Biogenic hierarchical porous rice husk SiO2 samples were prepared from pre-treating rice husk （RH） at low temperatures following TiO2 sol impregnation and pyrolysis process.The samples were characterized by scanning...Biogenic hierarchical porous rice husk SiO2 samples were prepared from pre-treating rice husk （RH） at low temperatures following TiO2 sol impregnation and pyrolysis process.The samples were characterized by scanning electron microscopy,X-ray diffraction and energy dispersive spectrometer.Biogenic hierarchical porous structure of untreated RH SiO2 starts to crack and break down from 800 ℃,whereas TiO2 grain film is formed on the pore wall and surface of RH SiO2 after sol impregnation and heat treatment,which enhances the skeleton strength ; the biogenic hierarchical porous structure of the rice husk still maintains after firing at 1 400 ℃.展开更多
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...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.展开更多
Transition-metal nitrides exhibit wide potential windows and good electrochemical performance, but usually experience imbalanced practical applications in the energy storage field due to aggregation, poor circulation ...Transition-metal nitrides exhibit wide potential windows and good electrochemical performance, but usually experience imbalanced practical applications in the energy storage field due to aggregation, poor circulation stability, and complicated syntheses. In this study, a novel and simple multiphase polymeric strategy was developed to fabricate hybrid vanadium nitride/carbon(VN/C) membranes for supercapacitor negative electrodes, in which VN nanoparticles were uniformly distributed in the hierarchical porous carbon 3D networks. The supercapacitor negative electrode based on VN/C membranes exhibited a high specific capacitance of 392.0 F g^(-1) at 0.5 A g^(-1) and an excellent rate capability with capacitance retention of 50.5% at 30 A g^(-1). For the asymmetric device fabricated using Ni(OH)_2//VN/C membranes, a high energy density of 43.0 Wh kg^(-1) at a power density of800 W kg^(-1) was observed. Moreover, the device also showed good cycling stability of 82.9% at a current density of 1.0 A g^(-1) after 8000 cycles. This work may throw a light on simply the fabrication of other high-performance transition-metal nitridebased supercapacitor or other energy storage devices.展开更多
As an efficient natural selection nutrient transport system,biomimetic leaf hierarchical porous structure has unique advantages in material transportation and energy transfer.Biomimetic leaf hierarchical porous struct...As an efficient natural selection nutrient transport system,biomimetic leaf hierarchical porous structure has unique advantages in material transportation and energy transfer.Biomimetic leaf hierarchical porous structure has been widely used in solar thermochemical reactions,photocatalysis,and energy storage.To improve the thermal efficiency and reduce the power consumption,the authors introduce the idea of bionic leaf hierarchical porous structure packed-bed latent heat thermal energy storage(LHTES)system.Under the same porosity,the diameter of the PCM capsules is designed to change along the flow direction to optimize the thermal performance.The effects of velocity on temperature distribution,pressure drop,liquid fraction,and thermal storage capacity of the conventional uniform model and bionic leaf hierarchical porous model are analyzed.The results show that the bionic leaf hierarchical porous structure can thin the thickness of the thermocline,reduce the pressure drop,increase the heat transfer area,and improve the thermal response of the packed-bed compared with the conventional uniform model.The maximum increases of liquid fraction and completion rate are 36.6%and 20.3%with pressure drop reduction of 25 Pa,respectively.The maximum decrease of the above-melting point(MP)thermocline is 51.7%as well.These results provide suggestions to optimize the packed-bed LHTES system and improve its thermal performance under practical conditions.展开更多
Stretchable color-changing fibers are urgently demanded for smart textiles/clothing due to their perfect implantability,permeability of vapor and heat,and flexibility/stretchability.Herein,stretchable electrothermochr...Stretchable color-changing fibers are urgently demanded for smart textiles/clothing due to their perfect implantability,permeability of vapor and heat,and flexibility/stretchability.Herein,stretchable electrothermochromic fibers were fabricated with unconventional stretchable conductive fibers as core layers and thermochromic coatings as shell layers.In the stretchable conductive fibers,hierarchical porous structures with percolative one-dimensional(1 D)conductive networks were constructed through phase inversion of carbon nanotube/polyurethane(CNT/PU)solutions.With the deposition of silver nanoparticles(AgN Ps)on the surface of micro-pores,electrically conductive dual-pathways consisting of0 D AgN Ps and 1 D CNTs were formed to significantly enhance the electric conductivity and thus improve the electrothermal performance of the fibers.More importantly,because of the connective CNTs and AgN Ps,such dual-pathways ensured the electron transport under the stretching state,preventing the sharp decay of conductivity and electrothermal performance.Through the continuous wet-spinning method,the stretchable conductive fibers can be easily obtained with the length up to several meters.At last,stretchable electrothermochromic fibers were prepared with two color-changing modes and implanted into textile perfectly,advancing their applications in wearable display and military adaptive camouflage of smart clothing.展开更多
A series of asymmetric cordierite ceramics with hierarchical porous structure were prepared and characterized.The macroporous support was obtained from natural raw materials (bauxite,silica sand,kaolinite,talc,and alu...A series of asymmetric cordierite ceramics with hierarchical porous structure were prepared and characterized.The macroporous support was obtained from natural raw materials (bauxite,silica sand,kaolinite,talc,and alumina) via ceramic technology.The prepared ceramic discs were characterized by a narrow pore size distribution.The average pore size was about 9.5 μm,and the open porosity was estimated to be 30％.Coating the discs with micro/mesoporous cordierite layer was performed using the sol-gel approach.Three-component sols were obtained from organic or inorganic precursors.Corresponding gels were calcined at 1200 ℃ to form the cordierite structure.The nature of precursor was found to affect the pore volume distribution.Narrow pore volume distribution was observed when organic precursors were used.Another key factor to control the parameters of final material was the drying condition.Supercritical drying of the gels has allowed us to increase the surface area in two orders of magnitude comparing with conventional drying procedure.展开更多
In the present study,porous bulk palladium samples were prepared by sodium chloride salt powder spacer incorporation and removal combined with dealloying.The obtained porous Pd bulks were characterized by X‐ray diffr...In the present study,porous bulk palladium samples were prepared by sodium chloride salt powder spacer incorporation and removal combined with dealloying.The obtained porous Pd bulks were characterized by X‐ray diffraction,field‐emission scanning electron microscopy and N2adsorption isotherm measurements.The prepared porous Pd bulk samples showed a hierarchical pore structure,a high porosity of^88%,a high surface area of^54m2/g,and a compression strength of^0.5MPa.Electrochemical measurements were performed to evaluate the electrocatalytic properties of the porous Pd bulk samples,revealing their effectiveness for ethanol oxidation.展开更多
With vigorous developments in nanotechnology,the elaborate regulation of microstructure shows attractive potential in the design of electromagnetic wave absorbers.Herein,a hierarchical porous structure and composite h...With vigorous developments in nanotechnology,the elaborate regulation of microstructure shows attractive potential in the design of electromagnetic wave absorbers.Herein,a hierarchical porous structure and composite heterogeneous interface are constructed successfully to optimize the electromagnetic loss capacity.The macro–micro-synergistic graphene aerogel formed by the ice template‑assisted 3D printing strategy is cut by silicon carbide nanowires(SiC_(nws))grown in situ,while boron nitride(BN)interfacial structure is introduced on graphene nanoplates.The unique composite structure forces multiple scattering of incident EMWs,ensuring the combined effects of interfacial polarization,conduction networks,and magnetic-dielectric synergy.Therefore,the as-prepared composites present a minimum reflection loss value of−37.8 dB and a wide effective absorption bandwidth(EAB)of 9.2 GHz(from 8.8 to 18.0 GHz)at 2.5 mm.Besides,relying on the intrinsic high-temperature resistance of SiC_(nws) and BN,the EAB also remains above 5.0 GHz after annealing in air environment at 600℃ for 10 h.展开更多
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 ong...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.展开更多
Stable non-noble metal bifunctional electrocatalysts are one of the challenges to the fluctuating overall water splitting driven by re-newable energy.Herein,a novel self-supporting hierarchically porous Ni_(x)Fe-S/NiF...Stable non-noble metal bifunctional electrocatalysts are one of the challenges to the fluctuating overall water splitting driven by re-newable energy.Herein,a novel self-supporting hierarchically porous Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure as bifunctional electrocatalyst was constructed based on porous Ni-Fe electrodeposition on three-dimensional(3D)carbon fiber cloth,in situ oxidation,and chemical sulfuration.Results showed that the Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure with a large specific surface area exhibits good bifunctional activity and stability for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)because of the abundance of active sites,synergistic effect of the heterostructure,superhydrophilic surface,and stable,self-supporting structure.The results further confirmed that the Ni_(x)Fe-S phase in the heterostructure is transformed into metal oxides/hydroxides and Ni_(3)S_(2) during OER.Compared with the commercial 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer,the self-supporting Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) electrolyzer exhibits better stability and lower cell voltage in the fluctu-ating current density range of 10-500 mA/cm^(2).Particularly,the cell voltage of Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) is only approximately 3.91 V at an industrial current density of 500 mA/cm^(2),which is lower than that of the 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer(i.e.,approximately 4.79 V).This work provides a promising strategy to develop excellent bifunctional electrocatalysts for fluctuating overall water splitting.展开更多
Supercapacitors with unique performance have been widely utilized in many fields. Herein, we report a nitrogen and sulfur co-doped graphene aerogel(N/S-GA-2) prepared using a low toxic precursor for high-performance s...Supercapacitors with unique performance have been widely utilized in many fields. Herein, we report a nitrogen and sulfur co-doped graphene aerogel(N/S-GA-2) prepared using a low toxic precursor for high-performance supercapacitors. The as-obtained material possesses a hierarchically porous structure and a large number of electrochemical active sites. At a current density of 1 Ag^-1, the specific capacitance of the N/S-GA-2 for supercapacitors with the ionic liquid as the electrolyte is 169.4 Fg^-1, and the corresponding energy density is 84.5 Wh kg^-1.At a power density of 8.9 k W kg^-1, the energy density can reach up to 75.7 Wh kg^-1, showing that the N/S-GA-2 has an excellent electrochemical performance. Consequently, the N/S-GA-2 can be used as a promising candidate of electrode materials for supercapacitors with high power density and high energy density.展开更多
Quasi-one-dimensional NiO with a hierarchically porous structure was synthesized through a facile coordination−precipitation method with the coupling effect of ammonia and a post-calcination treatment.The electrocatal...Quasi-one-dimensional NiO with a hierarchically porous structure was synthesized through a facile coordination−precipitation method with the coupling effect of ammonia and a post-calcination treatment.The electrocatalytic properties of NiO fibers for the oxidation of ethanol were compared with those of NiO spheres.The results show that the fibrous NiO possesses a larger specific surface area of 140.153 m2/g and a lower electrical resistivity of 4.5×105Ω·m,leading to an impressively superior electrocatalytic activity to spherical NiO for ethanol oxidation in alkaline media.The current decay on fibrous NiO at 0.6 V in 100−900 s was 0.00003%,which is much lower than that of spherical NiO,indicating its better stability.The unique morphology and hierarchically porous structure give the fibrous NiO great potential to be used as an anodic electrocatalyst for direct ethanol fuel cells.展开更多
Inspired by the nature,lotus leaf-derived gradient hierarchical porous C/MoS2 morphology genetic composites(GHPCM)were successfully fabricated through an in situ strategy.The biological microstructure of lotus leaf wa...Inspired by the nature,lotus leaf-derived gradient hierarchical porous C/MoS2 morphology genetic composites(GHPCM)were successfully fabricated through an in situ strategy.The biological microstructure of lotus leaf was well preserved after treatment.Different pores with gradient pore sizes ranging from 300 to 5μm were hierarchically distributed in the composites.In addition,the surface states of lotus leaf resulted in the Janus-like morphologies of MoS2.The GHPCM exhibit excellent electromagnetic wave absorption performance,with the minimum reflection loss of−50.1 dB at a thickness of 2.4 mm and the maximum effective bandwidth of 6.0 GHz at a thickness of 2.2 mm.The outstanding performance could be attributed to the synergy of conductive loss,polarization loss,and impedance matching.In particularly,we provided a brand-new dielectric sum-quotient model to analyze the electromagnetic performance of the non-magnetic material system.It suggests that the specific sum and quotient of permittivity are the key to keep reflection loss below−10 dB within a certain frequency range.Furthermore,based on the concept of material genetic engineering,the dielectric constant could be taken into account to seek for suitable materials with designable electromagnetic absorption performance.展开更多
With the rapid emergence of wearable devices, flexible lithium-ion batteries(LIBs) are much more needed than ever. Free-standing graphene-based composite paper electrodes with various active materials have appealed wi...With the rapid emergence of wearable devices, flexible lithium-ion batteries(LIBs) are much more needed than ever. Free-standing graphene-based composite paper electrodes with various active materials have appealed wide applications in flexible LIBs. However, due to the prone-to-restacking feature of graphene layers, a long cycle life at high current densities is rather difficult to be achieved. Herein, a unique threedimensional(3D) hierarchically porous NiO micro-flowers/graphene paper(fNiO/GP) electrode is successfully fabricated. The resulting fNiO/GP electrode shows superior long-term cycling stability at high rates(e.g., storage capacity of 359 mAh/g after 600 cycles at a high current density of 1 A/g). The facile 3D porous structure combines both the advantages of the graphene that is highly conductive and flexible to ensure rapid electrons/ions transfer and buffer the volume expansion of NiO during charge/discharge,and of the micro-sized NiO flowers that induces hierarchical between-layer pores ranging from nanomicro meters to promote the penetration of the electrolyte and prevent the re-stacking of graphene layers. Such structural design will inspire future manufacture of a wide range of active materials/graphene composite electrodes for high performance flexible LIBs.展开更多
Hierarchical porous TiOnanopills were synthesized using a titanium metal-organic framework MIL-125（Ti） as precursor. The as-synthesized TiOnanopills owned a large specific surface area of 102 m/g and unique porous s...Hierarchical porous TiOnanopills were synthesized using a titanium metal-organic framework MIL-125（Ti） as precursor. The as-synthesized TiOnanopills owned a large specific surface area of 102 m/g and unique porous structure. Furthermore, the obtained TiOnanopills were applied as anode materials for Na-ion batteries for the first time. The as-synthesized TiOnanopills achieved a high discharge capacity of 196.4 m Ah/g at a current density of 0.1 A/g. A discharge capacity of 115.9 m Ah/g was obtained at a high current density of 0.5 A/g and the capacity retention was remained as high as 90% even after 3000 cycles. The excellent electrochemical performance can be attributed to its unique hierarchical porous feature.展开更多
Porous nitrogen-doped carbon is an especially promising material energy storage due to its excellentconductivity, stable physicochemical properties, easy processability, controllable porosity and low price.Herein, we ...Porous nitrogen-doped carbon is an especially promising material energy storage due to its excellentconductivity, stable physicochemical properties, easy processability, controllable porosity and low price.Herein, we reported a novel well-designed hierarchically porous nitrogen-doped carbon （HPNC） via acombination of salt template （ZnC12） and hard template （SiO2） as sulfur host for lithium-sulfur batter-ies. The low-melting ZnC12 is boiled off and leaves behind micropores and small size mesopores duringpyrolysis process, while the silica spheres are removed by acid leaching to generate interconnected 3Dnetwork of macropores. The HPNC-S electrode exhibits an initial specific capacity of 1355 mAh g^-l at 0.IC （IC= 1675 mAh g^-1 ）, a high-rate capability of 623 mAh g-l at 2 C, and a small decay of 0.13% per cycleover 300 cycles at 0.2 C. This excellent rate capability and remarkable long-term cyclability of the HPNC-Selectrode are attributed to its hierarchical porous structures for confining the soluble lithium polysulfideas well as the nitrogen doping for high absorbability of lithium polysulfide.展开更多
Lithium metal is one of the most promising anode materials for next-generation electrochemical energy storage due to low electrochemical potential and high specific capacity.However,large volume change and uncontrolla...Lithium metal is one of the most promising anode materials for next-generation electrochemical energy storage due to low electrochemical potential and high specific capacity.However,large volume change and uncontrollable formation of lithium dendrite during cycling severely hinder the practical application of rechargeable Li metal batteries.Herein,we report a hierarchically porous Cu covered with lithiophilic CuxO(HPCu-CuxO) via femtosecond laser strategy in about 2 min as current collector for highperformance Li metal batteries.With precisely tunable pore volume and depth as well as lithiophilic CuxO interphase,the HPCu-CuxO not only guides homogeneous Li nucleation,resulting in a smooth and dendrite-free lithium surface,but also provides space to alleviate the volume expansion of Li metal anode,achieving excellent structure stability.Consequently,highly stable Coulombic efficiency and ultralow overpotential of 15 mV even up to 1000 h were achieved at the current density of 1 mA cm^(-2).Moreover,the resultant Li@HPCu-CuxO//LiFePO_(4) full battery delivered outstanding cycle stability and rate capability.These results offer a pathway toward high-energy-density and safe rechargeable Li metal batteries.展开更多
Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous st...Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.展开更多
Potassium-ion hybrid capacitors(KIHCs) have attracted increasing research interest because of the virtues of potassium-ion batteries and supercapacitors.The development of KIHCs is subject to the investigation of appl...Potassium-ion hybrid capacitors(KIHCs) have attracted increasing research interest because of the virtues of potassium-ion batteries and supercapacitors.The development of KIHCs is subject to the investigation of applicable K+storage materials which are able to accommodate the relatively large size and high activity of potassium.Here,we report a cocoon silk chemistry strategy to synthesize a hierarchically porous nitrogen-doped carbon(SHPNC).The as-prepared SHPNC with high surface area and rich N-doping not only offers highly efficient channels for the fast transport of electrons and K ions during cycling,but also provides sufficient void space to relieve volume expansion of electrode and improves its stability.Therefore,KIHCs with SHPNC anode and activated carbon cathode afford high energy of 135 Wh kg-1(calculated based on the total mass of anode and cathode),long lifespan,and ultrafast charge/slow discharge performance.This study defines that the KIHCs show great application prospect in the field of high-performance energy storage devices.展开更多
Nitrogen-rich porous carbonaceous materials have shown great potential in energy storage and conversion applications due to their facile fabrication,high electronic conductivity,and improved hydrophilic property.Herei...Nitrogen-rich porous carbonaceous materials have shown great potential in energy storage and conversion applications due to their facile fabrication,high electronic conductivity,and improved hydrophilic property.Herein,three-dimensional porous N-rich carbon foams are fabricated through a one-step carbonization-activation method of the commercial melamine foam,and displaying hierarchically porous structure(macro-,meso-,and micro-pores),large surface area(1686.5 m2 g^-1),high N-containing level(3.3 at%),and excellent compressibility.The as-prepared carbon foams as electrodes for quasi-solid-state supercapacitors exhibit enhanced energy storage ability with 210 F g^-1 and 2.48c at 0.1 A g^-1,and150 F g^-1 and 1.77 F cm^-2 at 1 A g^-1,respectively.Moreover,as an electrode for lithium-based dual-ion capacitor,this distinctive porous carbon also delivers remarkable specific capacitance with 143.6 F g^-1 at0.1 A g^-1 and 116.2 F g^-1 at 1 A g^-1.The simple preparation method and the fascinating electrochemical performance endow the N-rich porous carbon foams great prospects as high-performance electrodes for electrochemical energy storage.展开更多
基金the financial support from the New Century Excellent Talents in University ( NCET - 10 - 0137 )Department of Science and Technology of China ( 2012CB722702)
文摘Biogenic hierarchical porous rice husk SiO2 samples were prepared from pre-treating rice husk （RH） at low temperatures following TiO2 sol impregnation and pyrolysis process.The samples were characterized by scanning electron microscopy,X-ray diffraction and energy dispersive spectrometer.Biogenic hierarchical porous structure of untreated RH SiO2 starts to crack and break down from 800 ℃,whereas TiO2 grain film is formed on the pore wall and surface of RH SiO2 after sol impregnation and heat treatment,which enhances the skeleton strength ; the biogenic hierarchical porous structure of the rice husk still maintains after firing at 1 400 ℃.
基金National Natural Science Foundation of China,Grant/Award Numbers:52102260,52171211,51972220,61903235,U22A20145Shandong Provincial Natural Science Foundation,Grant/Award Numbers:ZR2020QB069,ZR2022ME051+4 种基金National Key Research and Development Program of China,Grant/Award Number:2022YFB4002004Scientific and Technological Innovation Ability Improvement Project of Minor Enterprises in Shandong Province,Grant/Award Number:2022TSGC1021Announce the List and Take Charge Project in Jinan,Grant/Award Number:202214012Major innovation project for integrating science,education and industry of Qilu University of Technology (Shandong Academy of Sciences),Grant/Award Numbers:2022JBZ01-07,2022PY044China Postdoctoral Science Foundation,Grant/Award Number:2022M711545。
文摘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.
基金supported by the National Natural Science Foundation of China (51203071,51363014,51463012,and 51763014)China Postdoctoral Science Foundation (2014M552509 and 2015T81064)+2 种基金Natural Science Funds of the Gansu Province (1506RJZA098)the Program for Hongliu Distinguished Young Scholars in Lanzhou University of Technology (J201402)Joint fund between Shenyang National Laboratory for Materials Science and State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals (18LHPY002)
文摘Transition-metal nitrides exhibit wide potential windows and good electrochemical performance, but usually experience imbalanced practical applications in the energy storage field due to aggregation, poor circulation stability, and complicated syntheses. In this study, a novel and simple multiphase polymeric strategy was developed to fabricate hybrid vanadium nitride/carbon(VN/C) membranes for supercapacitor negative electrodes, in which VN nanoparticles were uniformly distributed in the hierarchical porous carbon 3D networks. The supercapacitor negative electrode based on VN/C membranes exhibited a high specific capacitance of 392.0 F g^(-1) at 0.5 A g^(-1) and an excellent rate capability with capacitance retention of 50.5% at 30 A g^(-1). For the asymmetric device fabricated using Ni(OH)_2//VN/C membranes, a high energy density of 43.0 Wh kg^(-1) at a power density of800 W kg^(-1) was observed. Moreover, the device also showed good cycling stability of 82.9% at a current density of 1.0 A g^(-1) after 8000 cycles. This work may throw a light on simply the fabrication of other high-performance transition-metal nitridebased supercapacitor or other energy storage devices.
基金This work was supported by the National Key R&D Program of China(No.2018YFA0702300)the National Natural Science Foundation of China(Grant No.52076064)the Taishan Scholars of Shandong Province(tsqn201812105).
文摘As an efficient natural selection nutrient transport system,biomimetic leaf hierarchical porous structure has unique advantages in material transportation and energy transfer.Biomimetic leaf hierarchical porous structure has been widely used in solar thermochemical reactions,photocatalysis,and energy storage.To improve the thermal efficiency and reduce the power consumption,the authors introduce the idea of bionic leaf hierarchical porous structure packed-bed latent heat thermal energy storage(LHTES)system.Under the same porosity,the diameter of the PCM capsules is designed to change along the flow direction to optimize the thermal performance.The effects of velocity on temperature distribution,pressure drop,liquid fraction,and thermal storage capacity of the conventional uniform model and bionic leaf hierarchical porous model are analyzed.The results show that the bionic leaf hierarchical porous structure can thin the thickness of the thermocline,reduce the pressure drop,increase the heat transfer area,and improve the thermal response of the packed-bed compared with the conventional uniform model.The maximum increases of liquid fraction and completion rate are 36.6%and 20.3%with pressure drop reduction of 25 Pa,respectively.The maximum decrease of the above-melting point(MP)thermocline is 51.7%as well.These results provide suggestions to optimize the packed-bed LHTES system and improve its thermal performance under practical conditions.
基金supported by the National Natural Science Foundation of China(51672043)Donghua University Distinguished Young Professor Program(LZB2019002)+1 种基金Young Elite Scientists Sponsorship Program by China Association for Science and Technology(2017QNRC001)the Fundamental Research Funds for the Central Universities(CUSF-DH-D-2018006)。
文摘Stretchable color-changing fibers are urgently demanded for smart textiles/clothing due to their perfect implantability,permeability of vapor and heat,and flexibility/stretchability.Herein,stretchable electrothermochromic fibers were fabricated with unconventional stretchable conductive fibers as core layers and thermochromic coatings as shell layers.In the stretchable conductive fibers,hierarchical porous structures with percolative one-dimensional(1 D)conductive networks were constructed through phase inversion of carbon nanotube/polyurethane(CNT/PU)solutions.With the deposition of silver nanoparticles(AgN Ps)on the surface of micro-pores,electrically conductive dual-pathways consisting of0 D AgN Ps and 1 D CNTs were formed to significantly enhance the electric conductivity and thus improve the electrothermal performance of the fibers.More importantly,because of the connective CNTs and AgN Ps,such dual-pathways ensured the electron transport under the stretching state,preventing the sharp decay of conductivity and electrothermal performance.Through the continuous wet-spinning method,the stretchable conductive fibers can be easily obtained with the length up to several meters.At last,stretchable electrothermochromic fibers were prepared with two color-changing modes and implanted into textile perfectly,advancing their applications in wearable display and military adaptive camouflage of smart clothing.
文摘A series of asymmetric cordierite ceramics with hierarchical porous structure were prepared and characterized.The macroporous support was obtained from natural raw materials (bauxite,silica sand,kaolinite,talc,and alumina) via ceramic technology.The prepared ceramic discs were characterized by a narrow pore size distribution.The average pore size was about 9.5 μm,and the open porosity was estimated to be 30％.Coating the discs with micro/mesoporous cordierite layer was performed using the sol-gel approach.Three-component sols were obtained from organic or inorganic precursors.Corresponding gels were calcined at 1200 ℃ to form the cordierite structure.The nature of precursor was found to affect the pore volume distribution.Narrow pore volume distribution was observed when organic precursors were used.Another key factor to control the parameters of final material was the drying condition.Supercritical drying of the gels has allowed us to increase the surface area in two orders of magnitude comparing with conventional drying procedure.
基金supported by the National Natural Science Foundation of China(11572057)the School Foundation of Chengdu University(2080516030)~~
文摘In the present study,porous bulk palladium samples were prepared by sodium chloride salt powder spacer incorporation and removal combined with dealloying.The obtained porous Pd bulks were characterized by X‐ray diffraction,field‐emission scanning electron microscopy and N2adsorption isotherm measurements.The prepared porous Pd bulk samples showed a hierarchical pore structure,a high porosity of^88%,a high surface area of^54m2/g,and a compression strength of^0.5MPa.Electrochemical measurements were performed to evaluate the electrocatalytic properties of the porous Pd bulk samples,revealing their effectiveness for ethanol oxidation.
基金sponsored by National Natural Science Foundation of China(No.52302121,No.52203386)Shanghai Sailing Program(No.23YF1454700)+1 种基金Shanghai Natural Science Foundation(No.23ZR1472700)Shanghai Post-doctoral Excellent Program(No.2022664).
文摘With vigorous developments in nanotechnology,the elaborate regulation of microstructure shows attractive potential in the design of electromagnetic wave absorbers.Herein,a hierarchical porous structure and composite heterogeneous interface are constructed successfully to optimize the electromagnetic loss capacity.The macro–micro-synergistic graphene aerogel formed by the ice template‑assisted 3D printing strategy is cut by silicon carbide nanowires(SiC_(nws))grown in situ,while boron nitride(BN)interfacial structure is introduced on graphene nanoplates.The unique composite structure forces multiple scattering of incident EMWs,ensuring the combined effects of interfacial polarization,conduction networks,and magnetic-dielectric synergy.Therefore,the as-prepared composites present a minimum reflection loss value of−37.8 dB and a wide effective absorption bandwidth(EAB)of 9.2 GHz(from 8.8 to 18.0 GHz)at 2.5 mm.Besides,relying on the intrinsic high-temperature resistance of SiC_(nws) and BN,the EAB also remains above 5.0 GHz after annealing in air environment at 600℃ for 10 h.
基金The financial support of the Natural Science Foundation of China(21802079 and 22075159)the Postdoctoral Science Foundation of China(2018 M642605)+1 种基金the Youth Innovation Team Project of Shandong Provincial Education Department(2019KJC023)the Taishan Scholar Program for L.Zhang(202103058)are appreciated。
文摘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.
基金financially supported by the National Natural Science Foundation of China (Nos. 51874020 and 52004022)
文摘Stable non-noble metal bifunctional electrocatalysts are one of the challenges to the fluctuating overall water splitting driven by re-newable energy.Herein,a novel self-supporting hierarchically porous Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure as bifunctional electrocatalyst was constructed based on porous Ni-Fe electrodeposition on three-dimensional(3D)carbon fiber cloth,in situ oxidation,and chemical sulfuration.Results showed that the Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure with a large specific surface area exhibits good bifunctional activity and stability for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)because of the abundance of active sites,synergistic effect of the heterostructure,superhydrophilic surface,and stable,self-supporting structure.The results further confirmed that the Ni_(x)Fe-S phase in the heterostructure is transformed into metal oxides/hydroxides and Ni_(3)S_(2) during OER.Compared with the commercial 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer,the self-supporting Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) electrolyzer exhibits better stability and lower cell voltage in the fluctu-ating current density range of 10-500 mA/cm^(2).Particularly,the cell voltage of Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) is only approximately 3.91 V at an industrial current density of 500 mA/cm^(2),which is lower than that of the 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer(i.e.,approximately 4.79 V).This work provides a promising strategy to develop excellent bifunctional electrocatalysts for fluctuating overall water splitting.
基金Financial support from the National Natural Science Foundation of China (Nos. 21873026 and 21573058)the Program for Innovative Research Team in Science and Technology in University of Henan Province (17IRTSTHN 001) is gratefully acknowledged
文摘Supercapacitors with unique performance have been widely utilized in many fields. Herein, we report a nitrogen and sulfur co-doped graphene aerogel(N/S-GA-2) prepared using a low toxic precursor for high-performance supercapacitors. The as-obtained material possesses a hierarchically porous structure and a large number of electrochemical active sites. At a current density of 1 Ag^-1, the specific capacitance of the N/S-GA-2 for supercapacitors with the ionic liquid as the electrolyte is 169.4 Fg^-1, and the corresponding energy density is 84.5 Wh kg^-1.At a power density of 8.9 k W kg^-1, the energy density can reach up to 75.7 Wh kg^-1, showing that the N/S-GA-2 has an excellent electrochemical performance. Consequently, the N/S-GA-2 can be used as a promising candidate of electrode materials for supercapacitors with high power density and high energy density.
基金Project(51404306)supported by the National Natural Science Foundation of ChinaProject(JNJJ201613)supported by Jiana Foundation of Central South University,ChinaProject(2017YFC0210401)supported by the National Key Research and Development Program of China。
文摘Quasi-one-dimensional NiO with a hierarchically porous structure was synthesized through a facile coordination−precipitation method with the coupling effect of ammonia and a post-calcination treatment.The electrocatalytic properties of NiO fibers for the oxidation of ethanol were compared with those of NiO spheres.The results show that the fibrous NiO possesses a larger specific surface area of 140.153 m2/g and a lower electrical resistivity of 4.5×105Ω·m,leading to an impressively superior electrocatalytic activity to spherical NiO for ethanol oxidation in alkaline media.The current decay on fibrous NiO at 0.6 V in 100−900 s was 0.00003%,which is much lower than that of spherical NiO,indicating its better stability.The unique morphology and hierarchically porous structure give the fibrous NiO great potential to be used as an anodic electrocatalyst for direct ethanol fuel cells.
基金This project was supported by the National Natural Science Foundation of China(Nos.51971162,U1933112,51671146)the Program of Shanghai Technology Research Leader(18XD1423800)the Fundamental Research Funds for the Central Universities(22120180096).
文摘Inspired by the nature,lotus leaf-derived gradient hierarchical porous C/MoS2 morphology genetic composites(GHPCM)were successfully fabricated through an in situ strategy.The biological microstructure of lotus leaf was well preserved after treatment.Different pores with gradient pore sizes ranging from 300 to 5μm were hierarchically distributed in the composites.In addition,the surface states of lotus leaf resulted in the Janus-like morphologies of MoS2.The GHPCM exhibit excellent electromagnetic wave absorption performance,with the minimum reflection loss of−50.1 dB at a thickness of 2.4 mm and the maximum effective bandwidth of 6.0 GHz at a thickness of 2.2 mm.The outstanding performance could be attributed to the synergy of conductive loss,polarization loss,and impedance matching.In particularly,we provided a brand-new dielectric sum-quotient model to analyze the electromagnetic performance of the non-magnetic material system.It suggests that the specific sum and quotient of permittivity are the key to keep reflection loss below−10 dB within a certain frequency range.Furthermore,based on the concept of material genetic engineering,the dielectric constant could be taken into account to seek for suitable materials with designable electromagnetic absorption performance.
基金financially supported by the National Key R&D Program of China (No.2017YFE0111500)the National Natural Science Foundation of China (No.51673123 and 51222305)Sichuan Province Science and Technology Project (No.2016JQ0049)。
文摘With the rapid emergence of wearable devices, flexible lithium-ion batteries(LIBs) are much more needed than ever. Free-standing graphene-based composite paper electrodes with various active materials have appealed wide applications in flexible LIBs. However, due to the prone-to-restacking feature of graphene layers, a long cycle life at high current densities is rather difficult to be achieved. Herein, a unique threedimensional(3D) hierarchically porous NiO micro-flowers/graphene paper(fNiO/GP) electrode is successfully fabricated. The resulting fNiO/GP electrode shows superior long-term cycling stability at high rates(e.g., storage capacity of 359 mAh/g after 600 cycles at a high current density of 1 A/g). The facile 3D porous structure combines both the advantages of the graphene that is highly conductive and flexible to ensure rapid electrons/ions transfer and buffer the volume expansion of NiO during charge/discharge,and of the micro-sized NiO flowers that induces hierarchical between-layer pores ranging from nanomicro meters to promote the penetration of the electrolyte and prevent the re-stacking of graphene layers. Such structural design will inspire future manufacture of a wide range of active materials/graphene composite electrodes for high performance flexible LIBs.
基金supported by JSPS KAKENHI Grant Number15K00597Takahashi Industrial and Economic Research Foundation Japan Grant Number 06-003-154
文摘Hierarchical porous TiOnanopills were synthesized using a titanium metal-organic framework MIL-125（Ti） as precursor. The as-synthesized TiOnanopills owned a large specific surface area of 102 m/g and unique porous structure. Furthermore, the obtained TiOnanopills were applied as anode materials for Na-ion batteries for the first time. The as-synthesized TiOnanopills achieved a high discharge capacity of 196.4 m Ah/g at a current density of 0.1 A/g. A discharge capacity of 115.9 m Ah/g was obtained at a high current density of 0.5 A/g and the capacity retention was remained as high as 90% even after 3000 cycles. The excellent electrochemical performance can be attributed to its unique hierarchical porous feature.
基金financially supported by the National Key Research and Development Program of China (2016YFB0101202)the NSFC of China (Grants 91534205,21436003 and 21576031)Graduate Research and Innovation Foundation of Chongqing China (Grant No.CYB17021)
文摘Porous nitrogen-doped carbon is an especially promising material energy storage due to its excellentconductivity, stable physicochemical properties, easy processability, controllable porosity and low price.Herein, we reported a novel well-designed hierarchically porous nitrogen-doped carbon （HPNC） via acombination of salt template （ZnC12） and hard template （SiO2） as sulfur host for lithium-sulfur batter-ies. The low-melting ZnC12 is boiled off and leaves behind micropores and small size mesopores duringpyrolysis process, while the silica spheres are removed by acid leaching to generate interconnected 3Dnetwork of macropores. The HPNC-S electrode exhibits an initial specific capacity of 1355 mAh g^-l at 0.IC （IC= 1675 mAh g^-1 ）, a high-rate capability of 623 mAh g-l at 2 C, and a small decay of 0.13% per cycleover 300 cycles at 0.2 C. This excellent rate capability and remarkable long-term cyclability of the HPNC-Selectrode are attributed to its hierarchical porous structures for confining the soluble lithium polysulfideas well as the nitrogen doping for high absorbability of lithium polysulfide.
基金financially supported by the Fundamental Research Funds of the Central Universities(no.531107051048)the support from the Hunan Key Laboratory of Two-Dimensional Materials(No.801200005)。
文摘Lithium metal is one of the most promising anode materials for next-generation electrochemical energy storage due to low electrochemical potential and high specific capacity.However,large volume change and uncontrollable formation of lithium dendrite during cycling severely hinder the practical application of rechargeable Li metal batteries.Herein,we report a hierarchically porous Cu covered with lithiophilic CuxO(HPCu-CuxO) via femtosecond laser strategy in about 2 min as current collector for highperformance Li metal batteries.With precisely tunable pore volume and depth as well as lithiophilic CuxO interphase,the HPCu-CuxO not only guides homogeneous Li nucleation,resulting in a smooth and dendrite-free lithium surface,but also provides space to alleviate the volume expansion of Li metal anode,achieving excellent structure stability.Consequently,highly stable Coulombic efficiency and ultralow overpotential of 15 mV even up to 1000 h were achieved at the current density of 1 mA cm^(-2).Moreover,the resultant Li@HPCu-CuxO//LiFePO_(4) full battery delivered outstanding cycle stability and rate capability.These results offer a pathway toward high-energy-density and safe rechargeable Li metal batteries.
基金the financial support from the National Natural Science Foundation of China(22008032,22108034,and 22102026)the Guangdong Basic and Applied Basic Research Foundation(2019A1515110706)+2 种基金the Guangdong Provincial Key Lab of Green Chemical Product Technology(GC202111)the Medical Science and Technology Research Foundation of Guangdong Province(A2021189)the Shandong Provincial Natural Science Foundation(ZR2018ZC1458)。
文摘Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.
基金financially supported by the Fundamental Research Funds of the Central Universities(No.531118010112)the Double FirstClass University Initiative of Hunan University(No.531109100004)+1 种基金the Fundamental Research Funds of the Central Universities(No.531107051048)support from the Hunan Key Laboratory of TwoDimensional Materials(No.801200005)。
文摘Potassium-ion hybrid capacitors(KIHCs) have attracted increasing research interest because of the virtues of potassium-ion batteries and supercapacitors.The development of KIHCs is subject to the investigation of applicable K+storage materials which are able to accommodate the relatively large size and high activity of potassium.Here,we report a cocoon silk chemistry strategy to synthesize a hierarchically porous nitrogen-doped carbon(SHPNC).The as-prepared SHPNC with high surface area and rich N-doping not only offers highly efficient channels for the fast transport of electrons and K ions during cycling,but also provides sufficient void space to relieve volume expansion of electrode and improves its stability.Therefore,KIHCs with SHPNC anode and activated carbon cathode afford high energy of 135 Wh kg-1(calculated based on the total mass of anode and cathode),long lifespan,and ultrafast charge/slow discharge performance.This study defines that the KIHCs show great application prospect in the field of high-performance energy storage devices.
基金Financial supports from the National Natural Science Foundation of China(51872027)Beijing Natural Science Foundation(L172023)。
文摘Nitrogen-rich porous carbonaceous materials have shown great potential in energy storage and conversion applications due to their facile fabrication,high electronic conductivity,and improved hydrophilic property.Herein,three-dimensional porous N-rich carbon foams are fabricated through a one-step carbonization-activation method of the commercial melamine foam,and displaying hierarchically porous structure(macro-,meso-,and micro-pores),large surface area(1686.5 m2 g^-1),high N-containing level(3.3 at%),and excellent compressibility.The as-prepared carbon foams as electrodes for quasi-solid-state supercapacitors exhibit enhanced energy storage ability with 210 F g^-1 and 2.48c at 0.1 A g^-1,and150 F g^-1 and 1.77 F cm^-2 at 1 A g^-1,respectively.Moreover,as an electrode for lithium-based dual-ion capacitor,this distinctive porous carbon also delivers remarkable specific capacitance with 143.6 F g^-1 at0.1 A g^-1 and 116.2 F g^-1 at 1 A g^-1.The simple preparation method and the fascinating electrochemical performance endow the N-rich porous carbon foams great prospects as high-performance electrodes for electrochemical energy storage.
