Zeolite-encapsulated metal nanoclusters are at the heart of bifunctional catalysts,which hold great potential for petrochemical conversion and the emerging sustainable biorefineries.Nevertheless,efficient encapsulatio...Zeolite-encapsulated metal nanoclusters are at the heart of bifunctional catalysts,which hold great potential for petrochemical conversion and the emerging sustainable biorefineries.Nevertheless,efficient encapsulation of metal nanoclusters into a high-silica zeolite Y in particular with good structural integrity still remains a significant challenge.Herein,we have constructed Ru nanoclusters(~1 nm)encapsulated inside a high-silica zeolite Y(SY)with a SiO_(2)/Al_(2)O_(3) ratio(SAR)of 10 via a cooperative strategy for direct zeolite synthesis and a consecutive impregnation for metal encapsulation.Compared with the benchmark Ru/H-USY and other analogues,the as-prepared Ru/H-SY markedly boosts the yields of pentanoic biofuels and stability in the direct hydrodeoxygenation of biomass-derived levulinate even at a mild temperature of 180℃,which are attributed to the notable stabilization of transition states by the enhanced acid accessibility and properly sized constraints of zeolite cavities owing to the good structural integrity.展开更多
The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural...The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural using Hβ zeolite modified by organic acids for dealuminization to regulate its textural and acidic properties. It was found that citric acid-dealuminized Hβ zeolite possessed high specific surface areas, wide channels and high Brønsted acid amount, which facilitated the selective conversion of fructose to furfural with a maximum yield of 76.2% at433 K for 1 h in the γ-butyrolactone(GBL)-H_(2)O system, as well as the concomitant formation of 83.0% formic acid. The^(13)C-isotope labelling experiments and the mechanism revealed that the selective cleavage of C1–C2 or C5–C6 bond on fructose was firstly occurred to form pentose or C5 intermediate by weak Brønsted acid, which was then dehydrated to furfural by strong Brønsted acid. Also this dealuminized Hβ catalyst showed the great recycling performance and was active for the conversion of glucose and mannose.展开更多
Zeolites have been widely used as catalysts,ion-exchangers,and adsorbents in chemical industries,detergent industry,steel industry,glass industry,ceramic industry,medical and healthfield,and environmentalfield,and recen...Zeolites have been widely used as catalysts,ion-exchangers,and adsorbents in chemical industries,detergent industry,steel industry,glass industry,ceramic industry,medical and healthfield,and environmentalfield,and recently applied in energy storage.Seed-assisted synthesis is a very effective approach in promoting the crystallization of zeolites.In some cases,the target zeolite cannot be formed in the absence of seed zeolite.In homologous seed-assisted synthesis,the structure of the seed zeolite is the same to that of the target zeolite,while the structure of the seed zeolite is different to that of the target zeolite in the heterologous seed-assisted synthesis.In this review,we briefly summarized the heterologous seed-assisted syntheses of zeolites and analyzed the structure-directing effect of heterologous seeds and surveyed the“common composite building units(CBUs)hypothesis”and the“common secondary building units(SBUs)hypothesis”.However,both hypotheses cannot explain all observations on the heterologous seed-assisted syntheses.Finally,we proposed that the formation of the target zeolite does need nuclei with the structure of target zeolite and the formation of the nuclei of the target zeolite can be promoted by either the undissolved seed crystals with the same CBUs or SBUs to the target zeolite or by the facilitated appropriate distribution of the specific building units due to the presence of the heterologous seed that does not have any common CBUs and SBUs with the target zeolite.展开更多
A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal cry...A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.展开更多
Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficien...Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.展开更多
Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesi...Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesized by alkaline melting and hydrothermal two-step process,which had high crystallinity and excellent crystal control.And the optimum conditions for synthesis of zeolite were investigated:NaOH-EMR mass ratio=1.2,L/S=10,hydrothermal temperature=90℃,and hydrothermal time=6 h.Then,EMRZA and EMRZX showed excellent adsorption of Cd^(2+).When T=25℃,time=120min,pH=6,C0=518 mg·L^(-1),and quantity of absorbent=1.5 g·L^(-1),the adsorption capacities of EMRZA and EMRZX reached 314.2 and 289,5 mg·g^(-1),respectively,In addition,after three repeated adsorption-desorption cycles,EMRZA and EMRZX retained 80%and 74%of the initial zeolites removal rates,respectively.Moreover,adsorption results followed quasi-second-order kinetics and monolayer adsorption,which was regulated by a combination of chemisorption and intra-particle diffusion mechanisms.The adsorption mechanism was ions exchange between Cd^(2+)and Na+.In summary,it has been confirmed that EMRZA and EMRZX can be reused as highly efficient adsorbents to treat Cd^(2+)-contaminated wastewater.展开更多
Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were invest...Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.展开更多
A blast furnace slag zeolite(BFSZ)material was successfully synthesized from BFS by alkaline fusion and hydrothermal treatment.Via the analyses of XRD,FT-IR,FE-SEM,XRF,CEC and BET surface area measurement,when zeolite...A blast furnace slag zeolite(BFSZ)material was successfully synthesized from BFS by alkaline fusion and hydrothermal treatment.Via the analyses of XRD,FT-IR,FE-SEM,XRF,CEC and BET surface area measurement,when zeolite was synthesized at a crystallization temperature of 100℃with initial Si/Al ratio of 1:1,the main composition in the product is Na-A zeolite.Under the above conditions,the BFSZ was synthesized with CEC of 3.06 meq/g and maximum BET surface area of 37.55 m^(2)·g^(-1).Moreover,the incorporating of BFS-derived minor metals(such as Mg,Fe,and Ca)are found to be of little importance for the synthesis of BFSZ.Thus the obtained BFSZ material has a great adsorption performance for removing Mn^(2+),Cu^(2+),and NH_(4)^(+)ions diluted in water,owing to the higher CEC.展开更多
Tungsten (W) incorporated mobil-type eleven (MEL) zeolite membrane (referred to as W-MEL membrane) with high separation performance was firstly explored for the separation of oil/water mixtures under the influence of ...Tungsten (W) incorporated mobil-type eleven (MEL) zeolite membrane (referred to as W-MEL membrane) with high separation performance was firstly explored for the separation of oil/water mixtures under the influence of gravity.W-MEL membranes were grown on stainless steel (SS) meshes through in-situ hydrothermal growth method facilitated with (3-aminopropyl)triethoxysilane (APTES) modification of stainless steel meshes,which promote the heterogeneous nucleation and crystal growth of W-MEL zeolites onto the mesh surface.W-MEL membranes were grown on different mesh size supports to investigate the effect of mesh size on the separation performance of the membrane.The assynthesized W-MEL membrane supported on 500 mesh (25μm)(W-MEL-500) exhibit the hydrophilic nature with a water contact angle of 11.8°and delivers the best hexane/water mixture separation with a water flux and separation efficiency of 46247 L·m^(-2)·h^(-1)and 99.5%,respectively.The wettability of W-MEL membranes was manipulated from hydrophilic to hydrophobic nature by chemically modifying with the fluorine-free compounds (hexadecyltrimethoxysilane (HDTMS) and dodecyltrimethoxysilane(DDTMS)) to achieve efficient oil-permselective separation of heavy oils from water.Among the hydrophobically modified W-MEL membranes,W-MEL-500-HDTMS having a water contact angle of146.4°delivers the best separation performance for dichloromethane/water mixtures with a constant oil flux and separation efficiency of 61490 L·m^(-2)·h^(-1)and 99.2%,respectively along with the stability tested up to 20 cycles.Both W-MEL-500-HDTMS and W-MEL-500-DDTMS membranes also exhibit similar separation performances for the separation of heavy oil from sea water along with a 20-fold lower corrosion rate in comparison with the bare stainless-steel mesh,indicating their excellent stability in seawater.Compared to the reported zeolite membranes for oil/water separation,the as-synthesized and hydrophobically modified W-MEL membranes shows competitive separation performances in terms of flux and separation efficiency,demonstrating the good potentiality for oil/water separation.展开更多
In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides her...In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.展开更多
Encapsulation of Fe nanoparticles in zeolite is a promising way to significantly improve the catalytic activity and stability of Fe-based catalysts during the degradation process of organic pollutants.Herein,Fe nanoca...Encapsulation of Fe nanoparticles in zeolite is a promising way to significantly improve the catalytic activity and stability of Fe-based catalysts during the degradation process of organic pollutants.Herein,Fe nanocatalysts were encapsulated into silicalite-1(S-1)zeolite by using a ligand-protected method(with dicyandiamide(DCD)as a organic ligand)under direct hydrothermal synthesis condition.High-resolution transmission electron microscopy(HRTEM)results confirmed the high dispersion of Fe nanocatalysts which were successfully encapsulated within the voids among the primary particles of the S-1 zeolite.The developed S-1 zeolite encapsulated Fe nanocatalyst(Fe@S-1)exhibited significantly improved catalytic activity and reusability in the catalytic degradation process of methylene blue(MB).Specifically,the developed Fe0.021@S-1 catalyst showed high catalytic degradation activity,giving a high MB degradation efficiency of 100%in 30 min,outperformed the conventional impregnated catalyst(Fe/S-1).Moreover,the Fe@S-1 catalyst afforded an outstanding stability,showing only ca.7.9%activity loss after five cycling tests,while the Fe/S-1 catalyst presented a significantly activity loss of 50.9%after only three cycles.Notably,the encapsulation strategy enabled a relatively lower Fe loading in the Fe@S-1 catalyst in comparison with that of the Fe/S-1 catalyst,i.e.,0.35%vs.0.81%(mass).Radical scavenging experiments along with electron spin resonance(ESR)measurements confirmed that the major role ofOH in the MB degradation process.Specifically,Fe@S-1 catalyst with high molar ratio of[Fe(DCD)]Cl3 is beneficial to form Fe complexes/nanoclusters in the voids(which has large pore size of 1–2 nm)among the primary particles of the zeolite,and thus improving the diffusion and accessibility of reactants to Fe active sites,and thus exhibiting a relatively higher degradation efficiency.This work demonstrates that zeolite-encapsulated Fe nanocatalysts present potential applications in the advanced oxidation of wastewater treatment.展开更多
Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the pr...Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the preparation of a reusable Pd catalyst for reductive etherification remains to be a great challenge.In this study,a series of Si O_(2)supported Pd catalysts with particle size ranging from 2.2 nm to 28 nm were prepared.Their textural properties and catalytic performance in furfural reductive etherification have been systematically studied.The results herein shed light on the particle size effect on the competition between hydrogenation/hydrogenolysis of C=O in furfural over Pd surface.We found out that Pd nanoparticles larger than 3 nm are preferred for one step reductive etherification.Based on this finding,we prepared a Pd/ZSM-5 bifunctional catalyst comprising Pd nanoparticles larger than 3 nm and decreased acidity in presence of amino organosilane,which served as a bifunctional catalyst succeeding in one-pot synthesis of ether via reductive-etherification and direct-etherification.This strategy showed significant advantage in efficiently converting furfuryl acohol,a major side-product,into ether,while suppressing the undesired side-reactions.展开更多
The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an e...The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.展开更多
Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existin...Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existing catalyst is limited due to the poor activity and stability,which hinders its industrialization.Herein,we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI)for CO_(2)-ODP.Characterization results reveal that the Zn2+species are coordinated with the MFI zeolite matrix as isolated cations and the NPs of Pt,Rh,or Rh Pt are highly dispersed in the zeolite crystals.The isolated Zn2+cations are very effective for activating the propane and the small NPs are favorable for activating the CO_(2),which synergistically promote the selective transformation of propane and CO_(2)to propylene and CO.As a result,the optimal 0.25%Rh0.50%Pt@Zn-MFI catalyst shows the best propylene yield,satisfactory CO_(2)conversion,and long-term stability.Moreover,considering the tunable synergetic effects between the isolated cations and NPs,the developed approach offers a general guideline to design more efficient CO_(2)-ODP catalysts,which is validated by the improved performance of the bifunctional catalysts via simply substituting Sn4+cations for Zn2+cations in the MFI zeolite matrix.展开更多
Heat accumulation inside perovskite solar cells causes the decomposition of the perovskite layer and hole transport materials(HTMs)under working conditions,yielding a decrease in long-term stability.Here,we present a ...Heat accumulation inside perovskite solar cells causes the decomposition of the perovskite layer and hole transport materials(HTMs)under working conditions,yielding a decrease in long-term stability.Here,we present a zeolite-assisted heat conduction strategy by introducing economic zeolite crystals(e.g.,NaX,NaY,and ZSM-5)as a cooling filter to induce heat diffusion.The fitted thermal diffusion kinetic equation from real-time infrared thermal imaging technology reveals the zeolite skeleton assisted thermal co nduction mechanism of internal lattice vibration.Additionally,the nearly twofold improved conductivity of the modified HTM film is benefited from Na^(+)hopping on the supercages of the zeolite,therefore,the best-performed device with a rapid heat diffusion and defect inhibition obtains a remarkable power conversion efficiency of 23.42%.Both of NaX modified sprio-OMeTAD and PTAA based devices exhibit excellent operational stability after heating 1000 h at 85℃under N_(2)condition.This work demonstrates the potential application of economical porous zeolite materials in improving the thermal stability of PSCs.展开更多
Montmorillonite and clinoptilolite zeolite were used as representative materials to prepare calcined clay-cement binary cementitious materials in order to study the effect of calcination treatment on the activation of...Montmorillonite and clinoptilolite zeolite were used as representative materials to prepare calcined clay-cement binary cementitious materials in order to study the effect of calcination treatment on the activation of clay minerals and the activity difference between layered and framed clays in this research.The influence of different calcined clay content(2%,4%,6%,8%,10%)on the fluidity,compressive strength,microstructure,phase change,and hydration heat of cement-based materials were analyzed.The calcined clay improves the fluidity of cement-based materials as compared with the uncalcined group.The addition of calcined montmorillonite(CMT)improves the development of mechanical strength,and the optimal compressive strength reaches 85 MPa at 28 days with 8%CMT.However,the activity of calcined clinoptilolite zeolite(CZL)is weak with few reaction sites,which slightly reduced the mechanical strength as compared to the blank sample.The addition of CMT changes the microscopic morphology of hydration products such as C-S-H and C-A-H,leading to the formation and transformation of ettringite in the early stage.It promotes the gradual polymerization of Si-O bonds into Si-O-Si bonds simultaneously,which accelerates the early hydration process.However,CZL acts mainly as a filling function in the cementitious system.In brief,CMT as an admixture can improve the mechanical properties of cement,but CZL has little effect.This work provides a guideline for the applications of calcined clay in cement,considering the influence of clay type on workability and mechanical strength.展开更多
The electrocatalytic conversion of reactive nitrogen species to ammonia is a promising strategy for efficient NH_(3) synthesis.In this study,we reveal that the hybrid Cu^(+)/Cu~0 interface is catalytically active for ...The electrocatalytic conversion of reactive nitrogen species to ammonia is a promising strategy for efficient NH_(3) synthesis.In this study,we reveal that the hybrid Cu^(+)/Cu~0 interface is catalytically active for electrochemical ammonia synthesis from nitrate reduction.To maintain the hybrid Cu^(+)/Cu~0 state at negative reaction potentials,hydrophilic zeolite is used to modify Cu/Cu_(2)O electrocatalyst,which demonstrates an impressive NH_(3) production rate of 41.65 mg h^(-1) cm^(-2)with ~100% Faradaic efficiency of ammonia synthesis at-0.6 V vs.RHE.In-situ Raman spectroscopy unveil the high activity originates from the zeolite reconstruction at the electrode–electrolyte interface,which protects the valence state of Cu~0/Cu^(+) site under negative potential and promotes electrochemical activity towards NH_(3) synthesis.展开更多
The synthesis of a continuous IMF zeolite membrane was fabricated on tubular substrates by seeded growth for the first time. The straight channels of IMF zeolite with diameters of 0.53–0.59 nm are distinguishable for...The synthesis of a continuous IMF zeolite membrane was fabricated on tubular substrates by seeded growth for the first time. The straight channels of IMF zeolite with diameters of 0.53–0.59 nm are distinguishable for p-xylene from o-xylene molecules. Pure IMF-phase high-silica IM-5 zeolite seeds with uniform and fine crystal size were fabricated by a new sonication-assisted aging process. The seeds were coated on the support by dipcoating and induced the formation of continuous membrane. Separation performance in p-/o-xylene mixture was investigated at various temperature and pressure. The typical IM-5zeolite membrane had p-/o-xylene separation factor of 3.7. Our results suggest that IM-5 zeolite is a potentially good membrane material for the separation of xylene mixtures.展开更多
The use of some environmental functional minerals as backfill-modified materials may improve the leaching resistance of cemented uranium tailings backfill created from alkali-activated slag(CUTB),but these materials m...The use of some environmental functional minerals as backfill-modified materials may improve the leaching resistance of cemented uranium tailings backfill created from alkali-activated slag(CUTB),but these materials may participate in the hydration reaction of the cementitious materials,which could have a certain impact on the pore structure of the CUTB,thus affecting its mechanical properties and leaching resistance.In this paper,natural zeolite is selected as the backfill-modified material,and it is added to alkali-activated slag paste(AASP)and CUTB in cementitious material proportions of 4%,8%,12%,and 16%to prepare AASP mixtures and CUTB mixtures containing environmental functional minerals.After the addition of natural zeolite,the porosity of the CUTB generally increases,but when the content is 4%,the porosity decreases to 22.30%.The uniaxial compressive strength(UCS)of the CUTB generally decreases,but the decrease is the smallest when the content is 4%,and the UCS is 12.37 MPa.The addition of natural zeolite mainly reduces the number of fine pores in the CUTB,but the pores with relaxation times T_(2)of greater than 10 ms account for about 10%of the total pores,and there are a certain number of large pores in the CUTB.The main product of alkali-activated slag is calcium(alumino)silicate hydrate(C-(A)-S-H gel).When natural zeolite is added,the hydration products develop towards denser products with a high degree of polymerization and the formation of low polymerization products is reduced.This affects the internal fracture pores of the hydration products and the interface pores of the CUTB,has an irregular effect on the pore characteristics of the CUTB,and influences the UCS.展开更多
Pervaporation performance of NaY zeolite membranes is improved by ion-exchange with di-valent nitrate salt.Different nitrate salts,including Co(NO_(3))_(2),Mg(NO_(3))_(2),Zn(NO_(3))_(2),Ca(NO_(3))_(2),Cu(NO_(3))_(2),K...Pervaporation performance of NaY zeolite membranes is improved by ion-exchange with di-valent nitrate salt.Different nitrate salts,including Co(NO_(3))_(2),Mg(NO_(3))_(2),Zn(NO_(3))_(2),Ca(NO_(3))_(2),Cu(NO_(3))_(2),KNO_(3),and AgNO_(3),have great effects on the channel structure and water affinity of the NaY zeolite membrane.When the concentration of nitrate salt,ion-exchange temperature and time are 0.1 mol·L^(-1),50℃and 2 h,the ion-exchange degree order of NaY zeolites is Ag^(+)>K^(+)>Ca^(2+)>Zn^(2+)>>Co^(2+)>Mg^(2+).Especially,Ag^(+)and K^(+)cation exchange degree of NaY zeolites are achieved to 96.54% and 82.77% in this work.BET surface,total pore capacity,pore size distribution and water contact angle of the ion-exchanged NaY zeolites are all disordered by mono-and di-valent cations.Di-valent nitrate salt is favor for increasing the dehydration performance of NaY zeolite membranes by ion-exchange.When the ion-exchange solution is Zn(NO_(3))_(2),the total flux variation and separation factor variation of the NaY membrane(M-5)are -45% and 230% for separation of 10%(mass)H_(2)O/EtOH mixture by pervaporation,and the ion-exchanged membranes showed good reproducibility.展开更多
基金supported by the National Natural Science Foundation of China (22288101,21991090,21991091,22078316,22272171 and 22109167)the Sino-French International Research Network (Zeolites)+2 种基金the BL01B1 beamline of SPring-8 and the 1W1B station of Beijing Synchrotron Radiation Facility (BSRF)for the support of XAS measurementsthe Division of Energy Research Resources of Dalian Institute of Chemical Physics for the support of iDPC-STEM measurementsthe support of the Alexander von Humboldt Foundation (CHN 1220532 HFST-P)。
文摘Zeolite-encapsulated metal nanoclusters are at the heart of bifunctional catalysts,which hold great potential for petrochemical conversion and the emerging sustainable biorefineries.Nevertheless,efficient encapsulation of metal nanoclusters into a high-silica zeolite Y in particular with good structural integrity still remains a significant challenge.Herein,we have constructed Ru nanoclusters(~1 nm)encapsulated inside a high-silica zeolite Y(SY)with a SiO_(2)/Al_(2)O_(3) ratio(SAR)of 10 via a cooperative strategy for direct zeolite synthesis and a consecutive impregnation for metal encapsulation.Compared with the benchmark Ru/H-USY and other analogues,the as-prepared Ru/H-SY markedly boosts the yields of pentanoic biofuels and stability in the direct hydrodeoxygenation of biomass-derived levulinate even at a mild temperature of 180℃,which are attributed to the notable stabilization of transition states by the enhanced acid accessibility and properly sized constraints of zeolite cavities owing to the good structural integrity.
基金supported by Program for National Natural Science Foundation of China(Nos.22178135,21978104 and 22278419)the National Key Research and Development Program of China(No.2021YFC2101601)。
文摘The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural using Hβ zeolite modified by organic acids for dealuminization to regulate its textural and acidic properties. It was found that citric acid-dealuminized Hβ zeolite possessed high specific surface areas, wide channels and high Brønsted acid amount, which facilitated the selective conversion of fructose to furfural with a maximum yield of 76.2% at433 K for 1 h in the γ-butyrolactone(GBL)-H_(2)O system, as well as the concomitant formation of 83.0% formic acid. The^(13)C-isotope labelling experiments and the mechanism revealed that the selective cleavage of C1–C2 or C5–C6 bond on fructose was firstly occurred to form pentose or C5 intermediate by weak Brønsted acid, which was then dehydrated to furfural by strong Brønsted acid. Also this dealuminized Hβ catalyst showed the great recycling performance and was active for the conversion of glucose and mannose.
基金support from the National Key Research and Development Program of China(2021YFA1500401,2021YFA1501202)the National Natural Science Foundation of China(22288101)the 111 Project(B17020)for supporting this work.
文摘Zeolites have been widely used as catalysts,ion-exchangers,and adsorbents in chemical industries,detergent industry,steel industry,glass industry,ceramic industry,medical and healthfield,and environmentalfield,and recently applied in energy storage.Seed-assisted synthesis is a very effective approach in promoting the crystallization of zeolites.In some cases,the target zeolite cannot be formed in the absence of seed zeolite.In homologous seed-assisted synthesis,the structure of the seed zeolite is the same to that of the target zeolite,while the structure of the seed zeolite is different to that of the target zeolite in the heterologous seed-assisted synthesis.In this review,we briefly summarized the heterologous seed-assisted syntheses of zeolites and analyzed the structure-directing effect of heterologous seeds and surveyed the“common composite building units(CBUs)hypothesis”and the“common secondary building units(SBUs)hypothesis”.However,both hypotheses cannot explain all observations on the heterologous seed-assisted syntheses.Finally,we proposed that the formation of the target zeolite does need nuclei with the structure of target zeolite and the formation of the nuclei of the target zeolite can be promoted by either the undissolved seed crystals with the same CBUs or SBUs to the target zeolite or by the facilitated appropriate distribution of the specific building units due to the presence of the heterologous seed that does not have any common CBUs and SBUs with the target zeolite.
基金the financial supports from the National Natural Science Foundation of China(22322803,22178059,22208054,22221005,22072019)Key Technologies Innovation and Industrialization Projects of Fujian Province(2022G031)Qingyuan Innovation Laboratory(00121002,00523005)。
文摘A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.
基金The financial supports from the National Natural Science Foundation of China (22178059, 22208054 and 22072019)Natural Science Foundation of Fujian Province, China (2020J01513)+1 种基金Sinochem Quanzhou Energy Technology Co., Ltd. (ZHQZKJ-19-F-ZS0076)Qingyuan Innovation Laboratory (00121002)
文摘Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.
基金supported by the National Natural Science Foundation of China(52164036,U1960201,51764007)the Guizhou Province Graduate Research Fund(YJSKYJJ(2021)003).
文摘Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesized by alkaline melting and hydrothermal two-step process,which had high crystallinity and excellent crystal control.And the optimum conditions for synthesis of zeolite were investigated:NaOH-EMR mass ratio=1.2,L/S=10,hydrothermal temperature=90℃,and hydrothermal time=6 h.Then,EMRZA and EMRZX showed excellent adsorption of Cd^(2+).When T=25℃,time=120min,pH=6,C0=518 mg·L^(-1),and quantity of absorbent=1.5 g·L^(-1),the adsorption capacities of EMRZA and EMRZX reached 314.2 and 289,5 mg·g^(-1),respectively,In addition,after three repeated adsorption-desorption cycles,EMRZA and EMRZX retained 80%and 74%of the initial zeolites removal rates,respectively.Moreover,adsorption results followed quasi-second-order kinetics and monolayer adsorption,which was regulated by a combination of chemisorption and intra-particle diffusion mechanisms.The adsorption mechanism was ions exchange between Cd^(2+)and Na+.In summary,it has been confirmed that EMRZA and EMRZX can be reused as highly efficient adsorbents to treat Cd^(2+)-contaminated wastewater.
基金This work was financially supported by the Natural Science Foundation of Shandong Province(ZR2021MB134 and ZR2022MB019)the National Natural Science Foundation of China(22008131)+1 种基金the Talent Fund for Province and Ministry Co-construction Collaborative Innovation Center of Eco-chemical Engineering(STHGYX2220)the Opening Fund of State Key Laboratory of Heavy Oil Processing(SKLOP202002002).
文摘Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.
基金the Postdoctoral Research Foundation of China (No.2017M611799)the Basic Research Program of Jiangsu Province (No.BK20190690)。
文摘A blast furnace slag zeolite(BFSZ)material was successfully synthesized from BFS by alkaline fusion and hydrothermal treatment.Via the analyses of XRD,FT-IR,FE-SEM,XRF,CEC and BET surface area measurement,when zeolite was synthesized at a crystallization temperature of 100℃with initial Si/Al ratio of 1:1,the main composition in the product is Na-A zeolite.Under the above conditions,the BFSZ was synthesized with CEC of 3.06 meq/g and maximum BET surface area of 37.55 m^(2)·g^(-1).Moreover,the incorporating of BFS-derived minor metals(such as Mg,Fe,and Ca)are found to be of little importance for the synthesis of BFSZ.Thus the obtained BFSZ material has a great adsorption performance for removing Mn^(2+),Cu^(2+),and NH_(4)^(+)ions diluted in water,owing to the higher CEC.
基金Financial support from the Science Fund for Creative Research Groups of the National Science Foundation of China (22021005)the National Natural Science Foundation of China (21776032)the Innovation Team of Dalian University of Technology (DUT2017TB01)。
文摘Tungsten (W) incorporated mobil-type eleven (MEL) zeolite membrane (referred to as W-MEL membrane) with high separation performance was firstly explored for the separation of oil/water mixtures under the influence of gravity.W-MEL membranes were grown on stainless steel (SS) meshes through in-situ hydrothermal growth method facilitated with (3-aminopropyl)triethoxysilane (APTES) modification of stainless steel meshes,which promote the heterogeneous nucleation and crystal growth of W-MEL zeolites onto the mesh surface.W-MEL membranes were grown on different mesh size supports to investigate the effect of mesh size on the separation performance of the membrane.The assynthesized W-MEL membrane supported on 500 mesh (25μm)(W-MEL-500) exhibit the hydrophilic nature with a water contact angle of 11.8°and delivers the best hexane/water mixture separation with a water flux and separation efficiency of 46247 L·m^(-2)·h^(-1)and 99.5%,respectively.The wettability of W-MEL membranes was manipulated from hydrophilic to hydrophobic nature by chemically modifying with the fluorine-free compounds (hexadecyltrimethoxysilane (HDTMS) and dodecyltrimethoxysilane(DDTMS)) to achieve efficient oil-permselective separation of heavy oils from water.Among the hydrophobically modified W-MEL membranes,W-MEL-500-HDTMS having a water contact angle of146.4°delivers the best separation performance for dichloromethane/water mixtures with a constant oil flux and separation efficiency of 61490 L·m^(-2)·h^(-1)and 99.2%,respectively along with the stability tested up to 20 cycles.Both W-MEL-500-HDTMS and W-MEL-500-DDTMS membranes also exhibit similar separation performances for the separation of heavy oil from sea water along with a 20-fold lower corrosion rate in comparison with the bare stainless-steel mesh,indicating their excellent stability in seawater.Compared to the reported zeolite membranes for oil/water separation,the as-synthesized and hydrophobically modified W-MEL membranes shows competitive separation performances in terms of flux and separation efficiency,demonstrating the good potentiality for oil/water separation.
文摘In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.
基金support from the Jiangsu Province Dual Creative Phds Program(JSSCBS20210400)the Jiangsu Specially-Appointed Professors Program.
文摘Encapsulation of Fe nanoparticles in zeolite is a promising way to significantly improve the catalytic activity and stability of Fe-based catalysts during the degradation process of organic pollutants.Herein,Fe nanocatalysts were encapsulated into silicalite-1(S-1)zeolite by using a ligand-protected method(with dicyandiamide(DCD)as a organic ligand)under direct hydrothermal synthesis condition.High-resolution transmission electron microscopy(HRTEM)results confirmed the high dispersion of Fe nanocatalysts which were successfully encapsulated within the voids among the primary particles of the S-1 zeolite.The developed S-1 zeolite encapsulated Fe nanocatalyst(Fe@S-1)exhibited significantly improved catalytic activity and reusability in the catalytic degradation process of methylene blue(MB).Specifically,the developed Fe0.021@S-1 catalyst showed high catalytic degradation activity,giving a high MB degradation efficiency of 100%in 30 min,outperformed the conventional impregnated catalyst(Fe/S-1).Moreover,the Fe@S-1 catalyst afforded an outstanding stability,showing only ca.7.9%activity loss after five cycling tests,while the Fe/S-1 catalyst presented a significantly activity loss of 50.9%after only three cycles.Notably,the encapsulation strategy enabled a relatively lower Fe loading in the Fe@S-1 catalyst in comparison with that of the Fe/S-1 catalyst,i.e.,0.35%vs.0.81%(mass).Radical scavenging experiments along with electron spin resonance(ESR)measurements confirmed that the major role ofOH in the MB degradation process.Specifically,Fe@S-1 catalyst with high molar ratio of[Fe(DCD)]Cl3 is beneficial to form Fe complexes/nanoclusters in the voids(which has large pore size of 1–2 nm)among the primary particles of the zeolite,and thus improving the diffusion and accessibility of reactants to Fe active sites,and thus exhibiting a relatively higher degradation efficiency.This work demonstrates that zeolite-encapsulated Fe nanocatalysts present potential applications in the advanced oxidation of wastewater treatment.
基金financial support from the National Natural Science Foundation of China(21773067)the Open Research fund of Shanghai Key Laboratory of Green Chemistry and Chemical Processes。
文摘Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the preparation of a reusable Pd catalyst for reductive etherification remains to be a great challenge.In this study,a series of Si O_(2)supported Pd catalysts with particle size ranging from 2.2 nm to 28 nm were prepared.Their textural properties and catalytic performance in furfural reductive etherification have been systematically studied.The results herein shed light on the particle size effect on the competition between hydrogenation/hydrogenolysis of C=O in furfural over Pd surface.We found out that Pd nanoparticles larger than 3 nm are preferred for one step reductive etherification.Based on this finding,we prepared a Pd/ZSM-5 bifunctional catalyst comprising Pd nanoparticles larger than 3 nm and decreased acidity in presence of amino organosilane,which served as a bifunctional catalyst succeeding in one-pot synthesis of ether via reductive-etherification and direct-etherification.This strategy showed significant advantage in efficiently converting furfuryl acohol,a major side-product,into ether,while suppressing the undesired side-reactions.
基金the National Natural Science Foundation of China, China (Grant 21920102005, 22288101, and 21835002)the 111 Project, China (B17020)+2 种基金the European Union through the European Research Council, European Union (grant ERC-AdG-2014-671093, SynCatMatch)the Spanish Government through “Severo Ochoa”, Spain (SEV2016-0683, MINECO) for supporting this workthe financial support from China Scholarship Council, China
文摘The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.
基金supported by the National Natural Science Foundation of China(21902097,21636006 and 21761132025)the China Postdoctoral Science Foundation(2019M653861XB)+1 种基金the Natural Science Foundation of Shaanxi Province(2020JQ-409)the Fundamental Research Funds for the Central Universities(GK201901001 and GK202003035)。
文摘Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existing catalyst is limited due to the poor activity and stability,which hinders its industrialization.Herein,we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI)for CO_(2)-ODP.Characterization results reveal that the Zn2+species are coordinated with the MFI zeolite matrix as isolated cations and the NPs of Pt,Rh,or Rh Pt are highly dispersed in the zeolite crystals.The isolated Zn2+cations are very effective for activating the propane and the small NPs are favorable for activating the CO_(2),which synergistically promote the selective transformation of propane and CO_(2)to propylene and CO.As a result,the optimal 0.25%Rh0.50%Pt@Zn-MFI catalyst shows the best propylene yield,satisfactory CO_(2)conversion,and long-term stability.Moreover,considering the tunable synergetic effects between the isolated cations and NPs,the developed approach offers a general guideline to design more efficient CO_(2)-ODP catalysts,which is validated by the improved performance of the bifunctional catalysts via simply substituting Sn4+cations for Zn2+cations in the MFI zeolite matrix.
基金supported by the National Natural Science Foundation of China(22001050,22072034,21873025)the China Postdoctoral Science Foundation(2020T130147,2020M681084)+1 种基金the Postdoctoral Foundation of Heilongjiang Province(LBH-Z19059)the Natural Science Foundation of Heilongjiang Youth Fund(YQ2021B002)。
文摘Heat accumulation inside perovskite solar cells causes the decomposition of the perovskite layer and hole transport materials(HTMs)under working conditions,yielding a decrease in long-term stability.Here,we present a zeolite-assisted heat conduction strategy by introducing economic zeolite crystals(e.g.,NaX,NaY,and ZSM-5)as a cooling filter to induce heat diffusion.The fitted thermal diffusion kinetic equation from real-time infrared thermal imaging technology reveals the zeolite skeleton assisted thermal co nduction mechanism of internal lattice vibration.Additionally,the nearly twofold improved conductivity of the modified HTM film is benefited from Na^(+)hopping on the supercages of the zeolite,therefore,the best-performed device with a rapid heat diffusion and defect inhibition obtains a remarkable power conversion efficiency of 23.42%.Both of NaX modified sprio-OMeTAD and PTAA based devices exhibit excellent operational stability after heating 1000 h at 85℃under N_(2)condition.This work demonstrates the potential application of economical porous zeolite materials in improving the thermal stability of PSCs.
基金The research presented in this paper was supported by National Natural Science Foundation of China(Grant No.52272031)the Fundamental Research Funds for the Central Universities,China University of Geosciences(Wuhan),and the Opening Fund of Guangxi Key Laboratory of New Energy and Building Energy Saving(Grant No.19-J-22-2)+3 种基金Key Research and Development Program of Hubei Province(Grant No.2020BAB065)Key Research and Development Program of Jiangxi Province(Grant No.20201BBG71011)Fundamental Research Funds for the Central Universities,CHD(Grant No.300102211506)Opening Fund of Key Laboratory of Advanced Building Materials of Anhui Province(Grant No.JZCL001KF).
文摘Montmorillonite and clinoptilolite zeolite were used as representative materials to prepare calcined clay-cement binary cementitious materials in order to study the effect of calcination treatment on the activation of clay minerals and the activity difference between layered and framed clays in this research.The influence of different calcined clay content(2%,4%,6%,8%,10%)on the fluidity,compressive strength,microstructure,phase change,and hydration heat of cement-based materials were analyzed.The calcined clay improves the fluidity of cement-based materials as compared with the uncalcined group.The addition of calcined montmorillonite(CMT)improves the development of mechanical strength,and the optimal compressive strength reaches 85 MPa at 28 days with 8%CMT.However,the activity of calcined clinoptilolite zeolite(CZL)is weak with few reaction sites,which slightly reduced the mechanical strength as compared to the blank sample.The addition of CMT changes the microscopic morphology of hydration products such as C-S-H and C-A-H,leading to the formation and transformation of ettringite in the early stage.It promotes the gradual polymerization of Si-O bonds into Si-O-Si bonds simultaneously,which accelerates the early hydration process.However,CZL acts mainly as a filling function in the cementitious system.In brief,CMT as an admixture can improve the mechanical properties of cement,but CZL has little effect.This work provides a guideline for the applications of calcined clay in cement,considering the influence of clay type on workability and mechanical strength.
基金the support from the Fundamental Research Funds for the Central Universities (2022LHJH01-03, 2022ZFJH04, 2022QZJH14)Pioneer R&D Program of Zhejiang Province (2022C03040)+1 种基金the Ecological civilization project, Zhejiang Universitythe support from A Project Supported by Scientific Research Fund of Zhejiang University (XY2022013)。
文摘The electrocatalytic conversion of reactive nitrogen species to ammonia is a promising strategy for efficient NH_(3) synthesis.In this study,we reveal that the hybrid Cu^(+)/Cu~0 interface is catalytically active for electrochemical ammonia synthesis from nitrate reduction.To maintain the hybrid Cu^(+)/Cu~0 state at negative reaction potentials,hydrophilic zeolite is used to modify Cu/Cu_(2)O electrocatalyst,which demonstrates an impressive NH_(3) production rate of 41.65 mg h^(-1) cm^(-2)with ~100% Faradaic efficiency of ammonia synthesis at-0.6 V vs.RHE.In-situ Raman spectroscopy unveil the high activity originates from the zeolite reconstruction at the electrode–electrolyte interface,which protects the valence state of Cu~0/Cu^(+) site under negative potential and promotes electrochemical activity towards NH_(3) synthesis.
基金the financial supports that are from the National Natural Science Foundation of China (21921006, U22A20414 and 21938007)the Natural Science Foundation of Jiangsu Province (BK20220002)the open project of the State Key Laboratory of China (KL21-04 and D2021FK055)。
文摘The synthesis of a continuous IMF zeolite membrane was fabricated on tubular substrates by seeded growth for the first time. The straight channels of IMF zeolite with diameters of 0.53–0.59 nm are distinguishable for p-xylene from o-xylene molecules. Pure IMF-phase high-silica IM-5 zeolite seeds with uniform and fine crystal size were fabricated by a new sonication-assisted aging process. The seeds were coated on the support by dipcoating and induced the formation of continuous membrane. Separation performance in p-/o-xylene mixture was investigated at various temperature and pressure. The typical IM-5zeolite membrane had p-/o-xylene separation factor of 3.7. Our results suggest that IM-5 zeolite is a potentially good membrane material for the separation of xylene mixtures.
基金funded by the National Natural Science Foundation of China(No.51904154)Natural Science Foundation of Hunan Province(No.2020JJ5491).
文摘The use of some environmental functional minerals as backfill-modified materials may improve the leaching resistance of cemented uranium tailings backfill created from alkali-activated slag(CUTB),but these materials may participate in the hydration reaction of the cementitious materials,which could have a certain impact on the pore structure of the CUTB,thus affecting its mechanical properties and leaching resistance.In this paper,natural zeolite is selected as the backfill-modified material,and it is added to alkali-activated slag paste(AASP)and CUTB in cementitious material proportions of 4%,8%,12%,and 16%to prepare AASP mixtures and CUTB mixtures containing environmental functional minerals.After the addition of natural zeolite,the porosity of the CUTB generally increases,but when the content is 4%,the porosity decreases to 22.30%.The uniaxial compressive strength(UCS)of the CUTB generally decreases,but the decrease is the smallest when the content is 4%,and the UCS is 12.37 MPa.The addition of natural zeolite mainly reduces the number of fine pores in the CUTB,but the pores with relaxation times T_(2)of greater than 10 ms account for about 10%of the total pores,and there are a certain number of large pores in the CUTB.The main product of alkali-activated slag is calcium(alumino)silicate hydrate(C-(A)-S-H gel).When natural zeolite is added,the hydration products develop towards denser products with a high degree of polymerization and the formation of low polymerization products is reduced.This affects the internal fracture pores of the hydration products and the interface pores of the CUTB,has an irregular effect on the pore characteristics of the CUTB,and influences the UCS.
基金supported by the National Natural Science Foundation of China(21868012 and 21868013)Jiangxi Provincial Department of Science and Technology(20171BCB24005 and 20181ACH80003)。
文摘Pervaporation performance of NaY zeolite membranes is improved by ion-exchange with di-valent nitrate salt.Different nitrate salts,including Co(NO_(3))_(2),Mg(NO_(3))_(2),Zn(NO_(3))_(2),Ca(NO_(3))_(2),Cu(NO_(3))_(2),KNO_(3),and AgNO_(3),have great effects on the channel structure and water affinity of the NaY zeolite membrane.When the concentration of nitrate salt,ion-exchange temperature and time are 0.1 mol·L^(-1),50℃and 2 h,the ion-exchange degree order of NaY zeolites is Ag^(+)>K^(+)>Ca^(2+)>Zn^(2+)>>Co^(2+)>Mg^(2+).Especially,Ag^(+)and K^(+)cation exchange degree of NaY zeolites are achieved to 96.54% and 82.77% in this work.BET surface,total pore capacity,pore size distribution and water contact angle of the ion-exchanged NaY zeolites are all disordered by mono-and di-valent cations.Di-valent nitrate salt is favor for increasing the dehydration performance of NaY zeolite membranes by ion-exchange.When the ion-exchange solution is Zn(NO_(3))_(2),the total flux variation and separation factor variation of the NaY membrane(M-5)are -45% and 230% for separation of 10%(mass)H_(2)O/EtOH mixture by pervaporation,and the ion-exchanged membranes showed good reproducibility.
