Search

Double-shelled hollow carbon spheres with multiporosity, highly conductive graphite structure and Fe 3 O 4 species was initially prepared (C–C–Fe 3 O 4 ). The seamless combination between the Fe 3 O 4 species and the porous carbon network leads to a remarkably high capacitivity (1153 F g −1 at 2 A g −1 ) and good rate capability (514 F g −1 at 100 A g −1 ) of pseudocapacitive. In addition, the C–C–Fe 3 O 4 assembled asymmetric supercapacitor demonstrates excellent cycling stability (96.7% retention of the initial capacitance after 8000 cycles) and achieves high energy density (17–45 W h kg −1 ) at powder density of 400–8000 W kg −1 . The unique porous carbon structure and seamlessly integration between carbon and Fe 3 O 4 species generate synergistic effect to boost high performance and ideal durability, and high conductivity of the graphitized carbon, the large specific surface area of the hierarchical pore network and the perfectly distributed Fe 3 O 4 redox species in the carbon content also account for its ideal capacitive properties. The multiporous structure could allow efficient diffusion of electrolyte and promote interfacial redox reactions of supercapacitor by facilitating the accessibility of redox active sites, and the highly uniform distribution of Fe 3 O 4 species in the porous carbon makes the best use of conductive carbon network and facilitates good rate capability. [ABSTRACT FROM AUTHOR]

Noble metal nanocrystals (Au, Pt or AuPt) with controlled compositions and nanostructures were embedded into hollow silica submicrospheres with highly ordered radial mesopores through a one-step sol–gel process. 2,4-Dihydroxybenzoic acid–formaldehyde (RF-COOH) resin submicrospheres were utilized simultaneously as a hard template to create hollow interiors inside the silica submicrospheres and as carriers to transport pregrown metal nanocrystals, including Au nanoparticle (NP), Pt NP, and AuPt nanoalloy, into the submicrospheres. Calcination removes the resin submicrospheres and causes metal nanocrystals embedded into the RF-COOH submicrospheres break into multiple smaller nanoparticles (2–6 nm) that are randomly dispersed in the hollow space of SiO 2 submicrospheres M@SiO 2 (M = Au, Pt or AuPt). The AuPt@SiO 2 submicrospheres showed good catalytic performance for epoxidation of styrene with the conversion and selectivity of 74% and 85%, respectively. The approach reported in this study could potentially be used to simplify the fabrication process of noble metal nanoalloys, which usually entails multiple steps and a previously synthesized hard metal template, and thus guide the design and creation of high-performance catalysts. [ABSTRACT FROM AUTHOR]

Hierarchically macro–mesoporous ZrO 2 –TiO 2 composite materials were prepared based on a facile surfactant self-assembly method with titanium isopropoxide (TIP) and zirconium n-butoxide as precursors. The ZrO 2 content in the composites (2.0–9.8%) was easily controlled by adjusting the molar ratio of the two precursors, while maintaining the porous structures of the materials. SEM results demonstrated that the ZrO 2 –TiO 2 composites were featured by paralleled channels (50–500 nm) and interparticle pores (~8 nm) in the walls. The photocatalytic activities of the novel composites were remarkably higher than corresponding pure macro–mesoporous TiO 2 and ZrO 2 materials in the decomposition of Rhodamine B (RhB) under UV light radiation. The ZrO 2 –TiO 2 sample with 6.9% of ZrO 2 was proved to be the most efficient catalyst with degradation kinetic constant twice larger than that of the pure macroporous TiO 2 . Trapping experiments indicated that photogenerated holes and radicals were all vital to the photocatalytic process under UV light irradiation. ESR measurements gave the direct evidence that the active radicals •OH and O 2 • − were responsible for the photodecomposition of RhB. [ABSTRACT FROM AUTHOR]

Magnetic C–C@Fe3O4 hollow microspheres were prepared by using aerosol-based Fe3O4@C-SiO2 core–shell particles as templates. The magnetic double-shelled microspheres efficiently worked as carriers to load Pt nanoparticles, thus making the catalyst recyclable and reusable. [ABSTRACT FROM AUTHOR]

Magnetic C–C@Fe3O4 hollow microspheres were prepared by using aerosol-based Fe3O4@C-SiO2 core–shell particles as templates. The magnetic double-shelled microspheres efficiently worked as carriers to load Pt nanoparticles, thus making the catalyst recyclable and reusable. [ABSTRACT FROM AUTHOR]

Inthis study, double-shelled C/SiO2hollow sphereswith an outer hydrophilic silica shell and an inner hydrophobic carbonshell were initially prepared by activating a solid silica layer ofC/SiO2aerosol particles. This low-cost preparation technique,which can easily be scaled up, includes a rapid aerosol process anda subsequent dissolution–regrowth process. The large surfacearea (226.3 m2/g), high pore volume (0.51 cm3/g), and high mechanical stability of the spheres benefit their highadsorption capacities for methylene blue (MB) and metal ions. Thenovel spheres show a high adsorption capacity of 171.2 mg/g for MB,which is higher than the adsorption capacity of single-shelled silicahollow spheres (150.0 mg/g). The adsorption efficiency of the hollowspheres remains higher than 95% after five cycles of regeneration.The saturation adsorption values of Pb2+and Ag+ions on the hollow spheres were found to be 216.5 and 283.1 mg/g,respectively, which are higher than the corresponding values of 189.8and 213.4 mg/g on the single-shelled SiO2spheres. Moreover,the adsorption capacities of the five-times-recycled spheres for Pb2+and Ag+ions reached as high as ∼180 and∼245 mg/g, respectively. These results reveal that the outerporous silica layer with a ζ-potential of −37.4 mV makesthe main contribution to the excellent adsorption performance of thespheres. In addition to the contribution to the adsorption capacityof the double-shelled hollow spheres, the inner carbon layer playsa crucial role in supporting the outer silica shell and in improvingthe adsorption efficiency, mechanical stability, and recycling propertiesof the hollow spheres. [ABSTRACT FROM AUTHOR]

We have investigated the formation and evolution of zinc oxalate particles in internal aqueous droplets and their effects of emulsion interface properties. The formation of particles follows an aggregation-controlled mechanism that depends on the size of droplets and surfactant. The size of droplets determines the final shape of the particles by affecting the supersaturation ratio to form rod-like and sheet-like particles. The surfactant adsorbed on the particles changes the wettability, leading to the aggregation of the primary particles at the internal water-oil interface. Moreover, the adsorption can cause a higher level of impurity and defects in as-synthesized particles. This effect could be directly employed to fabricate heterojunction rectifier. [ABSTRACT FROM AUTHOR]

Highlights: [•] Preparation of PP-TiO2/CA microspheres with improved photoactivity. [•] The combined PP-TiO2/CA microsphere–membrane system preventing membrane fouling. [•] Recycling of PP-TiO2/CA by free settling method without energy consumption. [•] High permeation flux of 90L/m2 h for the combined microsphere–membrane system. [•] Force analysis revealing the suspending state of the microspheres in dye solution. [Copyright &y& Elsevier]

Highlights: [•] Preparation of new macroporous PPy TiO2 composite materials. [•] Stabilized organic–inorganic interface for improved charge injection and separation. [•] Enhanced visible light photoactivity and photoelectrical response. [•] Photocatalytic mechanisms under UV and visible light were discussed respectively. [Copyright &y& Elsevier]

Highlights: [•] Novel hierarchical macroporous PPy–TiO2 composite nanostructures. [•] Synergetic interaction between PPy and TiO2 for effective charge pair separation. [•] Improved photoactivity for degradation of MB under simulated sun light irradiation. [•] High H2O2 detecting sensitivity with appropriate PPy content in composites. [•] Dispersed PPy nanoparticles by etching the composites with HF acid. [Copyright &y& Elsevier]

Magneticmicrospheres with an Fe3O4coreand a SiO2–TiO2hybrid shell were preparedby a surfactant-assisted aerosol process and subsequent etching treatment.The core–shell spheres with robust and chemically stable Ti–O–Sishells exhibit excellent adsorption performance toward basic dyes.The maximum adsorption capacities were obtained at 147 mg/g for methyleneblue (MB) and 124.6 mg/g for basic fuchsin. MB with an initial concentrationof 20 mg/L can be completely removed in 5 min at a dosage of 0.5 mg/L,and the equilibrium time is 90 min in the MB concentration range 20–250mg/L. The adsorption kinetics follows the pseudo-second-order model.Furthermore, the dye saturated microspheres can be easily recycledby an external magnetic field and regenerated using 1–3 wt% NaOH aqueous solution. After six recycle runs, 98% of the adsorptioncapacity was still retained. The low-cost magnetic hollow sphereswith good adsorption capacity are a promising candidate for watertreatment. [ABSTRACT FROM AUTHOR]

Abstract: A novel core–shell sphere with controlled shell thickness was synthesized by in situ chemical oxidative polymerization of pyrrole on FTS (Fe2O3/TiO2/SiO2 composite) surface. The dual porosity of 2–3nm and 40–50nm in FTS core particle provides the hybrids with a high surface area to volume ratio, which enormously facilitates the molecule diffusion process. Furthermore, the porous FTS particle encapsulate Fe2O3 and TiO2 leading to its synergetic interaction with the PPy coating based on FTIR analysis. The unique structure and composition of the hybrid spheres result in new sensing property that is not available from their single counterparts. Cyclic voltammetry results demonstrate that the spheres with appropriate concentration of PPy exhibit enhanced electrocatalytic activity toward the reduction of H2O2 in 0.1M phosphate buffer solution. The sensing performance tests show that the hybrids possess good linear response in wide H2O2 concentration range (10–4000μM) and high sensitivity to H2O2 (0.653AM−1 cm−2) at room temperature. The formation mechanism of the spheres was proposed based on the fact that the FTS core was coated firstly by a smooth PPy layer and then PPy nanoparticles. The work reported here provides an alternative concept for preparation of functional materials with new nanostructures and properties. [Copyright &y& Elsevier]

Abstract: Dioctylsulfosuccinate sodium surfactant (AOT) was selected as a structure-directing agent to prepare mesoporous MgO adsorbent by a hydrothermal method. The anionic AOT surfactant combines with Mg(OH)2 crystallites to form AOT·Mg(OH)2 micelle colloids by hydrogen bonding and electrostatic attraction to template the mesopores with diameter of 10–20nm in MgO nanoplates The whole process is composed of three stages: nucleation, orientation growth, and porecreating. The results demonstrated that the presence of AOT surfactant was essential to produce the mesopores and to adjust the structural parameters of the nanoplates. Because of their higher specific surface area and porous structure, the MgO materials exhibit a satisfactory adsorptive property to three typical azo dye pollutants, Congo red (471–588mg/g), Methyl orange (∼370mg/g) and Sudan III (∼180mg/g), and good performance for decolorization of low-concentration dyes. The highly adsorption capacities of the adsorbents are ascribed to their mesoporous structures which can provide more interaction sites, facilitate the mass diffusion in pores and help the dye molecules to contact the adsorptive sites more easily. The present work provided an alternative approach for preparation of inorganic adsorbent with controlled porous structures and high adsorption ability for hazardous dyes. [Copyright &y& Elsevier]

The water solubilization capacity (W0) of microemulsion system determines its physicochemical properties and interior structures. In this study, the effects of different kinds of additives such as inorganic salt, nonaqueous polar solvent, organic salt, amino acid, and polyethylene glycols (PEG series) on the water solubilization behavior of heptane/hexanol/TritonX-100/water microemulsion system have been studied in detail. The influence mechanism of every additive on W0 has also been proposed and discussed. Furthermore, the droplet size distribution and the interaction among the droplets have been investigated by dynamic light scattering technique with the presence of additives. The result shows that the hydrodynamic diameter of microemulsion droplet and the attractive interaction between the droplets increase with the increase of the water content and the additive concentration. This work presents a facile method to adjust the structure parameters and the interface strength of microemulsion system by adding additive to the system, and to direct the applications of microemulsion system in nanomaterials preparation and drug controlled release. [ABSTRACT FROM AUTHOR]

Abstract: The validity of percolation theories on TritonX-100/heptane/alkanol/water W/O (water-in-oil) microemulsion has been investigated based on conductivity analysis. The experiment results have proved that the microemulsion follows both Bernasconi–Weismann (BW) and effective medium theory with dipole–dipole interaction (EMTDD, clusters) theories in the water content range from W 0 =1 to W 0 =7. The results here are different from the reported microemulsions with CTAB, AOT or SDS as ionic surfactant and alkanols as cosurfactants, and those microemulsions always follow effective medium theory (EMT) perfectly. This suggests that nonspherical surfactant aggregates and droplet clusters exist in the microemulsion solution due to the dipolar interaction between the dispersed droplets. The size of water pool, the hydrodynamic diameter of droplet, and the number of surfactant and cosurfactant per droplet have been evaluated according to the two validated theories. The dynamic state and the calculated size distribution of droplets are agreed with the results detected by dynamic light scattering technique. The research has indicated that the percolation theories are also adaptable to nonionic surfactant microemulsions with low water content and the structure parameters of droplets can be calculated by the effective theories. [Copyright &y& Elsevier]

Abstract: ZnO nanostructures with different morphologies and optical properties were prepared by a simple microemulsion process, and PEG400 was used as a directing agent. The samples were characterized by TEM, XRD, FTIR, and TG-DTA analysis. The XRD spectra indicate that the ZnO crystal has a hexagonal wurtzite structure. Needle-like, columnar, and spherical ZnO samples were synthesized respectively with the increase of PEG400 concentration in Zn(NO3)2 solution. TEM images and thermogravimetric analysis reveal that the microemulsion interface and the PEG400 agent have a synergistic effect on the morphology and crystalline size transition of ZnO nanostructures. The optical properties of the samples were investigated by measuring the UV–Vis absorbance spectra at room temperature. All the samples exhibit strong UV absorption at around 365 nm. ZnO products with band gap energies at 3.06, 3.02, 2.95, and 2.85 eV were obtained with 0, 12.5, 25.0, and 50.0% of PEG400 in Zn(NO3)2 solution, respectively. The formation mechanism of the ZnO nanostructures was proposed and discussed in detail. The synergistic control of the microemulsion interface and the agent on the growth of crystal nuclei reported here provides an alternative approach for preparation of other well-defined nanostructures. [Copyright &y& Elsevier]

Scalable yet flexible Fe x C/CM membrane with unique triple-layer structure was designed as integrated electrodes for high-performance Li-S batteries. Strong Li-N binding and Fe-S chemical adsorption of Fe x C induce polysulfides opposite diffusion into macropores as a trap, catalytic effect of Fe x C further promotes the polysulfides conversion to discharge product (Li 2 S/Li 2 S 2), realizing smooth trapping-diffusion-conversion process. The dense layer facilitates electrolyte transport instead of traditional Al foil current collector. • Fe x C dopped porous carbon membranes for integrated Al-free Li-S cathodes. • Strong adsorption trap polysulfides gradual diffusion into carbon membranes. • Hierarchical macropores for volume strain and reservoirs of polysulfides. • Trapping-diffusion-conversion mechanism of polysulfides was proposed. The shuttling effect in soluble polysulfides results in a sluggish redox reaction and poor cycling performance of Li-S batteries. Herein, a flexible asymmetric porous carbon membrane doped with iron carbide (Fe x C) nanoparticles was designed by a facile phase-inversion method to serve as an integrated electrode for high-performance Li-S batteries, replacing the traditional Al foil current collector. The strong Li-N binding of the membranes and Fe-S chemical adsorption of Fe x C can trap polysulfides and promote their gradual diffusion into the porous carbon membrane on the opposite side of the electrolyte. The unique triple-layer-structured multifunctional membrane is ideal as a Li-S battery electrode. The upper spongy-like pores realize physical confinement of polysulfides and sulfur loading; the hierarchical macropores can accommodate volume strain and provide reservoirs for the opposite diffusion of polysulfides; and the dense conductive lower layer can replace Al foil as a current collector. Furthermore, the electrocatalytic effect of Fe x C on promoting polysulfide conversion and accelerating redox reaction kinetics ensures a smooth trapping-diffusion-conversion mechanism, which greatly suppresses the shuttle effect. The opposite diffusion and catalytic conversion of this flexible membrane is expected to have significant potential for large-scale production in practical applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • Highly exposed isolated FeN 5 sites are embedded in N-doped carbon frameworks. • FeN 5 exhibits a maximum FE CO of 98% and over 95% from −0.4 to −1.0 V vs. RHE. • The axial coordinated N modulates the d -band center and facilitates CO desorption. • FeN 4 and axial coordinated N act synergistically to boost CO 2 -to-CO conversion. Electrochemical CO 2 conversion offers a sustainable approach to alleviate the energy crisis but remains a long-standing challenge. Herein, atomically dispersed FeN 5 sites anchored on N-doped carbon matrix templated by zeolitic imidazole framework-8 (ZIF-8) are facilely synthesized for efficient catalyzing CO 2 reduction. The FeN 5 single-atom catalyst (Fe-SA/ZIF) presents the Faradaic efficiency of 98% at −0.7 V vs. RHE and over 95% in a wide potential range from −0.4 to −1.0 V vs. RHE, surpassing most of the reported single-atom catalysts for CO 2 RR. Further density functional theory (DFT) calculations reveal that the outstanding activity of FeN 5 sites mainly originates from the lowered d -band center modulated by the out-of-plane coordinated pyridinic N, which reduces the CO adsorption energy from −1.71 to −1.49 eV compared to FeN 4 moieties. Thus, the synergistic effect between FeN 4 sites and the coordinated pyridine offers new insight in designing outstanding electrocatalysts for multiple applications. [ABSTRACT FROM AUTHOR]

Hollow micro- and nanostructured materials with controllable shapes are appealing materials for electrochemical energy storage devices with high energy and power densities. Herein, double-shelled hollow nickel sulfides with controlled shape (cube-, ellipsoid- and capsule-shaped) were successfully synthesized by using different morphological α-Fe 2 O 3 templates. The as-obtained nickel sulfides have uniform size and well-defined double shells that consist of crossed ultrathin NiS nanosheets. When evaluated as electrode materials for supercapacitors, the capsule-shaped structure exhibits the highest specific capacitance of 1159 F g −1 at a current density of 2 A g −1 due to its high specific surface area (100.2 m 2 g −1 ), low equivalent series resistance (0.80 Ω) and ion diffusive resistance. More importantly, the asymmetric capacitor NiS (capsule-shaped)||RGO@Fe 3 O 4 shows a high energy density of 43.7 Wh kg −1 at a power density of 664 W kg −1 (21.8 Wh kg −1 at 8000 W kg −1 ), and after 5000 charge–discharge cycles, 83.3% of its capacitance is remained at the current density of 5 A g −1 . [ABSTRACT FROM AUTHOR]

Targeted and high throughput manufacture of crystalline biominerals with diverse morphologies is of importance, due to the significant impact of shape and texture on the material properties, while tunable morphosynthesis of crystalline is restrained by the proper ion transfer process during the reactive crystallization, and is commonly regulated using organic soluble additives. Herein, Janus membranes (JMs) are facilely produced for the continuous confined reactive crystallization of calcium carbonate. Fabricated JM simultaneously achieves rapid and uniform directional CO32− ions transfer in the aqueous solution through the straight, uniform nanoscale hydrophilic channels, and the interfacial reactive crystallization is generated with confined ion adsorption and gating effect at the hydrophobic side. Hollow CaCO3 microcomposites via JM system are continuously and directly synthesized in the aqueous system without any assisted organic solvent or polymer additive, which is green and highly efficient. In addition, the reversed ion transfer direction in JM can be ideally managed resulting in highly selective manufacturing of cube or sphere‐type microcomposites. This study provides a feasible route for the rapid production of advanced particle materials with tunable morphology, displaying great potential applications of JM in material engineering. [ABSTRACT FROM AUTHOR]

In this study, we demonstrate a relatively independent UV photodetector which is composed of one layer of Au/Ag/Pt metal nanoparticles sandwiched between two layers of n-type TiO 2 semiconductor nanorods. Different from most reported Schottky junction based UV photodetectors, it can be driven only by two opposite Schottky junction in the sandwich structure, but no need for any external power supply except UV light when it works. Moreover, it displays high responsivity and fast response speed at the same time, giving a bright prospect for self-powered UV photodetectors. [ABSTRACT FROM AUTHOR]

Inspired by 'Hufu' in ancient China, we manufactured semiflexible micro crystallizer with two aspectant sessile platforms by 3D-printing technique that can construct a series of heteromorphic droplets (HDs) via stretching droplet height. By coordinating the gas–liquid interface and flow intensity (i.e., Ra/Ma), central-converging micro-flows were generated, which dominated solute and particle motion towards droplet center. Efficient harvest of single cubic NaCl crystal was achieved at platform center under wide volume and concentration ranges. [Display omitted] Droplet crystallization behavior held great potential in crystal preparation, micromaterial engineering, and molecular assembly. However, restricted by natural surface tension, the intrinsic crystallization regulation and efficient harvest of high quality crystal in diverse droplet features were still a great challenge. Herein, we developed a 3D printed semiflexible micro crystallizer with two aspectant sessile platforms that could simultaneously construct a series of heteromorphic droplets (HDs) and controllable HD shape. By shaping HD on the interface of the platform, central-converging micro-flows were generated by coordinating the gas–liquid interface and flow intensity (i.e., Ra/Ma) during HD crystallization from 'barrel', 'can', to 'sand clock' shape, which was validated via simulative and experimental research. Therefore, HDs, constructed in semiflexible micro crystallizer, exhibited efficient screening (>70 %) of single cubic crystal just at the center zone of platform, even under wide ranges of concentration and volume, manifesting excellent repeatability on high quality crystal harvest and relevant interfacial science research. [ABSTRACT FROM AUTHOR]

Hierarchically porous CNT@NC@GCN membranes with high porosity of 85% are fabricated facilely, the 3D hierarchical porous network can provide broad reaction interface and active sites for LiPSs anchoring. Furthermore, the uniform GCN layer can significantly improve the metallicity and conductivity of the frameworks, and strengthen Li+ and electron transport. The abundant N in the GCN coating can enrich active sites in the membrane for adsorption and catalysis conversion of LiPSs and Li 2 S at a low energy barrier. [Display omitted] Various challenges remain to be overcome in lithium-sulfur (Li-S) batteries, including the volume expansion and low conductivity of sulfur, the shuttle effect of lithium polysulfides and the sluggish redox reaction in the cell. Herein, we propose a multilayered conductive framework by the in situ growth of a conformal graphene-like C 3 N 4 (GCN) coating on porous CNT@NC networks with carbon nanotubes (CNTs) as the core and N -doped carbon (NC) as the crosslinking shell. The abundant N in the GCN coating increased the surface N concentration of the framework from 14.38% to 18.77%, which enriched the active sites in the frameworks for the adsorption and catalysis conversion of LiPSs and Li 2 S with a low energy barrier. Furthermore, the scalable frameworks can provide an 85% porosity for a sufficient reaction interface and accommodate the volume expansion of sulfur. The synergistic effect between GCN and the highly conductive hierarchical structure can accelerate the transport of Li+ and electrons as well as the diffusion of electrolyte. Benefitting from the above advantages, the Al-free CNT@NC@GCN electrode exhibits a reversible capacity of 647.6 mAh g−1 after cycling for 450 cycles at 1C with a low capacity fading rate of 0.09% per cycle. This proposed facile strategy creates inspiring insights into the design of novel cathode materials for Li-S batteries. [ABSTRACT FROM AUTHOR]

In this work, for the first time, a typical catalysis–membrane system was designed for highly efficient H 2 generation from catalytic hydrolysis of NH 3 BH 3 (AB). The Pt nanoparticles (NPs) were tightly deposited on RF (resin microspheres) surface and the Pt@RF microspheres were then uniformly confined in the macroporous framework of a poly (vinylidene fluoride) hollow fiber membrane (PVDF). Compared with the previous reports, granular catalysts can be easily recycled and reused in our catalysis–membrane system. Furthermore, the circular solution in the membrane module could flush away the adsorbed metaborate on the Pt NPs, preventing passivation of the Pt NPs and increasing the accessibility of the active sites. In addition, the activation energy of the system was calculated to be only 13.69 kJ · mol −1 , smaller than those of the previous noble metal catalysts or non-noble metal-based catalysts for the same reaction, indicating the superior catalytic performance of the membrane module. Due to the high activity, circular reaction system, and macroporous membrane support, a high H 2 generation rate of 258.1 mol H 2 /(mol cat · min · m 2 membrane) was obtained for the catalysis–membrane module. Moreover, catalytic efficiency of the system remains well after 60 days. For its easy operation, good recyclability, durability and longevity, it is believed that the catalyst–membrane system can be easily scaled up for practical H 2 generation, leading to applications for AB in the field of fuel cells and guiding new design of highly efficient catalysis module. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hollow ZIF-8 in micron accumulated continuously across membrane to construct transport highway. • The real CO 2 transport distance was reduced. • In-situ polymerization intensifies the interface affinity between ZIF-8 and PEO. The hollow filler has been verified to effectively enhance the CO 2 permeability of mixed matrix membrane (MMMs) by constructing low-resistance transport pathway. However, the in-continuity of hollow fillers across the membrane results in insufficient CO 2 permeability. In this work, the micron-sized hollow ZIF-8 (Mic-H-ZIF-8) were designed and proposed to accumulate continuously across the membrane to construct the transport highway for CO 2. Importantly, the in-situ polymerization was utilized to achieve continuous accumulation of the Mic-H-ZIF-8 fillers across the membrane. The Mic-H-ZIF-8 presents cavity size of 4 μm and shell thickness of 100 nm, and three or four Mic-H-ZIF-8 microspheres are aligned sequentially across the membrane, in which the effective gas transport distance is decreased from 13 μm to the range of 0.8–3 μm. Consequently, the CO 2 permeability of 5 wt% Mic-H-ZIF-8/PEO MMM is 224.6 % and 63.5 % higher than those of pure PEO membrane and nanosized hollow ZIF-8/PEO MMM at 0.1 MPa. Meanwhile, the CO 2 /N 2 selectivity is still as high as 70.0. This CO 2 separation performance is far exceeding the Robeson upper bound in 2008, and beyond the McKeown upper bound in 2019 as the feed pressure increasing, confirming the significance of continuous transport highway constructed by micron-sized hollow MOFs on improving CO 2 separation of MMMs. [ABSTRACT FROM AUTHOR]

Exploring anion exchange membranes (AEMs) with high conductivity and satisfactory stability is very meaningful for the advancement of alkaline fuel cells. Herein, a novel class of intrinsic microporous AEMs with pendent piperazinium are systematically fabricated for alkaline fuel cell performance testing. Contorted and rigid spirobisindane backbone structure expands the free volume of AEMs, inducing broad and interconnected ion transport channels. This unique feature endows membranes a leading advantage for the efficient transmission of hydroxide ions. Consequently, the prepared membrane displays excellent normalized hydroxide conductivity of 78.99 mS g cm−1 mmol−1 at 80 °C. Meanwhile, the hydroxide conductivity degrades by only 8.3 % after treatment in 1 M NaOH for 1000 h at 80 °C. Moreover, the peak power density of H 2 /O 2 single cell employing this membrane exhibits 1.06 W cm−2 at 80 °C and the cell can preserve 93.0 % of its initial voltage after operating for 18 h. [Display omitted] • A systematic approach is developed to prepare intrinsic microporous poly (phenyl-alkane)s containing piperazinium. • The spirobisindane structure facilitates the construction of well-developed ion channels in AEMs. • The intrinsic microporous membrane shows normalized hydroxide conductivity of as high as 78.99 mS g cm−1 mmol−1. • The prepared membrane shows excellent H 2 /O 2 fuel cell performance and durability. [ABSTRACT FROM AUTHOR]

Crosslinked poly (styrene sulfonic acid) (CrPSSA) is incorporated into sulfonated poly (ether ether ketone) (SPEEK) through the semi-interpenetrating polymer networks (sIPNs) method to improve proton conductivity of SPEEK proton exchange membranes (PEMs) at low relative humidity (RH). Thermogravimetric analysis indicates that the SPEEK/CrPSSA sIPN membrane can be stable up to 250 °C in N2. A single glass transition temperature (T g ) of the sIPN measured by differential scanning calorimetric measurements suggests good miscibility of the CrPSSA and SPEEK. At fixed RH the proton conductivity of the sIPN membranes increases as more CrPSSA is incorporated into SPEEK membranes. The sIPN membrane with 40 wt. % CrPSSA has a proton conductivity of 10−3 S cm−1 at 25% RH, which comparable to that of Nafion115 and is 2 orders of magnitude higher than that of the pristine SPEEK membranes (10−5 S cm−1 at RH 50%). The percolation threshold for proton conduction occurs at lower hydrophilic volume fractions with the increasing content of CrPSSA, suggesting different packing behavior of –SO3H groups in the SPEEK/CrPSSA sIPN membranes as compared with SPEEK and Nafion® membranes. [ABSTRACT FROM AUTHOR]

• Permselective interlayer was designed and fabricated for Li-S battery. • The networked porous structure amplifies the LiPSs adsorption and conversion performance of Co 4 S 3. • Co 4 S 3 and pyridinic N sites can synergistically facilitate the transmission of Li+. • The Li-S battery performance is remarkably improved by enhancing the permselective capability of the interlayer. Lithium-sulfur (Li-S) batteries have garnered significant research interest owing to their exceptional energy density, positioning them as a compelling candidate for next-generation energy storage technology. Nonetheless, their broad application faces challenges, primarily attributed to issues such as the shuttle effect induced by the lithium polysulfides (LiPSs) migration. The integration of a functional interlayer between cathode and separator has emerged as a straightforward, cost-effective, and efficient strategy, but its structure and composition need to be designed more elaborately. Herein, inspired by the semipermeable cell membrane in biology, we focused on improving the permselectivity of the interlayer by fabricating a Co 4 S 3 nanoparticles incorporated carbon-based permselective interlayer via phase inversion method combining in-situ sulfurization and carbonization. The networked porous structure makes the adsorptive and catalytic active Co 4 S 3 accessible to more LiPSs and realizes the blockage of LiPSs diffusion, and the Li+ diffusion is simultaneously facilitated attributed to the synergy of Co 4 S 3 and lithiophilic N sites. The Li-S battery, integrated with the proposed permselective interlayer, exhibits notable enhancements in both specific capacity and cycling stability. Remarkably, it maintains a specific capacity of 635.6 mAh/g after 500 cycles at 2.0 C, and a capacity of 563.5 mAh/g after 400 cycles at 4.0 C, demonstrating a comparable decay rate of only ∼ 0.09 %. This result demonstrates the effectiveness and necessity of augmenting the permselective capability of the interlayer to significantly enhance the overall performance of Li-S batteries. [ABSTRACT FROM AUTHOR]

Facilitated transport membrane with fixed and mobile carriers is essential yet challenging to improve the CO 2 capture. Herein, a facilitated transport membrane with continuous pathway was constructed by the in-situ interlinkage of mobile aniline with the fixed carriers distributing along electrospun polyacrylonitrile (PAN) nanofibers. In this membrane, fixed amine carriers are introduced through the alkalinous hydrolysis of PAN fibers (HPAN), and are distributed along the HPAN fibers to construct a long-range continuous transport pathway for CO 2. The mobile aniline carriers are introduced into the interfibrous voids of the HPAN nanofibers mat (NFM) by in-situ polymerization of Poly (ethylene glycol) diacrylate (PEGDA), which interlink the fixed amine carriers to achieve the facilitated transport pathway continuous completely. And the fixed amine and mobile aniline carriers are demonstrated to co-exist in the An/PEO@HPAN membrane (NFCM) by the FTIR and XPS results. Meanwhile, the XRD and DSC results indicate that the introduction of aniline increases the free volume of PEO matrix, which is beneficial for enhancing CO 2 permeation. Therefore, the 10 wt% An/PEO@HPAN-3h NFCM presents 90.81 % and 13.15 % increases in CO 2 permeability and CO 2 /N 2 selectivity under mixed gas at 0.3 MPa in contrast with the membrane without mobile aniline carriers. Under mixed gas conditions, this NFCM exhibits CO 2 permeability of 202.93 Barrer and CO 2 /N 2 selectivity of 83.89 at 0.1 MPa, reaching the 2019 McKeown upper bound. [Display omitted] • Fixed amine carriers are distributed along the HPAN nanofibers. • Mobile aniline carriers are introduced with in-situ polymerization of PEGDA. • Aniline interlinks the long-range continuous transport pathway in short range. • Continuous facilitated transport pathway improves CO 2 permeability. [ABSTRACT FROM AUTHOR]

Membrane distillation (MD) has attracted growing attention as a sustainable green membrane process technology for seawater and high saline water desalination, yet seriously challenged by the potential membrane wetting and fouling. Herein, a controllable approach to fabricate tailor-made MD membranes was proposed via combining in-situ growth of SiO2 nanoparticles with membrane surface activation and low surface energy substances. SiO2 nanoparticles distributed uniformly on the membrane surface and combined with the intrinsic microstructure of the membrane, a hybrid macro/micro-structure was constructed, further endowing the membrane with superhydrophobicity. The modified membranes exhibited excellent wetting-resistance properties and over 99.9 % salt rejection during vacuum membrane distillation (VMD) process. The surface wetting and anti-nucleation theory special for MD membranes was uncovered. This theory and VMD experiments synchronously indicated that the hybrid macro/micro structure with optimized nanoparticle size rendered the resulting fabricated membranes enhanced permeate flux and anti-fouling properties. The optimal L-F-3 membrane achieved high flux (16.08 kg/(m2·h)) under feed temperature of 60 °C with a water contact angle of 150° and LEP (liquid entry pressure) of 2.9 bar. Finally, the modified membranes possessed the enlarged effective evaporative surface and intensified the nucleation barrier as well as the interfacial nanoscale turbulent flow without potential scaling. • Composite membranes with hybrid macro/micro structure were fabricated via in-situ SiO 2 growth. • Coordinated macro/micro structure enhanced the permeation and anti-fouling property of VMD. • Anti-nucleation mechanism was proposed based on VMD performance. [ABSTRACT FROM AUTHOR]

[Display omitted] • A series of Co SACs were synthesized with tunable Co-N 5- x C x (x = 1, 2, 3) sites. • Engineering the hybrid N and C coordination greatly affect the CO 2 RR performance. • FE CO boosted from 54 to 76 and 92% at −0.8 V with increased ratio of Co-C. • Co-C promotes the electron donation and strengthen binding interaction with *COOH. Single-atom catalysts (SACs) with well-defined active sites provide an efficient route for catalyzing CO 2 reduction reaction (CO 2 RR). Although enormous attention has been focused on metal-N x moieties, understanding the effect of metal-C coordination and engineering of the hybrid metal-N/C sites have rarely been reported. Herein, we fabricated Co SACs with tunable isolated Co-N 5-x C x (x = 1, 2, 3) sites supported on porous carbon frameworks. Benefiting from the difference in electronegativity of the coordinated N and C atoms, the CO Faradaic efficiency (FE CO) enhanced considerably from 54% to 76% and 92% at −0.8 V vs. RHE for Co-N 4 C 1 , Co-N 3 C 2 , and Co-N 2 C 3 , respectively. Further density functional theory (DFT) calculations uncover that the increased ratio of Co-C coordination induced electron enrichment of Co atoms and upper-shift the d -band center to near Fermi level, and thus favorably promotes the electron-donating ability of Co centers and strengthens the adsorption of *COOH. [ABSTRACT FROM AUTHOR]

Abstract: Freeze/thaw treatment has been widely investigated for phase separation of oil-in-water (O/W) emulsions. However, it is a new application for destroying the inverted emulsions, water-in-oil (W/O) emulsions. In this study, freeze/thaw treatment was used to break the W/O emulsions with loosely packed droplets that were produced from the oils generally adopted as membrane phase in emulsion liquid membrane (ELM) process. The effects of emulsion system parameters and freezing conditions on demulsification performance were investigated. A near linear relationship was observed between demulsification performance and water content (30–65%). Demulsification performance greatly increased with the increase of droplet size (2.7–7.3μm), while it was slightly affected by oil type. Four freezing methods were employed including freezing in refrigerator, cryogenic bath, dry ice and liquid nitrogen. The best freezing method for water removal was freezing in cryogenic or dry ice, and its efficiency was over 70% for all experimental systems with 60% water content regardless of droplet size and oil phase type. Furthermore, microscopic process of demulsification was monitored using optical microscope and the coalescence of droplets was simulated. From the experiments, the gradual demulsification process induced by freeze/thaw was proven and a collision mechanism was proposed. Meanwhile, the volume expansion of water turning to ice and interfacial tension of oil–water interface were determined as main driving forces of demulsification. The proposed mechanism and driving forces can explain the influences of various parameters on demulsification performance well. [Copyright &y& Elsevier]

Table of contents for mechanism model of Cu-N 3 and Cu-N 4 moieties. • Highly exposed isolated Cu-N x sites were embedded in microporous carbon frameworks. • CO 2 -to-CO conversion was boosted with tailored Cu–N coordination environment. • Cu-N 4 exhibited a maximum FE CO of 98% and over 90% from −0.6 to −1.1 V vs. RHE. • Edge-hosted Cu-N 4 was identified as the accurate configuration of active site by DFT calculations. Although considerable progress has been achieved by Cu nanoparticles for catalyzing CO 2 reduction reaction (CO2RR), Cu single atom catalysts (Cu SACs) are generally suffered from inferior performance to that of widely investigated Fe, Co, Ni SACs. This phenomenon mainly ascribes to the lack of effective geometry and electronic engineering of copper active center from an atomic level. Herein, highly exposed atomically dispersed Cu-N x (x denotes Cu–N coordination number) sites anchored on 3D porous carbon matrix are successfully synthesized through facile one step thermal activation, and Cu-N 4 sites exhibit boosted activity and selectivity compared to its nearly inert Cu-N 3 counterparts. Aided by density functional theory (DFT) calculations, the edge-hosted Cu-N 4 moieties are revealed as key active sites for efficient CO generation via optimized local coordination environment and electronic properties, which strongly interact with *COOH intermediate and facilitate the desorption of *CO. As a result, Cu-N 4 catalyst achieves high CO Faradaic efficiency (FE CO) of over 90% from −0.6 to −1.1 V vs. RHE with a maximum value of 98%, surpassing the previously reported Cu SACs for CO 2 -to-CO conversion. This work provides new insight into proper Cu SACs design and fundamental mechanism understanding to boost CO2RR. [ABSTRACT FROM AUTHOR]

• Rational structure and composition design of interlayer was fabricated with modified phase inversion method. • This interlayer can physically block the shuttle of LiPSs with dense surface layer. • This interlayer can chemically capture and convert LiPSs with abundant Co nanoparticles in the honeycomb-like pores. • This interlayer can facilitate Li+ migration with abundant pyridinic N sites. • The Li-S battery assembled with this interlayer exhibits excellent performance under high current density. Lithium-sulfur (Li-S) battery has been considered to be the most promising next-generation secondary battery system, but the shuttle effect of lithium polysulfides (LiPSs) and sluggish redox kinetics of LiPSs conversion processes still hinder its commercial application. Herein, a honeycomb-like structured and dense layer coated interlayer with Co nanoparticles uniformly dispersed was fabricated via a modified phase inversion method followed by carbonization. This interlayer can suppress the LiPSs shuttling by physically blocking the diffusion of LiPSs and chemically capturing and accelerating the conversion of LiPSs due to the high catalytic activity of Co nanoparticles. Meanwhile, the abundant lithiophilic pyridinic N sites can also facilitate Li+ migration, which further promotes the reaction kinetics of LiPSs conversion. Consequently, the Li-S battery assembled with this interlayer can exhibit an excellent specific capacity of 586.6 mAh/g after 400 cycles at 4.0 C with a low decay rate of 0.10 %. Even when the sulfur loading is elevated to 5.1 mg cm−2, this battery can still maintain the specific capacity of 646.0 mAh/g after 100 cycles at 0.2 C. This work demonstrates the importance and potential of the rational design of interlayer structure and composition in improving the overall Li-S battery performance. [ABSTRACT FROM AUTHOR]

• Rational design of core-shelled Fe 2 O 3 microspheres doped in multi-lamellar rGO. • Fe 2 O 3 @rGO cathode actively catalyze polysulfides transformation to restrain the shuttle effect. • Enhance electrochemical performance of Li-S battery due to the synergistic effects of Fe 2 O 3 @rGO. We report a method based on 2,4-dihydroxybenzoic acid-formaldehyde (RF-COOH) microsphere hard templates to prepare core-shelled Fe 2 O 3 microspheres, which were then added to graphene oxide to obtain hierarchical reduced graphene oxide, ultimately dropping Fe 2 O 3 (Fe 2 O 3 @rGO) by Vitamin C reduction and freeze drying. When used as cathode materials for lithium-sulfur batteries, Fe 2 O 3 @rGO shows a high specific capacity of 400.5 mAh g−1 at 2 C after 500 cycles. The prominent performance is due to the collaborative assembly of rGO, which provides stable structural support and favourable conductivity, and core-shelled Fe 2 O 3 microspheres, which are certified to have a strong interaction with polysulfides. The loose and stable skeletons of highly electroconductive rGO can offer a conductive framework for rapid ion/electron transport. Meanwhile, the unique core-shelled structure of Fe 2 O 3 with the ample void space can anchor polysulfides through the strong chemical adsorption and buffer the mechanical stresses caused by volume expansion during the charge and discharge processes. Moreover, Fe 2 O 3 promotes the transformation of polysulfides to insoluble LiPSs during the discharging process, effectively alleviating the shuttling of the polysulfides. [ABSTRACT FROM AUTHOR]

A simultaneous optimization approach for heat exchanger network (HEN) synthesis and detailed shell-and-tube heat exchanger (HE) design including phase changes is proposed based on a genetic/simulated annealing algorithm (GA/SA). Firstly, a model for HEN synthesis considering utility HEs with phase change is established by combining the improved stage-wise superstructure model of HEN synthesis with non-isothermal mixing of splits and detailed design models of HEs involving phase change, the minimum total annual cost accounting for pumping cost is set as the key objective. Secondly, two alternative connection schemes for HEs, which are referred to as one-stream series-wound and one-stream parallel in the stage-wise superstructure of the HEN, were applied. Thirdly, a simultaneous optimization strategy is proposed. Required areas of HEs obtained by stage-wise superstructure, overall heat-transfer coefficients and pressure drops based on the dimension parameters of HEs are used to connect HEN synthesis and the detailed design of each HE. Finally, a flowchart of optimization procedures using GA/SA was presented to solve the problem, and an inner iterative loop of the area of HE is used to guarantee the feasibility of the solution. Two examples results are used to illustrate the availability of the proposed model and algorithm. • A model for HEN synthesis considering utility HEs with phase change is proposed. • A flowchart of simultaneous optimization procedure is proposed based on GA/SA. • An inner iteration loop is proposed to ensure the feasibility of the solutions. • GA/SA is used to synchronize the evolution of HEN and HE geometry parameters. • The optimal results of example 2 decrease TAC by 22.1%. [ABSTRACT FROM AUTHOR]

• In-situ position of ILs into cages of ZIF-8 was proposed to tune cage size. • CO 2 -philic cages constructed by ILs improve CO 2 adsorption. • Molecular simulation reveals increased CO 2 adsorption by increasing ILs in cages. • CO 2 /N 2 selectivity of MMMs is increased due to pore screening and CO 2 adsorption. The regulation on cage size and CO 2 -philic environment of metal–organic frameworks (MOFs) is essential to improve CO 2 capture. In this work, [Bmim][Tf 2 N] was proposed to position into cages of ZIF-8 to achieve the selective permeation of CO 2 by pore screening and CO 2 adsorption. [Bmim][Tf 2 N] was introduced into cages of ZIF-8 by "adsorption-infiltration" strategy. Due to the strong interaction between [Tf 2 N]− and ZIF-8, the cages present a CO 2 -philic environment, which preferentially attracts CO 2 to enter these cages, ensuring the dissolution selectivity of CO 2. Besides, the proper cage size tuned by [Bmim][Tf 2 N] provides CO 2 with a faster transport channel due to its smaller average kinetic diameter than N 2 , guaranteeing the diffusion selectivity of CO 2. Consequently, the CO 2 separation in [Bmim][Tf 2 N]@ZIF-8/Pebax MMMs is intensified. With increasing the [Bmim][Tf 2 N] content in cages of ZIF-8, the pore volume by BET results decreases and the CO 2 adsorption from molecular simulation increases. In response, the CO 2 /N 2 selectivity of [Bmim][Tf 2 N]@ZIF-8/Pebax MMMs is enhanced constantly. Meanwhile, the CO 2 permeability is declined due to the narrowed cage size. All of these results demonstrate the significance of pore screening and CO 2 adsorption induced by [Bmim][Tf 2 N]. Specifically, [Bmim][Tf 2 N] 8 @ZIF-8/Pebax MMM at filler loading of 15 wt% exhibits the CO 2 permeability of 108.3 Barrer and the CO 2 /N 2 selectivity of 86.7, exceeding the 2008 Robeson upper bound. Especially the CO 2 /N 2 selectivity locates at a higher level than those of most reported works, indicating that appropriate tuning of the physicochemical properties within the nanocages of MOFs is significative to improve CO 2 capture. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A highly scalable yet flexible porous Fe 3 C/APCM membrane for Li-ion batteries. • The membrane can work directly as both active materials and current collector. • The finger-like pores can facilitate ion transport for fast kinetics reaction. Abstract In traditional pulverous electrodes, the severe volume expansion that occurs during the intercalation and de-intercalation of lithium ions causes the active material to agglomerate and pulverize, eventually leading to active material that deviates from the current collector and result in poor electrochemical performances. Therefore, a new kind of Fe 3 C-doped asymmetric porous carbon membrane (Fe 3 C/APCM) binder-free integrated electrode materials is proposed by using a simple phase inversion method. The Fe 3 C/APCM electrodes that are obtained act as both active materials and current collector, saving the use of current collectors, conductive agents and binders. The effects of temperature and thickness on the conductivity and diffusion of ions are investigated, confirming the optimum temperature and thickness of the casting membrane solution to be 800 °C and 100 μm (Fe 3 C/APCM-100), respectively. Abundant finger-shaped and honeycomb-like pores are formed in the Fe 3 C/APCM-100, effectively accommodating the volume changes induced by the charge-discharge process. The specific surface area of the electrode materials reaches to 134.9 m2 g−1, enhancing the connection between active materials and electrolytes, leading to a high rate of electron transfer and ion diffusion. As the anode materials of a lithium-ion battery, the Fe 3 C/APCM-100 composites achieve an excellent rate capability and long cycling stability. The rate capability reaches to 605.5 mAh g−1 at a current density of 0.1 A g−1, and 601.0 mAh g−1 is retained when the current density returns to 0.1 A g−1. Even at a high current density of 1.0 A g−1, an excellent cyclic capacity of 212.9 mAh g−1 is still achieved after 200 cycles. No obvious structural and morphological changes are observed in SEM images of Fe 3 C/APCM-100 electrodes before and after a charge-discharge process. Fe 3 C/APCM is promising as an anode material for lithium-ion batteries. [ABSTRACT FROM AUTHOR]

• High-throughput ALMS-qPCR method enhanced Nosema spp. detection. • DNA preparation of ALMS-qPCR is fast, automatable, and cost-effective. • Common PCR inhibitory factors were overcome in ALMS-qPCR. • The limit of detection (LOD) was 0.045 parasites/μL. • ALMS-qPCR is promising for routine pébrine screening and epidemiological studies. Accurate diagnosis of pathogenic Nosema spp. in Antheraea pernyi samples is considered especially useful for reducing economic losses in sericulture and improving food safety by maintaining pathogen-free pupae. However, microscopy and immunologic methods have poor diagnostic sensitivity, while the more sensitive PCR methods remain costly and time-consuming for template preparation. To address this issue, we introduce a sensitive ALMS-qPCR method that combines fast, simple DNA extraction using A lkali L ysis followed by M agnetic bead S eparation (ALMS) and quantitative real-time PCR (qPCR). This approach is especially fit for large-scale pathogen molecular screening, because the DNA preparation procedure is fast (<0.94 min per sample) and is high-throughput (performs on a 96-well plate). It is cost-effective, since the most expensive materials can be made in the lab and can be recycled, while the automated procedure can help to minimize labor cost. Though the DNA preparation procedure was substantially simplified, common PCR inhibitory factors were not observed. The sensitivity of ALMS-qPCR is high and the limit of detection is 0.045 parasites/μL. Large-scale screening of Nosema spp. in 3000 Antheraea pernyi samples confirmed the efficacy of the ALMS-qPCR method. Sensitivity is much higher than clinical microscopy, especially for host groups with low infection prevalence and levels. High-throughput ALMS-qPCR, combining automated DNA preparation and sensitive qPCR, provides an enhanced approach for pébrine screening and epidemiological studies. The application of ALMS-qPCR in the sericulture industry will help to strengthen pébrine control and breed pathogen-free species, which means much safer food provision and better genetic resource conservation. [ABSTRACT FROM AUTHOR]

Abstract Vacuum membrane distillation (VMD) is a promising technology for high salinity wastewater treatment. One of the key issues in VMD research is improving the antifouling performance of the hydrophobic porous membrane under proper interface modification theory and approach. In this work, the polypropylene (PP) composite membrane coated with SiO 2 nanoparticles and fluorinated modification was fabricated to simultaneously enhance the interface roughness and superhydrophobicity. The fabricated superhydrophobic PP membrane was then applied to treat highly concentrated NaCl (15 wt%)/MgCl 2 (from 3 to 9 wt %) saline solution in VMD process under various flow conditions. The model concerning the surface roughness and surface nucleation free energy was constructed to predict the influence of membrane surface structure on potential anti-fouling and anti-wetting properties. Classical heterogeneous nucleation theory was introduced to illuminate the improved performance of developed membrane with targeted surface morphology on inhibiting the initial interfacial nucleation process. The experimental results illustrated the fabricated superhydrophobic PP membrane exhibited unique anti-fouling and anti-wetting abilities, as well as extremely stable permeating flux even under low feed rate and highly concentrated salt solution system during the continuous operation. In addition, it was also indicated that sodium ion and magnesium ion with distinct features in the structure of water-ion solution system had the potential impact on the permeate flux decline and concentration polarization effect, which was helpful for further improving the stability and durability of this series modified membrane when treating the high concentrated multiple solution system. Highlights • Superhydrophobic PP membrane with modified antifouling interface is fabricated for VMD application. • Classical nucleation theory was introduced to illuminate the inhibiting nucleation mechanism of the membrane with targeted surface structure. • Fabricated membrane exhibited unique antiwetting and antifouling abilities when treating highly concentrated multiple saline water. [ABSTRACT FROM AUTHOR]

Highlights • Superhydrophobic PP composite membranes with modified surface were successfully fabricated for membrane distillation. • The impact of deposited nanoparticle size on the surface roughness, and heterogeneous nucleation barrier was simulated and investigated. • The fabricated membrane possessed good anti-wetting ability, stable antifouling performance and high salt rejection in the corresponding conditions. • Fouling rate of the fabricated superhydrophobic membrane was only 1/5 of the one of the original membrane under high salinity feed condition. Abstract In this work, the superhydrophobic polypropylene (PP) composite membranes with modified surface were successfully fabricated by loading the SiO 2 nanoparticles and attaching low surface energy 1H,1H,2H,2H-perfluorodecyltriethoxysilane. The impact of deposited nanoparticle size on the surface roughness, heterogeneous nucleation barrier and critical nucleus size versus the loaded nanoparticle size (d ∗ nuclear / d) was simulated by the model combining the surface roughness and superhydrophobility with the critical nucleation energy. The optimized loaded nanoparticles size maintained the proper roughness and d ∗ nuclear / d to ensure the desired performance of antifouling. The improved superhydrophobic surface enhanced the anti-wetting ability of the membrane for vacuum membrane distillation (VMD) purpose. The resulting modified membrane possessed good anti-wetting ability and stable anti-fouling performance during long-term continuous and batch operation of VMD treating high salinity water system. The fouling rate of the fabricated membrane was decreased to 20% of the one of the original membrane under 15 wt% high salinity feed condition. [ABSTRACT FROM AUTHOR]

Droplet evaporative crystallization on a micro-structured platform with limited interfacial area has potential applications in crystallization theory, bioengineering, and particle drug preparation. Here, an efficient and versatile approach is discussed for multiple drop-evaporative crystallization processes on a micro-crystallization chip fabricated via three-dimensional printing. A chip with limited interfacial area could be fabricated on a highly controlled crystallizer interface. During liquid injection, various drop locations and evaporative conditions can be used, which enables flexible and distinct crystallization processes. This reveals controlling mechanisms and identifies nucleation locations and growth paths. Various classic crystallization systems were introduced to evaluate the chip performance. Controlled nucleation and growth mechanisms at stable evaporative rates were revealed. From the final crystal morphologies, particle locations, and distributions, the effects of the initial concentration and droplet contact conditions at the triple-phase interface could be investigated with high adjustability. Moreover, the results can provide insights into the ‘coffee ring’ formation during evaporative crystallization, dendritic crystal growth, and hydrate crystallization mechanisms. In the limited microstructure, the capillary flow of a liquid drop can spontaneously drive the crystal distribution and morphology. Finally, incorrect liquid drop locations that led to unpredictable crystal formation and distributions were discussed to improve repeatability and efficiency. Applications include the manufacture of particle drugs and flow chemistry. [ABSTRACT FROM AUTHOR]

Ni and Co doped Fe 2 O 3 hollow microspheres of yolk-shell type were designed and synthesized by using resin (RF-COOH) microspheres as hard template and subsequent calcination. Specific morphologies (walnut-like, jingle-bell-like and ball-like) and compositions of Fe 2 O 3 with different amounts of Ni and Co doping were obtained by tuning metal precursor concentration to optimize their performance in lithium-ion battery application. When Ni and Co doped Fe 2 O 3 hollow microspheres were used as anode materials for lithium-ion batteries, jingle-bell-like and ball-like morphologies showed better electrochemical performance with specific capacities of 415.7 and 414.1 mA h/g, respectively up to 200 cycles due to their stable construction with hollow cavity, porous shell and Ni and Co dopants. However, the specific capacity of Ni and Co doped Fe 2 O 3 @TiO 2 hollow microspheres increased to 562 mA h/g. This work showed a new avenue for designing and fabricating yolk-shell hollow structures with specific morphologies and compositions in order to optimize their specific capacity for use in lithium-ion batteries. [ABSTRACT FROM AUTHOR]

Ultrathin graphene wrapped Ni-Co double hydroxide nanosheets (∼10 nm) were synthesized by a facile and rapid electrodeposition process, and evaluated as electrocatalysts for oxygen evolution reaction (OER) and anode materials for Li-ion batteries. The conformal graphene coating on the nanosheets significantly increased the conductivity and surface area of the Ni-Co double hydroxide electrodes. As the OER electrocatalyst, the Ni-Co graphene hybrids show a superior catalytic activity with a small Tafel slope of 67 mV per decade due to the synergy between the abundant active sites of the Ni-Co hydroxides and the conductive graphene coating, and a modest overpotential of 280 mV at a current density of 10 mA cm −2 . Impressively, the electrodes exhibit an excellent stability evaluated by chronopotentiometry under a high current density of 30 mA cm −2 for 12 h. As Li-ion battery anode, the materials show a high specific capacity of 373 mA h g −1 up to 500 cycles even at a high current density of 1000 mA g −1 . This study provides a new strategy to develop robust and affordable alternative OER catalyst and anode material for high-performance lithium ion batteries. [ABSTRACT FROM AUTHOR]

Pore size adjustment has been considered to be a successful strategy for enhancing the sieving of MOF-based mixed matrix membranes (MMMs). However, the increase in CO 2 /N 2 selectivity usually comes at the expense of permeability. Herein, the regulating on the pore size of polystyrene-modified hollow NH 2 -MIL-101 (PHNM) is achieved by controlling the confined dissolving of PSA polymer chain. During the etching of PSA template, the dissolved PSA polymer chains diffused outward through the pores and intergranular space of NH 2 -MIL-101 under the concentration difference. As a consequence, the pores of NH 2 -MIL-101 were unavoidably constrained by the partly dissolved PSA segments, achieving the regulation on the pore size. Meanwhile, there are also some PSA segments adhering to the surface of NH 2 -MIL-101 to form a PSA coating layer. In this unique PHNM, the reduced pore size endows it with better CO 2 /N 2 selectivity than NH 2 -MIL-101. Meanwhile, the high interface compatibility provided by surface-modified PSA segments and the enhanced CO 2 affinity of PHNM resulting from amino groups also synergistically improve the CO 2 /N 2 selectivity. Additionally, the hollow core offers gas molecules a low-resistance transfer channel, improving the permeability of CO 2. The hollow size of PHNM was adjusted from 33 to 57 nm by controlling the etching time of PSA, and the pore size of PHNM was regulated from 0.58 to 0.83 nm by controlling the confined dissolving process of PSA. Thus, the PHNM-based MMMs exhibit high CO 2 permeability as well as high CO 2 /N 2 selectivity. Compared with NH 2 -MIL-10/Pebax MMM, the MMM with PHNM-2 loading of 10 wt% shows 30% and 21% enhancements in the CO 2 permeability (226.3 Barrer) and CO 2 /N 2 selectivity (71.3), respectively, far exceeding the Robeson upper bound (2008). These results reveal that the PHNM based MMMs express a great potential in CO 2 separation. [Display omitted] • Confined dissolving of PSA polymer chain is proposed to tune pore size. • Pore size of MIL-101 is regulated from 0.58 to 0.83 nm. • Surface-modified PSA and amino groups intensify interface compatibility. • Hollow structure constructs low-resistance region to improve CO 2 permeability. [ABSTRACT FROM AUTHOR]

[Display omitted] • CO 2 was preferentially adsorbed due to the aldehyde group in the imidazolide skeleton of ZIF-93 zeolite. • CO 2 permeability and CO 2 /N 2 selectivity were improved with NH 2 -ZIF-93 addition. • Gas storage space is formed to improve gas separation efficiency of Pebax MMMs. In this study, amino organic compounds were grafted on the porous ZIF-93 surface by grafting modification to create a villous organic layer with CO 2 adsorption. Pebax-1657-based mixed matrix membrane (MMMs) is created using modified ZIF-93 as filler. The presence of this organic layer not only improves the adsorption of CO 2 gas by the filler, but also improves the rich storage space for the gas transport in the MMMs. Thus, the permeability and CO 2 /N 2 selectivity are improved. The MMMs with 10 wt% NH 2 -ZIF-93 showed the best separation performance, exhibiting distinct increases of 87.32% and 96.32% compared to primitive Pebax-1657 membrane, and passed Robeson's upper bound. [ABSTRACT FROM AUTHOR]

Highly-ordered flower-like Co(OH)F architectures are fabricated in the conductive membrane substrate. The hierarchically porous CNT@NC membrane can strengthen the transport of Li+ and electrons in the electrode, and the ordered Co(OH)F bundles with divergent and open-ended structures provide the catalyst with the broad reaction interface and active sites for polysulfides anchoring and catalytic conversion at low energy barrier, significantly facilitate the diffusion of ions and electrolyte in the catalyst, and thus effectively alleviating the shuttle effect. The proposed facile strategy provides insights regarding design of novel cathode materials for high-areal-capacity Li–S batteries. [Display omitted] • Scalable porous membrane with a high porosity (86%) for growing flower-like Co(OH)F. • The Co(OH)F flowers have broad reaction interface and active site for LiPSs anchoring. • The sandwiched structure fasten the diffusion of ion and electrolyte in the membrane. • Excellent long-term cycling performance with 622 mAh·g−1 at 1C after 600 cycles. Here, the conventionally disordered Co(OH)F filaments are rearranged to form highly-ordered flower-like Co(OH)F architectures in a conductive membrane substrate. The important findings contribute to designing delicate nanostructures and improving the catalytic activity of advanced materials for energy applications. The hierarchically porous CNT@NC membrane with CNT as the core and N -doped carbon as the crosslinking shell is scalably designed firstly for strengthening the transport of Li+ and electrons in the electrode, providing an ultrahigh porosity for growing flower-like Co(OH)F on both surfaces and interior of the membrane, as well as offering electrons for the redox reactions through the roots of the Co(OH)F flowers. Furthermore, the ordered Co(OH)F bundles with divergent and open-ended structures provide the catalyst with the broad reaction interface and active sites for polysulfides (LiPSs) anchoring and catalytic conversion at a low energy barrier, significantly facilitating the diffusion of ions and electrolyte in the catalyst, and thus effectively alleviating the shuttle effect. Owing to the synergistic effect between the conductive membrane substrate and the grown Co(OH)F catalyst, the Co(OH)F-CNT@NC cathode generates a high reversible capacity and excellent long-term cycling performance (622 mAh·g−1 at 1C after 600 cycles). Conclusively, the proposed facile strategy provides insights regarding the design of novel cathode materials for high-areal-capacity Li–S batteries. [ABSTRACT FROM AUTHOR]

• A partial element stage cut electrochemical hydrogen pump (EHP) model was proposed. • Three real factors were embedded into the model to describe EHP performance accurately. • The acuracy of EHP model was verified for four aspects under four different feedstock systems. • The variation law of current density caused by GDL mass transfer and PEM resistance was simulated and analyzed quantitatively. • The back-diffusion behavior of hydrogen under cathode high pressure was simulated and analyzed quantitatively. In this work, a partial element stage cut electrochemical hydrogen pump (EHP) model for the separation of multiple H 2 -contaning gases and hydrogen compression was proposed to realize fast prediction of the EHP's performance (nearly 10 s for one I EHP – E point). Three real factors, namely, anode impurity diffusion, hydrogen back-diffusion and anode catalyst deactivation, were embedded into the model. The model accuracy was verified for four aspects (current density distribution, polarization curve, hydrogen recovery and purity) under four feedstock systems (H 2 /N 2 , H 2 /CH 4 , H 2 /He and H 2 /CO 2) and a wide cathode pressure range of 0.1–1.0 MPa. The model had good accuracy ( R 2 ≥ 0.90). Benefiting from the embedding of the real factor of the hydrogen back-diffusion, hydrogen back-diffusion ratio was simulated accurately under a wide cathode pressure range of 0.13–20 MPa. By considering the dual- effect on current density caused by PEM proton conduction and GDL mass transformation resistance, optimal region of hydrogen recovery rate, energy efficiency and hydrogen purity can be simulated. About 64 % and 53 % for hydrogen recovery rate and energy efficiency can be achieved under low hydrogen feedstock of 20 mol%. In summary, it is promising to realize the "hydrogen economy" in the future under the utilization of EHP. [ABSTRACT FROM AUTHOR]

• Two flow regimes were observed in membrane assisted reactive crystallization (MARC). • Reversible transitions between liquid layer and droplet can be achieved on membrane surface. • Controllable mixing and ions diffusion conditions were achieved via MARC. • Crystals with narrow nano/micro size distribution were obtained via MARC. Herein, membrane-assisted reactive crystallization (MARC) with effective interfacial flow regimes was proposed to achieve the effective mass transfer control during reactive crystallization. Three tube-shell side solution systems (EtOH-H 2 O, Butanol-H 2 O and H 2 O-H 2 O) were chosen to form different flow regimes on the membrane surface, including the microscale liquid layer and the uniform droplets. The fundamental mechanisms of 'rising and falling tide' phenomenon, and flexible layer thickness control were uncovered. A force analysis model was established to illustrate the transition behavior of the droplet and liquid layer on the membrane surface. Molecular simulations additionally demonstrated that MARC implemented various ion diffusion conditions in different solution systems. Compared to the conventional reactive crystallization, MARC with multiple flow regimes can achieve effective control of CaCO 3 crystal size ranging from 700 nm to 3 μm and obtain uniform size distribution (coefficient of variation less than 15.1 %), which shed light on the advanced material manufacture with reactive crystallization process. [ABSTRACT FROM AUTHOR]