Effects of Zeolitization of Diatomite on Benzene Adsorption

Diatomite, a type of biogenic mineral, is sourced from deposition and accumulation of diatom shell. Diatom shells are mainly composed of amorphous hydrated silica, which is categorized as non-crystalline opal-A according to the mineralogical classification. Diatomite has a characteristic macro/mesoporous structure and unique physical and chemical capabilities, such as high thermal stability, strong acid resistance, and high adsorption capacity, and thus is widely used as the filter aid, catalytic support, and adsorbent. However, the low surface area of diatomite shows disadvantage in adsorption. Moreover, the hydrophilic surface which contains abundant silanols is usually covered by adsorbed water, resulting in that the adsorption sites of diatomite were occupied and the adsorption capacity of hydrophobic guests decreased. In previous reports, zeolitization was employed to increase the specific surface area (SBET) and porosity of diatomite. However, the hydrophilic property of diatomite was not changed after zeolitization. It is due to that the zeolite formed on the surface area of diatomite contained some aluminum in its structure, which was highly hydrophilic. Therefore, it is significantly interesting to prepare the zeolitized diatomite with both large SBET and high hydrophobicity.

Hierarchically Structured Monolithic ZSM-5 through Macroporous Silica Gel Zeolitization

The hierarchically structured ZSM-5 monolith was prepared through transforming the skeletons of the macroporous silica gel into ZSM-5 by the steam-assisted conversion method. The morphology and monolithic shapes of macroporous silica gel were well preserved. The hierarchically structured ZSM-5 monolith exhibited the hierarchical porosity, with mesopores and macropores existing inside the macroporous silica gel, and micropores formed by the ZSM-5. The products have been characterized properly by using the XRD, SEM and N2 adsorption–desorption methods.

Hierarchical Porous ZSM-5 Zeolite Synthesized by in situ Zeolitization and Its Coke Deposition Resistance in Aromatization Reaction

Hierarchical ZSM-5 zeolites with micro-, meso- and macroporosity were prepared from diatomite zeolitization through a vapor-phase transport process on solid surfaces. The aromatization performance of the catalysts was in- vestigated on a fixed bed reactor by using FCC gasoline as feedstock. The crystal phase, morphology, pore struc- tures, acidity and coke depositions of the hierarchical ZSM-5 zeolites were characterized by means of X-ray diffrac- tion （XRD）, scanning electron microscope （SEM）, N2 adsorption/desorption, Fourier transform infrared （FT-IR） and thermogravimetry-mass spectrogram （TG-MS）, respectively. The results show that the prepared hierarchical ZSM-5 zeolite possesses excellent porosity and high crystallinity, displaying an improved aromatization performance and carbon deposition resistance due to its meso- and macroporous structures.

The structure-directing role of heterologous seeds in the synthesis of zeolite

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.

Facile synthesis of hierarchical NaX zeolite from natural kaolinite for efficient Knoevenagel condensation

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.

Dealuminated Hβ zeolite for selective conversion of fructose to furfural and formic acid

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.

构筑开放锡位点实现酸性增强的二甲醚羰基化丝光沸石催化剂设计

Due to their tunable acidity,shape selectivity,and excellent stability,zeolites are of great importance as solid acid materials in industrial catalysis.Tuning the properties of the acid sites in zeolites allows for the rational design and fabrication of catalysts for target reactions.Dimethyl ether(DME)carbonylation,a critical chain-growth reaction for C1 resource utilization,is selectively catalyzed by the Brønsted acid sites within the eight-membered rings(8-MRs)of mordenite(MOR).It is anticipated that strengthening the Brønsted acidity—particularly in 8-MRs—will improve the catalytic performance of MOR.In this work,density functional theory(DFT)calculations are first employed and the results used to design a modified MOR with stannum(Sn)and to predict the corresponding changes in acidity.Guided by the theoretical studies,a series of Sn-modified MOR are synthesized via a defect-engineering and subsequent heteroatom-substitution strategy.After partial desilication,isolated tetrahedral Sn species in an open configuration are successfully synthesized for the first time,within which tetrahedrally coordinated Al sites are preserved.An acidic characterization is used to confirm that the acidity of the Brønsted acid sites is enhanced by the introduction of the Sn species;as a result,the sample exhibits excellent activity in DME carbonylation reaction.Kinetic and DFT studies reveal that this strengthened acidity facilitates the adsorption of DME and reduces the activation barriers of DME dissociation and acetyl formation,accounting for the improved activity.The work demonstrates mechanistic insights into the promoting effects of strong acidity on DME carbonylation and offers a promising strategy to precisely control the acidic strength of zeolites.

Unveiling the tailorable electrochemical properties of zeolitic imidazolate framework-derived Ni-doped LiCoO_(2) for lithium-ion batteries in half/full cells

As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.

Synthesis of mordenite by solvent-free method and its application in the dimethyl ether carbonylation reaction

Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.

Synthesis of spherical nano-ZSM-5 zeolite with intergranular mesoporous for alkylation of ethylbenzene with ethanol to produce m-diethylbenzene

Catalytic synthesis of m-diethylbenzene(m-DEB)through alkylation of ethylbenzene(EB)may be a promising alternative route in comparison with traditional rectification of mixed DEB,for which the top priority is to develop efficient and stable heterogeneous catalysts.Here,the spherical nano-ZSM-5 zeolite with abundant intergranular mesoporous is synthesized by the seed-mediated growth method for alkylation of EB with ethanol to produce m-DEB.The results show that the spherical nano-ZSM-5 zeolite exhibits better stability and higher alkylation activity at a lower temperature than those of commercial micropore ZSM-5.And then,the spherical nano-ZSM-5 is further modified by La_(2)O_(3) through acid treatment followed by immersion method.The acid treatment causes nano-ZSM-5 to exhibit the increased pore size but decreased the acid sites,and subsequent La_(2)O_(3) loading reintroduces the weak acid sites.As a result,the HNO_(3)-La_(2)O_(3)-modified catalyst exhibits a slight increase in EB conversion and DEB yield in comparison with unmodified one,and meanwhile,it still maintains high m-DEB selectivity.The catalyst after acid treatment achieves higher catalytic stability besides maintaining the high alkylation activity of EB with ethanol.The present study on the spherical nano-HZSM-5 zeolite and its modification catalyst with excellent alkylation ability provides new insights into the production of mDEB.

Production of linear alkylbenzene over Ce containing Beta zeolites

Ce-encapsulated Beta zeolite was synthesized by a one-pot hydrothermal method with citric acid complexing Ce in the absence of Na species.Additional citric acid can effectively prevent the deposition of Ce species during the hydrothermal synthesis of zeolites,leading to uniform distribution of Ce cluster in the framework of Beta zeolites.Moreover,the sodium-free synthesis system resulted that the Brønsted acid sites were mainly located on the straight channels and external surface of Beta zeolites,improving the utilization of Brønsted acid sites.In addition,Ce encapsulated Beta zeolites showed enhanced activity and robust stability in the alkylation of benzene with 1-dodecene based on the synergistic effect between Ce species and Brønsted acid sites,which pave the way for its practical application in the production of alkylbenzene.

A concise review on surface and structural modification of porous zeolite scaffold for enhanced hydrogen storage

Investigating zeolites as hydrogen storage scaffolds is imperative due to their porous nature and favorable physicochemical properties.Nevertheless,the storage capacity of the unmodified zeolites has been rather unsatisfactory(0.224%-1.082%(mass))compared to its modified counterpart.Thus,the contemporary focus on enhancing hydrogen storage capacities has led to significant attention towards the utilization of modified zeolites,with studies exploring surface modifications through physical and chemical treatments,as well as the integration of various active metals.The enhanced hydrogen storage properties of zeolites are attributed to the presence of aluminosilicates from alkaline and alkaline-earth metals,resulting in increased storage capacity through interactions with the charge density of these aluminosilicates.Therefore,there is a great demand to critically review their role such as well-defined topology,pore structure,good thermal stability,and tunable hydrophilicity in enhanced hydrogen storage.This article aimed to critically review the recent research findings based on modified zeolite performance for enhanced hydrogen storage.Some of the factors affecting the hydrogen storage capacities of zeolites that can affect the rate of reaction and the stability of the adsorbent,like pressure,structure,and morphology were studied,and examined.Then,future perspectives,recommendations,and directions for modified zeolites were discussed.

Phosphotungstic acid immobilized on amino-functionalized TS-1 zeolite as a solid acid catalyst for the synthesis of tributyl citrate

The amino-functionalization of TS-1 zeolite followed by immobilization of phosphotungstic acid(HPW)was presented to prepare a strong solid acid catalyst for the synthesis of bio-based tributyl citrate from the esterification of citric acid and n-butanol.γ-Aminopropyltriethoxysilane(APTES)was first grafted on the TS-1 zeolite via the condensation reactions with surface hydroxyl groups,and subsequently the HPW was immobilized via the reaction between the amino groups and the protons from HPW-forming strong ionic bonding.The Keggin structure of HPW and MFI topology of TS-1 zeolite were well maintained after the modifications.The amino-functionalization generated abundant uniformly distributed active sites on TS-1 for HPW immobilization,which promoted the dispersity,abundance,as well as the stability of the acid sites.The tetrahedrally coordinated framework titanium and non-framework titania behaved as weak Lewis acid sites,and the protons from the immobilized HPW acted as the moderate or strong Brønsted acid sites.An optimized TBC yield of 96.2%(mol)with a conversion of-COOH of 98.1%(mol)was achieved at 150℃for 6 h over the HPW immobilized on amino-functionalized TS-1.The catalyst exhibited good stability after four consecutive reaction runs,where the activity leveled off at still a relatively high level after somewhat deactivation possibly caused by the leaching of a small portion of weakly anchored APTES or HPW.

Hydrophobic CHA-ZIFs with a junctional trap between cha and d6r cages for adsorption of 2,3-butanediol in aqueous solution

The adsorption and separation of diols from dilute aqueous solution using hydrophobic materials is very challenging due to the strong diol-water hydrogen-bonding interactions. Herein, we screened hydrophobic zeolitic imidazolate frameworks(ZIFs) with chabazite(CHA) topology for separation of 2,3-butanediol(2,3-BDO) and 1,3-propanediol(1,3-PDO), which had junctional and hydrophobic traps matching the two end methyl groups of the 2,3-BDO molecule. Based on CHA-ZIFs with the same small-sized ligand 2-methylimidazole(mIm) and different large-sized ligand benzimidazole derivatives(RbIm),CHA-ZIFs with larger surface areas were obtained by the addition of excess small-sized ligand mIm in the synthesis process. We showed that all of the hydrophobic CHA-ZIFs preferentially adsorbed 2,3-BDO over 1,3-PDO by static batch adsorption and dynamic column adsorption experiments. But ZIF-301 and ZIF-300 with halogen groups exhibited better adsorptive separation performance for 2,3-BDO/1,3-PDO than ZIF-302 with methyl groups. For a typical ZIF-301, its adsorption capacity for 2,3-BDO was 116.4 mg·g^(-1)and selectivity for 2,3-BDO/1,3-PDO was 3.8 in dynamic column adsorption of the binary-component system(2,3-BDO/1,3-PDO: 50 g·L^(-1)/50 g·L^(-1)). Computational simulations revealed that 2,3-BDO preferentially adsorbed in a trap at the junction between the cha and d6r cages of CHA-ZIFs,meaning the strong host-guest interactions. Therefore, the hydrophobic CHA-ZIFs with a junctional trap were promising candidate materials for adsorbing 2,3-BDO, which also provided a new perspective for separating diols in dilute aqueous solutions.

High-silica faujasite zeolite-tailored metal encapsulation for the low-temperature production of pentanoic biofuels

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.

Preparation of a zeolite-palladium composite membrane for hydrogen separation:Influence of zeolite film on membrane stability

With the development of hydrogen energy,palladium-based membranes have been widely used in hydrogen separation and purification.However,the poor chemical stability of palladium composite membranes limits their commercial applications.In this study,a zeolite-palladium composite membrane with a sandwich-like structure was obtained by using a TS-1 zeolite film grown on the surface of palladium membrane.The membrane microstructure was characterized by SEM and EDX.The effects of the TS-1 film on the hydrogen permeability and stability of palladium composite membrane were investigated in details.Benefited from the protection of the TS-1 zeolite film,the stability of palladium composite membrane was enhanced.The results indicate that the TS-1-Pd composite membrane was stable after eight cycles of the temperature exchange cycles between 773 K and 623 K.Especially,the loss of hydrogen permeance for TS-1-Pd composite membrane was much smaller than that of the pure palladium membrane when the membrane was tested in the presence of C3H6atmosphere.It indicated that the TS-1-Pd composite membrane had better chemical stability in comparison with pure palladium membrane,owing to its sandwich-like structure.This work provides an efficient way for the deposition of zeolite film on palladium membrane to enhance the membrane stability.

Promoted catalytic property of Cu/SSZ-13 by introducing a minority of Mn for NO removal from diesel engine exhaust

The Cu-exchanged SSZ-13 with the small-pore chabazite framework is considered as a highly efficient catalyst for selective catalytic reduction of NO with NH_(3)(NH_(3)-SCR).In order to further improve the catalytic property,a series of Mn ion-assisted Cu/SSZ-13 powder catalysts were prepared by co-exchange method and stepwise exchange method.It is found that the NH_(3)-SCR activity,N_(2) selectivity,hydrothermal stability and sulfur resistance of Cu/SSZ-13 are promoted by introducing a minority of Mn(0.15%to 0.23%(mass))through co-exchange method.Characterization results reveal that the Cu,Mn co-exchange enables the higher amounts of Cu^(2+)active sites,the abundant medium strong and strong acid,the optimized ratio of Lewis acid to Brønsted acid etc.,which are required for a good NH_(3)-SCR catalytic property over broad temperature range and under harsh working environment.Moreover,a monolithic catalyst was prepared by impregnating a cordierite ceramic support into the coating slurry containing the optimized CuMn/SSZ-13 powder.The diesel engine bench tests show that Cu,Mn co-exchange gives the monolith catalyst a better catalytic property than commercial catalysts.This work provides an important guidance for the rational design of secondary-ion-assisted zeolites applied in NH_(3)-SCR.

Efficient nitric oxide capture and reduction on Ni-loaded CHA zeolites

As a prominent contributor to air pollution,nitric oxide(NO)has emerged as a critical agent causing detrimental environmental and health ramifications.To mitigate emissions and facilitate downstream utilization,adsorption-based techniques offer a compelling approach for direct NO capture from both stationary and mobile sources.In this study,a comprehensive exploration of NO capture under oxygen-lean and oxygenrich conditions was conducted,employing Ni ion-exchanged chabazite(CHA-type)zeolites as the adsorbents.Remarkably,Ni/Na-CHA zeolites,with Ni loadings ranging from 3 to 4 wt%,demonstrate remarkable dynamic uptake capacities and exhibit exceptional NO capture efficiencies(NO-to-Ni ratio)for both oxygen-lean(0.17-0.31 mmol/g,0.32-0.43 of NO/Ni)and oxygen-rich(1.64-1.18 mmol/g)under ambient conditions.An NH3 reduction methodology was designed for the regeneration of absorbents at a relatively low temperature of 673 K.Comprehensive insights into the NO_(x) adsorption mechanism were obtained through temperature-programmed desorption experiments,in situ Fourier transform infrared spectroscopy,and density functional theory calculations.It is unveiled that NO and NO_(2) exhibit propensity to coordinate with Ni^(2+) via N-terminal or O-terminal,yielding thermally stable complexes and metastable species,respectively,while the low-temperature desorption substances are generated in close proximity to Na^(+).This study not only offers micro-level perspectives but imparts crucial insights for the advancement of capture and reduction technologies utilizing precious-metal-free materials.

Development and Catalytic Cracking Performance of Ultrastable Y Zeolite Rich in Secondary Pores

A novel ultra-stable zeolite, NSZ, rich in secondary pores was developed through the combination of gas-phase andmild hydrothermal methods. This zeolite was successfully tested in an industrial setting for the first time in the world. The porestructure characteristics of the NSZ zeolite prepared for industrial use were analyzed and characterized using BET. The resultsindicate a significant increase in the secondary pore volume of NSZ zeolite compared to the existing ultra-stable zeolite HSZ-5, which is produced through a conventional gas-phase method. The average secondary pore volume to total pore volume ratioin NSZ zeolite was found to be 58.96% higher. The catalytic cracking performance of NSZ zeolite was evaluated. The resultsshowed that the NSC-LTA catalyst, with NSZ as the active component, outperformed the HSC-LTA catalyst with HSZ-5 zeolitein terms of obtaining more high-value products (gasoline and liquefied petroleum gas) during the hydrogenated light cycle oilprocessing. Additionally, the NSC-LTA catalyst showed a significant improvement in coke selectivity.

Ni/ZSM-5 Catalysts for Light Olefin Oligomerization:Effects of Supports and Ni Sites on Activity and Selectivity

A series of Ni/ZSM-5 containing a small amount of Ni was prepared by an ion exchanged method.The impact of the n(SiO_(2))/n(Al_(2)O_(3))ratio on the catalytic activity was studied using the samples 0.09Ni/ZSM-5(60)and 0.09Ni/ZSM-5(130).To determine the interaction between the Ni species and acid sites on the surface of the catalyst,the catalysts were characterized by N2 adsorption-desorption,X-ray diffraction(XRD),scanning electron microscopy(SEM),and UV-vis spectroscopy.The performance of the catalysts for the catalytic oligomerization of 1-hexene was investigated in detail.The nickel species were found to be uniformly distributed in all the catalysts.It was discovered that the oligomerization activity of the catalyst can be improved using Ni species;however,the contribution of Brønsted acids in oligomerization reactions is greater than that of Ni sites and Lewis acids.