Mesoporous TiO2 Nanofiber as Highly Efficient Sulfur Host for Advanced Lithium–Sulfur Batteries

Currently, lithium–sulfur batteries su er from several critical limitations that hinder their practical application, such as the large volumetric expansion of electrode, poor conductivity and lower sulfur utilization. In this work, TiO2 nanofibers with mesoporous structure have been synthesized by electrospinning and heat treating. As the host material of cathode for Li–S battery, the as prepared samples with novelty structure could enhance the conductivity of cathode composite, promote the utilization of sulfur, and relieve volume expansion for improving the electrochemical property. The initial discharge capacity of TiO2/S composite cathode is 703 mAh/g and the capacity remained at 652 mAh/g after 200 cycles at 0.1 C, whose the capacity retention remains is at 92.7%, demonstrating great prospect for application in high-performance Li–S batteries.

Screening non-noble metal oxides to boost the low-temperature combustion of polyethylene waste in air

Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.

Experiment and modeling of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites

Since paraffins catalytic cracking was of significant importance to light olefins and aromatics production,this work was intended to gain insights into the feature and model of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites. 18 tests of n-heptane catalytic cracking were designed and carried out over HZSM-5 zeolites in a wide range of operating conditions. A particular attention was paid to the measurement of the conversion, product distribution, coke content, and the porosity and acidity of the fresh and spent HZSM-5 zeolites. It was found that alkene and aromatic promoted coke formation, and it reduced the pore volume and acid site of HZSM-5 zeolites, tailoring its performance in n-heptane catalytic cracking. The specific relationship between HZSM-5 zeolites, n-heptane conversion, product distribution and coke formation was quantitively characterized by the exponential and linear function. Based on the reaction network, the coupled scheme of coke formation and catalyst deactivation were specified for n-heptane catalytic cracking. The dual-model was proposed for the process simulation of n-heptane catalytic cracking over HZSM-5 zeolites. It predicted not only the conversion and product distribution but also coke content with the acceptable errors.

Preparation of ZIF-8@PEBAX/PVDF nanocomposite membrane by the combination of self-assembly and in-situ growth for removing thiophene from the model gasoline

Metal-organic frameworks(MOFs)have gained attention in the development of MOFs/polymer hybrid membranes for pervaporation.However,the agglomeration of MOFs particles and interfacial defects limit its further application.In this study,we present a novel approach to fabricate a ZIF-8@PEBAX/PVDF nanocomposite membrane for removing thiophene from the model gasoline by combination of selfassembly and in-situ growth.Firstly,a PVDF supporting membrane was modified to have a negative charge.Next,positively charged zinc ions were attracted onto the negatively charged PVDF supporting membrane through electrostatic interaction.Afterwards,the Zinc ions deposited PVDF membrane was immersed into dimethylimidazole solution to form a uniform ZIF-8 layer.Finally,the ZIF-8 layer was coated with poly(ether-block-amide)(PEBAX)using the pouring method.Experimental results showed that the separating efficiency of the ZIF-8@PEBAX/PVDF nanocomposite membrane was improved significantly compared to that of pristine PEBAX membrane.The optimal permeation flux and enrichment factor of membrane were 27.80 kg(m^(2)h)^(-1)and 6.9,respectively.

Amino-functionalized UiO-66-doped mixed matrix membranes with high permeation performance and fouling resistance

For the reduction of bovine serum proteins from wastewater,a novel mixed matrix membrane was prepared by functionalizing the substrate material polyaryletherketone(PAEK),followed by carboxyl groups(C-SPAEKS),and then adding amino-functionalized UiO-66-NH_(2)(Am-UiO-66-NH_(2)).Aminofunctionalization of UiO-66 was accomplished by melamine,followed by an amidation reaction to immobilize Am-UiO-66-NH_(2),which was immobilized on the surface of the membrane as well as in the pore channels,which enhanced the hydrophilicity of the membrane surface while increasing the negative potential of the membrane surface.This nanoparticle-loaded ultrafiltration membrane has good permeation performance,with a pure water flux of up to 482.3 L·m^(-2)·h^(-1) for C-SPAEKS/AmUiO-66-NH_(2) and a retention rate of up to 98.7%for bovine serum albumin(BSA)-contaminated solutions.Meanwhile,after several hydrophilic modifications,the flux recovery of BSA contaminants by this series of membranes increased from 56.2%to 80.55%of pure membranes.The results of ultra-filtration flux time tests performed at room temperature showed that the series of ultrafiltration membranes remained relatively stable over a test time of 300 min.Thus,the newly developed mixed matrix membrane showed potential for high efficiency and stability in wastewater treatment containing bovine serum proteins.

Amine-functionalized metal organic framework@graphene oxide as filler in PAEK-containing carboxyl group membrane for ultrafiltration with ultra-high permeability and strong fouling resistance

Achieving high fouling resistance and permeability using membrane separation technology in water treatment processes remains a challenge.In this work,a novel mixed-matrix membrane(MMM)(poly(arylene ether ketone)[PAEK]-containing carboxyl groups[PAEK-COOH]/UiO-66-NH_(2)@graphene oxide[GO])with superb fouling resistance and high permeability was prepared by the nonsolvent-induced phase separation method,by in-situ growth of UiO-66-NH_(2) on the GO layer,and by preparing hydrophilic PAEK-COOH.On the basis of the structure and performance analysis of the MMM,the maximum water flux reached 591.25 L·m^(-2)·h^(-1) for PAEK-COOH/UiO-66-NH_(2)@GO,whereas the retention rate for bovine serum albumin increased from 85.40%to 94.87%.As the loading gradually increased,the hydrophilicity of the MMMs increased,significantly enhancing their fouling resistance.The strongest anti-fouling ability observed was 94.74%,which was 2.02 times greater than that of the pure membrane.At the same time,the MMMs contained internal amide and hydrogen bonds during the preparation process,forming a cross-linked structure,which further enhanced the mechanical strength and chemical stability.In summary,the MMMs with high retention rate,strong permeability,and anti-fouling ability were successfully prepared.

Empirical modeling of normal/cyclo-alkanes pyrolysis to produce light olefins

Due to the complexity of feedstock,it is challenging to build a general model for light olefins production.This work was intended to simulate the formation of ethylene,propene and 1,3-butadiene in alkanes pyrolysis by referring the effects of normal/cyclo-structures.First,the pyrolysis of n-pentane,n-hexane,n-heptane,n-octane,n-nonane,n-decane,cyclohexane,methylcyclohexane,n-hexane and cyclohexane mixtures,and n-heptane and methylcyclohexane mixtures were carried out at 650–800℃,and a particular attention was paid to the measurement of ethylene,propene and 1,3-butadiene.Then,pseudo-first order kinetics was taken to characterize the pyrolysis process,and the effects of feedstock composition were studied.It was found that chain length and cyclo-alkane content can be qualitatively and quantitively represented by carbon atom number and pseudo-cyclohexane content,which made a significant difference on light olefins formation.Furthermore,the inverse proportional/quadratic function,linear function and exponential function were proposed to simulate the effects of chain length,cycloalkane content and reaction temperature on light olefins formation,respectively.Although the obtained empirical model well reproduced feedstock conversion,ethylene yield and propene yield in normal/cycloalkanes pyrolysis,it exhibited limitations in simulating 1,3-butadiene formation.Finally,the accuracy and flexibility of the present model was validated by predicting light olefins formation in the pyrolysis of multiple hydrocarbon mixtures.The prediction data well agreed with the experiment data for feedstock conversion,ethylene yield and propene yield,and overall characterized the changing trend of 1,3-butadiene yield along with reaction temperature,indicating that the present model could basically reflect light olefins production in the pyrolysis process even for complex feedstock.

Role of Heating Condition in Polyethylene Behaviors under Nitrogen and Air Atmosphere

Recycle of plastic waste is an indisputable means to alleviate both environment and energy crisis.In this work,effects of heating condition on polyethylene behaviors in nitrogen and air were studied.It was observed that polyethylene behavior was a single step in nitrogen,while the multiple steps occurred in air.According to the weight loss and heat flow curves,polyethylene behaviors in air were divided into three regions:low-temperature(<340 ℃),middle-temperature(340 – 380 ℃) and high-temperature(> 380 ℃) regions.Kinetic analysis revealed that the partial oxidization took the dominance in the low-temperature region,which seldom formed CO and CO_(2);the combustion took the dominance in the middle-temperature region,which was positive to the formation of CO and CO_(2);the pyrolysis was initiated and enhanced in the high-temperature region,which inhibited the formation of CO and CO;.According to the kinetic simulation,a synergistic effect between the pyrolysis and combustion was proposed to account for the acceleration of polyethylene conversion.This work may provide useful information about polyethylene behaviors under heating condition,and help to design and optimize plastic waste incineration process.

Effects of Operating Conditions on the Catalytic Performance of HZSM-5 Zeolites in n-Pentane Cracking

In this work,n-pentane catalytic cracking over HZSM-5 zeolites was studied at 650°C under atmosphere pressure.A particular attention was paid to the measurement of n-pentane conversion,light olefins production,product distribution,coke deposit,etc.Several indexes were defined to evaluate the effects of operating conditions on the catalytic performance of HZSM-5 zeolites.It was found that decreasing the weight hourly space velocity,increasing the reactant partial pressure,and increasing the carrier gas flow rate could inhibit C-H bond breaking and enhance the C-C bond breaking and hydride transfer reactions,leading to reduced alkenes selectivity,which suppressed the formation of external coke and alleviated the deactivation of HZSM-5 zeolites.It was deduced that the catalytic stability of HZSM-5 zeolites was improved at the cost of alkenes selectivity.Compared with decreasing the weight hourly space velocity and increasing the reactant partial pressure,increasing the carrier gas flow rate could enhance the diffusion process and protect alkenes from being consumed in coke formation in order to improve the catalytic stability of HZSM-5 zeolites with less reduction of alkenes selectivity.

Semi-interpenetrating network anion exchange membranes based on quaternized polyvinyl alcohol/poly(diallyldimethylammonium chloride)

The semi-interpenetrating network anion exchange membranes(AEMs)based on quaternized polyvinyl alcohol(QPVA)and poly(-diallyldimethylammonium chloride)(PDDA)are synthesized.The chemical cross-linking structure is formed between hydroxyl groups of QPVA and aldehyde groups of glutaraldehyde(GA),which makes PDDA more stable embed in the QPVA matrix and also improves the mechanical properties and dimensional stability of AEMs.Due to the phase separation phenomenon of AEMs swelling in water,a microporous structure may be formed in the membrane,which reduces the transmission resistance of hydroxide ions and provides a larger space for the transfer of hydroxide ions,thus improving the conductivity.The ring structure of PDDA is introduced as a cationic group to transfer hydroxide ions,and shields the nucleophilic attack of the hydroxide ions through the steric hindrance effect,which improves alkaline stability.The hydroxide conductivity of semi-interpenetrating network membrane(QPVA/PDDA0.5-GA)is 36.5 mS cm^(-1) at 60℃.And the membrane of QPVA/PDDA0.5-GA exhibits excellent mechanical property with maximum tensile strength of 19.6 MPa.After immersing into hot 3 mol L^(-1) NaOH solutions at 60℃ for 300 h,the OHconductivity remains 78%of its initial value.The semi-interpenetrating network AEMs with microporous structure exhibit good ionic conductivity,mechanical strength and alkaline durability.

A Luminescent Metal-Organic Framework with LON Topology for Highly Effective Fluorescence Sensing of Fe^(3+) and TNP

A luminescent Ag-based metal-organic framework(compound 1)has been synthesized and its structure has been characterized.Compound 1 was fabricated using the Ag+and bbimb2−ligands and manifestes a rare LON topology.Compound 1 is selective not only in detecting traces of Fe^(3+)and 2,4,6-trinitrophenol(TNP)via luminescence quenching,but also demonstrates high selectivity in the presence of other competitors.Compound 1’s K sv values towards Fe^(3+)can reach as high as 9.3×l0^(3) L/mol,which is higher than those of several other MOF materials.It is also a recyclable luminous sensor with the potential to be utilized for detecting TNP.Hence,based on its characteristics,compound 1 can be regarded as a prospective luminescence sensor for detecting Fe^(3+)and TNP.

Modulating carrier density of the(Ag)_(x)(MoO_(3))_(y)system to enhance SERS:Localized surface plasmon resonance contribution

Semiconductors typically exhibit long-wavelength LSPR absorption in the infrared region due to lower carrier density.Tuning the carrier density of semiconductors and blue-shifting their LSPR absorption to the visible and near-infrared region has always been a great challenge.Herein,we discussed how the controllable carrier of(Ag)x(MoO_(3))y composite influences the LSPR based on SERS test and UVeViseNIR absorption spectra.We were surprised to find that the LSPR absorption wavelength can be easily tuned from 950 to 735 nm by changing the sputtering power of MoO_(3)of the(Ag)x(MoO_(3))_(y)composite.This shows that LSPR can be precisely adjusted by increasing the semiconductor content and even the carrier density.In addition,the carrier density was measured by Hall effect to investigate the SERS intensity change caused by electromagnetic(EM)enhancement,and obtain the relationship between the two.The findings of this work provide an idea for tunable LSPR and the research of EM contributions to SERS.

Covalent triazine frameworks modified by ultrafine Pt nanoparticles for efficient photocatalytic hydrogen production

Pt nanoparticles(PtNPs)as active species have always been considered as one of the best semiconductor materials for photocatalytic hydrogen production.In this study,a Schottky heterojunction has been successfully constructed by evenly loading ultrafine PtNPs onto a triazine-based covalent organic frameworks(COFs).This strategy maintained the high activity of these ultra-small PtNPs while maximizing the utilization of the Pt active sites.The fabricated PtNPs@covalent triazine-based framework-1(CTF-1)composite accomplished a significantly high rate of hydrogen evolution(20.0 mmol·g^(−1)·h^(−1),apparent quantum efficiency(AQE)=7.6%,atλ=450 nm)with 0.40 wt.%Pt loading,giving rise to a 44-fold-increase in the efficiency of the photocatalytic hydrogen production compared to the pristine CTF-1.Theoretical calculations revealed that the strong electron transfer(Q(Pt)=−0.726 qe,in the analysis of Bader charge,Q(Pt)is the charge quantity transferred from Pt cluster to CTF-1,and qe is the unit of charge transfer quantity)between PtNPs and CTF-1 triggers a strong interaction,which makes PtNPs being firmly attached to the structure of CTF-1,thereby enabling high stability and excellent hydrogen production efficiency.Importantly,the hydrogen binding free energy(ΔGH*)of PtNPs@CTF-1 is much lower than that of the unmodified CTF-1,leading to a much lower intermediate state and hence a significant improvement in photocatalytic performance.The overall findings of this work provide a new platform to incorporate metallic NPs into COFs for the design and fabrication of highly efficient photocatalysts.

Sulfonated poly(aryl ether ketone sulfone)modified by polyoxometalates LaW_(10) clusters for proton exchange membranes with high proton conduction performance

Polyoxometalates(POMs)are classified as solid superacids which can exhibit notable proton conductivity,making them a promising functional inorganic filler for enhancing the proton conductivity of proton exchange membranes(PEMs).In this study,a series of hybrid membranes were obtained by molecular-level hybridization of Weakley-type POM Na_(7)H_(2)LaW_(10)O_(36)(LaW_(10))clusters into sulfonated poly(aryl ether ketone sulfone)(SPAEKS).All hybrid membranes exhibited greater proton conductivity than the pristine membrane in the 30–80℃temperature range.When the doping amount of LaW 10 reached 7 wt.%,the proton conductivity of M-LaW 10^(-7)achieved 64 mS·cm^(−1)at 80℃.Lanthanide ions'high coordination number property and variable coordination environment can aid to attract more water molecules from the environment.LaW 10 and these bound water can construct denser hydrogen bonds with–SO_(3)H of SPAEKS.These intensive hydrogen bonds will facilitate the constitution of more continuous proton transport channels,and improve the proton conductivity of the hybrid membrane.This work off ers a fresh approach to using POMs containing rare-earth components in PEMs.

Hofmeister Effect-Assisted Strong Natural Biopolymer-Based Hydrogels with Multi-Functions

Natural biopolymer-based hydrogels have been extensively studied in recent years due to their excellent biocompatibility.However,the preparation of multi-functional and tough natural biopolymer-based hydrogels is still a challenging problem.Herein,a natural biopolymer-based hydrogel is prepared using gelatin and carboxymethyl chitosan(CMCS)through a one-step soaking method.The prepared hydrogel without any synthetic polymers and crosslinking agents has a fully physical crosslinking structure.Due to the hydrophobic interaction brought by the Hofmeister effect,the mechanical properties of soaked hydrogels(tensile stress and strain can reach 3.77 MPa and 1082%)are superior to conventional protein hydrogels.In addition,the prepared gelatin/carboxymethyl chitosan(Gel/CMCS)hydrogels exhibit a variety of appealing properties,including good shape memory,fatigue resistance,electrical conductivity,water retention,drug releasing,antibacterial property,and recyclability.This strategy opens up a new horizon to fabricate hydrogels with excellent mechanical properties and multiple functions,which can extend their applications in the biomedicine area and other related fields.

Preparation and application of graphene-based wearable sensors

With the development of digital healthcare technology,the demand for non-invasive monitoring of human health is rapidly increasing.In recent years,the research and application of timely,economical,and easy-to-operate wearable sensing devices have attracted much attention.Among recent studies,graphene has been widely used to improve the sensing performance of wearable sensors due to its advantages in mechanical,electrical,and thermal properties.This review mainly focuses on summarizing graphene and its derivative-based wearable sensors and their latest developments in personal health monitoring.We will first introduce the novel structure and sensing mechanism of different types of graphene sensors.Then,we summarize the latest applications of the graphene wearable sensors in human health monitoring,including human activity,heart rate,pulse,electrophysiological signal,and electronic skin.Finally,the future challenges and prospects of graphene wearable devices will be discussed.

Preparation of quaternarized N-halamine-grafted graphene oxide nanocomposites and synergetic antibacterial properties

At present,frequent outbreaks of bacteria and viruses have seriously affected people's normal lives.Therefore,the study of broad-spectrum antibacterial nanocomposites is very promising.However,most antibacterial materials have some disadvantages,such as single bactericidal mechanisms and unrepeatable use.Based on the current situation,a kind of nanocomposite with three structures of graphene oxide(GO),quaternary ammonium salt(QAs)and N-halamine was prepared,which showed synergistic effect to improve antibacterial activity and combined with a variety of sterilization mechanisms.Meanwhile,GO can provide richer ways of sterilization and high specific surface area,which is conducive to the grafting of quaternarized N-halamine.The advantages of physical sterilization of GO,charge adsorption of QAs,reuse of N-halamine and efficient sterilization are fully utilized.The results showed that the quaternarized N-halamine-grafted GO was obtained successfully.GO grafted with quaternarized N-halamine polymer showed strong speedy bactericidal activity against Escherichia coli(E.coli)and Staphylococcus aureus(S.aureus)(99%).It had good storage and regeneration properties.

Mechanical and Adhesive Properties of Ploy（ethylene glycerol） Diacrylate Based Hydrogels Plasticized with PEG and Glycerol

Using polyethylene glycol（PEG） or glycerol as the plasticizer, we synthesized the hydrogels from poly（ethylene glycol） diacrylate（PEGDA）, polyvinylpyrrolidone（PVP） and poly（vinyl alcohol）（PVA） under UV radiation. The effects of different plasticizers on the mechanical properties and adhesion properties of the hydrogels were investigated. The results show that the plasticizer can improve the elongation and peeling force. The most pronotmced changes in the tensile property of the hydrogels are due to the addition of glycerol followed by PEG, the lower the plasticizer＇s molecular weight, the greater its effect. The maximum peeling force is 0.317 or 0.257 N with PEG or glycerol as plasticizer, respectively, and their adhesion properties are due to the formation of hydrogen bonds.

Fabrication and catalytic performance of meso-ZSM-5 zeolite encapsulated ferric oxide nanoparticles for phenol hydroxylation

An encapsulation-structured Fe_(2)O_(3)@mesoZSM-5(Fe@MZ5)was fabricated by confining Fe_(2)O_(3) nanoparticles(ca.4 nm)within the ordered mesopores of hierarchical ZSM-5 zeolite(meso-ZSM-5),with ferric oleate and amphiphilic organosilane as the iron source and meso-porogen,respectively.For comparison,catalysts with Fe_(2)O_(3)(ca.12 nm)encapsulated in intra-crystal holes of meso-ZSM-5 and with MCM-41 or ZSM-5 phase as the shell were also prepared via sequential desilication and recrystallization at different pH values and temperatures.Catalytic phenol hydroxylation performance of the as-prepared catalysts using H_(2)O_(2) as oxidant was compared.Among the encapsulation-structured catalysts,Fe@MZ5 showed the highest phenol conversion and hydroquinone selectivity,which were enhanced by two times compared to the Fe-oxide impregnated ZSM-5(Fe/Z5).Moreover,the Fe-leaching amount of Fe@MZ5 was only 3% of that for Fe/Z5.The influence of reaction parameters,reusability,and ·OH scavenging ability of the catalysts were also investigated.Based on the above results,the structure-performance relationship of these new catalysts was preliminarily described.

Small nanoparticles bring big prospect: The synthesis, modification,photoluminescence and sensing applications of carbon dots

As a new type of carbon-based fluorescent nanomaterials, carbon dots(CDs) are provided with the advantages of small size, excellent photoluminescence(PL) property, easy surface modification, robust stability,good water solubility and biocompatibility, which endow them with great potential in sensing. In this review, we first describe the preparation of CDs from different starting materials via various techniques, and pre-/post-modification strategies to modulate their PL properties. Second, we outline the optical properties of CDs, including UV-vis absorption and PL, especially the PL mechanisms of CDs are presented in detail from the size effect, molecular state, surface state and defect state. Third, we summarize the research progress of CDs in sensing environmental pollutants, bioactive substances, biological microenvironments,bacteria and viruses via different mechanisms. In addition, we envision the future development trends and prospects for CDs-based nanosensors. We believe that this type of small nanoparticles will bring about big prospect in the near future.