Micropores regulating enables advanced carbon sphere catalyst for Zn-air batteries

Energy conversion technologies like fuel cells and metal-air batteries require oxygen reduction reaction(ORR)electrocatalysts with low cost and high catalytic activity.Herein,N-doped carbon spheres(N-CS)with rich micropore structure have been synthesized by a facile two-step method,which includes the polymerization of pyrrole and formaldehyde and followed by a facile pyrolysis process.During the preparation,zinc chloride(ZnCl2)was utilized as a catalyst to promote polymerization and provide a hypersaline environment.In addition,the morphology,defect content and activity area of the resultant N-CS catalysts could be regulated by controlling the content of ZnCl2.The optimum N-CS-1 catalyst demonstrated much better catalytic activity and durability towards ORR in alkaline conditions than commercial 20 wt%Pt/C catalysts,of which the half-wave potential reached 0.844 V vs.RHE.When applied in the Zn-air batteries as cathode catalysts,N-CS-1 showed a maximum power density of 175 mW cm^(-2) and long-term discharging stability of over 150 h at 10 mA cm^(-2),which outperformed 20 wt%Pt/C.The excellent performance could be due to its ultrahigh specific surface area of 1757 m2 g
1 and rich micropore channels structure.Meanwhile,this work provides an efficient method to synthesize an ultrahigh surface porous carbon material,especially for catalyst application.

Characterizing the Micropores in Lacustrine Shales of the Late Cretaceous Qingshankou Formation of Southern Songliao Basin, NE China

Micropores of shale are significant to the gas content and production potential of shale, which has been verified in the research of marine shale gas; while, few studies have been conducted on lacustrine shales. This study collected 42 samples from three wells in the Late Cretaceous Qingshankou Formation of the southern Songliao Basin, NE China, and investigated these samples by the focused ion beam-scanning electron microscope(FIB–SEM) and nitrogen adsorption analysis techniques. Four types of micropores were identified in the samples, i.e., intergranular pore, intracellular pore, organic matter pore and microfracture. The pore structure type is characterized by open slit pores and "ink type" pores which are mainly 1.5–5 nm in diameter with mesopores as the main pores. The mesopores account for 74.01% of the pore volume and 54.68% of the pore surface area. Compared with the lacustrine shales from the Triassic Yanchang Formation in the Ordos Basin and Xujiahe Formation in the Sichuan Basin, the intergranular clay mineral interlayer pores are considered to be the main reservoir space for shale gas storage in the study area, followed by intraparticle pores, organic matter pores and microfractures. Maturity and micropore are the key controlling factors which affect the shale gas content of the Qingshankou Formation in southern Songliao Basin.

CONCENTRATION PARTITION OF PROTEIN SOLUTION IN A MICROPORE:EFFECT OF ELECTROSTATIC INTERACTION

A theory for calculating the electrostatic interaction between protein molecules and the wallof a liquid-filled micropore is established in terms of solving the Laplace and the linearPoisson-Boltzmann equations.The surface charge of protein molecules is measured by theelectrophoresis velocity,whilethe charge of the pore wall is obtained by the ionic Donnan equilibrium.The theory is then used to study the influence of solute-pore electrostatic interaction on theconcentration partition of protein solution in a micropore under different solution properties.Experi-mental verification is performed by detecting the hindered diffusion of bovine serum albumin in thetrack-etched polycarbonate membranes.A good consistence between the theoretical and experimentaldata is being achieved.

A Universal Strategy For N-Doped 2D Carbon Nanosheets With Sub-Nanometer Micropore For High-Performance Supercapacitor

Preparing carbon nanosheets with precise control of open porous morphology via universal process and understanding the relationship between structure and capacitive performance are very urgent for achieving advanced supercapacitors.Herein,we propose a simple yet effective additive-free method to transform a bulk layered potassium phthalimide salt to novel nitrogen-doped twodimensional carbon sheets by self-activation during calcination.The obtained samples showed large-sized and flat structure with lateral size around 10μm,uniform sub-nanometer micropore size distribution of about 0.65 nm dimension,large specific surface area up to 2276.7 m^(2)g^(-1),and suitable nitrogen doping.Benefited from these merits,the optimized sample delivers a high specific capacitance of 345 F g^(-1)at 1 A g^(-1)and retains 270 F g^(-1)even at 50 A g^(-1)in6.0 M KOH electrolyte.Remarkably,the symmetric supercapacitor shows maximum energy densities of 16.43 Wh kg^(-1)and 23.6 Wh kg^(-1)in 6.0 M KOH and 1.0 M Na_(2)SO_(4)electrolytes,respectively.Importantly,on account the universality and simplicity of this method,the undoped as-prepared carbon sheet with uniform sub-nanometer micropore distribution can be synthesized from different potassium-containing salts with layered structure,which can be employed as a model for a deep understanding the effect of sub-nanometer micropores on capacitive performances.We find the number of micropores centered at 0.65 nm can be applied as one indicator to clarify the correlation between capacitance and critical pore size below 1 nm.

Effect of Thermal Treatment of the Hydroxyapatite Powders on the Micropore and Microstructure of Porous Biphasic Calcium Phosphate Composite Granules

The effect of thermal treatment of the hydroxyapatite powders on the micropore structure of porous biphasic calcium phosphate (BCP) granules was examined. The porous BCP granules could be attained through mixing and sintering/fracturing thermally treated 60 wt% hydroxyapatite powders and calcined 40 wt% β-tricalcium phosphate powders. The observed Scanning electron microscopy (SEM) morphologies showed that the density of micropores (0.1 - 2.0 μm) including interconnected micropores of the porous BCP granules mixed with hydroxyapatite powders thermally treated at 900°C was significantly improved and the composite particles of porous BCP granules were homogeneously mixed and distributed. This result indicates that the particles of hydroxyapatite powders that have a tendency to agglomerate at a room temperature were well isolated and dispersed through thermal treatment processing before mixing with calcined β-tricalcium phosphate powders. The microstructural characterizations such as phase purity and composition of porous BCP granules were performed and verified by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) analysis.

Comparative Analysis of Statistical Thickness Models for the Determination of the External Specific Surface and the Surface of the Micropores of Materials: The Case of a Clay Concrete Stabilized Using Sugar Cane Molasses

In this work, four empirical models of statistical thickness, namely the models of Harkins and Jura, Hasley, Carbon Black and Jaroniec, were compared in order to determine the textural properties (external surface and surface of micropores) of a clay concrete without molasses and clay concretes stabilized with 8%, 12% and 16% molasses. The results obtained show that Hasley’s model can be used to obtain the external surfaces. However, it does not allow the surface of the micropores to be obtained, and is not suitable for the case of simple clay concrete (without molasses) and for clay concretes stabilized with molasses. The Carbon Black, Jaroniec and Harkins and Jura models can be used for clay concrete and stabilized clay concrete. However, the Carbon Black model is the most relevant for clay concrete and the Harkins and Jura model is for molasses-stabilized clay concrete. These last two models augur well for future research.

Hyper-crosslinked Conjugated Microporous Polymers with Increased Micropores Promotes Confining Polymerization for Electromagnetic Absorption Application

Conjugated microporous polymers have excellent skeleton structures but poor electrical conductivity limits their applications in microwave absorption.To solve this problem,a strategy of molecular expansion and confining polymerization is proposed in this work to synthesize conductive hyper-crosslinked conjugated microporous polymer.The topology of the conjugated microporous polymer is changed into a three-dimensional skeleton structure with high specific surface area by using molecular expansion technique,and the controlled growth of polypyrrole in the channel constructs a unique network structure.The balance of excellent composite backbone structure,proper conductivity,attenuation capability and impedance matching enable the material to exhibit electromagnetic wave absorption performance.As a result,with low filler loading of 10 wt%,a strongest reflection loss of-52.68 d B and a maximum effective bandwidth of 5.76 GHz.Additionally,CST simulations of the radar scattering cross section have been carried out to verify the excellent material properties.This study provides new concepts for new conductive polymers and broadens the application of hyper-crosslinked conjugated microporous polymer in the field of electromagnetic wave absorption.

The Soft X-ray Imager(SXI)on the SMILE Mission

The Soft X-ray Imager(SXI)is part of the scientific payload of the Solar wind Magnetosphere Ionosphere Link Explorer(SMILE)mission.SMILE is a joint science mission between the European Space Agency(ESA)and the Chinese Academy of Sciences(CAS)and is due for launch in 2025.SXI is a compact X-ray telescope with a wide field-of-view(FOV)capable of encompassing large portions of Earth’s magnetosphere from the vantage point of the SMILE orbit.SXI is sensitive to the soft X-rays produced by the Solar Wind Charge eXchange(SWCX)process produced when heavy ions of solar wind origin interact with neutral particles in Earth’s exosphere.SWCX provides a mechanism for boundary detection within the magnetosphere,such as the position of Earth’s magnetopause,because the solar wind heavy ions have a very low density in regions of closed magnetic field lines.The sensitivity of the SXI is such that it can potentially track movements of the magnetopause on timescales of a few minutes and the orbit of SMILE will enable such movements to be tracked for segments lasting many hours.SXI is led by the University of Leicester in the United Kingdom(UK)with collaborating organisations on hardware,software and science support within the UK,Europe,China and the United States.

Influence of Thermal Temperature on the Structure and Sealed Micropores of Stabilized Polyacrylonitrile Fibers

Thermal stabilization is an important process in carbon fibers＇ production, during which the polyacryloni-trile fibers are heated from 180℃ to 280 ℃ in air. In this study, the samples were characterized by X-ray diffraction,Fourier infrared spectroscopy, differential scanning calorimetry, small angle X-ray Scattering（SAXS） and mechanicaltensile tests. A new rule was suggested by the results of structural characterization for the cyclization, dehydrogena-tion and oxidation reactions that were observed to be drastic from 200 ℃ to 220 ℃, from 220 ℃ to 250 ℃, and inthe later period of the thermal stabilization reactions, respectively. The sizes, shapes and distributions of the sealedmicropores were obtained from the SAXS data. The breaking elongation was significantly affected by the drasticcyclization and dehydrogenation reactions. The breaking force was affected considerably by the bigger micropores,especially from 220 ℃ to 250 ℃, owing to the drastic dehydrogenation reactions.

Sealing functional ionic liquids in conjugated microporous polymer membrane by solvent-assisted micropore tightening

Porous organic polymers hold great promise for molecular sieving membrane separation.Although the inclusion of functional ionic liquid(IL)in the pores offers a facile way to manipulate their separation properties,the IL leaching during the separation process is difficult to avoid.Herein,we report a strategy to in-situ encapsulate ILs into the micropores of the conjugated microporous polymer membrane via a 6-min electropolymerization and further seal the aperture of the pores to prevent ILs leaching by solvent-assisted micropore tightening(SAMT).Upon screening the binding energy between different ILs and gas molecules,two ILs were selected to be incorporated into the membrane for CO_(2)/CH_(4) and O_(2)/N_(2) gas separations.The resultant separation performances surpass the 2008 Robeson upper bound.Notably,the ILs can be locked in the micropores by a facile high surface tension solvent treatment process to improve their separation stability,as evidenced by a 7-day continuous test.This simple and controllable process not only enables efficient and steady separation performance but also provides an effective strategy for confining and sealing functional guest molecules in the porous solids for various applications.

Salt-Lake Basin Bedrock Weathered Crust Gas Reservoir in the Altun Mountains Front of the Qaidam Basin,Western China

The bedrock weathered crust in front of the Altun Mountains in the Qaidam Basin,western China,is different from others because this is a salt-lake basin,where saline water fluid infiltrates and is deposited in the overlying strata.A large amount of gypsum infills the bedrock weathered crust,and this has changed the pore structure.Using core observation,polarized light microscopy,electron probe,physical property analysis and field emission scanning electron microscopy experiments,the characteristics of the weathered bedrock have been studied.There are cracks and a small number of dissolved pores in the interior of the weathered crust.Matrix micropores are widely developed,especially the various matrix cracks formed by tectonics and weathering,as well as the stress characteristics of small dissolved pores,and physical properties such as porosity and permeability.This‘dual structure’developed in the bedrock is important for guiding the exploration of the lake basin bedrock for natural gas.

Porous Carbon Derived from Poplar Catkins and Its High-performance CO_(2)Capture

In order to deal with the increasingly serious environmental problems,it is important and necessary to lower the concentration of greenhouse gases,especially the CO_(2)gas.CO_(2)capture and storage are the relative suitable options for the reduction of these harmful gas concentration.Through the variation of mass ratio of KOH to bio-char,the as prepared active carbon PC-4 exhibits a higher specific surface area of 2491.57 cm^(3)·g^(−1),with the ultra-micropores of 0.5 and 1.2 nm.At 298 K/1 bar,the CO_(2)adsorption capacity of PC-4 also represents the highest value of 5.81 mmol/g.This work demonstrates that the both the pore size and the specific surface area are equally important to enhance the CO_(2)adsorption.This work provides a sustainable method to develop high efficiency waste-based adsorbents to deal with environmental issues of CO_(2)gas.

Gas‐phase fluorination of conjugated microporous polymer microspheres for effective interfacial stabilization in lithium metal anodes

Lithium(Li)metal anodes have attracted extensive attention due to their ultrahigh theoretical capacity and low potential.However,the uneven deposition of Li near the unstable electrode/electrolyte interfaces leads to the growth of Li dendrites and the degradation of active electrodes.Herein,we directly fluorinate alkyne-containing conjugated microporous polymers(ACMPs)microspheres with fluorine gas(F_(2))to introduce a novel fluorinated interlayer as an interfacial stabilizer in lithium metal batteries.Using density functional theory methods,it is found that as-prepared fluorinated ACMP(FACMP)has abundant partially ionic C–F bonds.The C–F bonds with electrochemical lability yield remarkable lithiophilicity during cycling.The in situ reactions between the active C–F bonds and Li ions enable transfer of lithium fluoride microcrystals to the solid electrolyte interphase(SEI)layers,guaranteeing effective ionic distribution and smooth Li deposition.Consequently,Li metal electrodes with the fluorinated interlayers demonstrate excellent cycling performances in both half-batteries and full cells with a lithium bis(trifluoromethanesulfonyl)imide electrolyte as well as a nonfluorinated lithium bis(oxalate)borate electrolyte system.This strategy is highly significant in customizable SEI layers to stabilize electrode interfaces and ensure high utilization of Li metal anodes,especially in a nonfluorinated electrolyte.

Effect of Porogenic Agents on Properties of Microporous Mullite Aggregates

Microporous mullite aggregates were prepared from bauxite by dry pressing and firing at 1700℃for 3 h with corn starch,PMMA microspheres or rice husk powder as the porogenic agent.The effects of some porogenic agents and their additions(mass fraction of 0,5%,10%,15%and 20%,respectively)on the properties of the microporous mullite aggregates were analyzed by XRD,SEM and Image-Pro Plus software.The results show that the comprehensive performance of the sample with 10%rice husk powder is the best:the closed porosity is 7.1%;the bulk density is 2.63 g·cm^(-3);the compressive strength is 122 MPa;the median pore size is 15.16μm;and the thermal conductivity at 500℃is 2.30 W·m^(-1)·K^(-1).

Fabrication and Improving Properties of Lightweight Al_(2)O_(3)-MgO Castables for L adle Working Lining

Three lightweight Al_(2)O_(3)-MgO castables were fabricated with tabular alumina or microporous corundum as the aggregates,reactiveα-Al_(2)O_(3)micropowder,tabular alumina powder,and fused magnesia powder as the matrix,calcium aluminate cement as the binder,and MgO ultrafine powder(d50=5.4μm)and Al(OH)3 ultrafine powder(d50=8.2μm)as additives.The influence of aggregates and ultrafine powders on the properties,including pore size distribution,heat conductivity,thermal shock resistance,and slag resistance of lightweight refractory castables was investigated.The results show that the incorporation of microporous corundum reduces the bulk density of Al_(2)O_(3)-MgO castables,and MgO and Al(OH)3 ultrafine powders further increases the proportion of micropores in castables,which is beneficial to reducing the heat conductivity,and improving the thermal shock resistance and slag resistance of castables.Additionally,MgO ultrafine powder and Al(OH)3 ultrafine powder increase the fluidity and the strength of castables.

CO_2 isothermal adsorption models of coal in the Haishiwan Coalfield

Since the capacity of CO2 adsorption of coal is a key factor in coal and CO2 outbursts,an experimental study was carried out on CO2 isothermal adsorption with high-pressure volumetry with dry coal samples from the No.2 coal seam in the Haishiwan Coalfield.Four different equations(Langmuir,BET,D-R and D-A) were used to fit the experimental data.We discuss adsorption mechanisms.The results show that the amount of CO2 adsorption increases rapidly under low relative pressure,i.e.,the ratio of equilibrium pressure and saturated vapor pressure,which indicates that molecular layer adsorption or micropore filling may occur in coal.No clear equilibrium state was observed on the isothermal adsorption curves under relative pressure(P /P0 ) ranging from 0 to 0.8.The fitted results show that the accuracy of the D-A equation is highest with n=1.Micropores are more developed in coal by comparing the BET equation with a pressure mercury injection method on the surface area.The D-A equation(n=1) provides the best fit.By comparing the calculated specific surface area of the BET equation and the mercury intrusion method,it is found that micropore adsorption of CO2 occupies a dominant position.

Three-dimensional characteristics of Fe-rich intermetal ics in gravity-cast Al-6Si alloys

Fe-rich intermetallics, especially β-Fe phase, usually forming in the microstructure of cast aluminum alloys, are very detrimental to mechanical properties. In the present work, the effects of Fe content on phase transformation and microstructures were analyzed using a 3D X-ray microscope. Based on the highresolution 3D X-ray computed tomography, the 3D characteristics of Fe-rich intermetallics and micropores in the gravity-cast Al-6 Si alloys with different Fe contents were investigated. In addition, the effect of intermetallics on the microporosity was discussed. The results show that with increasing the Fe content from 0.10 wt.% to 0.60 wt.%, the volume fraction of Fe-rich intermetallics and the volume of the largest size Fe-rich intermetallic increased, and the 3D morphology of intermetallics changed from fine flake to network aggregation. As the Fe contents increased, the shrinkage pores were characterized, which were rather complex due to the micropores promoted by the intermetallics interactions.

Naphthalene-modulated microporous carbon layers of LiFePO_4 improve the high-rate electrochemical performance

Carbon layers with microporous structures fine-modulated by naphthalene(NAP) were prepared to coat on LiFePO_4, aiming to enhance the Li+diffusion coefficient for Li-ion batteries. Characterized by BET, XRD, TEM, EIS, etc., it is indicated that in the presence of NAP, the carbon-coated LiFePO_4/C-NAP composites have the enlarged micropore size of 1.66 nm and the enhanced Li^+ diffusion coefficient of2.83 × 10^(-12)cm^2s^(-1), which is about five times higher than that of LiFePO4/C prepared in the absence of NAP. At a high rate of 20 C, the discharge capacity of the LiFePO_4/C-NAP is up to 120.1 mA h g^(-1) and maintains a good retention rate of 93.2% after 400 cycles. It is suggested that the NAP-modulated carbon coating is a promising route to accelerate the Li-ion diffusion rate and enhance the electrochemical performance for lithium ion batteries.

Synthesis of Highly Microporous Sulfur-Containing Activated Carbons by a Multistep Modification Process

The sulfur-containing activated carbons(SACs)were prepared by CO2 activation and sulfur impregnation.The sulfur-containing samples were then oxidized in air.The SACs were characterized by N2 adsorption,elemental analysis,thermogravimetric analysis,X-ray photoelectron spectroscopy,Raman spectroscopy,and X-ray diffraction.The CO2 activation provided precursor carbons with high porosity,which in turn were sulfurized effectively.Oxidation in air at 200℃enlarged pores and redistributed amorphous sulfur in the hierarchical pores.A typical SAC containing 17.89%sulfur exhibited a surface area of 1464 m2/g.This work may open up a valid route to prepare highly microporous SACs with high sulfur loading for applications where the presence of sulfur is beneficial.

The Role of Microstructure of Highly Purified Beta-Tricalcium Phosphate for Osteoinduction in Canine Dorsal Muscles

Porous β-tricalcium phosphate (TCP) displays osteoinductivity in certain animals in the absence of osteoinductive agents. We evaluated whether the microstructure may be an important determinant of osteoinduction, and also investigated how bone formation was promoted using β-TCP combined with bone marrow aspirates. We prepared two types of β-TCP, namely, β-TCP A, which possessed interconnected macropores and micropores, and β-TCP B, which possessed macropores but had less detectable micropores. These were implanted with or without marrow in canine muscles. Bone formation and the resorption of each β-TCP implant were evaluated histologically. Newly formed bone began to appear at day 42 in the implants of β-TCP A alone, but the implants of β-TCP B alone did not show any bone formation by day 42. Meanwhile, bone formation was already evident on day 14 by loading with bone marrow aspirates with or without micropores. By immunohistochemistry, the number of cathepsin K-positive cells (osteoclasts) increased as time passed in the implants of β-TCP A alone, while the number of the osteoclasts did not change obviously in the implants of β-TCP B alone from day 14 to 56. Reticular fibrils were evident within the β-TCP A, and were barely observed in the β-TCP B in the silver impregnation. The present result would bring about the possible role to enhance the importance of the surface microstructure for the better osteoinductivity. Our findings suggest that the combination of porous β-TCP and bone marrow facilitates bone formation.