Insights into the Organotemplate-Free Synthesis of Zeolite Catalysts

As the most important nanoporous material, zeolites, which have intricate micropores, are essential heterogeneous catalysts in industrial processes. Zeolites are generally synthesized with organic templates under hydrothermal conditions; however, this method is environmentally unfriendly and costly due to the formation of harmful gases and polluted water. This article briefly summarizes the role of organic templates and describes designed routes for the organotemplate-free synthesis of zeolites, aided by zeolite seeds and zeolite seeds solution. Furthermore, this review explicates that the micmpore volume decreases with an increase of the Si/Al ratios in the organotemplate-free synthesis of zeolite products, where Na^＋ exists as an alkali cation. This feature is very important in directing the synthesis of zeolite catalysts with controllable Si/AI ratios under organotemplate-free conditions, and is thus important for the efficient design of zeolites.

Template-free synthesis of morphology- and size-controlled nano indium hydroxide

Morphology-and size-controlled In（OH）3 nanocrystals were synthesized via a novel, low-cost and low-temperature （70°C） route in the absence of any template and surfactant. The as-prepared products were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and high-resolution transmission electron microscopy （HRTEM） with selected area electron diffraction （SAED）. The morphology and size of In（OH）3 nanostructures can be controlled by adjusting the reaction conditions such as the reaction time, the concen-tration of the alkali, and the alkaline source. A possible mechanism for the evolution of the morphology- and size-controlled In（OH）3 was proposed. In addition, the optical properties of the In（OH）3 prepared by this method were studied by diffuse reflection spectra （DRS） and photoluminescence （PL） spectroscopy, and the results exhibit an obvious change of adsorption edges. The thermal behaviors of the as-prepared products were also explored by thermo-gravimetric （TG） and differential scanning calorimetry （DSC） measurements. According to the results of TG-DSC, the pure phase and uniformity of the In2O3 nanocube and nanorod can be obtained by annealing In（OH）3 precur-sors directly at 300°C.

Template-free Synthesis of a Novel 3D Cage-like Nanostructured α-Fe_2O_3

Synthesis of inorganic nanostructures with specific size and well defined morphologies has attracted considerable attention due to their superior electrical, optical, magnetic, and chemical properties. Up to now, various kinds of metal oxide, sulfide, and hydrate with controlled hierarchical and complex morphologies have been successfully synthesized.

Template-Free Synthesis of Aligned Polyaniline Nanorods/Tubes and Copper/Copper Hydroxide Nanowires for Application as Fillers in Polymer Nanocomposites

Aligned polyaniline nanorods were synthesized in the presence of salicylic acid. Nanorods and nanotubes were also formed in the presence of camphorsulfonic acid (CSA) and para-toluenesulfonic acid (pTSA). Electrical conductivity measurements showed that the aligned nanorods had better electrical conductivity than the non-aligned nanostructures. Nanospheres were also observed in some cases. The formation of elongated nanostructures or spheres depended on the aniline monomer to surfactant molar ratio. This method in which nanostructures are formed using soft templates is often referred to as the template-free approach. Our success motivated us to explore the feasibility of obtaining similar metallic nanostructures without the use of a template. We successfully synthesized copper and copper hydroxide nanowires. While the copper nanowires formed as a mesh, the copper hydroxide nanowires formed as winding bundles. Upon switching the order in which the reactants were added, copper hydroxide nanoribbons were formed instead of bundles. Characterization of these nanostructures was done using Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR) and the Four-point probe to measure electrical conductivity. Both metallic and organic nanowires that are fabricated by template-free methods are potential candidates for use as fillers in polymer nanocomposites. Polymer nanocomposites are found to be used in many advanced modern applications such as thermal interface materials in electronic devices which continue to be miniaturized, aerospace engineering where lightweight and robustness are important, sensors, medicine and catalytic activity.

Template-free synthesis of hollow carbon-based nanostructures from MOFs for rechargeable battery applications

Hollow carbon-based nanostructures(HCNs)have found broad applications in various fields,particularly rechargeable batteries.However,the syntheses of HCNs usually rely on template methods,which are time-consuming,low-yield,and environmentally detrimental.Metal-organic frameworks(MOFs),constructed by organic ligands and inorganic metal nodes,have been identified as effective platforms for preparing HCNs without adding extra templates.This review summarized the recent progress in template-free synthesis of HCNs enabled by MOFs and their applications in rechargeable batteries.Different template-free strategies were introduced first with mechanistic insights into the hollowing mechanism.Then the electrochemical performances of the HCNs were discussed with highlight on the structure-function correlation.It is found that the built-in cavities and nonporous for HCNs is of critical importance to increase the storage sites for high capacity,to enhance charge and mass transport kinetics for high-rate capability,and to ensure the resilient electrode structure for stable cycling.Finally,the challenges and opportunities regarding MOFs-derived HCNs and their applications in rechargeable batteries were discussed.

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.

Facile Template-free Synthesis of Carbonated Hydroxyapatite Spheres in Aqueous Solution

Prickly carbonated hydroxyapatite（CHAp） spheres were obtained via a facile template-free self-assembly method with Na2HPO4 and self-made cubic CaCO3 as reactants. X-ray diffraction results of the product revealed CHAp with high crystallinity could be successfully prepared in a short reaction time. A nucleation mechanism was proposed according to the results of characterizing the resultant powders and analyzing the growth process. It shows that the self-made CaCO3 particles play an important role in the template-free synthesis of prickly spheres.

Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

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.

Optimal synthesis of heat-integrated distillation configurations using the two-column superstructure

In the realm of the synthesis of heat-integrated distillation configurations,the conventional approach for exploring more heat integration possibilities typically entails the splitting of a single column into a twocolumn configuration.However,this approach frequently necessitates tedious enumeration procedures,resulting in a considerable computational burden.To surmount this formidable challenge,the present study introduces an innovative remedy:The proposition of a superstructure that encompasses both single-column and multiple two-column configurations.Additionally,a simultaneous optimization algorithm is applied to optimize both the process parameters and heat integration structures of the twocolumn configurations.The effectiveness of this approach is demonstrated through a case study focusing on industrial organosilicon separation.The results underscore that the superstructure methodology not only substantially mitigates computational time compared to exhaustive enumeration but also furnishes solutions that exhibit comparable performance.

Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Boosting Fischer-Tropsch Synthesis via Tuning of N Dopants in TiO_(2)@CN-Supported Ru Catalysts

Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.

Recent advances in cobalt phosphide-based materials for electrocatalytic water splitting:From catalytic mechanism and synthesis method to optimization design

Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.

Metagenomic analysis revealing the metabolic role of microbial communities in the free amino acid biosynthesis of Monascus rice vinegar during fermentation

Free amino acid(FAA)is the important component of vinegar that infl uences quality perception and consumer acceptance.FAA is one of the major metabolites produced by microorganisms;however,the microbial metabolic network on FAA biosynthesis remains unclear.Through metagenomic analysis,this work aimed to elucidate the roles of microbes in FAA biosynthesis during Monascus rice vinegar fermentation.Taxonomic profiles from functional analyses showed 14 dominant genera with high contributions to the metabolism pathways.The metabolic network for FAA biosynthesis was then constructed,and the microbial distribution in different metabolic pathways was illuminated.The results revealed that 5 functional genera were closely involved in FAA biosynthesis.This study illuminated the metabolic roles of microorganisms in FAA biosynthesis and provided crucial insights into the functional attributes of microbiota in vinegar fermentation.

Cost-Effective Method of Gene Synthesis by Sequencing from Microchip-Derived Oligos for Droplet Cloning

Gene synthesis has provided important contributions in various fields including genomics and medicine. Current genes are 7 - 30 cents depending on the assembly and sequencing methods performed. Demand for gene synthesis has been increasing for the past few decades, yet available methods remain expensive. A solution to this problem involves microchip-derived oligonucleotides (oligos), an oligo pool with a substantial number of oligo fragments. Microchips have been proposed as a tool for gene synthesis, but this approach has been criticized for its high error rate during sequencing. This study tests a possible cost-effective method for gene synthesis utilizing fragment assembly and golden gate assembly, which can be employed for quicker manufacturing and efficient execution of genes in the near future. The droplet method was tested in two trials to determine the viability of the method through the accuracy of the oligos sequenced. A preliminary research experiment was performed to determine the efficacy of oligo lengths ranging from two to four overlapping oligos through Gibson assembly. Of the three oligo lengths tested, only two fragment oligos were correctly sequenced. Two fragment oligos were used for the second experiment, which determined the efficacy of the droplet method in reducing gene synthesis cost and speed. The first trial utilized a high-fidelity polymerase and resulted in 3% correctly sequenced oligos, so the second trial utilized a non-high-fidelity polymerase, resulting in 8% correctly sequenced oligos. After calculating, the cost of gene synthesis lowers down to 0.8 cents/base. The final calculated cost of 0.8 cents/base is significantly cheaper than other manufacturing costs of 7 - 30 cents/base. Reducing the cost of gene synthesis provides new insight into the cost-effectiveness of present technologies and protocols and has the potential to benefit the fields of bioengineering and gene therapy.

Nucleosynthesis in the little bang

A new approach based on relativistic kinetic equations is proposed to solve the long-standing puzzle of light cluster formation, also called nucleosynthesis, in high-energy heavy-ion collisions. This method addresses the tension between STAR data and previous studies relying on either statistical equilibrium or coalescence approaches.

N,S,Br co-doped carbon dots:One-step synthesis and fluorescent detection of 6-mercaptopurine in tablet

6-mercaptopurine(6-MP),a purine derivative(3,7-dihydropurine-6-thione),has been utilized as an effective immunosuppressive drug for clinically treating leukemia and other autoimmune diseases[1].6-MP and its corresponding metabolites can suppress the function of RnaseH,and thus they are cytotoxic and threaten the human health[2].Therefore,the accurate quantification of 6-MP is crucial.To date,researchers continue to expend considerable effort in developing 6-MP detection methods.Fluorescence analysis eliminates disadvantages,such as toxic solvents,expensive equipment.

Synthesis Methods and Property Control of Two-Dimensional Magnetic Materials

Two-dimensional(2D)magnetic materials have been demonstrated to have excellent chemical,optical,electrical,and magnetic properties,particularly in the development of multifunctional electronic and spin electronic devices,showcasing tremendous potential.Therefore,corresponding synthesis techniques for 2D magnetic materials that offer high quality,high yield,low cost,time-saving,and simplicity are highly desired.This review provides a comprehensive overview of recent research advances in preparation of magnetic 2D materials,with a particular focus on the preparation methods employed.Moreover,the characteristics and applications of these magnetic materials are also discussed.Finally,the challenges and prospects of synthesis methods for magnetic 2D materials are briefly addressed.This review serves as a guiding reference for the controlled synthesis of 2D magnetic materials.

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 Silver Nanoparticles from Honeybees and Its Antibacterial Potential

Honeybees (Apis mellifera) are important pollinators of flowering plants and agricultural crops contributing annually to billions of dollars in revenues to crop production. Honeybees have an average lifespan between 8 weeks to 5 years. Dead honeybees are abundantly available in beehives and can be utilized as an alternative source to synthesize nanoparticles. In recent years, biologically synthesized nanoparticles have been preferred over their chemical counterparts. However, honeybee-based-green synthesis of nanoparticles has not been explored yet. Herein, we report the biosynthesis of silver nanoparticles from honeybees and its antibacterial activity. The synthesis of silver nanoparticles was monitored visually through a gradual change in color. Furthermore, the biosynthesized nanoparticles were confirmed and characterized by UV-visible spectroscopy. Scanning Electron Microscope was utilized to analyze the average size and morphologies of the biosynthesized nanoparticles. Subsequently, the antibacterial potential of the biosynthesized silver nanoparticles was tested against selected Gram-positive and Gram-negative bacterial strains. It was found that a distinct color change from yellow to brown in the reaction solution suggested the formation of silver nanoparticles. The biosynthesized nanoparticles exhibited absorption maxima at 430 nm. The SEM analysis confirmed the spherical and cuboidal shape of the biosynthesized silver nanoparticles with a size range between 10 - 40 nm. Furthermore, the biosynthesized silver nanoparticles exhibited strong antimicrobial potential against tested Gram-positive and Gram-negative bacteria strains by aggregating on the cell surface. This study showcases the biomedical and agricultural applications of biosynthesized silver nanoparticles from honeybee wings. .