ZrTiO_(x)because it had a stronger acid intensity and a suitable B/L ratio.As a result,the relative heat duty was reduced by 47%compared to 30%aqueous MEA,and the maximum CO_(2)desorption rate was increased by 83%.The Bader charge indicated that the W atoms of HPW/ZrTiO_(x)lost more electrons(0.18)than those of WO_(3)/ZrTiO_(x),which can weaken the O±H bond energy.Consequently,the calculated deprotonation energy is as low as 257 kJ mol^(-1)for HPW/ZrTiO_(x).
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.
基金Financial support from the National Natural Science Foundation of China(51972016)the Fundamental Research Funds for the Central Universities(JD2417)is gratefully acknowledged.
文摘Although solar steam generation strategy is efficient in desalinating seawater,it is still challenging to achieve continuous solar-thermal desalination of seawater and catalytic degradation of organic pollutants.Herein,dynamic regulations of hydrogen bonding networks and solvation structures are realized by designing an asymmetric bilayer membrane consisting of a bacterial cellulose/carbon nanotube/Co_(2)(OH)_(2)CO_(3)nanorod top layer and a bacterial cellulose/Co_(2)(OH)_(2)CO_(3)nanorod(BCH)bottom layer.Crucially,the hydrogen bonding networks inside the membrane can be tuned by the rich surface–OH groups of the bacterial cellulose and Co_(2)(OH)_(2)CO_(3)as well as the ions and radicals in situ generated during the catalysis process.Moreover,both SO_(4)^(2−)and HSO_(5)−can regulate the solvation structure of Na^(+)and be adsorbed more preferentially on the evaporation surface than Cl^(−),thus hindering the de-solvation of the solvated Na^(+)and subsequent nucleation/growth of NaCl.Furthermore,the heat generated by the solar-thermal energy conversion can accelerate the reaction kinetics and enhance the catalytic degradation efficiency.This work provides a flow-bed water purification system with an asymmetric solar-thermal and catalytic membrane for synergistic solar thermal desalination of seawater/brine and catalytic degradation of organic pollutants.
