Preparation and Conducting Behavior of Amphibious Organic/Inorganic Hybrid Proton Exchange Membranes Based on Benzyltetrazole

A series of novel amphibious organic/inorganic hybrid proton exchange membranes with H3PO4 doped which could be used under both wet and dry conditions was prepared through a sol-gel process based on acrylated triethoxysilane（A-TES） and benzyltetrazole-modified triethoxysilane（BT-TES）.The dual-curing approach including UV-curing and thermal curing was used to obtain the crosslinked membranes.Polyethylene glycol（400） diacrylate（PEGDA） was used as an oligomer to form the polymeric matrix.The molecular structures of precursors were characterized by 1 H,13 C and 29 Si NMR spectra.The thermogravimetric analysis（TGA） results show that the membranes exhibit acceptable thermal stability for their application at above 200 oC.The differential scanning calorimeter（DSC） determination indicates that the crosslinked membranes with the mass ratios of below 1.6 of BT-TES to A-TES and the same mass of H3PO4 doped as that of A-TES possess the-T g s,and the lowest T g（-28.9 ℃） exists for the membrane with double mass of H3PO4 doped as well.The high proton conductivity in a range of 9.4―17.3 mS/cm with the corresponding water uptake of 19.1%―32.8% of the membranes was detected at 90 oC under wet conditions.Meanwhile,the proton conductivity in a dry environment for the membrane with a mass ratio of 2.4 of BT-TES to A-TES and double H3PO4 loading increases from 4.89×10-2 mS/cm at 30 ℃ to 25.7 mS/cm at 140 ℃.The excellent proton transport ability under both hydrous and anhydrous conditions demonstrates a potential application in the polymer electrolyte membrane fuel cells.

Enhanced H_(2) permeation and CO_(2) tolerance of self-assembled ceramic-metal-ceramic BZCYYb-Ni-CeO_(2) hybrid membrane for hydrogen separation

Perovskite-type mixed protonic-electronic conducting membranes have attracted attention because of their ability to separate and purify hydrogen from a mixture of gases generated by industrial-scale steam reforming based on an ion diffusion mechanism.Exploring cost-effective membrane materials that can achieve both high H_(2) permeability and strong CO_(2)-tolerant chemical stability has been a major challenge for industrial applications.Herein,we constructed a triple phase(ceramic-metal-ceramic)membrane composed of a perovskite ceramic phase BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(3-δ)(BZCYYb),Ni metal phase and a fluorite ceramic phase CeO_(2).Under H_(2) atmosphere,Ni metal in-situ exsolved from the oxide grains,and decorated the grain surface and boundary,thus the electronic conductivity and hydrogen separation performance can be promoted.The BZCYYbNi-CeO_(2)hybrid membrane achieved an exceptional hydrogen separation performance of 0.53 mL min^(-1)cm^(-2) at 800℃ under a 10 vol% H_(2) atmosphere,surpassing all other perovskite membranes reported to date.Furthermore,the CeO_(2) phase incorporated into the BZCYYb-Ni effectively improved the CO_(2)-tolerant chemical stability.The BZCYYbNi-CeO_(2) membrane exhibited outstanding long-term stability for at least 80 h at 700℃ under 10 vol%CO_(2)-10 vol%H_(2).The success of hybrid membrane construction creates a new direction for simultaneously improving their hydrogen separation performance and CO_(2) resistance stability.

Removal of Chromium from Aqueous Solution Using Hybrid Membrane of Chitosan and Silicon Dioxide

Adsorption experiment from aqueous solutions containing known amount of chromium （Cr） using hybrid membrane of chitosan and silicon dioxide was explored to evaluate the efficiency of the membrane as sorbent for Cr（VI）. Some variable parameters such as pH, contact time and the dosage of the membrane were optimized. Adsorption isotherms of Cr（VI） onto the hybrid membrane were measured with varying initial concentrations under optimized condition. Furthermore, the sorption mechanism of Cr by the membrane was investigated by applying Langmuir and Freundlich isotherm equations to the data obtained. The surface morphology of the membrane was determined by SEM （scanning electron microscope） for material characterization. The concentrations of Cr in solution are determined by ICP-MS （inductively coupled plasma mass spectrometry）. Hybrid membrane of chitosan and silicon dioxide can be an efficient sorbent for Cr（VI）.

Reconstructing proton channels via Zr-MOFs realizes highly ion-selective and proton-conductive SPEEK-based hybrid membrane for vanadium flow battery

There is an urgent need to break through the trade-off between proton conductivity and ion selectivity of proton exchange membrane(PEM)in vanadium flow battery(VFB).Proton channels in PEM are the key to controlling the ion sieving and proton conductivity in VFB.Herein,two types of proton channels are reconstructed in the hybrid membrane via introducing modified Zr-MOFs(IM-UIO-66-AS)into SPEEK matrix.Internal proton channels in IM-UIO-66-AS and interfacial proton channels between grafted imidazole groups on Zr-MOFs and SPEEK greatly improve the conductivity of the IM-UIO-66-AS/SPEEK hybrid membrane.More importantly,both reconstructed proton channels block the vanadium-ion permeation to realize enhanced ion selectivity according to the size sieving and Donnan exclusion effects,respectively.Moreover,the hybrid membrane exhibits good mechanical property and dimensional stability.Benefiting from such rational design,a VFB loading with the optimized membrane exhibits enhanced voltage efficiency of 79.9%and outstanding energy efficiency of 79.6%at 200 m A cm^(-2),and keeps a notable cycle stability for 300 cycles in the long-term cycling test.Therefore,this study provides inspiration for preparing next-generation PEMs with high ion selectivity and proton conductivity for VFB application.

Membrane Potentials Across Hybrid Charged Mosaic Membrane in Organic Solutions

Membrane potentials across hybrid charged mosaic membrane in organic solutions were measured. Equilibrium swelling degree （SD） and fixed charge density in both organic solutions and water were also determined. Ethylene glycol, ethanol, n-propanol and glycerol were used as organic solutes; meanwhile 0.001mol-dm^-3 aqueous KCl solution was utilized as a strong electrolyte to measure the electrical difference. Equilibrium swelling degree indicated that it could be affected by the density of organic solutes; while it enhanced with the increasing density of these solutes. The measurement of fixed charge density showed that the membrane had the maximal absolute value in water among these solvents whether for cationic or anionic groups; the difference of dielectric constant between the water and the organic solutes might be responsible for these change trends. It was confirmed that membrane potentials increased with both the increasing concentration of the organic solutions and the elevated pH values. These results demonstrated that the characteristics of the hybrid charged mosaic membrane could be highly impacted by the properties of the organic solutes. A theoretical modal for charged membranes in ternary ion systems of weak electrolyte can be used to explain the above-mentioned phenomena.

Ionic polymer metal composites actuators with enhanced driving performance by incorporating graphene quantum dots

In order to further improve the driving performance of ionic polymer metal composites(IPMCs),Nafion/graphene quantum dots(GQDs)hybrid membranes incorporating GQDs with various contents of 0,0.1 wt.%,0.5 wt.%,1.0 wt.%,2.0 wt.%and 4.0 wt.%were fabricated by solution casting,and then IPMCs were manufactured by electroless plating.The water contents and elastic moduli of the hybrid membranes were tested.The morphology characteristics of the hybrid membranes and the IPMCs were observed,and the current,AC impedance,blocking force and displacement of the IPMCs were measured.The results show that the elastic modulus of the hybrid membranes decreases,the water content increases,and the actuation performance of the IPMCs improves significantly after the addition of GQDs.IPMC with 1.0 wt.%GQDs exhibits the best driving property.Compared with the IPMC without GQDs,the working current,ion conductivity,blocking force,and tip displacement increase by 94.67%,311.11%,53.66%,and 66.07%,respectively.These results lay a solid foundation for the preparation of IPMCs with high performance,and further broaden their applications in biomedical devices and bionic robots.

Analysis of Circumstance Influence Factors on HMBR for Waste-water Reclamation in Dwelling District

Circumstance influence factors on Hybrid Membrane Bio-Reactor (HMBR) process for the wastewater reclamation in dwelling district was analyzed. The main characteristic of this process is that sludge and nitrified effluent can be recycled automatically, which simplifies the operation of system and is beneficial to get the high removal of organics and nitrogen. Based on the analysis of circumstance influence factors, it is recommended that water temperature of about 20℃, influent pH of 6 -7 and DO of 1. 0 mg/L - 1. 5 mg/L in the aerobic compartment. Under these conditions, COD, BOD5, NH4+ -N, and TN were removed effectively in HMBR and the average removal efficiencies were 94.5%, 99.3%, 99.4% and 84.7%, respectively. SS and coliforms were both below the detection limits in the permeate of UF membrane module, and turbidity was less than 1NTU. The treated effluent meets the Miscellaneous Domestic Water Quality Standard (CJ25.1-89), and can be reused multipurposely such as watering of green belts, cleaning and toilet flushing water after disinfection.

Remarkable enhancement of gas selectivity on organosilica hybrid membranes using urea-modulated metal-organic framework nanoparticles

Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher permeance compared to commercial polymers.However,the selectivities of the reported membranes are moderate.Here,we have incorporated urea-modulated metal-organic frameworks into organosilica membranes to greatly enhance its separation performance.The urea-modulated metal-organic frameworks exhibit less-defined edges of crystallographic facets and high defect density.They can be well-dispersed in the organosilica layer,which substantially suppresses the interfacial defects between metal-organic frameworks and organosilica,which is beneficial for improving the selectivity of membranes for gas separation.The results have shown that the enhanced ideal selectivity of H_(2)/CH_(4) was 165 and that of CO_(2)/CH_(4) was 43,with H_(2) permeance of about 1.25×10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) and CO_(2) permeance of 3.27×10^(−7) mol·m^(−2)·s^(−1)·Pa^(−1) at 0.2 MPa and 25℃.In conclusion,the high level of hybrid membranes can be used to separate H_(2)(or CO_(2))from the binary gas mixture H_(2)/CH_(4)(or CO_(2)/CH_(4)),which is important for gas separation in practical applications.Moreover,the simple and feasible modulation of metal-organic framework is a promising strategy to tune different metal-organic frameworks for membranes according to the actual demands.

Hybrid nanoarchitectonics of TiO_(2)/aramid nanofiber membranes with softness and durability for photocatalytic dye degradation

TiO_(2)-based films are one of the most attractive photocatalysts owing to their highly cost-effective properties.Nevertheless,most TiO_(2)-based photocatalytic films for dye degradation are in the form of robust films(without flexibility),TiO_(2)coatings on carbon matrix(with leakage risk),or surface-covered TiO_(2)hybrids(not favorite to contact with external molecules).Therefore,the development of durable and highly efficient TiO_(2)photocatalytic films for dye degradation is still needed.Here,we fabricated soft photocatalytic hybrid membranes(TANFs)from TiO_(2)nanotubes(Ti NT)and aramid nanofiber(ANF)by a facile vacuum filtration process.The similar morphology and dimension of Ti NT and ANF enable them intricately intertwine with each other in the membrane network.Under an appropriate mixing ratio,the TANF exhibited significantly improved optical and mechanical properties.When used for dye degradation,the membrane showed excellent photocatalytic performance and could keep stable activity and integrated state for repeated usage.

Leukocyte/platelet hybrid membrane-camouflaged dendritic large pore mesoporous silica nanoparticles co-loaded with photo/chemotherapeutic agents for triple negative breast cancer combination treatment

Triple-negative breast cancer(TNBC)is an aggressive subset of breast cancer and currently lacks effective therapeutic targets.As two main phototherapeutic methods,photothermal therapy(PTT)and photodynamic therapy(PDT)show many advantages in TNBC treatment,and their combination with chemotherapy can achieve synergistic therapeutic effects.In the present study,a biomimetic nanoplatform was developed based on leukocyte/platelet hybrid membrane(LPHM)and dendritic large pore mesoporous silicon nanoparticles(DLMSNs).A near infrared(NIR)fluorescent dye IR780 and a chemotherapeutic drug doxorubicin(DOX)were co-loaded into the large pores of DLMSNs to prepare DLMSN@DOX/IR780(DDI)nanoparticles(NPs),followed by camouflage with LPHM to obtain LPHM@DDI NPs.Through the mediation of LPHM,LPHM@DDI NPs showed an excellent TNBC-targeting ability and very high PTT/PDT performances in vitro and in vivo.Upon NIR laser irradiation,LPHM@DDI NPs exhibited synergistic cytotoxicity and apoptosis-inducing activity in TNBC cells,and effectively suppressed tumor growth and recurrence in TNBC mice through tumor ablation and anti-angiogenesis.These synergistic effects were sourced from the combination of PTT/PDT and chemotherapy.Altogether,this study offers a promising biomimetic nanoplatform for efficient co-loading and targeted delivery of photo/chemotherapeutic agents for TNBC combination treatment.

Freestanding and Ultra‑flexible PAN/ZIF‑67 Hybrid Membrane with Controlled Porosity for High‑Performance and High‑Safety Lithium Batteries Separator

Herein,a flexible ZIF-67/PAN hybrid membrane was successfully prepared by the incorporation of ZIF-67 nanoparticles and PAN nanofibers through electrospinning method.The hybrid membrane presented tomatoes on sticks structures with one single PAN fiber stringing series of ZIF-67 nanoparticles.The morphology,electrolyte wettability,heat resistance,flexibility,and electrochemical properties of the electrospun ZIF-67/PAN membranes were discussed.Among the membranes prepared with different percentage of ZIF-67,the 30% ZIF-67/PAN membrane exhibited outstanding heat shrinkage resistance(remained intact at 200℃ for 1 h),excellent electrolyte uptake(556.39%),wide electrochemical window(~5.25 V)and high ionic conductivity(2.98 mS cm^(−1)).When used as lithium-ion batteries(LIBs)separators,the cells assembled by 30% ZIF-67/PAN membrane presented excellent rate capacity and high capacity retention of 86.9% after 300 cycles at 1C.More importantly,the cells assembled with ZIF-67/PAN membranes repeated bent for 1000 times also exhibited high rate performance and maintained capacity retention of 92% after 100 cycles at 1 C.The characterization and the electrochemical testing suggest the electrospinning prepared ZIF-67/PAN flexible membranes can be expected to be used as potential separator for advanced batteries with high safety and high performance.

Effect of ozone on the performance of a hybrid ceramic membrane-biological activated carbon process

Two hybrid processes including ozonation-ceramic membrane-biological activated carbon （BAC） （Process A） and ceramic membrane-BAC （Process B） were compared to treat polluted raw water. The performance of hybrid processes was evaluated with the removal efficiencies of turbidity, ammonia and organic matter. The results indicated that more than 99% of particle count was removed by both hybrid processes and ozonation had no significant effect on its removal. BAC filtration greatly improved the removal of ammonia. Increasing the dissolved oxygen to 30.0 mg/L could lead to a removal of ammonia with concentrations as high as 7.80 mg/L and 8.69 mg/L for Processes A and B, respectively. The average removal efficiencies of total organic carbon and ultraviolet absorbance at 254 nm （UV254, a parameter indicating organic matter with aromatic structure） were 49% and 52% for Process A, 51% and 48% for Process B, respectively. Some organic matter was oxidized by ozone and this resulted in reduced membrane fouling and increased membrane flux by 25%-30%. However, pre-ozonation altered the components of the raw water and affected the microorganisms in the BAC, which may impact the removals of organic matter and nitrite negatively.

Recent advances of metal-organic frameworks-based proton exchangemembranes in fuel cell applications

In recent years,proton exchange membrane(PEM)fuel cell(FC;PEMFC)has been widely studied and gradually applied to vehicle power supply,portable supply,communication base station backup,emergency power supply,and so on.Especially in new energy vehicles,PEMFC has absolute advantages and a broad market.PEM,which is the core component of PEMFC,has a close correlation between its property and the performance of FC.Therefore,developing excellent PEMs is the focus of researchers.Metal–organic frameworks(MOFs)composed of metal ions/clusters and organic ligands have attracted extensive attention in the field of proton conduction.The hybrid membranes formed by MOFs and polymers show excellent performances and design concepts,which have great prospects in commercial application.This paper summarizes the research progress of MOFs-based hybrid membranes as PEMs applied in hydrogen–oxygen FCs and direct methanol FCs,in which the different polymers used as substrates are also summed up.

SERS imaging for label-free detection of the phospholipids distribution in hybrid lipid membrane

A label-free and low-cost mapping method based on SERS imaging was reported for illustrating the distribution of phospho- lipids with similar structures in binary lipid membranes on Ag nanoparticles （Ag NPs） films. The Ag NPs films exhibited strong SERS activity and good reproducibility which were investigated with p-aminothiopbenol （p-ATP） as probe molecules. Atomic force microscope （AFM） measurement proved that compact lipid membranes formed on the Ag NPs films. Basing on the Ag NPs films, the SERS spectra of phospholipids in the mixed lipid membranes were achieved and the inherent vibration of 1,2-dimyristoyl-sn-lycero-3-phosphoglycerol, sodium salt （DMPG）, 1482 cm-1, was used to distinguish between DMPG and dimyristoylphosphatidylcholine （DMPC）. The proportions of phospholipids in the mixed lipid membranes were represented by the intensity ratio of peaks at 1482 cm-1 and 1650 cm1 （R1482/1650） simultaneously： increasing R1482/1650 indicated higher propor- tion of DMPG and lower proportion of DMPC. SERS imaging of the lipid membranes was constructed as a combination of spacial information and the semiquantitative detection of phospholipids according to R1482/1650, which showed that the charged phospholipids, DMPG, aggregated in the hybrid lipid membranes. The presented mapping strategy based on SERS imaging carried out on Ag NPs films supplied a facile, label-free and inexpensive way for potential applications in the research on the structure of the lipid membrane, such as lipid domains and rafts.

Cancer-macrophage hybrid membrane-camouflaged photochlor for enhanced sonodynamic therapy against triple-negative breast cancer

Sonodynamic therapy(SDT)has aroused considerable momentum in cancer therapy due to its abilities of deep penetration,low toxicity,and noninvasion,while insufficient tumor accumulation of sonosensitizers is a major obstacle for SDT effect.Here,we developed a 4T1 cancer cell-macrophage hybrid membrane(HM)-camouflaged sonosensitizer nanoplatform by encapsulating photochlor(HPPH)-loaded albumin nanoparticles(PHNPs).The experimental results proved that the HM-coated biomimetic NPs(PHNPs@HM)could express the characteristic membrane proteins of both cancer cells and macrophages,remarkedly enhancing the effective targeting and endocytosis to 4T1 cells through homologous adhesion recognition and immune escaping.Meanwhile,as a novel sonosensitizer,HPPH could generate amount of reactive oxygen species(ROS)under ultrasound(US)irradiation and exhibit obvious SDT efficiency to inhibit 4T1 tumor growth through ROS-induced cell apoptosis.This study provides a novel and multifunctional biomimetic sonosensitizer system to enhance SDT efficiency.

Drinking water treatment using a submerged internal-circulation membrane coagulation reactor coupled with permanganate oxidation

A submerged internal circulating membrane coagulation reactor （MCR） was used to treat surface water to produce drinking water. Polyaluminum chloride （PAC1） was used as coagulant, and a hydrophilic polyvinylidene fluoride （PVDF） submerged hollow fiber microfiltration membrane was employed. The influences of trans-membrane pressure （TMP）, zeta potential （ZP） of the suspended particles in raw water, and KMnO4 dosing on water flux and the removal of turbidity and organic matter were systematically investigated. Continuous bench-scale experiments showed that the permeate quality of the MCR satisfied the requirement for a centralized water supply, according to the Standards for Drinking Water Quality of China （GB B749-2006）, as evaluated by turbidity （〈1 NTU） and total organic carbon （TOC） （〈5 mE/L） measurements. Besides water flux, the removal of turbidity, TOC and dissolved organic carbon （DOC） in the raw water also increased with increasing TMP in the range of 0.01-0.05 MPa. High ZP induced by PAC1, such as 5-9 mY, led to an increase in the number of fine and total particles in the MCR, and consequently caused serious membrane fouling and high permeate turbidity. However, the removal of TOC and DOC increased with increasing ZP. A slightly positive ZP, such as 1-2 mV, corresponding to charge neutralization coagulation, was favorable for membrane fouling control. Moreover, dosing with KMnO4 could further improve the removal of turbidity and DOC, thereby mitigating membrane fouling. The results are helpful for the application of the MCR in producing drinking water and also beneficial to the research and application of other coagulation and membrane separation hybrid processes.

Membrane-camouflaged supramolecular nanoparticles for co-delivery of chemotherapeutic and molecular-targeted drugs with siRNA against patient-derived pancreatic carcinoma

Pancreatic cancer remains one of the most lethal malignancies worldwide. The combination of the first-line standard agent gemcitabine(GEM) with the molecular-targeted drug erlotinib(Er) has emerged as a promising strategy for pancreatic cancer treatment. However, the clinical benefit from this combination is still far from satisfactory due to the unfavorable drug antagonism and the fibrotic tumor microenvironment. Herein, we propose a membrane-camouflaged dual stimuliresponsive delivery system for the co-delivery of GEM and Er into pancreatic cancer cells and tissues to block the antagonism, as well as reshapes profibrotic tumor microenvironment via simultaneous delivery of small interference RNA(siRNA) for synergistic pancreatic cancer treatment. This “all-in-one”delivery system exhibits sensitive GSH and pH-dependent drug release profiles and enhances the inhibitory effects on the proliferation and migration of tumor cells in vitro. Excitingly, the systemic injection of such a biomimetic drug co-delivery system not only resulted in superior inhibitory effects against orthotopic pancreatic tumor and patient-derived tumor(PDX), but also greatly extended the survival rate of tumor-bearing mice. Our findings provide a promising therapeutic strategy against pancreatic cancer through the enhanced synergistic effect of target therapy, chemotherapy and anti-fibrotic therapy, which represents an appealing way for pancreatic cancer treatment.

Enhanced desulfurization performance of hybrid membranes using embedded hierarchical porous SBA-15

The utilization of materials with a hierarchical porous structure as multi-functional additives is highly attractive in the preparation of hybrid membranes.In this study,novel hybrid membranes are designed by embed-ding hierarchical porous Santa Barbara Amorphous 15(SBA-15)with a dual-pore architecture(micropores and mesopores)for pervaporation desulfurization.The SBA-15 with cylindrical mesopores provides molecular transport expressways to ensure improved permeability,while micropores on the wall have molecular sieving effects that are essential for the enhancement of permselectivity of thiophene molecules.Considering thiophene/n-octane mixture as a model system,the hybrid membrane with embedded 6 wt-%SBA-15 exhibits optimal pervaporation desulfurization performance with a permeation flux of 22.07 kg·m^-2·h^-1 and an enrichment factor of 6.76.Moreover,the detailed structure and properties of hybrid membranes are systematically characterized.This study demonstrates the immense potential of hierarchical porous materials as additives in membranes to simultaneously increase permeability and permselectivity.

Ionic Transfer in Hybrid Inorganic/Organic Membranes

1 Results In last years increasing interest has been devoted to the development and research of transport properties of hybrid organic/inorganic membranes. Traditionally, these membranes are used as electrolyte in fuel cells. However a number of their properties allow considering them as perspective materials for water treatment and substance purification. In this work transport properties of some ion exchange membranes modified by inorganic nanoparticles (hydrated oxides or solid acids) are discussed. ...

Sulfonated Polyarylene Ether Sulfone（SPES） and Ga2O3 Based Hybrid Polymer Electrolyte Membrane for Direct Methanol Fuel CelIs（DMFCs）

Novel hybrid polymer electrolyte membrane, based on sulfonated polyarylene ether sulfone（SPES） and Ga2O3, was prepared and characterized. The structure of the composite membrane substantially modified the properties of SPES in terms of thermal stability, mechanical properties, methanol permeability, and so on. The structure and performance of the hybrid membrane were investigated by means of Fourier transform infrared spectrophotometry（FTIR）, scanning electron microscopy（SEM）, electrochemical impedance spectroscopy（EIS）, thermal gravimetric analysis（TGA）, and water uptake（WU） test. The hybrid polymer electrolyte membrane containing a certain quantity of Ga2O3 was found to gain good proton transport characteristics, particularly at relatively high temperatures. In ad- dition, this membrane reduced methanol permeability and improved thermal stability in comparison to an unfilled reference membrane. The hybrid membrane was found suitably to be used as a polymer electrolyte membrane（PEM） in direct methanol fuel cells（DMFCs）.