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.

A Novel Hierarchical Porous 3D Structured Vanadium Nitride/Carbon Membranes for High-performance Supercapacitor Negative Electrodes

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.

Nitrogen and sulfur co-doped graphene aerogel with hierarchically porous structure for high-performance supercapacitors

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.

Self-supporting and hierarchically porous Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure as a bifunctional electrocatalyst for fluctuating overall water splitting

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.

Synthesis of Cu/ZnO Flower-like Hierarchical Porous Structures and Investigation of Their Catalytic Performance for Dimethyl Oxalate Hydrogenation

The Cu/ZnO flower-like hierarchical porous structures were successfully synthesized via the cetyltrimethyl ammonium bromide(CTAB) assisted hydrothermal method. The morphology and structure as well as the catalytic performance for dimethyl oxalate(DMO) hydrogenation to ethylene glycol(EG) were investigated. Through annealing the zinc copper hydroxide carbonate(ZCHC) precursors, the Cu/ZnO flower-like hierarchical porous structures were obtained, which were assembled by a number of porous nanosheets. The catalyst made of these well-defined flower-like hierarchical porous structures with large specific surface area and effective gas diffusion path via the well-aligned porous structures showed higher EG selectivity and yield as compared to the Cu/ZnO catalyst obtained by conventional co-precipitation technique. The results indicated that the Cu/ZnO flower-like hierarchical porous structures have excellent potential application for manufacture of high performance catalysts.

Fabrication, characterization and electrochemical properties of porous palladium bulk samples with high porosity and hierarchical pore structure

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.

Dynamic Adsorption of Toluene on Hierarchical Porous Carbons with Varying Pore Structure

Hierarchical porous carbon material(MMC)was successfully fabricated via hard template synthesis method by carbonization of furfury alcohol within the template(MCM-41).The prepared MMC was studied with characterization methods including scanning electron microscopy(SEM),transmission electron microscopy(TEM),nitrogen adsorption-desorption analyses,and infrared spectral analysis(FTIR).To investigate kinetics of toluene adsorption of hierarchical porous carbon materials,the adsorption performances of these carbon samples with varying pore structure(MC-1,MMC,MMHPC)were analyzed via dynamic adsorption.And the Langmuir model and Freundlich equation were employed to correspond with adsorption isotherms to study the adsorption mechanism.The experimental results demonstrate that the Langmuir model is more appropriate to describe the adsorption process.The capacities of toluene adsorption follow the order of MMC<MMHPC(micro-meso hierarchical porous carbon)<MC-1(microporous carbon).MC-1 has satisfactory absorption performance due to its large pore volume and high ratio of micropores.MMHPC has excellent toluene adsorption performance for proper amounts of surface oxygen containing groups.Long saturation time,interconnected hierarchical pore channels,and large specific surface area make MMC also a promising material for VOCs treatment.These data reveal that the pore channel structure,rational pore distribution,high surface area and reasonable amounts of surface oxygen groups are the main factors contributed to excellent toluene adsorption performance,which proposes theoretical basis for hierarchical porous carbon materials to further engineering application.

Boosting ethanol oxidation over nickel oxide through construction of quasi-one-dimensional morphology and hierarchically porous structure

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.

Effect of TiO_2 Sol Impregnation on Biogenic Hierarchical Porous Structure of Rice Husk after High Temperature Treatment

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 ℃.

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.

A highly stable membrane with hierarchical structure for wide pH range flow batteries

A membrane with high stability and ion conductivity in wide pH range is essential for energy storage devices.Here,we report a novel membrane with hierarchical core-shell structure,which demonstrates high stability and ion conductivity,simultaneously under a wide pH range applications.Spectral characterizations and theoretical calculation indicate that the non-solvent induces the chain segment configuration and eventually leads to polymer-polymer phase separation,thus forming hierarchical porous core-shell structure.Benefiting from this structure,an acidic vanadium flow battery(VFB)with such a membrane shows excellent performance over 400 cycles with an energy efficiency(EE)of above 81%at current density of 120 mA cm^(-2) and an alkaline zinc-iron flow battery(AZIFB)delivers a cycling stability for more than 200 cycles at 160 mA cm^(-2),along with an EE of above 82%.This paper provides a cost-effective and simple way to fabricate membranes with high performance for variety of energyrelated devices.

Lotus Leaf‑Derived Gradient Hierarchical Porous C/MoS2 Morphology Genetic Composites with Wideband and Tunable Electromagnetic Absorption Performance

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.

Hierarchically porous nitrogen-doped carbon as cathode for lithium–sulfur batteries

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.

Recent advances in the synthesis of nanoscale hierarchically porous metal–organic frameworks

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.

Hierarchically porous Cu current collector with lithiophilic CuxO interphase towards high-performance lithium metal batteries

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.

Hierarchically porous N-doped carbon derived from biomass as oxygen reduction electrocatalyst for high-performance Al–air battery

Developing large-scale and highly efficient oxygen reduction reaction(ORR)catalysts acts a vital role in realizing wide application of metal–air batteries.Here,we propose a gas-foaming strategy to fabricate sustainable and 3D hierarchically porous N-doped carbon with high specific surface area and abundant defects sites derived from biomass.The obtained catalyst exhibits prominent ORR property with higher half-wave potential(0.861 V)and slightly lower kinetic current density(32.44 m A cm^-2),compared to Pt/C(0.856 V and 43.61 m A cm^-1).Furthermore,employing it as catalyst of air cathode,the Al–air battery delivers remarkable discharge performance with excellent power density of 401 m W cm^-2,distinguished energy density of 2453.4 Wh kg^-1 and extremely high open-circuit voltage of 1.85 V among the reported metal–air batteries in the literatures.This gas-foaming strategy for full utilization of biomass affords a chance to explore scalable advanced catalysts in metal–air battery.

Nitrogen-rich hierarchically porous carbon foams as high-performance electrodes for lithium-based dual-ion capacitor

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.

3D hierarchically porous NiO/Graphene hybrid paper anode for long-life and high rate cycling flexible Li-ion batteries

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.

Cocoon Silk-Derived, Hierarchically Porous Carbon as Anode for Highly Robust Potassium-Ion Hybrid Capacitors

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.

Enhanced stability of highly-dispersed copper catalyst supported by hierarchically porous carbon for long term selective hydrogenation

Copper based catalysts have high potential for the substituent of noble-metal based catalysts as their high selectivity and moderate activity for selective hydrogenation reaction;however,achieving further high catalytic stability is very difficult.In this work,the carbonization process of Cu-based organic frameworks was explored for the synthesis of highly-dispersed Cu supported by hierarchically porous carbon with high catalytic performance for selective hydrogenation of 1,3-butadiene.The porous hierarchy of carbon support and the dispersion of copper nanoparticles can be precisely tuned by controlling the carbonization process.The resultant catalyst carbonized at 600°C exhibits a rather low reaction temperature at 75°C for 100%butadiene conversion with 100%selectivity to butenes,due to its reasonable porous hierarchy and highly-dispersed copper sites.More importantly,unprecedentedly stability of the corresponding Cu catalyst was firstly observed for selective 1,3-butadiene hydrogenation,with both 100%butadiene conversion and 100%butenes selectivity over 120 h of reaction at 75°C.This study verifies that a simply control the carbonization process of metal organic frameworks can be an effective way to obtain Cu-based catalysts with superior catalytic performance for selective hydrogenation reaction.