Effect of carbon material and surfactant on ink property and resulting surface cracks of fuel-cell microporous layers

Ensuring the consistency of electrode structure in proton-exchange-membrane fuel cells is highly desired yet challenging because of wide-existing and unguided cracks in the microporous layer(MPL). The first thing is to evaluate the homogeneity of MPL with cracks quantitatively. This paper proposes the homogeneity index of a full-scale MPL with an area of 50 cm~2, which is yet to be reported in the literature to our knowledge. Besides, the effects of the carbon material and surfactant on the ink and resulting MPL structure have been studied. The ink with a high network development degree produces an MPL with low crack density, but the ink with high PDI produces an MPL with low crack homogeneity. The polarity of the surfactant and the non-polarity of polytetrafluoroethylene(PTFE) are not mutually soluble,resulting in the heterogeneous PTFE distribution. The findings of this study provide guidelines for MPL fabrication.

Conjugated microporous polymers-scaffolded enzyme cascade systems with enhanced catalytic activity

Enhancing catalytic activity of multi-enzyme in vitro through substrate channeling effect is promis-ing yet challenging.Herein,conjugated microporous polymers(CMPs)-scaffolded integrated en-zyme cascade systems(I-ECSs)are constructed through co-entrapping glucose oxidase(GOx)and horseradish peroxidase(HRP),in which hydrogen peroxide(H_(2)O_(2)) is the intermediate product.The interplay of low-resistance mass transfer pathway and appropriate pore wall-H_(2)O_(2) interactions facilitates the directed transfer of H_(2)O_(2),resulting in 2.4-fold and 5.0-fold elevation in catalytic activ-ity compared to free ECSs and separated ECSs,respectively.The substrate channeling effect could be regulated by altering the mass ratio of GOx to HRP.Besides,I-ECSs demonstrate excellent stabili-ties in harsh environments and multiple recycling.

High-Performance Na-Ion Storage of S-Doped Porous Carbon Derived from Conjugated Microporous Polymers

Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs.However,the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions.In this work,we report a creative and facile strategy for preparing S-doped porous carbons(SCs)via the pyrolysis of conjugated microporous polymers(CMPs).Briefly,thiophene-based CMPs served as the precursors and doping sources simultaneously.Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures.When used as an anode for NIBs,the SCs exhibited a high reversible capacity of 440 mAh g?1 at 50 mA g?1 after 100 cycles,superior rate capability,and excellent cycling stability(297 mAh g?1 after 1000 cycles at 500 mA g?1),outperforming most S-doped carbon materials reported thus far.The excellent performance of the SCs is attributed to the expanded lattice distance after S doping.Furthermore,we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation,which can highlight the role of doped S for Na-ion storage.

Preparation and Characterization of Microporous Nano-Tungsten Trioxide and Its Photocatalytic Activity after Doping Rare Earth

Aqueous sols and gels of tungstic acid were prepared from Na2WO4 with protonated cation-exchange resin. Nano-tungsten oxide of a microporous lamella was synthesized by means of washing of WO3· 2H2O with distilled water under ultrasonic wave agitation and centrifuging repeatedly, and the specific surface area tended to increase gradually with washing and centrifuging. The sample of centrifuged 7 h has more than 2 times highs specific surface area and more high photocatalytic activity . The mechanisms are also discussed.

Improvement of antifouling characteristics in a bioreactor of polypropylene microporous membrane by the adsorption of Tween 20

Surface modification by physical adsorption of Tween 20 was accomplished on polypropylene microporous membranes （PPMMs）. Attenuated total reflection-Fourier transform infrared spectroscopy （ATR/FT-IR） and field emission scanning electron microscope （FE- SEM） were used to characterize the chemical and morphological changes on the membrane surfaces. Water contact angles and relative pure water fluxes were measured. The data showed that the hydrophilic performance for the modified membranes increased with the increase in the adsorption amount of Tween 20 onto the surface or into the pores of polypropylene microporous membranes. To test the antifouling property of the membranes by the adsorption of Tween 20 in a membrane bioreactor （MBR）, filtration for active sludge was performed using synthetic wastewater. With the help of the data of water fluxes and the FE-SEM photos of the modified PPMMs before or after operating in a MBR for about 12 d, the PPMMs with monolayer adsorption of Tween 20 showed higher remained flux and stronger antifouling ability than unmodified membrane and other modification membranes studied.

Facile synthesis of microporous carbon through a soft-template pathway and its performance in desulfurization and denitrogenation

Wormlike/lamellar microporous carbons were prepared by using long alkyl chain primary amine hydrochloride as the template and resorci- nol/formaldehyde as the carbon source under highly acidic conditions. The template can be eliminated by high temperature treatment under an inert atmosphere. The obtained carbon materials were characterized by N2 adsorption-desorption, transmission electron microscopy, ther- mogravimetry and scanning electron microscopy. The results show that dodecylamine hydrochloride surfactant can be used as the template of wormlike micropores structure while octadecylamine hydrochloride results in both lamellar and wormlike micropores. The obtained carbon materials have the similar pore size in the range of 0.5-0.59 nm, but with various morphologies such as monolith, spheres, and coralline. The microporous carbon obtained from dodecylamine hydrochloride surfactant shows good adsorption performance to remove the refractory sulfur compounds and nitrogen-containing compounds in fuel.

Large-scale carambola-like V_(2)O_(5) nanoflowers arrays on microporous reed carbon as improved electrochemical performances lithium-ion batteries cathode

To search for new cathode materials with high energy density of Lithium-ion batteries(LIBs) is one of the most challenging issues. Vanadium pentoxide(V2 O5) with high theoretical specific capacity is believed to be a promising candidate for the next generation cathode materials, yet still suffers from low lithium ion diffusion coefficient and poor electronic conductivity resulting in low cycling life and poor rate performances. Here, we report new large-scale carambola-like V2 O5 nanoflowers arrays anchored on microporous reed carbon as high performances LIBs cathode. Each individual pore space of the microporous reed carbon is like a hexagonal cylinder, and the area of each carbon wall is more than103 um2, which is favorable for the growth of V2 O5 nanostructure arrays. After hydrothermal, the largescale carambola-like V2 O5 nanoflowers arrays can directly grow on the surface of microporous carbon.Due to the novel composite structures, the V2 O5 nanoflowers arrays@microporous carbon stabilizes at273 mA h g^(-1) after 100 cycles at 0.2 C. When cycling at 1.0 C over 500 cycles, the capacity still maintains at 180 mAh g^(-1). The demonstrated approach in this work paves the way for the development of high rate capability and excellent cycling stability V2 O5-based cathode materials.

Core-shell meso/microporous carbon host for sulfur loading toward applications in lithium-sulfur batteries

Lithium-sulfur（Li-S） batteries belong to one of the promising technologies for high-energy-density rechargeable batteries.However,sulfur cathodes suffer from inherent problems of its poor electronic conductivity and the shuttling of highly dissoluble lithium polysulfides generated during the cycles.Loading sulfur into porous carbons has been proved to be an effective approach to alleviate these issues.Mesoporous and microporous carbons have been widely used for sulfur accommodation,but mesoporous carbons have poor sulfur confinement,whereas microporous carbons are impeded by low sulfur loading rates.Here,a core-shell carbon,combining both the merits of mesoporous carbon with large pore volume and microporous carbon with effective sulfur confinement,was prepared by coating the mesoporous CMK-3 with a microporous carbon（MPC） shell and served as the carbon host（CMK-3 @MPC） to accommodate sulfur.After sulfur infusion,the as-obtained S/（CMK-3@MPC） cathode delivered a high initial capacity of up to 1422 mAh·g-1 and sustained 654 mAh·g-1 reversible specific capacity after 36 cycles at 0.1 C.The good performance is ascribed to the unique core-shell structure of the CMK-3@MPC matrix,in which sulfur can be effectively confined within the meso/microporous carbon host,thus achieving simultaneously high electrochemical utilization.

An Ultra-microporous Carbon Material Boosting Integrated Capacitance for Cellulose-Based Supercapacitors

A breakthrough in advancing power density and stability of carbon-based supercapacitors is trapped by inefficient pore structures of electrode materials.Herein,an ultramicroporous carbon with ultrahigh integrated capacitance fabricated via one-step carbonization/activation of dense bacterial cellulose(BC)precursor followed by nitrogen/sulfur dual doping is reported.The microporous carbon possesses highly concentrated micropores(~2 nm)and a considerable amount of sub-micropores(<1 nm).The unique porous structure provides high specific surface area(1554 m^2 g^-1)and packing density(1.18 g cm^-3).The synergistic effects from the particular porous structure and optimal doping effectively enhance ion storage and ion/electron transport.As a result,the remarkable specific capacitances,including ultrahigh gravimetric and volumetric capacitances(430 F g^-1 and 507 F cm^-3 at 0.5 A g^-1),and excellent cycling and rate stability even at a high current density of 10 A g^-1(327 F g^-1 and 385 F cm^-3)are realized.Via compositing the porous carbon and BC skeleton,a robust all-solid-state cellulose-based supercapacitor presents super high areal energy density(~0.77 mWh cm^-2),volumetric energy density(~17.8 W L^-1),and excellent cyclic stability.

Surface Modification of Polypropylene Microporous Membrane by Atmospheric-pressure Plasma Induced N-vinyl-2-pyrrolidone Graft Polymerization

Membrane surfaces modified with poly（N-vinyl-2-pyrrolidone） （PNVP） can be endowed with hydrophilicity, biocompatibility and functionality. In this work, atmospheric pressure dielectric barrier discharge plasma graft polymerization of N-vinyl-2-pyrrolidone （NVP） onto polypropylene （PP） microporous membrane surface was studied. The experimental results reveal that plasma treatment conditions, such as discharge power, treatment time and adsorbed NVP amount, have remarkable effects on the grafting degree of NVP. Structural and morphological changes on the membrane surfaces were characterized by attenuated total reflection-Fourier transform infrared spectroscopy （FT-IR/ATR）, X-ray photoelectron spectroscope （XPS） and field emission scanning electron microscopy （FE-SEM）. Water contact angles of the membrane surfaces were also measured by the sessile drop method. Water contact angles on the membrane surfaces decrease with the increase of NVP grafting degree, which indicates an enhanced hydrophilicity for the modified membranes. The effects of grafting degrees on pure water fluxes were also measured. It is shown that pure water fluxes increase with grafting degree firstly and then decrease adversely. Finally, filtration of bovine serum albumin （BSA） solution and platelets adhesion of the PNVP modified membranes show good protein resistance and potential biocompatibility due to the enhancement of surface hydrophilicity.

SURFACE MODIFICATION OF POLYPROPYLENE MICROPOROUS MEMBRANES BY THE ADSORPTION OF NON-IONIC SURFACTANTS

Surface modification by physical adsorption of a series of non-ionic surfactants including Tween 20, Tween 40, Tween 60, Tween 80 and Tween 85, was accomplished on polypropylene microporous hollow fiber and flat membranes. The adsorption curve of the membrane surface was analyzed by weight measurements and the typical results showed a twoplatform character similarly. Differences in the degree and curve shape of adsorption resulting from such factors as concentration, temperature, as well as water cleaning time were observed for Tween 85 among other Tweens. Attenuated total reflection - Fourier transform infrared spectroscopy analysis and field emission scanning electron microscopy observation showed that the adsorption of Tween on polypropylene microporous membrane （PPMM） is effective and occurs mainly in the pores of PPMMs at low adsorption amount, and on the membrane surface also at high adsorption value.

Surface Modification of Polypropylene Microporous Membrane by Atmospheric-Pressure Plasma Immobilization of N,N-dimethylamino Ethyl Methacrylate

Surface modification of polypropylene microporous membrane （PPMM） was performed by atmospheric pressure dielectric barrier discharge plasma immobilization of N,Ndimethylamino ethyl methacrylate （DMAEMA）. Structural and morphological changes on the membrane surface were characterized by attenuated total reflection-Fourier transform infrared spectroscopy （FT-IR/ATR）, X-ray photoelectron spectroscope （XPS） and field emission scanning electron microscopy （FE-SEM）. Water contact angles of the membrane surfaces were also measured by the sessile drop method. Results reveal that both the plasma-treating conditions and the adsorbed DMAEMA amount have remarkable effects on the immobilization degree of DMAEMA. Peroxide determination by 1,1-diphenyl-2-picrvlhydrazyl （DPPH） method verifies the exsistence of radicals induced by plasma, which activize the immobilization reaction. Pure water contact angle on the membrane surface decreased with the increase of DMAEMA immobilization degree, which indicates an enhanced hydrophilicity for the modified membranes. The effects of immobilization degrees on pure water fluxes were also measured. It is shown that pure water fluxes first increased with immobilization degree and then decreased. Finally, permeation of bovine serum albumin （BSA） and lysozyme solution were measured to evaluate the antifouling property of the DMAEMA-modified membranes, from which it is shown that both hydrophilicity and electrostatic repulsion are beneficial for membrane antifouling.

SURFACE MODIFICATION OF POLYPROPYLENE MICROPOROUS MEMBRANE BY TETHERING POLYPEPTIDES

Two kinds of polypeptides were tethered onto the surface of polypropylene microporous membrane （PPMM） through a ring opening polymerization of L-glutamate N-carboxyanhydride initiated by amino groups which were introduced by ammonia plasma and y-aminopropyl triethanoxysilane treatments. X-ray photoelectron spectroscopy （XPS）, attenuated total reflectance Fourier transform infrared spectroscopy （FT-IR/ATR）, scanning electron microscopy （SEM）, together with water contact angle measurements were used to characterize the modified membranes. XPS analyses and FT-IR/ATR spectra demonstrated that polypeptides are actually grafted onto the membrane surface. The wettability of the membrane surface increases at first and then decreases with the increase in grafting degrees of polypeptide. Platelet adhesion and murine macrophage attachment experiments reveal an enhanced hemocompatibility for the polypeptide modified PPMMs. All these results give evidence that polypeptide grafting can simultaneously improve the hemocompatibility as well as reserve the hydrophobicity for the membrane, which will provide a potential approach to improve the performance of polypropylene hollow fiber microporous membrane used in artificial oxygenator.

FORMATION AND MICROSTRUCTURE OF POLYETHYLENE MICROPOROUS MEMBRANES THROUGH THERMALLY INDUCED PHASE SEPARATION

Microporous membranes of low-high density polyethylene and their blends were prepared bythermally-induced phase separation of polymer/long-aliphatic chain alcohol (diluent) mixtures.The microstructures of this particular membrane, which depends on the diluent properties,polymer concentration and cooling rate, were observed by scanning electron microscopy.'Beehive-type,'leafy-like, and lacy porous structure morphologies can be formed,depending onthe blend composition and phase separation conditions, which were discussed by the polymer anddiluent crystallization processes.

Effect of sol size on nanofiltration performance of a sol-gel derived microporous zirconia membrane

This paper reports the effect of sol size on nanofiltration performances of sol–gel derived microporous zirconia membranes. Microstructure, pure water flux, molecular weight cut-off(MWCO) and salt retention of zirconia membranes derived from zirconia sols with different sizes were characterized. Thermal evolution, phase composition, microstructure and chemical stability of unsupported zirconia membranes(powder) were determined by thermogravimetric and differential thermal analysis, X-ray diffraction, nitrogen adsorption–desorption and static solubility measurements. Results show that nanofiltration performance of zirconia membranes is highly dependent on sol size. The sol with an average size of 3.8 nm, which is smaller than the pore size of the γ-Al2O3support(pore size: 5–6 nm), forms a discontinuous zirconia separation layer because of excessive penetration of sol into the support. This zirconia membrane displays a MWCO value towards polyethylene glycol higher than 4000 Da. A smooth and defect-free zirconia membrane with a MWCO value of 1195 Da(pore size: 1.75 nm) and relative high retention rates towards Mg Cl2(76%) and Ca Cl2(64%) was successfully fabricated by dip-coating the sol with an appropriate size of 8.6 nm. Zirconia sol with an average size of 12 nm exhibits colloidal nature and forms a zirconia membrane with a MWCO value of 2332 Da(pore size: 2.47 nm). This promising microporous zirconia membrane presents sufficiently high chemical stability in a wide p H range of 1–12.

MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO_2 INDUCED PHASE SEPARATION

Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO_2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the similar...

Affinity Adsorption of Bilirubin on Cibacron Blue F3GA-modified Microporous Polytetrafluoroethylene Capillary

Bilirubin removal from human plasma was obtained via an affinity microporous polytetrafluoroethylene（MPTFE） capillary. The new adsorbent comprised grafted glycidyl methacrylate（GMA） via radiation-induced polymerization as hydrophilic coating and reactive sites; ethylenediamine（EDA） as a spacer arm; Cibacron Blue F3GA（CB F3GA） as an affinity ligand; MPTFE capillary as the supporting matrix. The average density of CB F3GA attachment to MPTFE capillaries was found to be 136.5 μmol/g. The capacity of bilirubin adsorbed on affinity MPTFE capillaries is 76.1 mg bilirubin/g polymer（at 25℃）. This new adsorbent has advantages over both membrane and traditional micro-column, and this system is stable and easy to operate. The results of blood tests suggest the CB F3GA affinity capillary has good blood compatibility.

PREPARATION AND CHARACTERIZATION OF PVDF-HFP MICROPOROUS MEMBRANE BY TEMPLATE METHOD

Porous poly（vinylidene fluoride-co-hexafluoropropylene） （PVDF-HFP） membranes were successfully prepared using dibutyl phthalate （DBP）, polyvinylpyrrolidone （PVP-K30）, polyethylene glycol 200 （PEG200） as templates. SEM was used to examine the morphology of the PVDF-HFP porous membranes. It was found that these membranes have an asymmetric structure and the blends of PVDF-HFP/DBP formed nanoporous membranes, whereas the blends of PVDF- HFP/PVP-K30 formed ＂sponge-like＂ and microporous membranes. Moreover, the average pore size and porosity was about 0.3 μm and 48.7%, respectively. The crystallinity, thermal stability and mechanical strength of membranes were characterized by XRD, DSC, TGA and stress-strain tests. The results showed that the membranes are a crystals with excellent thermal stability. It was an effective way to regulate pore size and morphology of the PVDF-HFP membranes.

Synergy of staggered stacking confinement and microporous defect fixation for high‐density atomic Fe^(Ⅱ)‐N_(4)oxygen reduction active sites

The development of high‐performance nonprecious metal catalysts(NPMCs)to supersede Pt‐based catalysts for the oxygen reduction reaction(ORR)in polymer electrolyte membrane fuel cells is highly desirable but remains challenging.In this paper,we present a pyrolysis strategy for spatial confinement and active‐site fixation using iron phthalocyanine(FePc),phthalocyanine(Pc)and Zn salts as precursors.In the obtained carbon‐based NPMC with a hierarchically porous nanostructure of thin‐layered carbon nanosheets,nearly 100%of the total Fe species are Fe^(Ⅱ)‐N_(4) active sites.In contrast,pyrolyzing FePc alone forms Fe‐based nanoparticles embedded in amorphous carbon with only 5.9%Fe^(Ⅱ)‐N_(4) active sites.Both experimental characterization and density functional theory calculations reveal that spatial confinement through the staggeredπ–πstacking of Pc macrocycles effectively prevents the demetallation of Fe atoms and the formation of Fe‐based nanoparticles via aggregation.Furthermore,Zn‐induced microporous defects allow the fixation of Fe^(Ⅱ)‐N_(4) active sites.The synergistic effect of staggered stacking confinement and microporous defect fixation results in a high density of atomic Fe^(Ⅱ)‐N_(4) active sites that can enhance the ORR.The optimal Fe^(Ⅱ)‐N_(4)‐C electro‐catalyst outperforms a commercial Pt/C catalyst in terms of half‐wave potential,methanol toler‐ance,and long‐term stability in alkaline media.This modulation strategy can greatly advance efforts to develop high‐performance NPMCs.

Knitted Microporous Polymers as Efficient Adsorbents for Wastewater Treatment: Effects of Skeleton Structure and Pore Distribution

Hyper-cross-linked microporous organic polymers(MOP) with controlled skeleton structure and pore distribution were prepared by Friedel-Crafts alkylation reaction. The hyper-cross-linked polymers(HCPs) produced by knitting aromatic functional groups posses the typical micro-and meso-porous composite structure and specific surface areas of up to 957 m^2·g^(-1). The obtained materials were evaluated as adsorbents for methylene blue(MB) and subjected to several batch adsorption tests to investigate the effects of adsorbent dosage, concentration of MB, temperature, and pH on MB removal. The maximum adsorbed capacity(q_m) of KAPs-Ph(381 mg·g^(-1), knitted using benzene) exceeded those of less mesoporous KAPs-PhPh_3(310 mg·g^(-1) knitted using 1,3,5-triphenylbenzene) and chloromethyl polystyrene resin(58 mg·g^(-1)). Moreover, KAPs-Ph could be regenerated by Soxhlet extraction with ethanol and reused for up to 15 times with minimal loss of adsorption capacity. The results illustrate that adsorption performance can be improved by controlling the pore structure of the adsorbing materials, and KAPs-Ph has a potential application values for the industrial removal of organic dyes from wastewater.