Diesel engine exhaust comprises nitrogen oxides(NOx)and soot particles,which cause serious air pollution.However,owing to the contradictory nature of NO_(x)reduction and soot oxidation,a trade-off exists in the simult...Diesel engine exhaust comprises nitrogen oxides(NOx)and soot particles,which cause serious air pollution.However,owing to the contradictory nature of NO_(x)reduction and soot oxidation,a trade-off exists in the simultaneous removal of NO_(x)and soot.Consequently,catalytic technology has become a hot research topic.This study prepared MOδ/Fe-Beta(M=Fe,Co,Ni,Mn,Cu)catalysts through incipient wetness impregnation using Fe-Beta as the support and explored the catalytic performance of the above catalysts.The results exhibited the good performance of the prepared catalysts.The introduction of Mn resulted in a lower peak temperature of soot combustion for the catalyst,and slightly decreased deNOx performance of Fe-Beta.The soot combustion temperature was as low as 422℃,and the temperature window for 80%NO conversion was 164-423℃.The interaction between MnOd and zeolite can regulate the acid sites and produce sufficient active oxygen species for the catalyst.The catalytic activity of the MnOδ/Fe-Beta catalyst is due to its strong redox property,the appropriate number of acid sites,and sufficient number of active oxygen species.In addition,the catalyst had good stability and water and sulfur resistance,therefore it had great potential for future application in the simultaneous removal of NO_(x)and soot from diesel engine exhaust.展开更多
FAU zeolites have emerged as multifunctional materials with broad applications in catalysis and adsorption,owing to their hierarchical pore architectures,elevated specific surface areas,and adjustable extra-framework ...FAU zeolites have emerged as multifunctional materials with broad applications in catalysis and adsorption,owing to their hierarchical pore architectures,elevated specific surface areas,and adjustable extra-framework cationic sites.This review provides a critical overview of recent advances in FAU zeolite research with emphasis on their roles in environmental pollutant mitigation.A bibliometric analysis was performed to ascertain worldwide research trends,cooperation networks,and principal theme areas.Strategies for synthesis and functionalization,including crystallization pathways,one-pot methods,and post-synthetic modifications,were systematically evaluated for their capacity to tailor structural and physicochemical properties.Environmental applications were discussed in detail,particularly in heavy metal extraction,CO_(2)capture,and catalytic NOx reduction.Despite these advances,challenges persisted,notably restricted chemical stability under extreme pH conditions,scalability obstacles from laboratory to industrial production,and the necessity for enhanced catalytic efficiency.By integrating fundamental understanding with application-oriented perspectives,this review identifies existing knowledge gaps and delineates future directions for the rational design of FAU zeolites toward sustainable environmental remediation.展开更多
Recycling rare earth elements(REEs)from waste is necessary for an environmentally sustainable reuse and wastewater management approach.Na-A zeolite was synthesized from coal fly ash(CFA)and applied for Ce^(3+)adsorpti...Recycling rare earth elements(REEs)from waste is necessary for an environmentally sustainable reuse and wastewater management approach.Na-A zeolite was synthesized from coal fly ash(CFA)and applied for Ce^(3+)adsorption.Fourier transform infrared(FTIR)spectra show peaks at 790,500 and 467 cm^(-1),which are bond vibrations of Si-O-Si,Si with Al-O and Si-O-.The surface area is 15.88 m^(2)/g,with a pore size of 2.14 nm.SEM images show a cubic shape,which indicates the formation of zeolite.Field emission and energy disperse spectroscopy(EDS)shows the formation of Si,Al,Na,and O.Na-A zeolite was applied for Ce^(3+)adsorption.The optimum conditions for Ce^(3+)adsorption are 50 ppm concentration,360 min,and pH 6.The maximum adsorption capacity is 176.49 mg/g.Based on the results,it is found that the adsorption of Ce^(3+)by Na-A zeolite is pseudo-second-order.The desorption test using HNO_(3) is more effective than using HCl and H_(2)SO_(4).A desorption efficiency of 97.22%is obtained at 4 cycles.Adsorption test using real sample wastewater demonstrates an adsorption efficiency of 83.35%.展开更多
Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive st...Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.展开更多
Zeolite-loaded noble metal catalysts have demonstrated excellent performance in addressing cold-start automotive exhaust NOx emissions and catalytic oxidation of VOCs applications.Pd and Pt are the most commonly used ...Zeolite-loaded noble metal catalysts have demonstrated excellent performance in addressing cold-start automotive exhaust NOx emissions and catalytic oxidation of VOCs applications.Pd and Pt are the most commonly used active metals in PNA and VOC catalysts,respectively.However,despite the same metal/zeolite composition,the efficient active sites for PNA and VOC catalysts have been viewed as mainly Pd^(2+) and Pt^(0),respectively,both of which are different from each other.As a result,various methods need to be applied to dope Pd and Pt in zeolitic support respectively for different usages.No matter which type of metal species is needed,the common requirement for both PNA and VOC catalysts is that the metal species should be highly dispersed in zeolite support and stay stable.The purpose of this paper is to review the progress of synthetic means of zeolite-coated noble metals(Pd,Pt,etc.)as effective PNA or VOC catalysts.To give a better understanding of the relationship between efficient metal species and the introduced methods,the species that contributed to the NOx adsorption(PNA)and VOCs deep catalytic oxidation were first summarized and compared.Then,based on the above discussion,the detailed construction strategies for different active sites in PNA and VOC catalysts,respectively,were elaborated in terms of synthetic routes,precursor selection,and zeolite carrier requirements.It is hoped that this will contribute to a better understanding of noble metal adsorption/catalysis in zeolites and provide promising strategies for the design of adsorption/catalysts with high activity,selectivity and stability.展开更多
Hydrocracking technology represents a crucial position in the conversion of heavy oil and the transformation development from oil refining to the chemical industry.The properties of catalysts are one of the key factor...Hydrocracking technology represents a crucial position in the conversion of heavy oil and the transformation development from oil refining to the chemical industry.The properties of catalysts are one of the key factors in the hydrocracking process.As the main acidic component of hydrocracking catalyst,the influence of zeolite properties on the reaction performance has been the focus of research.In this study,a series of NiMo/Al_(2)O_(3)-Y catalysts were prepared using different Y zeolites as acidic components,and their performances in the hydrocracking of n-C_(10)were also evaluated.The structure-activity relationship between Y zeolite and the cracking performance of n-C_(10)was investigated with machine learning.First,a database of the physical and chemical properties of Y zeolite and their performance was established,and the correlation analysis was also conducted.Parameters such as the cell constant,acid content,acid strength,B/L ratio,mesopore volume,micropore volume of Y zeolite,and the reaction temperature were selected as independent variables.The conversion of n-C_(10)and the ratios of products C_(3)/C_(7)and i-C_(4)/n-C_(4)were selected as dependent variables.A model was established by the random forest algorithm and a new zeolite was predicted based on it.The results of model prediction were in good agreement with the experimental results.The R^(2)of the n-C_(10)conversion,C_(3)/C_(7)ratio,and i-C_(4)/n-C_(4)ratio were 0.9866,0.9845,and 0.9922,and the minimum root mean square error values were 0.0163,0.101,and 0.0211,respectively.These results can provide reference for the development of high performance hydrocracking catalyst and technology.展开更多
High-capacity LiBH_(4)is a promising solid hydrogen storage material.However,the large electron cloud density between the B-H bonds in LiBH_(4)induces high dehydrogenation temperatures and sluggish dehydrogenation kin...High-capacity LiBH_(4)is a promising solid hydrogen storage material.However,the large electron cloud density between the B-H bonds in LiBH_(4)induces high dehydrogenation temperatures and sluggish dehydrogenation kinetics.To solve the above problems,it is proposed to enhance the hydrogen storage properties of LiBH_(4)through the synergistic effect of Brønsted and Lewis acid in Hβzeolite.Composite hydrogen storage systems with different mass ratios were prepared by simple ball-milling.At a LiBH_(4)-to-Hβmass ratio of 6:4,the 6LiBH_(4)-4Hβsystem released hydrogen at 190℃and achieved a hydrogen release capacity of 7.0 wt%H_(2)upon heating to 400℃.More importantly,the hydrogen release capacity of the system reached 6.02 wt%at 350℃under isothermal conditions after 100 min and 7.2 wt%at 400℃under isothermal conditions after 80 min,whereas the pristine LiBH_(4)only achieved 2.2 wt%.The improvement in hydrogen storage performance of the system was mainly attributed to two factors:(i)Lewis acid sites with acceptable electrons in the Hβweaken the electron density of B-H bonds in LiBH_(4),and(ii)the H+proton from the Brønsted acid sites and H−of LiBH_(4)undergo a H^(+)+H^(−)=H_(2)reaction.Theoretical calculations revealed that the Lewis and Brønsted acid sites in the Hβzeolite are conducive to the weakening of B-H bonds and that storage charge transfer occurs near the Lewis acid sites.The present work provides new insights into improving the hydrogen storage performance of LiBH_(4)by weakening the B-H bonds in the LiBH_(4).展开更多
Nitrogen oxides(NO_(x))from diesel engine exhaust,is one of the major sources of environmental pollution.Currently,selective catalytic reduction with ammonia(NH_(3)-SCR)is considered to be the most effective protocol ...Nitrogen oxides(NO_(x))from diesel engine exhaust,is one of the major sources of environmental pollution.Currently,selective catalytic reduction with ammonia(NH_(3)-SCR)is considered to be the most effective protocol for reducing NO_(x)emissions.Nowadays,zeolitebased NH_(3)-SCR catalysts have been industrialized and widespread used in this field.Nevertheless,with the increasingly stringent environmental regulations and implementation of the requirement of“zero emission”of diesel engine exhaust,it is extremely urgent to prepare catalysts with superior NH_(3)-SCR activity and exceptional resistance to poisons(SO2,alkali metals,hydrocarbons,etc.).Core-shell structure zeolite-based catalysts(CSCs)have shown great promise in NH_(3)-SCR of NO_(x)in recent years by virtue of its relatively higher low-temperature activity,broader operation temperature window and outstanding resistance to poisons.This review mainly focuses on the recent progress of CSCs for NH_(3)-SCR of NO_(x)with three extensively investigated SSZ-13,ZSM-5,Beta zeolites as cores.The reaction mechanisms of resistance to sulfur poisoning,alkali metal poisoning,hydrocarbon poisoning,and hydrothermal aging are summarized.Moreover,the important role of interfacial effect between core and shell in the reaction of NH_(3)-SCR was clarified.Finally,the future development and application outlook of CSCs are prospected.展开更多
The cerium-silicate pillared MWW zeolites are fabricated by introducing Ce species into the silica pillars within adjacent MWW layers through a liquid-phase pillaring method,and the multiple-layer structure of MWW zeo...The cerium-silicate pillared MWW zeolites are fabricated by introducing Ce species into the silica pillars within adjacent MWW layers through a liquid-phase pillaring method,and the multiple-layer structure of MWW zeolites is well maintained.However,it's found that these Ce^(3+)species can produce the Bronsted acid sites by the dissociation of water molecules owing to the electrostatic field of Ce^(3+)cations,the splitting of water molecules occurs following[Ce(H_2O)_n]^(3+)■Ce[(OH)(H_2O)_(n-1)]^(2+)+H^(+)equation based on the Plank-Hirschler mechanism,leading to superior activity of resultant cerium-silicate pillared MWW zeolites in the alkylation between benzene with 1-dodecene.Moreover,the additional Ce species located in the silica pillars can be easily accessed by vip molecules due to the presence of mesopores between neighboring MWW layers,which can strongly active benzene molecules by polarization effect,and dodecyl carbenium ions are preferred to attack the carbon atoms located in activated benzene molecules,resulting in the long lifetime of cerium-silicate pillared MWW zeolites since the oligomerization of long-chain olefins is suppressed.Under harsh reaction conditions(benzene/1-dodecene=10,WHSV=20 h^(-1)),the optimized cerium-silicate pillared MWW zeolite shows outstanding activity(>40%)and excellent selectivity(>85%)of 2-LAB in the alkylation of benzene with 1-dodecene.展开更多
Organic structure directingagents(OSDAs),suchas tetrapropylammonium(TPA)cations,serve as crucial templates for the formation of zeolite frameworks.These organic molecules interact with inorganic species,guiding the as...Organic structure directingagents(OSDAs),suchas tetrapropylammonium(TPA)cations,serve as crucial templates for the formation of zeolite frameworks.These organic molecules interact with inorganic species,guiding the assembly of the zeolite structure.In this study,we inves-tigate the complex interplay between boron species and TPA cations during the crystallization of[B,Al]-ZSM-5 zeolites.Two-dimensional(2D)11B-{1H}cross-polarization heteronuclear correlation(CP-HECTOR)NMRexperiments elucidate distinct interactions between two boron species,B(IV)-1 and B(IV)-2,and the propyl chain of the TPAs.Amorphous B(IV)-1 species exhibit a strong preference for proximity to the nitrogen cation center of the OSDAs,while framework B(IV)-2 species engage with components situated at greater distances from the cation center.Moreover,13C-{11B}symmetry-based resonance-echo saturation-pulse double-resonance(S-RESPDOR)experiments revealed that framework boron species preferentially occupy the straight channels of the MFI structure,as evidenced by their interaction with specificmethyl groups on the TPAmolecules.This observation provides valuable insights into the crystallization mechanism of boron-based zeolites,suggesting that the conformation and orientation of the OSDA molecules play a critical role in determining the location of boron atoms within the zeolite framework.展开更多
A combination of experimental and statistical analysis presents a comprehensive understanding of the microwave pyrolysis technique for catalytic deconstruction of mixed-density plastics.By optimizing the process param...A combination of experimental and statistical analysis presents a comprehensive understanding of the microwave pyrolysis technique for catalytic deconstruction of mixed-density plastics.By optimizing the process parameters and catalyst selection,it is possible to maximize the production of valuable solid and energy products,contributing to sustainable waste management.In this work,different mixed-density plastics were pyrolyzed with different catalysts and residence times to yield liquid fuel,syngas,and structured carbon residue.The effect of inputs on the product type,yield and composition was statistically evaluated using ANOVA,which showed an F value of 4.108 and a p-value of 0.098(>1.00).FTIR and GC-MS revealed that the oil product consisted of C13+fractions in the form of alkanes,alkenes,and aromatics.The microscopic analysis of the residue confirmed the formation of carbon nanotubes along with other amorphous products.The presence of impurities in the solid product was further analyzed through XRD analysis.The pyrolytic liquid fuel revealed the presence of conjugated aromatic structure and carbonyl group in their concentration.This research demonstrated that converting mixed-density plastics using sodium zeolite,aluminum oxide,and nickel oxide catalysts yields 84%valuable products,confirming wasted plastics as a lucrative energy feedstock for producing hydrogen and high-value carbon compounds.展开更多
A comparative study of products of thermal and thermocatalytic cracking of polypropylene(PP) in the presence of potassium polytitanate(PPT) synthesized by treatment of TiO_(2)(rutile) powder with molten mixture of KOH...A comparative study of products of thermal and thermocatalytic cracking of polypropylene(PP) in the presence of potassium polytitanate(PPT) synthesized by treatment of TiO_(2)(rutile) powder with molten mixture of KOH and KNO_(3) taken in a weight ratio of 30∶30∶40 has been carried out.It was shown that the studied type of PPT powder exhibits catalytic properties in the reaction of thermal decomposition of PP,compared to the effect of commercial zeolite catalyst CBV-780 traditionally used for this purpose.Based on the analysis performed,the differences in the mechanism of catalytic action of PPT and the zeolite were considered.The reasons for the observed differences in the composition of PP cracking products and in the rate of coke formation on the surface of studied catalysts were analyzed.Considering the obtained results,it has been proposed that the CBV-780 catalyst promoted more intensive production of the gaseous hydrocarbons compared to PPT,due to higher specific surface area(internal surface) accessible for relatively light and small-sized hydrocarbon products of cracking.However,intensive coke formation on the outer surface of the microporous zeolite contributes to the blocking of transport channels and the rapid loss of catalytic action.At the same time,PPT,which initially has a smaller specific surface area,retains its catalytic activity significantly longer due to slit-shaped flat pores and higher transport accessibility of the inner surface.展开更多
The hydrothermal stability of zeolites is essential for their potential applications in biomass conversion,especially in processes involving elevated temperatures alongside the use or generation of H_(2)O.In this stud...The hydrothermal stability of zeolites is essential for their potential applications in biomass conversion,especially in processes involving elevated temperatures alongside the use or generation of H_(2)O.In this study,we employed F-ions as mineralizers to synthesize hydrothermally stable ZSM-5 zeolites under acidic conditions.The acidic synthesis system promotes zeolites with fewer silanol-terminated lattice defects(ZSM-5(A))compared to the traditional basic conditions(ZSM-5(B)),endowing materials with substantially higher structural integrity and hydrophobicity.After 10 days of autoclave treatment at 200℃ in aqueous phase,H-ZSM-5(A)demonstrated nearly unchanged reaction rates in the dehydration of cyclohexanol,while H-ZSM-5(B)lost>50%of the dehydration activity.Additionally,H-ZSM-5(A)delivered higher initial dehydration rates compared to H-ZSM-5(B).The different measured activation energies further revealed variations in reaction pathways during cyclohexanol dehydration,i.e.,the monomer-or dimer-mediated routes depending on the concentration of alcohol molecule within zeolite pores,providing additional evidence for the strengthened hydrophobic nature of H-ZSM-5(A).Beyond this,the zeolite surface properties and the strength of cyclohexanol-zeolite interactions may impose additional transport/adsorption barriers attributed to multi-phase phenomena on the more polar H-ZSM-5(B)zeolite surfaces.More importantly,the hydrothermal treatment did not induce significant desilication and dealumination in H-ZSM-5(A),thereby preserving its active acid sites and ensuring exceptional hydrothermal stability.The present work fundamentally studies the synthesis of hydrothermally stable zeolites in an acidic medium using fluorides and expands the understanding of polar interactions in catalysis,characterized by the dehydration of cyclohexanol,for future application in biomass conversion.展开更多
Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally ...Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally friendly and cost-effective alternatives.In this study,we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co_(1)O_(3)H_(x) structure by regulating silanol nests in purely siliceous Beta zeolites.Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity.Additionally,the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles.Notably,the optimized Co_(0.3%)/deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol_(C3H6) g_(cat)^(-1) h^(-1),with an exceptional propylene selectivity of 99.1%at 550℃.Moreover,the Co_(0.3%)/deAl-meso-Beta catalyst demonstrated excellent stability,with negligible deactivation after 5 consecutive regeneration cycles.This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites,providing valuable insights for the design of high-activity,high-stability,and low-cost PDH catalysts.展开更多
Precisely tailoring metal single-atoms within zeolite scaffolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis.Herein,we...Precisely tailoring metal single-atoms within zeolite scaffolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis.Herein,we have successfully fabricated Ni single-atoms within BEA zeolite(Ni_(1)@Beta)through a facile in situ two-step hydrothermal strategy,notably without using any chelating agent for stabilizing Ni species.With the aid of advanced characterization techniques,such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy,etc.,and combined with density functional theory calculations,the nature and micro-environment of isolated Ni species,which are incorporated within 6-membered rings and stabilized by four skeletal oxygens of Beta zeolite,have been identified.The as-obtained Ni1@Beta exhibits a superior performance in terms of activity(with a turnover frequency value up to 114.1 h^(-1))and stability(for 5 consecutive runs)in the selective hydrogenation of furfural,surpassing those of Ni nanoparticle analogues and previously reported Ni-based heterogeneous catalysts.This study provides an efficient strategy for the fabrication of non-noble metal single-atoms within zeolites,which could be of great help for the design of metal-zeolite combinations in the chemoselective reactions involved in biomass conversion and beyond.展开更多
Zeolites are crystalline microporous materials widely used in catalysis,adsorption,and ion exchange owing to their tunable pore structures and acid centers[1].Traditional zeolites,however,often suffer from limitations...Zeolites are crystalline microporous materials widely used in catalysis,adsorption,and ion exchange owing to their tunable pore structures and acid centers[1].Traditional zeolites,however,often suffer from limitations such as restricted molecular diffusion and rapid coking,which hinder their efficiency in processing large molecules.展开更多
ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a signifi...ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a significant synthetic challenge.Herein,we demonstrate the possibility to control the Al distribution in ITR zeolites using zeolite A as an aluminum source(A-ITR).The A-ITR exhibited similar crystallinity,nanosheet morphology,textual parameters,and acidic concentration with those of conventional ITR made zeolites using aluminum isopropoxide as an aluminum source(C-ITR).Characterizations of the zeolite product with^(27)Al MQ.MAS NMR spectra,^(27)Al MAS NMR spectra,and 1-hexene cracking reveal that the A-ITR zeolites have more Al species distributed in T6 and T8 sites located in relatively smaller micropores of the framework than C-ITR.As a result,the A-ITR gave enhanced catalyst lifetime and propylene selectivity due to the suppression of the aromatic cycle in the MTP reaction,compared with the C-ITR.This work provides an alternative approach to prepare efficient ITR zeolites for MTP reaction.展开更多
Membrane-based vapor permeation(VP) is regarded as a highly efficient technology,featuring low energy consumption and free salt fouling.In this study,we have demonstrated upscaling chabazite(CHA) zeolite membranes on ...Membrane-based vapor permeation(VP) is regarded as a highly efficient technology,featuring low energy consumption and free salt fouling.In this study,we have demonstrated upscaling chabazite(CHA) zeolite membranes on the 19-channel α-Al_(2)O_(3) monolithic supports synthesized from high-silica gel(SiO_(2)/Al_(2)O_(3) ratio of 200) for the dehydration of acetic acid by VP.The monolithic membrane presents higher surface-to-volume ratio and a-tenfold greater mechanical strength compared to tubular ones.The micromorphology and crystallinity of the monolithic CHA zeolite membranes were characterized by scanning electron micrographs and X-ray diffraction analysis.The single-gas permeation test and the effects of temperature,feed water content and feed flow rate on the VP separation performance of monolithic CHA zeolite membrane for dehydration of acetic acid were investigated.Moreover,the stability test of monolithic CHA zeolite membranes was carried out.The 19-channel monolithic membrane achieved a comparable separation performance(water flux of 0.63 kg m^(-2)·h^(-1) and selectivity of 369 at 393 K) with the reported small-area zeolite membranes in water/acetic acid mixtures.It is demonstrated that the monolithic CHA zeolite membranes could be transformative candidates for industrial dehydration of acetic acid under harsh environments.展开更多
The effectiveness of Elodea nuttallii combined with a mixture of hydrous ferric oxide,zeolite and calcite(HZC)to reduce the internal loading of phosphorus(P)from sediment and its mechanism were studied,and the effect ...The effectiveness of Elodea nuttallii combined with a mixture of hydrous ferric oxide,zeolite and calcite(HZC)to reduce the internal loading of phosphorus(P)from sediment and its mechanism were studied,and the effect of Elodea nuttallii combined with HZC on the composition and function of the microbial communities in the surface sediment was also investigated.The results showed that the combination utilization of Elodea nuttallii and HZC can decrease the risk of phosphorus liberation from sediment to the overlying water,and the controlling efficiency of Elodea nuttallii combined with HZCwas higher than that of Elodea nuttallii or HZC alone.The passivation of labile P measured by diffusive gradient in thin film device and mobile P played a crucial role in the control of internal P loading from sediment by the combined Elodea nuttallii+HZC treatment.HZC capping had a promoting effect on the growth of Elodea nuttallii.This was beneficial to the absorption of phosphorus from sediment by Elodea nuttallii.The combined application of Elodea nuttallii and HZC not only had a certain negative effect on the diversity of bacteria in the surface sediment,but also changed themicrobial compositions of the surface sediment at the levels of phylum and genus.However,the microbial communities in the surface sediment still can perform good ecological function.The above results suggest that the combined application of Elodea nuttallii and HZC has a high potential in the management of internal P loading from sediment.展开更多
Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst an...Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst and the number of acceptable H*receptors.This study prepares highly dispersed Ni nanoparticles(NPs)catalysts on a Beta substrate via precursor structure topology transformation.In contrast to traditional support materials,the coordination and electronic structure changes between the Ni NPs and the support were achieved,further optimizing the active interface sites and enhancing hydrogen activation and hydrogenation performance.Additionally,the-OH groups at the strong acid sites in zeolite effectively intensified the hydrogen spillover effect as receptors for H^(*)migration and anchoring,accelerating the hydrogenation rate of aromatic rings.Under solvent-free conditions,this catalyst was used for the hydrogenation reaction of aromatic-rich oils,directly producing a C_(8)-C_(14)branched cycloalkanes mixture with an aromatic conversion rate of>99%.The cycloalkanes mixture produced by this method features high density(0.92 g/mL)and a low freezing point(<-60℃),making it suitable for use as high-density aviation fuel or as an additive to enhance the volumetric heat value of conventional aviation fuels in practical applications.展开更多
基金supported by National Natural Science Foundation of China(22372107,22072095,22202058)Postgraduate Education Reform Project of Liaoning Province(LNYJG2022400,LNYJG2023280)+3 种基金National Key Research and Development Program of China(2022YFB3506200,2022YFB3504100)Excellent Youth Science Foundation of Liaoning Province(2022-YQ-20)Shenyang Science and Technology Planning Project(22-322-3-28)Liaoning Xingliao talented youth Top talent program(XLYC2203007).
文摘Diesel engine exhaust comprises nitrogen oxides(NOx)and soot particles,which cause serious air pollution.However,owing to the contradictory nature of NO_(x)reduction and soot oxidation,a trade-off exists in the simultaneous removal of NO_(x)and soot.Consequently,catalytic technology has become a hot research topic.This study prepared MOδ/Fe-Beta(M=Fe,Co,Ni,Mn,Cu)catalysts through incipient wetness impregnation using Fe-Beta as the support and explored the catalytic performance of the above catalysts.The results exhibited the good performance of the prepared catalysts.The introduction of Mn resulted in a lower peak temperature of soot combustion for the catalyst,and slightly decreased deNOx performance of Fe-Beta.The soot combustion temperature was as low as 422℃,and the temperature window for 80%NO conversion was 164-423℃.The interaction between MnOd and zeolite can regulate the acid sites and produce sufficient active oxygen species for the catalyst.The catalytic activity of the MnOδ/Fe-Beta catalyst is due to its strong redox property,the appropriate number of acid sites,and sufficient number of active oxygen species.In addition,the catalyst had good stability and water and sulfur resistance,therefore it had great potential for future application in the simultaneous removal of NO_(x)and soot from diesel engine exhaust.
基金supported by foundation of Guizhou Provincial Basic Research Program Natural Sciencel Youth Guidance Project(No.QN[2025]090)Special post of Guizhou University(No.[2024]20).
文摘FAU zeolites have emerged as multifunctional materials with broad applications in catalysis and adsorption,owing to their hierarchical pore architectures,elevated specific surface areas,and adjustable extra-framework cationic sites.This review provides a critical overview of recent advances in FAU zeolite research with emphasis on their roles in environmental pollutant mitigation.A bibliometric analysis was performed to ascertain worldwide research trends,cooperation networks,and principal theme areas.Strategies for synthesis and functionalization,including crystallization pathways,one-pot methods,and post-synthetic modifications,were systematically evaluated for their capacity to tailor structural and physicochemical properties.Environmental applications were discussed in detail,particularly in heavy metal extraction,CO_(2)capture,and catalytic NOx reduction.Despite these advances,challenges persisted,notably restricted chemical stability under extreme pH conditions,scalability obstacles from laboratory to industrial production,and the necessity for enhanced catalytic efficiency.By integrating fundamental understanding with application-oriented perspectives,this review identifies existing knowledge gaps and delineates future directions for the rational design of FAU zeolites toward sustainable environmental remediation.
基金Project supported by Rumah Program 2023 and Net Zero Emission Program(1507/Ⅱ.7/HK.01.00/6/2023)a research facility from the National Research and Innovation Agency of Republic of Indonesia。
文摘Recycling rare earth elements(REEs)from waste is necessary for an environmentally sustainable reuse and wastewater management approach.Na-A zeolite was synthesized from coal fly ash(CFA)and applied for Ce^(3+)adsorption.Fourier transform infrared(FTIR)spectra show peaks at 790,500 and 467 cm^(-1),which are bond vibrations of Si-O-Si,Si with Al-O and Si-O-.The surface area is 15.88 m^(2)/g,with a pore size of 2.14 nm.SEM images show a cubic shape,which indicates the formation of zeolite.Field emission and energy disperse spectroscopy(EDS)shows the formation of Si,Al,Na,and O.Na-A zeolite was applied for Ce^(3+)adsorption.The optimum conditions for Ce^(3+)adsorption are 50 ppm concentration,360 min,and pH 6.The maximum adsorption capacity is 176.49 mg/g.Based on the results,it is found that the adsorption of Ce^(3+)by Na-A zeolite is pseudo-second-order.The desorption test using HNO_(3) is more effective than using HCl and H_(2)SO_(4).A desorption efficiency of 97.22%is obtained at 4 cycles.Adsorption test using real sample wastewater demonstrates an adsorption efficiency of 83.35%.
基金Joint Project of Dalian University of Technology-Dalian Institute of Chemical Physics (HX20230236)。
文摘Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.
基金supported by Zhongtian Iron and Steel-University of Science and Technology Beijing Youth Science and Technology Innovation Fund(No.FZTNTC2024050005)National Engineering Laboratory for Mobile Source Emission Control Technology,China(No.NELMS2020A07)The Fundamental Research Funds for the Central Universities,China(No.FRF-AT-20-12)。
文摘Zeolite-loaded noble metal catalysts have demonstrated excellent performance in addressing cold-start automotive exhaust NOx emissions and catalytic oxidation of VOCs applications.Pd and Pt are the most commonly used active metals in PNA and VOC catalysts,respectively.However,despite the same metal/zeolite composition,the efficient active sites for PNA and VOC catalysts have been viewed as mainly Pd^(2+) and Pt^(0),respectively,both of which are different from each other.As a result,various methods need to be applied to dope Pd and Pt in zeolitic support respectively for different usages.No matter which type of metal species is needed,the common requirement for both PNA and VOC catalysts is that the metal species should be highly dispersed in zeolite support and stay stable.The purpose of this paper is to review the progress of synthetic means of zeolite-coated noble metals(Pd,Pt,etc.)as effective PNA or VOC catalysts.To give a better understanding of the relationship between efficient metal species and the introduced methods,the species that contributed to the NOx adsorption(PNA)and VOCs deep catalytic oxidation were first summarized and compared.Then,based on the above discussion,the detailed construction strategies for different active sites in PNA and VOC catalysts,respectively,were elaborated in terms of synthetic routes,precursor selection,and zeolite carrier requirements.It is hoped that this will contribute to a better understanding of noble metal adsorption/catalysis in zeolites and provide promising strategies for the design of adsorption/catalysts with high activity,selectivity and stability.
文摘Hydrocracking technology represents a crucial position in the conversion of heavy oil and the transformation development from oil refining to the chemical industry.The properties of catalysts are one of the key factors in the hydrocracking process.As the main acidic component of hydrocracking catalyst,the influence of zeolite properties on the reaction performance has been the focus of research.In this study,a series of NiMo/Al_(2)O_(3)-Y catalysts were prepared using different Y zeolites as acidic components,and their performances in the hydrocracking of n-C_(10)were also evaluated.The structure-activity relationship between Y zeolite and the cracking performance of n-C_(10)was investigated with machine learning.First,a database of the physical and chemical properties of Y zeolite and their performance was established,and the correlation analysis was also conducted.Parameters such as the cell constant,acid content,acid strength,B/L ratio,mesopore volume,micropore volume of Y zeolite,and the reaction temperature were selected as independent variables.The conversion of n-C_(10)and the ratios of products C_(3)/C_(7)and i-C_(4)/n-C_(4)were selected as dependent variables.A model was established by the random forest algorithm and a new zeolite was predicted based on it.The results of model prediction were in good agreement with the experimental results.The R^(2)of the n-C_(10)conversion,C_(3)/C_(7)ratio,and i-C_(4)/n-C_(4)ratio were 0.9866,0.9845,and 0.9922,and the minimum root mean square error values were 0.0163,0.101,and 0.0211,respectively.These results can provide reference for the development of high performance hydrocracking catalyst and technology.
基金supported by the National Natural Science Foundation of China(No.52201274)the Project of Education Department of Shanxi Province(No.22JK0419).
文摘High-capacity LiBH_(4)is a promising solid hydrogen storage material.However,the large electron cloud density between the B-H bonds in LiBH_(4)induces high dehydrogenation temperatures and sluggish dehydrogenation kinetics.To solve the above problems,it is proposed to enhance the hydrogen storage properties of LiBH_(4)through the synergistic effect of Brønsted and Lewis acid in Hβzeolite.Composite hydrogen storage systems with different mass ratios were prepared by simple ball-milling.At a LiBH_(4)-to-Hβmass ratio of 6:4,the 6LiBH_(4)-4Hβsystem released hydrogen at 190℃and achieved a hydrogen release capacity of 7.0 wt%H_(2)upon heating to 400℃.More importantly,the hydrogen release capacity of the system reached 6.02 wt%at 350℃under isothermal conditions after 100 min and 7.2 wt%at 400℃under isothermal conditions after 80 min,whereas the pristine LiBH_(4)only achieved 2.2 wt%.The improvement in hydrogen storage performance of the system was mainly attributed to two factors:(i)Lewis acid sites with acceptable electrons in the Hβweaken the electron density of B-H bonds in LiBH_(4),and(ii)the H+proton from the Brønsted acid sites and H−of LiBH_(4)undergo a H^(+)+H^(−)=H_(2)reaction.Theoretical calculations revealed that the Lewis and Brønsted acid sites in the Hβzeolite are conducive to the weakening of B-H bonds and that storage charge transfer occurs near the Lewis acid sites.The present work provides new insights into improving the hydrogen storage performance of LiBH_(4)by weakening the B-H bonds in the LiBH_(4).
基金supported by the Key Technologies Research and Development Program(No.2022YFB3504102)the National Natural Science Foundation of China(Nos.22035009,22002050,and 22202087)+2 种基金the National Engineering Laboratory for Mobile Source Emission Control Technology(No.NELMS2020B01)Fuyang Normal University Open Fund(No.FSKFKT006D)the Postdoctoral Science Foundation of China(Nos.2022T150765 and 2020M683154).
文摘Nitrogen oxides(NO_(x))from diesel engine exhaust,is one of the major sources of environmental pollution.Currently,selective catalytic reduction with ammonia(NH_(3)-SCR)is considered to be the most effective protocol for reducing NO_(x)emissions.Nowadays,zeolitebased NH_(3)-SCR catalysts have been industrialized and widespread used in this field.Nevertheless,with the increasingly stringent environmental regulations and implementation of the requirement of“zero emission”of diesel engine exhaust,it is extremely urgent to prepare catalysts with superior NH_(3)-SCR activity and exceptional resistance to poisons(SO2,alkali metals,hydrocarbons,etc.).Core-shell structure zeolite-based catalysts(CSCs)have shown great promise in NH_(3)-SCR of NO_(x)in recent years by virtue of its relatively higher low-temperature activity,broader operation temperature window and outstanding resistance to poisons.This review mainly focuses on the recent progress of CSCs for NH_(3)-SCR of NO_(x)with three extensively investigated SSZ-13,ZSM-5,Beta zeolites as cores.The reaction mechanisms of resistance to sulfur poisoning,alkali metal poisoning,hydrocarbon poisoning,and hydrothermal aging are summarized.Moreover,the important role of interfacial effect between core and shell in the reaction of NH_(3)-SCR was clarified.Finally,the future development and application outlook of CSCs are prospected.
基金supported by the National Natural Science Foundation of China(22278090,21978055)Natural Science Foundation of Guangdong Province,China(2022A1515012088)。
文摘The cerium-silicate pillared MWW zeolites are fabricated by introducing Ce species into the silica pillars within adjacent MWW layers through a liquid-phase pillaring method,and the multiple-layer structure of MWW zeolites is well maintained.However,it's found that these Ce^(3+)species can produce the Bronsted acid sites by the dissociation of water molecules owing to the electrostatic field of Ce^(3+)cations,the splitting of water molecules occurs following[Ce(H_2O)_n]^(3+)■Ce[(OH)(H_2O)_(n-1)]^(2+)+H^(+)equation based on the Plank-Hirschler mechanism,leading to superior activity of resultant cerium-silicate pillared MWW zeolites in the alkylation between benzene with 1-dodecene.Moreover,the additional Ce species located in the silica pillars can be easily accessed by vip molecules due to the presence of mesopores between neighboring MWW layers,which can strongly active benzene molecules by polarization effect,and dodecyl carbenium ions are preferred to attack the carbon atoms located in activated benzene molecules,resulting in the long lifetime of cerium-silicate pillared MWW zeolites since the oligomerization of long-chain olefins is suppressed.Under harsh reaction conditions(benzene/1-dodecene=10,WHSV=20 h^(-1)),the optimized cerium-silicate pillared MWW zeolite shows outstanding activity(>40%)and excellent selectivity(>85%)of 2-LAB in the alkylation of benzene with 1-dodecene.
基金supported by the National Energy R&D Center of Petroleum Refining Technology(RIPP,SINOPEC),the National Natural Science Foundation of China(Grants 22161132028,22172177,22225205,22372191 and 22372178)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0540000)+2 种基金the International Partnership Program of the Chinese Academy of Sciences(314GJH2022022FN)Natural Science Foundation of Hubei Province(2021CFA021)Hubei International Scientific and Technological Cooperation Program(2024EHA043)and Base(SH2303).
文摘Organic structure directingagents(OSDAs),suchas tetrapropylammonium(TPA)cations,serve as crucial templates for the formation of zeolite frameworks.These organic molecules interact with inorganic species,guiding the assembly of the zeolite structure.In this study,we inves-tigate the complex interplay between boron species and TPA cations during the crystallization of[B,Al]-ZSM-5 zeolites.Two-dimensional(2D)11B-{1H}cross-polarization heteronuclear correlation(CP-HECTOR)NMRexperiments elucidate distinct interactions between two boron species,B(IV)-1 and B(IV)-2,and the propyl chain of the TPAs.Amorphous B(IV)-1 species exhibit a strong preference for proximity to the nitrogen cation center of the OSDAs,while framework B(IV)-2 species engage with components situated at greater distances from the cation center.Moreover,13C-{11B}symmetry-based resonance-echo saturation-pulse double-resonance(S-RESPDOR)experiments revealed that framework boron species preferentially occupy the straight channels of the MFI structure,as evidenced by their interaction with specificmethyl groups on the TPAmolecules.This observation provides valuable insights into the crystallization mechanism of boron-based zeolites,suggesting that the conformation and orientation of the OSDA molecules play a critical role in determining the location of boron atoms within the zeolite framework.
基金supported by the Researchers Supporting Project(RSPD2025R985),King Saud University,Riyadh,Saudi Arabia.
文摘A combination of experimental and statistical analysis presents a comprehensive understanding of the microwave pyrolysis technique for catalytic deconstruction of mixed-density plastics.By optimizing the process parameters and catalyst selection,it is possible to maximize the production of valuable solid and energy products,contributing to sustainable waste management.In this work,different mixed-density plastics were pyrolyzed with different catalysts and residence times to yield liquid fuel,syngas,and structured carbon residue.The effect of inputs on the product type,yield and composition was statistically evaluated using ANOVA,which showed an F value of 4.108 and a p-value of 0.098(>1.00).FTIR and GC-MS revealed that the oil product consisted of C13+fractions in the form of alkanes,alkenes,and aromatics.The microscopic analysis of the residue confirmed the formation of carbon nanotubes along with other amorphous products.The presence of impurities in the solid product was further analyzed through XRD analysis.The pyrolytic liquid fuel revealed the presence of conjugated aromatic structure and carbonyl group in their concentration.This research demonstrated that converting mixed-density plastics using sodium zeolite,aluminum oxide,and nickel oxide catalysts yields 84%valuable products,confirming wasted plastics as a lucrative energy feedstock for producing hydrogen and high-value carbon compounds.
文摘A comparative study of products of thermal and thermocatalytic cracking of polypropylene(PP) in the presence of potassium polytitanate(PPT) synthesized by treatment of TiO_(2)(rutile) powder with molten mixture of KOH and KNO_(3) taken in a weight ratio of 30∶30∶40 has been carried out.It was shown that the studied type of PPT powder exhibits catalytic properties in the reaction of thermal decomposition of PP,compared to the effect of commercial zeolite catalyst CBV-780 traditionally used for this purpose.Based on the analysis performed,the differences in the mechanism of catalytic action of PPT and the zeolite were considered.The reasons for the observed differences in the composition of PP cracking products and in the rate of coke formation on the surface of studied catalysts were analyzed.Considering the obtained results,it has been proposed that the CBV-780 catalyst promoted more intensive production of the gaseous hydrocarbons compared to PPT,due to higher specific surface area(internal surface) accessible for relatively light and small-sized hydrocarbon products of cracking.However,intensive coke formation on the outer surface of the microporous zeolite contributes to the blocking of transport channels and the rapid loss of catalytic action.At the same time,PPT,which initially has a smaller specific surface area,retains its catalytic activity significantly longer due to slit-shaped flat pores and higher transport accessibility of the inner surface.
文摘The hydrothermal stability of zeolites is essential for their potential applications in biomass conversion,especially in processes involving elevated temperatures alongside the use or generation of H_(2)O.In this study,we employed F-ions as mineralizers to synthesize hydrothermally stable ZSM-5 zeolites under acidic conditions.The acidic synthesis system promotes zeolites with fewer silanol-terminated lattice defects(ZSM-5(A))compared to the traditional basic conditions(ZSM-5(B)),endowing materials with substantially higher structural integrity and hydrophobicity.After 10 days of autoclave treatment at 200℃ in aqueous phase,H-ZSM-5(A)demonstrated nearly unchanged reaction rates in the dehydration of cyclohexanol,while H-ZSM-5(B)lost>50%of the dehydration activity.Additionally,H-ZSM-5(A)delivered higher initial dehydration rates compared to H-ZSM-5(B).The different measured activation energies further revealed variations in reaction pathways during cyclohexanol dehydration,i.e.,the monomer-or dimer-mediated routes depending on the concentration of alcohol molecule within zeolite pores,providing additional evidence for the strengthened hydrophobic nature of H-ZSM-5(A).Beyond this,the zeolite surface properties and the strength of cyclohexanol-zeolite interactions may impose additional transport/adsorption barriers attributed to multi-phase phenomena on the more polar H-ZSM-5(B)zeolite surfaces.More importantly,the hydrothermal treatment did not induce significant desilication and dealumination in H-ZSM-5(A),thereby preserving its active acid sites and ensuring exceptional hydrothermal stability.The present work fundamentally studies the synthesis of hydrothermally stable zeolites in an acidic medium using fluorides and expands the understanding of polar interactions in catalysis,characterized by the dehydration of cyclohexanol,for future application in biomass conversion.
文摘Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally friendly and cost-effective alternatives.In this study,we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co_(1)O_(3)H_(x) structure by regulating silanol nests in purely siliceous Beta zeolites.Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity.Additionally,the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles.Notably,the optimized Co_(0.3%)/deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol_(C3H6) g_(cat)^(-1) h^(-1),with an exceptional propylene selectivity of 99.1%at 550℃.Moreover,the Co_(0.3%)/deAl-meso-Beta catalyst demonstrated excellent stability,with negligible deactivation after 5 consecutive regeneration cycles.This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites,providing valuable insights for the design of high-activity,high-stability,and low-cost PDH catalysts.
文摘Precisely tailoring metal single-atoms within zeolite scaffolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis.Herein,we have successfully fabricated Ni single-atoms within BEA zeolite(Ni_(1)@Beta)through a facile in situ two-step hydrothermal strategy,notably without using any chelating agent for stabilizing Ni species.With the aid of advanced characterization techniques,such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy,etc.,and combined with density functional theory calculations,the nature and micro-environment of isolated Ni species,which are incorporated within 6-membered rings and stabilized by four skeletal oxygens of Beta zeolite,have been identified.The as-obtained Ni1@Beta exhibits a superior performance in terms of activity(with a turnover frequency value up to 114.1 h^(-1))and stability(for 5 consecutive runs)in the selective hydrogenation of furfural,surpassing those of Ni nanoparticle analogues and previously reported Ni-based heterogeneous catalysts.This study provides an efficient strategy for the fabrication of non-noble metal single-atoms within zeolites,which could be of great help for the design of metal-zeolite combinations in the chemoselective reactions involved in biomass conversion and beyond.
基金the support of the National Natural Science Foundation of China(Nos.22205207 and 22378369).
文摘Zeolites are crystalline microporous materials widely used in catalysis,adsorption,and ion exchange owing to their tunable pore structures and acid centers[1].Traditional zeolites,however,often suffer from limitations such as restricted molecular diffusion and rapid coking,which hinder their efficiency in processing large molecules.
基金supported by the National Key Research and Development Program of China(2022YFA1503602)the National Natural Science Foundation of China(22288101,U21B20101 and 22172141)+1 种基金the BASF International Network of Centers of Excellence projectthe Zhejiang Provincial Natural Science Foundation of China(LR24B030001)。
文摘ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a significant synthetic challenge.Herein,we demonstrate the possibility to control the Al distribution in ITR zeolites using zeolite A as an aluminum source(A-ITR).The A-ITR exhibited similar crystallinity,nanosheet morphology,textual parameters,and acidic concentration with those of conventional ITR made zeolites using aluminum isopropoxide as an aluminum source(C-ITR).Characterizations of the zeolite product with^(27)Al MQ.MAS NMR spectra,^(27)Al MAS NMR spectra,and 1-hexene cracking reveal that the A-ITR zeolites have more Al species distributed in T6 and T8 sites located in relatively smaller micropores of the framework than C-ITR.As a result,the A-ITR gave enhanced catalyst lifetime and propylene selectivity due to the suppression of the aromatic cycle in the MTP reaction,compared with the C-ITR.This work provides an alternative approach to prepare efficient ITR zeolites for MTP reaction.
基金financially supported by the National Key Research and Development Program of China (2023YFB3810700)the National Natural Science Foundation of China (22378189,U22A20414 and 22378188)+1 种基金the Natural Science Foundation of Jiangsu Provincial Department of Science and Technology(BK20232010 and BG2024018)National State Key Laboratory of Material-oriented Chemical Engineering (SKL-MCE-22A02 and SKL-MCE23B14)。
文摘Membrane-based vapor permeation(VP) is regarded as a highly efficient technology,featuring low energy consumption and free salt fouling.In this study,we have demonstrated upscaling chabazite(CHA) zeolite membranes on the 19-channel α-Al_(2)O_(3) monolithic supports synthesized from high-silica gel(SiO_(2)/Al_(2)O_(3) ratio of 200) for the dehydration of acetic acid by VP.The monolithic membrane presents higher surface-to-volume ratio and a-tenfold greater mechanical strength compared to tubular ones.The micromorphology and crystallinity of the monolithic CHA zeolite membranes were characterized by scanning electron micrographs and X-ray diffraction analysis.The single-gas permeation test and the effects of temperature,feed water content and feed flow rate on the VP separation performance of monolithic CHA zeolite membrane for dehydration of acetic acid were investigated.Moreover,the stability test of monolithic CHA zeolite membranes was carried out.The 19-channel monolithic membrane achieved a comparable separation performance(water flux of 0.63 kg m^(-2)·h^(-1) and selectivity of 369 at 393 K) with the reported small-area zeolite membranes in water/acetic acid mixtures.It is demonstrated that the monolithic CHA zeolite membranes could be transformative candidates for industrial dehydration of acetic acid under harsh environments.
基金supported by the Capacity Building Project of Local University of Shanghai Municipal Science and Technology Commission(No.10230502900)the Program for Shanghai Collaborative Innovation Center for Cultivating Elite Breeds and Green-culture of Aquaculture animals(No.2021-KJ-02-12)the Innovation Project for Chongming Agriculture Industry from Chongming District Agriculture Commission of Shanghai(No.2022CNKC-01-05).
文摘The effectiveness of Elodea nuttallii combined with a mixture of hydrous ferric oxide,zeolite and calcite(HZC)to reduce the internal loading of phosphorus(P)from sediment and its mechanism were studied,and the effect of Elodea nuttallii combined with HZC on the composition and function of the microbial communities in the surface sediment was also investigated.The results showed that the combination utilization of Elodea nuttallii and HZC can decrease the risk of phosphorus liberation from sediment to the overlying water,and the controlling efficiency of Elodea nuttallii combined with HZCwas higher than that of Elodea nuttallii or HZC alone.The passivation of labile P measured by diffusive gradient in thin film device and mobile P played a crucial role in the control of internal P loading from sediment by the combined Elodea nuttallii+HZC treatment.HZC capping had a promoting effect on the growth of Elodea nuttallii.This was beneficial to the absorption of phosphorus from sediment by Elodea nuttallii.The combined application of Elodea nuttallii and HZC not only had a certain negative effect on the diversity of bacteria in the surface sediment,but also changed themicrobial compositions of the surface sediment at the levels of phylum and genus.However,the microbial communities in the surface sediment still can perform good ecological function.The above results suggest that the combined application of Elodea nuttallii and HZC has a high potential in the management of internal P loading from sediment.
基金financially supported by the National Natural Science Foundation of China(Grant 22278439,21776313)the Shandong Province Higher Education Youth Innovation Technology Support Program(Grant 2022KJ074)。
文摘Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst and the number of acceptable H*receptors.This study prepares highly dispersed Ni nanoparticles(NPs)catalysts on a Beta substrate via precursor structure topology transformation.In contrast to traditional support materials,the coordination and electronic structure changes between the Ni NPs and the support were achieved,further optimizing the active interface sites and enhancing hydrogen activation and hydrogenation performance.Additionally,the-OH groups at the strong acid sites in zeolite effectively intensified the hydrogen spillover effect as receptors for H^(*)migration and anchoring,accelerating the hydrogenation rate of aromatic rings.Under solvent-free conditions,this catalyst was used for the hydrogenation reaction of aromatic-rich oils,directly producing a C_(8)-C_(14)branched cycloalkanes mixture with an aromatic conversion rate of>99%.The cycloalkanes mixture produced by this method features high density(0.92 g/mL)and a low freezing point(<-60℃),making it suitable for use as high-density aviation fuel or as an additive to enhance the volumetric heat value of conventional aviation fuels in practical applications.
