Effect of mesopore spatial distribution of HZSM-5 catalyst on zinc state and product distribution in 1-hexene aromatization

1-hexene aromatization is a promising technology to convert excess olefin in fluid catalytic cracking(FCC)gasoline to high-value benzene(B),toluene(T),and xylene.Besides,the increasing market demand of xylene has put forward higher requirements for new generation of catalyst.For increasing xylene yield in 1-hexene aromatization,the effect of mesopore structure and spatial distribution on product distribution and Zn loading was studied.Catalysts with different mesopore spatial distribution were prepared by post-treatment of parent HZSM-5 zeolite,including NaOH treatment,tetra-propylammonium hydroxide(TPAOH)treatment,and recrystallization.It was found the evenly distributed mesopore mainly prolongs the catalyst lifetime by enhancing diffusion properties but reduces the aromatics selectivity,as a result of damage of micropores close to the catalyst surface.While the selectivity of high-value xylene can be highly promoted when the mesopore is mainly distributed interior the catalyst.Besides,the state of loaded Zn was also affected by mesopores spatial distribution.On the optimized catalyst,the xylene selectivity was enhanced by 12.4%compared with conventional Zn-loaded parent HZSM-5 catalyst at conversion over 99%.It was attributed to the synergy effect of mesopores spatial distribution and optimized acid properties.This work reveals the role of mesopores in different spatial positions of 1-hexene aromatization catalysts in the reaction process and the influence on metal distribution,as well as their synergistic effect two on the improvement of xylene selectivity,which can improve our understanding of catalyst pore structure and be helpful for the rational design of high-efficient catalyst.

Synthesis of Novel Virus-Like Mesoporous Silica-ZnO-Ag Nanoparticles and Quercetin Synergize with NIR Laser for Omicron Mutated Covid-19 Virus Infectious Diseases Treatment

This work shows that novel virus-like mesopore silica-zinc oxide/Ag nanoparticles (SZnOAg) synthesized and professionally collected on NIR laser irradiation with quercetin to improve the elimination the mutated virus as a biomedical application. A unique type of silica nanoparticles with a self-in- flating tubular surface has been successfully synthesized using a novel single-micelle epitaxial growth process. The properties of the nanoparticles can be tuned with respect to their core diameter, tubular length, and outer diameter. Due to their biomimetic appearance, they can rapidly transform living cells into virus-like particles, this SZnOAg nanomaterial has specific elimination effect on bacteriophage and Covid-19. Using epitaxial growth, we can construct virus-like structures that can be used for biomedicine applications. These nanomaterials and NIR laser could open the way to a new range of antiviral materials, due to the low-efficiency cellular uptake of current nanoparticles, their applications in the biomedical field are limited. Herein, it clearly shows that novel mesoporous silica nanoparticles can be easily exhibited superior cellular uptake property.

Characterisation and separation of infectious bursal disease virus-like particles using aqueous two-phase systems

Infectious bursal disease(IBD)causes considerable economic losses in the commercial poultry industry worldwide.The principal way to control IBD virus(IBDV),the causative agent of IBD,is still through vaccination programs.Virus-like particles(VLPs)are recognised as a safe and potent recombinant vaccine platform.This research work explores the characterisation and separation of infectious bursal disease virus-like particles(IBD-VLPs)from crude feedstock.Various characteristics were studied with highperformance size-exclusion chromatography(HP-SEC),sodium dodecyl sulphate–polyacrylamide gel electrophoresis(SDS-PAGE)and transmission electron microscopy(TEM)analyses.Subsequently,the separation of IBD-VLPs using polyethylene glycol(PEG)/sodium citrate-based aqueous two-phase systems(ATPSs)was conducted and optimised.Moreover,a scale-up study of the best ATPS constituted of 15%PEG 6000,11%sodium citrate and 10%crude feedstock was performed to compare the separation performance of IBD-VLPs with and without centrifugation-assisted.The results indicated that the optimised ATPS with centrifugation-assisted for both 5 g and 50 g systems showed good recovery of IBDVLPs of>97%in the interphase between the PEG-rich top and salt-rich bottom phases.These optimised systems also showed high removal efficiencies of impurities of>95%.The results demonstrated that aqueous two-phase extraction could be a promising technology for efficient VLPs separation.

Core-shell mesoporous carbon hollow spheres as Se hosts for advanced Al-Se batteries

Incorporating a selenium(Se)positive electrode into aluminum(Al)-ion batteries is an effective strategy for improving the overall battery performance.However,the cycling stability of Se positive electrodes has challenges due to the dissolution of intermediate reaction products.In this work,we aim to harness the advantages of Se while reducing its limitations by preparing a core-shell mesoporous carbon hollow sphere with a titanium nitride(C@TiN)host to load 63.9wt%Se as the positive electrode material for Al-Se batteries.Using the physical and chemical confinement offered by the hollow mesoporous carbon and TiN,the obtained core-shell mesoporous carbon hollow spheres coated with Se(Se@C@TiN)display superior utilization of the active material and remarkable cycling stability.As a result,Al-Se batteries equipped with the as-prepared Se@C@TiN composite positive electrodes show an initial discharge specific capacity of 377 mAh·g^(-1)at a current density of 1000 mA·g^(-1)while maintaining a discharge specific capacity of 86.0 mAh·g^(-1)over 200 cycles.This improved cycling performance is ascribed to the high electrical conductivity of the core-shell mesoporous carbon hollow spheres and the unique three-dimensional hierarchical architecture of Se@C@TiN.

Tetraethylenepentamine-functionalized magnetic mesoporous composites as a novel adsorbent for the removal Cr(Ⅲ)-ethylenediaminetetraacetic acid in complex solution

A novel tetraethylenepentamine(TEPA) functionalized magnetic mesoporous silica adsorbent(FNMs/TEPA) was prepared for the adsorption of Cr(Ⅲ)-ethylenediaminetetraacetic acid(EDTA)from wastewater. The characterization of the prepared adsorbent certified that TEPA was modified onto the magnetic mesoporous silicon(FNMs), while FNMs/TEPA maintained the ordered mesoporous and pristine magnetic properties. The batch adsorption experiments demonstrated that TEPA significantly enhanced the removal capacity of the adsorbent for Cr(Ⅲ)-EDTA. FNMs/TEPA exhibited an excellent adsorption property(13.84 mg·g-1) at p H 4.0. Even in the presence of high concentrations of coexisting ions and organic acids, the adsorption performance of FNMs/TEPA was stable. Experimental characterization and DFT demonstrated that the adsorption of Cr(Ⅲ)-EDTA was ascribed to the electrostatic interaction, hydrogen bonding, and complexation between Cr(Ⅲ)-EDTA and amino groups on the adsorbent surface. The analysis of the independent gradient model(IGM) shows that electrostatic interaction is the main mode of action in the adsorption process. Moreover, FNMs/TEPA demonstrated remarkable reusability in three regeneration cycles. These findings indicated that FNMs/TEPA possessed excellent application prospects in the disposal of wastewater containing Cr(Ⅲ)-EDTA.

Enhanced activation of peroxymonosulfate by Fe/N co-doped ordered mesoporous carbon with dual active sites for efficient removal of m-cresol

The novel Fe-N co-doped ordered mesoporous carbon with high catalytic activity in m-cresol removal was prepared by urea-assisted impregnation and simple pyrolysis method.During the preparation of the Fe-NC catalyst,the complexation of N elements in urea could anchor Fe,and the formation of C3N4during urea pyrolysis could also prevent migration and aggregation of Fe species,which jointly improve the dispersion and stability of Fe.The FeN4sites and highly dispersed Fe nanoparticles synergistically trigger the dual-site peroxymonosulfate (PMS) activation for highly efficient m-cresol degradation,while the ordered mesoporous structure of the catalyst could improve the mass transfer rate of the catalytic process,which together promote catalytic degradation of m-cresol by PMS activation.Reactive oxygen species (ROS) analytic experiments demonstrate that the system degrades m-cresol by free radical pathway mainly based on SO_(4)^(-)·and·OH,and partially based on·OH as the active components,and a possible PMS activation mechanism by 5Fe-50 for m-cresol degradation was proposed.This study can provide theoretical guidance for the preparation of efficient and stable catalysts for the degradation of organic pollutants by activated PMS.

Hard-carbon hybrid Li-ion/metal anode enabled by preferred mesoporous uniform lithium growth mechanism

To achieve high energy density in lithium batteries,the construction of lithium-ion/metal hybrid anodes is a promising strategy.In particular,because of the anisotropy of graphite,hybrid anode formed by graphite/Li metal has low transport kinetics and is easy to causes the growth of lithium dendrites and accumulation of dead Li,which seriously affects the cycle life of batteries and even causes safety problems.Here,by comparing graphite with two types of hard carbon,it was found that hybrid anode formed by hard carbon and lithium metal,possessing more disordered mesoporous structure and lithophilic groups,presents better performance.Results indicate that the mesoporous structure provides abundant active site and storage space for dead lithium.With the synergistic effect of this structure and lithophilic functional groups(–COOH),the reversibility of hard carbon/lithium metal hybrid anode is maintained,promoting uniform deposition of lithium metal and alleviating formation of lithium dendrites.The hybrid anode maintains a 99.5%Coulombic efficiency(CE)after 260 cycles at a specific capacity of 500 m Ah/g.This work provides new insights into the hybrid anodes formed by carbon-based materials and lithium metal with high specific energy and fast charging ability.

Fabrication of a nano-sized ZSM-5 zeolite with intercrystalline mesopores for conversion of methanol to gasoline

Carbon deposition during methanol to hydrocarbons leads to the quick deactivation of ZSM-5 catalyst and it is one of the major problems for this technology. Decreasing the crystal size or introducing mesopores into ZSM-5 zeolites can improve its diffusion property and decrease the coke formation. In this paper, nano-sized ZSM-5 zeolite with intercrystalline mesopores combining the mesoporous and nano sized structure was fabricated. For comparison, the mesoporous ZSM-5 and nano-sized ZSM-5 were also prepared. These catalyst samples were characterized by XRD, BET, NH3-TPD, TEM, Py-IR and TG techniques and used on the conversion of methanol to gasoline in a fixed-bed reactor at T=405 degrees C, WHSV =4.74 h(-1) and P=1.0 MPa. It was found that the external surface area of the nano-sized ZSM-5 zeolite with intercrystalline mesopores reached 104 m(2)/g, larger than that of mesoporous ZSM-5 (66 m(2)/g) and nano sized ZSM-5 (76 m(2)/g). Catalytic lifetime of the nano-sized ZSM-5 zeolite with intercrystalline mesopores was 93 h, which was only longer than that of mesoporous ZSM-5 (86 h), but shorter than that of nano sized ZSM-5 (104 h). Strong acidity promoted the coke formation and thus decreased the catalytic lifetime of the nano-sized ZSM-5 zeolite with intercrystalline mesopores though it presented large external surface that could improve the diffusion property. The special zeolite catalyst was further dealuminated to decrease the strong acidity. After this, its coke formation rate was slowed and catalytic lifetime was prolonged to 106 h because of the large external surface area and decreased weak acidity. This special structural zeolite is a potential catalyst for methanol to gasoline reaction. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Research on a New Process of Preparation for Nano-SiO_2 with High Activity and Mesopores

Nano-SiO_2 with high activity and mesopores was prepared through sol-gel synthesis followed by low-temperatureheat treatment and ball milling firstly in our experiments. TEM was performed to measure particle sizes. Nitrogenadsorption experiments were carried out to estimate specific surface area, porous distribution and porous ratio by BETand BJH methods. The content of Si-OH in SiO_2 surface was calculated by analysis of the results of hydrogen-oxygencontent mensuration (HOCM). As a result, appropriate heat treatment system and ball milling time are important topreparation for nano-SiO_2 with high activity and mesopores, which are 5～50 nm particles, 5～6 nm average aperture,85%～93% porous ratio, and 51%～55% Si-OH content in surface. Nano-SiO_2 with that structure has high surfaceenergy and activity. This process, which has simple facilities and operation rules, is a new way of preparation fornano-SiO_2 with high activity and mesopores.

Creating mesopores in ZSM-48 zeolite by alkali treatment: Enhanced catalyst for hydroisomerization of hexadecane

ZSM-48 zeolites with various Si/Al ratios were hydrothermally synthesized in the H;N（CH;）;NH;（HDA）-containing media. The obtained samples were highly crystallized with minor mixed phases as evidenced by X-ray powder diffraction（XRD）. The alkaline treated ZSM-48 zeolites maintained its structure under different concentrations of Na OH aqueous solution. Micropores remained unchanged while mesopores with wide pore size distribution formed after the alkaline treatment. The surface area increased from 228 to 288 m;/g. The Br?nsted acid sites had little alteration while an obvious increase of Lewis acid sites was observed. The hydroisomerization of hexadecane was performed as the model reaction to test the effects of the alkali treatment. The conversion of hexadecane had almost no change, which was attributed to the preservation of the Br?nsted acid sites. While high selectivity to iso-hexadecane with an improved iso to normal ratio of alkanes was due to the mesopore formation and improved diffusivity.

Hollow Bio-derived Polymer Nanospheres with Ordered Mesopores for Sodium-Ion Battery

Bio-inspired hierarchical self-assembly provides elegant and powerful bottom-up strategies for the creation of complex materials.However,the current self-assembly approaches for natural bio-compounds often result in materials with limited diversity and complexity in architecture as well as microstructure.Here,we develop a novel coordination polymerization-driven hierarchical assembly of micelle strategy,using phytic acid-based natural compounds as an example,for the spatially controlled fabrication of metal coordination bio-derived polymers.The resultant ferric phytate polymer nanospheres feature hollow architecture,ordered meso-channels of^12 nm,high surface area of 401 m2 g−1,and large pore volume of 0.53 cm3 g−1.As an advanced anode material,this bio-derivative polymer delivers a remarkable reversible capacity of 540 mAh g−1 at 50 mA g−1,good rate capability,and cycling stability for sodium-ion batteries.This study holds great potential of the design of new complex bio-materials with supramolecular chemistry.

Optimization of battery life and capacity by setting dense mesopores on the surface of nanosheets used as electrode

Nanosheets with mesopores on the surface have been prepared using molybdenum trioxide(α-MoO3).The effect of mesopores on the performance of the electrode remains elusive.The MoO3 nanosheets obtained in this study exhibited great battery performance, including good capacity, prolonged recycling life cycles, and excellent rate performance;e.g., 780 mAh/g when charged under a super high current-density of 1000 m A/g.These nanosheets demonstrated excellent stability, maintaining a capacity of 1189 mAh/g after 20 cycles, and 1075 mAh/g after 50 cycles;thus preventing the capacity to decrease to values under the scanning rate of 100 mA/g.These high-purity MoO3 nanosheets are well-ordered and have dense mesopores on the surface;these micropores contribute to the excellent electrode performance of the host electrode materials;the performance parameters include prolonged battery life and capacity.Setting mesopores or active sites on the electrode surface can be an alternative way to obtain stable electrodes in the future.

Carboxyl Terminus Truncated Human Papillomavirus Type 58 L1 Protein Maintains Its Bioactivity and Ability to Form Virus-like Particles

Summary: To prepare carboxyl terminus truncated human papillomavirus type 58 L1(HPV58L1) protein and evaluate its ability to form virus-like particles, the baculovirus and Sf-9 insect cells was used to express HPV58L1 protein, and pFastBac-Htb containing HPV58L1 gene sequence of carboxyl terminus truncation was generated. Then Sf-9 cells were infected with recombinant baculovirus. After being cultured, the post-infected cells expressing-HPV58L1 protein-were harvested and analyzed by SDS-PAGE and Western blot. The ProBond~TM purification system was used for protein purification. The bio-activity of purified protein was identified by mouse erythrocyte hemagglutination assay, and the VLP formation was examined with transmission electron microscope. Our results showed that the recombinant baculovirus was generated and the Sf-9 cells was infected with the recombinant baculovirus, and after collecting, total cellular proteins were extracted. Truncated HPV58L1 protein with MW 58KD was revealed by SDS-PAGE and confirmed by Western blot. The purified L1 proteins under native condition could cause mouse erythrocytes to agglutinate and form VLP. It is concluded that HPV58L1 protein with carboxyl terminus truncation could be efficiently expressed. In baculovirus Sf-9 cells expression system, the purified protein could self-assemble into virions in vitro, and induce agglutination of mouse erythrocytes, indicating that carboxyl terminus truncation does not interfere with the bioactivity of HPV58L1 protein.

The codon-optimized capsid gene of duck circovirus can be highly expressed in yeast and self-assemble into virus-like particles

The capsid （Cap） protein, which is the only structural protein of duck circovirus （DuCV）, is the most important antigen for the development of vaccines against DuCV and the virus＇s serological diagnostic methods. In order to use yeast expression system to produce a large quantities of DuCVCap protein which is close to its natural form to display the antigen peptides perfectly, the Cap gene was optimized into the codon-optimized capsid （Opt-Cap） gene towards the preference of yeast firstly. Then, the genes of Cap and Opt-Cap were separately cloned into pPIC9K plasmid and transformed into Picha pas- toris GSl15. The strains that displayed the phenotype of Mut~ and contained multiple inserts of expression cassette were selected from those colonies. After the induction expression, the secretory type of Cap protein, which was about 43 kDa, was best expressed under 0.5% （v/v） methanol and sorbitol induction. Compared with the Cap gene, the expression level of Opt-Cap gene was much higher. What＇s more, the purified Cap protein had a good reactivity to its specific polyclone antibody and DuCV-positive serum, and it was able to self-assemble into virus-like particles （VLPs）. These VLPs, with a diameter of 15-20 nm and without a nucleic acid structure, showed a high level of similarity to DuCV particles in size and shape. All of the resultsdemonstrated that, based on the codon-optimization, it is suitable to use the P. pastoris expression system to produce DuCV VLPs on a large scale. It is the first time that a large amounts of DuCV VLPs were produced successfully in P. pastoris, which might be particularly useful for the further studies of serological diagnosis and vaccines of DuCV.

Efficient Humoral and Cellular Immune Responses Induced by a Chimeric Virus-like Particle Displaying the Epitope of EV71 without Adjuvant

Objective To eliminate the side effects of aluminum adjuvant and His-tag,we constructed chimeric VLPs displaying the epitope of EV71（SP70） without His-tagged.Then evaluating whether the VLPs could efficiently evoke not only humoral but also cellular immune responses against EV71 without adjuvant.Methods The fusion protein was constructed by inserting SP70 into the MIR of truncated HBc Ag sequence,expressed in E.Coli,and purified through ion exchange chromatography and density gradient centrifugation.Mice were immunized with the VLPs and sera were collected afterwards.The specific antibody titers,Ig G subtypes and neutralizing efficacy were detected by ELISA,neutralization assay,and EV71 lethal challenge.IFN-γ and IL-4 secreted by splenocytes were tested by ELISPOT assay.Results HBc-SP70 proteins can self-assemble into empty VLPs.After immunization with HBc-SP70 VLPs,the detectable anti-EV71 antibodies were effective in neutralizing EV71 and protected newborn mice from EV71 lethal challenge.There was no significant difference for the immune efficacy whether the aluminum adjuvant was added or not.The specific Ig G subtypes were mainly IgG1 and IgG2 b and splenocytes from the mice immunized produced high levels of IFN-γ and IL-4.Conclusion The fusion proteins without His-tagged was expressed and purified as soluble chimeric HBc-SP70 VLPs without renaturation.In the absence of adjuvant,they were efficient to elicit high levels of Th1/Th2 mixed immune response as well as assisted by aluminum adjuvant.Furthermore,the chimeric VLPs have potential to prevent HBV and EV71 infection simultaneously.

Thick free-standing electrode based on carbon-carbon nitride microspheres with large mesopores for high-energy-density lithium-sulfur batteries

The development of sulfur cathodes with high areal capacity and high energy density is crucial for the practical application of lithium-sulfur batteries(LSBs).LSBs can be built by employing(ultra)high-loading sulfur cathodes,which have rarely been realized due to massive passivation and shuttling.Herein,microspheres of a carbon-carbon nitride composite(C@CN)with large mesopores are fabricated via molecular cooperative assembly.Using the C@CN-based electrodes,the effects of the large mesopores and N-functional groups on the electrochemical behavior of sulfur in LSB cells are thoroughly investigated under ultrahigh sulfur-loading conditions(>15 mgS cm^(-2)).Furthermore,for high-energy-density LSBs,the C@CN powders are pelletized into a thick free-standing electrode(thickness:500^m;diameter:11 mm)via a simple briquette process;here,the total amount of energy stored by the LSB cells is 39 mWh,corresponding to a volumetric energy density of 440 Wh L-1 with an areal capacity of 24.9 and 17.5 mAh cm^(-2) at 0.47 and 4.7 mA cm^(-2),respectively(at 24mgS cm^(-2)).These results have significantly surpassed most recent records due to the synergy among the large mesopores,(poly)sulfide-philic surfaces,and thick electrodes.The developed strategy with its potential for scale-up successfully fills the gap between laboratory-scale cells and practical cells without sacrificing the high areal capacity and high energy density,providing a solid foundation for the development of practical LSBs.

Template-free synthesis of core-shell Fe_(3)O_(4)@MoS_(2)@mesoporous TiO_(2) magnetic photocatalyst for wastewater treatment

TiO_(2)is the dominant and most widely researched photocatalyst for environmental remediation,however,the drawbacks,such as only responding to UV light(<5%of sunlight),low charge separation efficiency,and difficulties in recycling,have severely hindered its practical application.Herein,we synthesized magnetically separable Fe_(3)O_(4)@MoS_(2)@mesoporous TiO_(2)(FMmT)photocatalysts via a simple,green,and template-free solvothermal method combined with ultrasonic hydrolysis.It is found that FMmT possesses a high specific surface area(55.09 m2·g−1),enhanced visible-light responsiveness(~521 nm),and remarkable photogenerated charge separation efficiency.In addition,the photocatalytic degradation efficiencies of FMmT for methylene blue(MB),rhodamine B(RhB),and tetracycline(TC)are 99.4%,98.5%,and 89.3%within 300 min,respectively.The corresponding degradation rates are 4.5,4.3,and 3.1 times higher than those of pure TiO_(2)separately.Owing to the high saturation magnetization(43.1 A·m^(2)·kg^(−1)),FMmT can achieve effective recycling with an applied magnetic field.The improved photocatalytic activity is closely related to the effective transport of photogenerated electrons by the active interlayer MoS_(2) and the electron–hole separation caused by the MoS_(2)@TiO_(2)heterojunction.Meanwhile,the excellent light-harvesting ability and abundant reactive sites of the mesoporous TiO_(2)shell further boost the photocatalytic efficiency of FMmT.This work provides a new approach and some experimental basis for the design and performance improvement of magnetic photocatalysts by innovatively incorporating MoS2 as the active interlayer and integrating it with a mesoporous shell.

Size Determination of Ultramicropores and Small Mesopores Using a Calculation Procedure Based on the Tangents of Comparison Plot

Pore size distribution（PSD） curves of synthesized hollow silica spheres with ultrmicropores and small mesopores were obtained from calculations based on the BJH,KJS,SF,MP,NLDFT models and Prof.Zhu＇s method.Comparisons indicate that Zhu＇s method not only gives reasonable small mesopore size but also could be further extended to the ultramicropores region for the PSD evaluation.

Facile One-Pot Synthesis of ZSM-5 Aggregates with Interand Intra-Crystalline Mesopores for Methanol to Gasoline Conversion

ZSM-5 aggregates consisting of superfine and hierarchical nanocrystals(combined with micropores and intra-crystalline mesopores) with an average size of 30 nm were prepared through one-pot synthesis with the assistance of anionic polyacrylamide(APAM). The resultant zeolites(AHN-ZSM-5) were characterized by XRD, ICP-OES, SEM, TEM, BET, NH_3-TPD, Py-IR, and TG analyses and evaluated in the methanol to gasoline(MTG) reaction. Characterization results show that the hierarchical ZSM-5 aggregates possessed two kinds of mesopores, namely inter-and intra-crystalline mesopores. The amount of APAM considerably influenced the mesoporosity and textural properties of AHN-ZSM-5 zeolites. With the addition of APAM in the synthesis, the AHN-ZSM-5 zeolites exhibited large mesopore volume, large external surface area, and appropriate acidity. When applied in the MTG reaction, AHN-ZSM-5 demonstrated a catalytic lifetime that was 1.6 times longer than that of conventional ZSM-5 synthesized in the absence of APAM.