Nano-Au-decorated hierarchical porous cobalt sulfide derived from ZIF-67 toward optimized oxygen evolution catalysis:Important roles of microstructures and electronic modulation

Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.

Research Progress of Eco-Friendly Portland Cement Porous Concrete:A Review

With the great impetus of energy conservation and emission reduction policies in various countries,the proposal of concepts such as“Sponge City”and“Eco-City”,and the emphasis on restoration and governance of ecological environment day by day,portland cement porous concrete(PCPC),as a novel building material,has attracted more and more attention from scientific researchers and engineers.PCPC possesses the peculiar pore structure,which owns numerous functions like river embankment protection,vegetation greening as well as air-cleaning,and has been of wide application in different engineering fields.This paper reviews the salient properties of PCPC,detailedly expounds the research progress of domestic and foreign literature about this subject in the past ten years(2010–2020),conducts the statistical analysis of the distribution rule of its major properties around the world,combines with the engineering application to summarize the excellent properties of PCPC,and makes a forecast of future research direction.

Hierarchically porous Co@N-doped carbon fiber assembled by MOF-derived hollow polyhedrons enables effective electronic/mass transport:An advanced 1D oxygen reduction catalyst for Zn-air battery

Developing advanced oxygen reduction reaction(ORR)electrocatalysts with rapid mass/electron transport as well as conducting relevant kinetics investigations is essential for energy technologies,but both still face ongoing challenges.Herein,a facile approach was reported for achieving the highly dispersed Co nanoparticles anchored hierarchically porous N-doped carbon fibers(Co@N-HPCFs),which were assembled by core-shell MOFs-derived hollow polyhedrons.Notably,the unique one-dimensional(1D)carbon fibers with hierarchical porosity can effectively improve the exposure of active sites and facilitate the electron transfer and mass transfer,resulting in the enhanced reaction kinetics.As a result,the ORR performance of the optimal Co@N-HPCF catalysts remarkably outperforms that of commercial Pt/C in alkaline solution,reaching a limited diffusion current density(J)of 5.85 m A cm^(-2)and a half-wave potential(E_(1/2))of 0.831 V.Particularly,the prepared Co@N-HPCF catalysts can be used as an excellent air-cathode for liquid/solid-state Zn-air batteries,exhibiting great potentiality in portable/wearable energy devices.Furthermore,the reaction kinetic during ORR process is deeply explored by finite element simulation,so as to intuitively grasp the kinetic control region,diffusion control region,and mixing control region of the ORR process,and accurately obtain the relevant kinetic parameters.This work offers an effective strategy and a reliable theoretical basis for the engineering of first-class ORR electrocatalysts with fast electronic/mass transport.

Effects of binder strength and aggregate size on the compressive strength and void ratio of porous concrete

To test the influence of binder strength, porous concretes with 4 binder strengths between 30.0-135.0 MPa and 5 void ratios between 15%-35% were tested. The results indicated that for the same aggregate, the rates of strength reduction due to the increases in void ratio were the same for binders with different strengths. To study the influence of aggregate size, 3 single size aggregates with nominal sizes of 5.0, 13.0 and 20.0 mm （Nos. 7, 6 and 5 according to JIS A 5001） were used to make porous concrete. The strengths of porous concrete are found to be dependent on aggregate size. The rate of strength reduction of porous concrete with small aggregate size is found to be higher than that with larger aggregate size. At the same void ratio, the strength of porous concrete with large aggregate is larger than that with small aggregate. The general equations for porous concrete are related to compressive strength and void ratio for different binder strengths and aggregate sizes.

Efficient catalytic conversion of carbohydrates into 5-ethoxymethylfurfural over MIL-101-based sulfated porous coordination polymers

In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.

Porous conductive interlayer for dendrite-free lithium metal battery

Lithium(Li) metal,possessing ultrahigh theoretical capacity and the lowest electrode potential,is regarded as a promising new generation anode material.However,the uncontrollable growth of Li dendrites during cycling process gives rise to problems as capacity decay and short circuit,suppressing the cycling and safety performances of Li metal battery.In this contribution,porous conductive interlayer(PCI),composed of carbon nanofibers(CNFs) and polyisophthaloyl metaphenylene diamine(PMIA),is developed to suppress Li dendrites and stabilize Li metal anode.PCI possesses the excellent conductive ability of CNFs and the preeminent mechanical properties of PMIA at the same time.When Li metal contacts with PCI during cycling process,an equipotential surface forms on their interface,which eliminates the tip effect on Li anode and homogenizes Li-ions flux in combination with the uniform porous structure of PCI.Employed PCI,the Li|Cu cell exhibits a remarkable cycling stability with a high average Coulombic efficiency of 97.5% for 100 cycles at 0.5 mA cm^(-2).And the Li|LiFePO_4 cell exhibits improved rate capability(114.7 mAh g^(-1) at 5.0 C) and enhanced cycling performance(78.9% capacity retention rate over 500 cycles at 1.0 C).This work provides a fresh and effective solving strategy for the problem of dendrites in Li metal battery.

Influence of absorbent on electromagnetic wave absorbing property of porous concrete

Influences of ferrite content and iron ore powder content on electromagnetic wave absorbing property of porous concrete are studied.The radar cross section(RSC)of samples was tested in a microwave anechoic chamber.Results show that the optimum content of ferrite is 15%,and the minimum,maximum and average reflectivity of the sample is-46.60 dB,-10.84 dB and-23.75 dB,respectively.And the sample's improved bandwidth is 8.2 GHz.The optimum content of iron ore powder is 20%,and the minimum,maximum and average reflectivity of the sample is-34.69 dB,-9.25 dB and-20.69 dB,respectively.And the sample's improved bandwidth is 6 GHz.In conclusion,appropriate ferrite and iron ore powder can improve wave absorbing property and widen wave absorption bandwidth of porous concrete.

Porous core–shell CoMn_2O_4 microspheres as anode of lithium ion battery with excellent performances and their conversion reaction mechanism investigated by XAFS

Porous core-shell CoMn204 microspheres of ca. 3-5μm in diameter were synthesized and served as an-ode of lithium ion battery. Results demonstrate that the as-synthesized CoMn204 materials exhibit excel-lent electrochemical properties. The CoMn204 anode can deliver a large capacity of 1070 mAh g-1 in thefirst discharge, a reversible capacity of 500 mAh g^-1 after 100 cycles with a coulombic efficiency of 98.5% at a charge-discharge current density of 200 mA g^-l, and a specific capacity of 385 mAh g^-1 at a muchhigher charge-discharge current density of 1600mA g^-1. Synchrotron X-ray absorption fine structure（XAFS） techniques were applied to investigate the conversion reaction mechanism of the CoMn204 anode.The X-ray absorption near edge structure （XANES） spectra revealed that, in the first discharge-charge cy-cle, Co and Mn in CoMn204 were reduced to metallic Co and Mn when the electrode was discharged to0.01 V, while they were oxidized respectively to CoO and MnO when the electrode was charged to 3.0V.Experiments of both XANE5 and extended X-ray absorption fine structure （EXAFS） revealed that neithervalence evolution nor phase transition of the porous core-shell CoMn204 microspheres could happen inthe discharge plateau from 0.8 to 0.6V, which demonstrates the formation of solid electrolyte interface（SEI） on the anode.

In-situ self-templated preparation of porous core-shell Fe_(1-x)S@N,S co-doped carbon architecture for highly efficient oxygen reduction reaction

Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial role in determining the ORR performance.In this work,we for the first time report the successful fabrication of porous core-shell Fe_(1-x)S@N,S co-doped carbon(Fe_(1-x)S@NSC-t,t represents etching time)by a novel in-situ self-template induced strategy using Fe3O4 nanospheres and pyrrole as sacrificial self-template.The post-polymerization of pyrrole can be accomplished by the Fe^(3+)released through the etching of Fe_(3)O_(4) by HCl acid.Thus,the etching time has a significant effect on the morphology,structure,composition a nd ORR performance of Fe_(1-x)S@NSC-t.Based on the cha racterizations,we find Fe_(1-x)S@NSC-24 can realize effective and balanced combination of Fe_(1-x)S and NSC,possessing porous core-shell architecture,optimized structure defect,specific surface area and doped heteroatoms configurations(especially for pyridinic N,graphitic N and Fe-N structure).These features thus lead to outstanding catalytic activity and cycling stability towards ORR.Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.

Poroelastic finite-difference modeling for ultrasonic waves in digital porous cores

Scattering attenuation in short wavelengths has long been interesting to geophysicists. Ultrasonic coda waves, observed as the tail portion of ultrasonic wavetrains in laboratory ultrasonic measurements, are important for such studies where ultrasonic waves interact with smallscale random heterogeneities on a scale of micrometers, but often ignored as noises because of the contamination of boundary reflections from the side ends of a sample core. Numerical simulations with accurate absorbing boundary can provide insight into the effect of boundary reflections on coda waves in laboratory experiments. The simulation of wave propagation in digital and heterogeneous porous cores really challenges numerical techniques by digital image of poroelastic properties, numerical dispersion at high frequency and strong heterogeneity, and accurate absorbing boundary schemes at grazing incidence. To overcome these difficulties, we present a staggered-grid high-order finite-difference （FD） method of Biot＇s poroelastic equations, with an arbitrary even-order （2L） accuracy to simulate ultrasonic wave propagation in digital porous cores with strong heterogeneity. An unsplit convolutional perfectly matched layer （CPML） absorbing boundary, which improves conventional PML methods at grazing incidence with less memory and better computational efficiency, is employed in the simulation to investigate the influence of boundary reflections on ultra- sonic coda waves. Numerical experiments with saturated poroelastic media demonstrate that the 2L FD scheme with the CPML for ultrasonic wave propagation significantly improves stability conditions at strong heterogeneity and absorbing performance at grazing incidence. The boundary reflections from the artificial boundary surrounding the digital core decay fast with the increase of CPML thick- nesses, almost disappearing at the CPML thickness of 15 grids. Comparisons of the resulting ultrasonic coda Qsc values between the numerical and experimental ultrasonic S waveforms for a cylindrical rock sample demonstrate that the boundary reflection may contribute around one-third of the ultrasonic coda attenuation observed in laboratory experiments.

The Aggregate Gradation for the Porous Concrete Pervious Road Base Material

The effects of the proportion of fine aggregate, the maximum size of the aggregate and the proportion of the 9.5 mm to 4.75 mm particle in the coarse aggregate on the properties of the porous concrete are investigated. Results indicate that the porous concrete with a cement dosage only 150 kg/m^3 has high strength and satisfying permeability when the aggregate has a passing percentage of 4.75 mm around 10% to 15%, with the increase of the maximum size of the aggregate, the strength of the porous concrete decreases and the permeability increases. When the proportion of the 9.5 mm to 4.75 mm particle in the coarse aggregate is about 20%, there are no interference among the particles by Weymouth theory, the strength of the pervious porous concrete reaches the peak value. The optimum continues gradation limit of the aggregate for porous concrete pervious road base material is recommended according to the theoretical calculation and experimental results.

Effect of strain rate on the compressive deformation behaviors of lotus-type porous copper

Lotus-type porous copper was fabricated by unidirectional solidification, and compressive experiments were subsequently conducted in the strain rate range of 10-3-2400 s-1 with the compressive direction parallel to the pores. A GLEEBLE-1500 thermal-mechanical simulation system and a split Hopkinson pressure bar （SHPB） were used to investigate the effect of strain rate on the compressive deforma-tion behaviors of lotus-type porous copper. The influence mechanism of strain rate was also analyzed by the strain-controlling method and by high-speed photography. The results indicated that the stress-strain curves of lotus-typed porous copper consist of a linear elastic stage, a plateau stage, and a densification stage at various strain rates. At low strain rate （〈1.0 s^-1）, the strain rate had little influence on the stress-strain curves; but when the strain rate exceeded 1.0 s^-1, it was observed to strongly affect the plateau stage, showing obvious strain-rate-hardening characteristics. Strain rate also influenced the densification initial strain. The densification initial strain at high strain rate was less than that at low strain rate. No visible inhomogeneous deformation caused by shockwaves was observed in lotus-type porous copper during high-strain-rate deformation. However, at high strain rate, the bending deformation characteristics of the pore walls obviously differed from those at low strain rate, which was the main mechanism by which the plateau stress exhibited strain-rate sensitivity when the strain rate exceeded a certain value and exhibited less densification initial strain at high strain rate.

Preparation and characterization of the n-HA/PVA/CS porous composite hydrogel☆

In this paper,a new method combines chemical/physical crosslinking,and emulsification-foaming porogenic was adopted to prepare n-hydroxyapatite(n-HA)/polyvinyl alcohol(PVA)/chitosan(CS)porous composite hydrogel using artificial cornea scaffold materials.The fabricate conditions,including the type and amount of emulsification-foaming porogen,mixing time and speed etc.were researched.The results showed the optimal condition that the alkylphenol polyoxyethylene ether(OP)acted as emulsification-foaming porogen,with the ratio of WPVA/WOP as 3.75,and mixing 15 min with a stirring speed of 800 r·min-1.Additionally,the fabricated composite hydrogel scaffold materials possessed interconnected internal holes,a moisture content of above 65%,and tensile strength of above 6 MPa.In vitro cytotoxicity and acute systemic toxicity assay confirmed that the scaffolds did not show any cytotoxicity.The as-prepared hydrogel could be a promising candidate for artificial cornea scaffold material.

Effects of environmental factors on corrosion behaviors of metal-fiber porous components in a simulated direct methanol fuel cell environment

Abstract： To enable the use of metallic components in direct methanol fuel cells （DMFCs）, issues related to corrosion resistance must be considered because of an acid environment induced by the solid electrolyte. In this study, we report the electrochemical behaviors of metal-fiber-based porous sintered components in a simulated corrosive environment of DMFCs. Three materials were evaluated： pure copper, AISI304, and AISI316L. The environmental factors and related mechanisms affecting the corrosion behaviors were analyzed. The results demonstrated that AISI316L exhibits the best performance. A higher SO4^2- concentration increases the risk of material corrosion, whereas an increase in methanol concentration inhibits corrosion. The morphological features of the corroded samples were also characterized in this study.

PVP-assisted synthesis of porous CoO prisms with enhanced electrocatalytic oxygen evolution properties

Hollow metal oxide materials with nanometer-to-micrometer dimensions have attracted tremendous attention because of their potential applications in energy conversion and storage systems. Numerous efforts have been focused on developing versatile methods for the rational synthesis of various hollow structures to act as efficient water oxidation catalysts. In this work, a unique porous and hollow CoO tetragonal prism-like structure has been successfully synthesized via a facile and efficient co-precipitation method with polyvinylpyrrolidone（PVP K30） followed by a heating treatment of the resulted precipitates.The as-prepared porous and hollow CoO microprisms displayed a high activity and stability for water oxidation in 1.0 M KOH solution. To reach a current density of 10 m A/cm, a low overpotential of 280 m V is required. The remarkable activity can be attributed to the synergistic effect between two different but well-distributed CoO crystalline phases, uniform particle size, ameliorative crystallinity, high surface area and the low mass transfer resistance benefitted from the unique porous structure.

Synthesis and Structure of a New Gadolinium Porous Complex Assembled from 2,3-Pyrazinedicarboxylic Acid and Ammonia

A new gadolinium porous complex,(NH4)2[Gd2(pzdc)4(H2O)2],was synthesized through hydrothermal reaction of 2,3-pyrazinedicarboxylic acid and Gd(NO3)3·6 H2O with the pH value adjusted by ammonia.It was characterized by elemental analysis,FT-IR,TGA and further by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/c with a=14.249(7),b=15.889(8),c=12.846(7)A,β=95.724(10)°,V=2894(3)A^3,Z=4,Dc=2.385 g/cm^3,μ(Mo Ka)=4.65 mm^–1 and F(000)=1976.1976 reflections were measured and 6446 independent reflections(Rint=0.0985)were used in further refinement.The complex exhibits a 3D framework constructed from the[Gd2(pzdc)4(H2O)2]2-building blocks.It is scarce that the NH4+cations are located in the channels and balance the charge of anion framework.Furthermore,the ion exchange property of this complex has also been studied.The NH4+cations can be replaced by Na+cations,which is an uncommon phenomenon for gadolinium-containing porous complex.

Pore structure analysis of directionally solidified porous copper

Directionally solidified porous copper is considered as a potential candidate in the field of microchannel heat sinks.By the Bridgman-type directional solidification method,a porous copper ingot was fabricated.Evolution of the porosity,pore number density,average pore diameter and average interpore spacing at different ingot heights was investigated.The results show that with the increase of ingot height,the porosity firstly increases and then basically remains unchanged from the ignot height of 65 mm;the pore number density rapidly decreases at first,and the decreasing speed becomes slower when the ignot height higher than 85 mm;the average pore diameter increases and then remains unchanged from the ingot height of 85 mm;the average interpore spacing increases,and the increasing speed of average interpore spacing becomes slower with the increase of height to higher than 85 mm.In order to study the evolution of diameter and spatial distribution of pores,the distribution ranges of pore diameter,nearest-neighbor distance and radial cumulative pore number were analyzed.As the ingot height increases,the distribution ranges of pore diameter and nearest-neighbor distance firstly increase and then tend to be stable.There are no pore clusters and for long distance,the spatial distribution of pores is uniform at different ingot heights.Pore structure and 3D pore morphology of porous copper were observed with the help of light illumination and X-ray tomography.Pore nucleation,pore interruption,pore coalescence,diameter change of pores and lateral displacement of pores were found to exist in the pore structure.

Design and Preparation of Bone Tissue Engineering Scaffolds with Porous Controllable Structure

A novel method of designing and preparing bone tissue engineering scaffolds with controllable porous structure of both macro channels and micro pores was proposed. The CAD software UG NX3.0 was used to design the macro channels＇ shape, size and distribution. By integrating rapid prototyping and traditional porogen technique, the macro channels and micro pores were formed respectively. The size, shape and quantity of micro pores were controlled by porogen particulates. The sintered β-TCP porous scaffolds possessed connective macro channels of approximately 500 μm and micro pores of 200-400 μm. The porosity and connectivity of micro pores became higher with the increase of porogen ratio, while the mechanical properties weakened. The average porosity and compressive strength offl-TCP scaffolds prepared with porogen ratio of 60wt% were 78.12% and 0.2983 MPa, respectively. The cells＇ adhesion ratio of scaffolds was 67.43%. The ALP activity, OCN content and cells micro morphology indicated that cells grew and proliferated well on the scaffolds.

Research in Moisture Transport through One and Two-layered Porous Composites

Research into the moisture transport processes in porous materials is primarily important for theoretical modelling and industrial applications in the design of energy saving buildings and living environments, etc. Based on experimental investigation, we propose new models which describe one-dimensional transport through one-layered uniform materials and dissimilar two-layered composites. Diffusivity as a function of moisture content is obtained through a Boltzman transformation, master curves, and combined numerical and regression techniques. Transport processes in one and two-layered composites are simulated on the basis of extended unsaturated Darcy’s Law using the finite element method (FEM). Simulation results show significantly different transport patterns of moisture profile when moisture migrates in different directions, and high agreement with experimental moisture profiles. Keywords Porous materials - moisture transport - two-layered composites - modelling and simulation Qingguo Wang graduated from Hebei Normal University, China, in 1985. He received the M.Sc. degree from Beijing Petroleum University in 1988 and the Ph.D. degree from the University of Luton, UK, in 2005. He is currently a Research Associate in the Department of Electrical Engineering and Electronics at the University of Liverpool, UK and an Associate Professor of Shijiazhuang Mechanical Engineering College, China. His research interests include measurement and control, mass and heat transportation, EMC, etc.Kemal Ahmet graduated in physics from the University of Leeds. Following the completion of his masters degree, he completed his Ph.D. at the University of London in the area of nuclear instrumentation in 1992. Until recently, he was a Principal Lecturer at the University of Luton, leading a research group in moisture instrumentation, measurement and monitoring. In 2004 he joined Medtronic, world leader in medical technology, and is currently working in the Neurologic Technologies division as a specialist in powered surgical instrumentation.Young Yue is a Principal Lecturer at the University of Luton, UK. He holds a B.Sc. in mechanical engineering from the Northeastern University, China, and a Ph.D. from Heriot-Watt University, UK. He is a chartered engineer and a member of the Institution of Mechanical Engineers, UK. Dr. Yue has been working in academia for 15 years following his 8 years of industrial experience. His main research interests are CAD/CAM, geometric modelling, virtual reality, and pattern recognition. He has over 70 publications in refereed books, journals and conferences.