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.

Integration of Multiple Heterointerfaces in a Hierarchical 0D@2D@1D Structure for Lightweight,Flexible,and Hydrophobic Multifunctional Electromagnetic Protective Fabrics

The development of wearable multifunctional electromagnetic protective fabrics with multifunctional,low cost,and high efficiency remains a challenge.Here,inspired by the unique flower branch shape of“Thunberg’s meadowsweet”in nature,a nanofibrous composite membrane with hierarchical structure was constructed.Integrating sophisticated 0D@2D@1D hierarchical structures with multiple heterointerfaces can fully unleash the multifunctional application potential of composite membrane.The targeted induction method was used to precisely regulate the formation site and morphology of the metal–organic framework precursor,and intelligently integrate multiple heterostructures to enhance dielectric polarization,which improves the impedance matching and loss mechanisms of the electromagnetic wave absorbing materials.Due to the synergistic enhancement of electrospinning-derived carbon nanofiber“stems”,MOF-derived carbon nanosheet“petals”and transition metal selenide nano-particle“stamens”,the CoxSey/NiSe@CNSs@CNFs(CNCC)composite membrane obtains a minimum reflection loss value(RL_(min))of-68.40 dB at 2.6 mm and a maximum effective absorption bandwidth(EAB)of 8.88 GHz at a thin thickness of 2.0 mm with a filling amount of only 5 wt%.In addition,the multi-component and hierarchical heterostructure endow the fibrous membrane with excellent flexibility,water resistance,thermal management,and other multifunctional properties.This work provides unique perspectives for the precise design and rational application of multifunctional fabrics.

Advancing the pressure sensing performance of conductive CNT/PDMS composite film by constructing a hierarchical-structured surface

Flexible pressure sensors have attracted wide attention due to their applications to electronic skin,health monitoring,and human-machine interaction.However,the tradeoff between their high sensitivity and wide response range remains a challenge.Inspired by human skin,we select commercial silicon carbide sandpaper as a template to fabricate carbon nanotube(CNT)/polydimethylsiloxane(PDMS)composite film with a hierarchical structured surface(h-CNT/PDMS)through solution blending and blade coating and then assemble the h-CNT/PDMS composite film with interdigitated electrodes and polyurethane(PU)scotch tape to obtain an h-CNT/PDMS-based flexible pressure sensor.Based on in-situ optical images and finite element analysis,the significant compressive contact effect between the hierarchical structured surface of h-CNT/PDMS and the interdigitated electrode leads to enhanced pressure sensitivity and a wider response range(0.1661 kPa^(-1),0.4574 kPa^(-1)and 0.0989 kPa^(-1)in the pressure range of 0–18 kPa,18–133 kPa and 133–300 kPa)compared with planar CNT/PDMS composite film(0.0066 kPa^(-1)in the pressure range of 0–240 kPa).The prepared pressure sensor displays rapid response/recovery time,excellent stability,durability,and stable response to different loading modes(bending and torsion).In addition,our pressure sensor can be utilized to accurately monitor and discriminate various stimuli ranging from human motions to pressure magnitude and spatial distribution.This study supplies important guidance for the fabrication of flexible pressure sensors with superior sensing performance in next-generation wearable electronic devices.

A hierarchically structured tin-cobalt composite with an enhanced electronic effect for high-performance CO_(2) electroreduction in a wide potential range

Earth-abundant and nontoxic Sn-based materials have been regarded as promising catalysts for the electrochemical conversion of CO_(2)to C1 products,e.g.,CO and formate.However,it is still difficult for Snbased materials to obtain satisfactory performance at low-to-moderate overpotentials.Herein,a simple and facile electrospinning technique is utilized to prepare a composite of a bimetallic Sn-Co oxide/carbon matrix with a hollow nanotube structure(Sn Co-HNT).Sn Co-HNT can maintain>90%faradaic efficiencies for C1 products within a wide potential range from-0.6 VRHE to-1.2 VRHE,and a highest 94.1%selectivity towards CO in an H-type cell.Moreover,a 91.2%faradaic efficiency with a 241.3 m A cm^(-2)partial current density for C1 products could be achieved using a flow cell.According to theoretical calculations,the fusing of Sn/Co oxides on the carbon matrix accelerates electron transfer at the atomic level,causing electron deficiency of Sn centers and reversible variation between Co^(2+)and Co^(3+)centers.The synergistic effect of the Sn/Co composition improves the electron affinity of the catalyst surface,which is conducive to the adsorption and stabilization of key intermediates and eventually increases the catalytic activity in CO_(2)electroreduction.This study could provide a new strategy for the construction of oxide-derived catalysts for CO_(2)electroreduction.

Constructing a hollow core-shell structure of RuO_(2) wrapped by hierarchical porous carbon shell with Ru NPs loading for supercapacitor

Hollow core-shell structure nanomaterials have been broadly used in energy storage, catalysis, reactor,and other fields due to their unique characteristics, including the synergy between different materials,a large specific surface area, small density, large charge carrying capacity and so on. However, their synthesis processes were mostly complicated, and few researches reported one-step encapsulation of different valence states of precious metals in carbon-based materials. Hence, a novel hollow core-shell nanostructure electrode material, RuO_(2)@Ru/HCs, with a lower mass of ruthenium to reduce costs was constructed by one-step hydrothermal method with hard template and co-assembled strategy, consisting of RuO_(2) core and ruthenium nanoparticles(Ru NPs) in carbon shell. The Ru NPs were uniformly assembled in the carbon layer, which not only improved the electronic conductivity but also provided more active centers to enhance the pseudocapacitance. The RuO_(2) core further enhanced the material’s energy storage capacity. Excellent capacitance storage(318.5 F·g^(-1)at 0.5 A·g^(-1)), rate performance(64.4%) from 0.5 A·g^(-1)to 20 A·g^(-1), and cycling stability(92.3% retention after 5000 cycles) were obtained by adjusting Ru loading to 0.92%(mass). It could be attributed to the wider pore size distribution in the micropores which increased the transfer of electrons and protons. The symmetrical supercapacitor device based on RuO_(2)@Ru/HCs could successfully light up the LED lamp. Therefore, our work verified that interfacial modification of RuO_(2) and carbon could bring attractive insights into energy density for nextgeneration supercapacitors.

A hierarchical salt-rejection strategy for sustainable and high-efficiency solar-driven desalination

Solar steam generation(SSG)is widely regarded as one of the most sustainable technologies for seawater desalination.However,salt fouling severely compromises the evaporation performance and lifetime of evaporators,limiting their practical applications.Herein,we propose a hierarchical salt-rejection(HSR)strategy to prevent salt precipitation during long-term evaporation while maintaining a rapid evaporation rate,even in high-salinity brine.The salt diffusion process is segmented into three steps—insulation,branching diffusion,and arterial transport—that significantly enhance the salt-resistance properties of the evaporator.Moreover,the HSR strategy overcomes the tradeoff between salt resistance and evaporation rate.Consequently,a high evaporation rate of 2.84 kg m^(-2) h^(-1),stable evaporation for 7 days cyclic tests in 20 wt%NaCl solution,and continuous operation for 170 h in natural seawater under 1 sun illumination were achieved.Compared with control evaporators,the HSR evaporator exhibited a>54%enhancement in total water evaporation mass during 24 h continuous evaporation in 20 wt%salt water.Furthermore,a water collection device equipped with the HSR evaporator realized a high water purification rate(1.1 kg m^(-2) h^(-1)),highlighting its potential for agricultural applications.

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.

Hierarchical structure observation and nanoindentation size effect characterization for a limnetic shell

In the present research, hierarchical structure observation and mechanical property characterization for a type of biomaterial are carried out. The investigated bioma- terial is Hyriopsis cumingii, a typical limnetic shell, which consists of two different structural layers, a prismatic ＂pillar＂ structure and a nacreous ＂brick and mortar＂ structure. The prismatic layer looks like a ＂pillar forest＂ with variationsection pillars sized on the order of several tens of microns. The nacreous material looks like a ＂brick wall＂ with bricks sized on the order of several microns. Both pillars and bricks are composed of nanoparticles. The mechanical properties of the hierarchical biomaterial are measured by using the nanoindentation test. Hardness and modulus are measured for both the nacre layer and the prismatic layer, respectively. The nanoindentation size effects for the hierarchical structural materials are investigated experimentally. The results show that the prismatic nanostructured material has a higher stiffness and hardness than the nacre nanostructured material. In addition, the nanoindentation size effects for the hierarchical structural materials are described theoretically, by using the trans-scale mechanics theory considering both strain gradient effect and the surface/interface effect. The modeling results are consistent with experimental ones.

One-dimensional ZnS-based Hetero-,Core/shell and Hierarchical Nanostructures

A focus of the current nanotechnology has shifted from routine fabrication of nanostructures to designing functional electronic devices and realizing their immense potentials for applications. Due to infusion of multi-functionality into a single system, the utilization of hetero-, core/shell and hierarchical nanostructures has become the key issue for building such devices. ZnS, due to its direct wide bandgap, high index of refraction, high transparency in the visible range and intrinsic polarity, is one of the most useful semiconductors for a wide range of electronics applications. This article provides a dense review of the state-of-the-art research activities in one-dimensional （1D） ZnS-based hetero-, core/shell and hierarchical nanostructures. The particular emphasis is put on their syntheses and applications.

A novel 300 kW arc plasma inverter system based on hierarchical controlled building block structure

To date, the high power arc plasma technology is widely used. A next generation high power arc plasma system based on building block structure is presented. The whole arc plasma inverter system is composed of 12 paralleled units to increase the system output capability. The hierarchical control system is adopted to improve the reliability and flexibility of the high power arc plasma inverter. To ensure the reliable turn on and off of the IGBT module in each building block unit, a special pulse drive circuit is designed by using pulse transformer. The experimental result indicates that the high power arc plasma inverter system can transfer 300 kW arc plasma energy reliably with high efficiency.

Tuning Metallic Co0.85Se Quantum Dots/Carbon Hollow Polyhedrons with Tertiary Hierarchical Structure for High-Performance Potassium Ion Batteries

Potassium-ion batteries(KIBs)are a potential candidate to lithium-ion batteries(LIBs)but possess unsatisfactory capacity and rate properties.Herein,the metallic cobalt selenide quantum dots(Co0.85Se-QDs)encapsulated in mesoporous carbon matrix were designed via a direct hydrothermal method.Specifically,the cobalt selenide/carbon composite(Co0.85Se-QDs/C)possesses tertiary hierarchical structure,which is the primary quantum dots,the secondary petals flake,and the tertiary hollow micropolyhedron framework.Co0.85Se-QDs are homogenously embedded into the carbon petals flake,which constitute the hollow polyhedral framework.This unique structure can take the advantages of both nanoscale and microscale features:Co0.85Se-QDs can expand in a multidimensional and ductile carbon matrix and reduce the K-intercalation stress in particle dimensions;the micropetals can restrain the agglomeration of active materials and promote the transportation of potassium ion and electron.In addition,the hollow carbon framework buffers volume expansion,maintains the structural integrity,and increases the electronic conductivity.Benefiting from this tertiary hierarchical structure,outstanding K-storage performance(402 mAh g?1 after 100 cycles at 50 mA g?1)is obtained when Co0.85Se-QDs/C is used as KIBs anode.More importantly,the selenization process in this work is newly reported and can be generally extended to prepare other quantum dots encapsulated in edge-limited frameworks for excellent energy storage.

MULTI-HIERARCHICAL STRUCTURE AND JUMP OF TEMPERATUREFOR THE GLOBE, CHINA AND YUNNAN OVER THE PAST 100 YEARS

An analysis has been conducted of the multi-hierarchical structure and jump of temperature variation for the globe, China and Yunnan Province over the past 100 years using an auto-adaptive, multi-resolution data filter set up in You, Lin and Deng (1997). The result is shown below in three aspects. (l1 The variation of global temperature in this period is marked by warming on a large scale and can be divided into three stages of being cold (prior to 1919), warm (between 1920 and 1978) and warmer (since 1 979). Well-defined jumps are with the variation in correspondence with the hierarchical evolution on such scale, occurring in 1920 and 1979 when there is the most substantial jump towards warming. For the evolution on smaller scales, however, the variation has shown more of alternations of cold and warm temperatures. The preceding hierarchical structure and warming jump are added with new ones. (2) The trend in which temperature varies is much the same for China and the Yunnan Province, but it is not consistent with that globally, the largest difference being that a weak period of cold temperature in 1955 - 1978 across the globe was suspended in 1979 when it jumped to a significant warming,while a period of very cold temperature in 1955 - 1986 in China and Yunnan was not followed by warming in similar extent until 1987. (3) Though there are consistent hierarchical structure and jumping features throughout the year in Yunnan, significant changes with season are also present and the most striking difference is that temperature tends to vary consistently with China in winter and spring but with the globe in summer and fall.

Crashworthiness Design and Multi-Objective Optimization for Bio-Inspired Hierarchical Thin-Walled Structures

Thin-walled structures have been used in many fields due to their superior mechanical properties.In this paper,two types of hierarchical multi-cell tubes,inspired by the self-similarity of Pinus sylvestris,are proposed to enhance structural energy absorption performance.The finite element models of the hierarchical structures are established to validate the crashworthiness performance under axial dynamic load.The theoreticalmodel of themean crushing force is also derived based on the simplified super folded element theory.The finite element results demonstrate that the energy absorption characteristics and deformation mode of the bionic hierarchical thin-walled tubes are further improved with the increase of hierarchical sub-structures.It can be also obtained that the energy absorption performance of corner self-similar tubes is better than edge self-similar tubes.Furthermore,multiobjective optimization of the hierarchical tubes is constructed by employing the response surface method and genetic algorithm,and the corresponding Pareto front diagram is obtained.This research provides a new idea for the crashworthiness design of thin-walled structures.

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.

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.

Hydrogen etching induced hierarchical meso/micro-pore structure with increased active density to boost ORR performance of Fe-N-C catalyst

Rational regulation on pore structure and active site density plays critical roles in enhancing the performance of Fe-N-C catalysts. As the microporous structure of the carbon substrate is generally regarded as the active site hosts, its hostility to electron/mass transfer could lead to the incomplete fulfillment of the catalytic activity. Besides, the formation of inactive metallic Fe particles during the conventional catalyst synthesis could also decrease the active site density and complicate the identification of real active site. Herein, we developed a facial hydrogen etching methodology to yield single site Fe-N-C catalysts featured with micro/mesoporous hierarchical structure. The hydrogen concentration in pyrolysis process was designated to effectively regulate the pore structure and active site density of the resulted catalysts.The optimized sample achieves excellent ORR catalytic performance with an ultralow H2O2 yield(1%)and superb stability over 10,000 cycles. Our finding provides new thoughts for the rational design of hierarchically porous carbon-based materials and highly promising non-precious metal ORR catalysts.

Analysis of SSRs Uncovers Hierarchical Structure and Genetic Diversity in Chinese Soybean Landraces

For clarifying the hierarchical patterns of population structure of soybean landraces in China, the seven clusters previously identified using Bayesian clustering of 1 504 soybean landraces based on SSR markers genotyping data were further analyzed. Using the largest value of AK, these landraces could be split into 20 sub-clusters, which was supported by highly significant pairwise Fst-values and generally in accordance with the geographic origin and sowing types. The autumn-sowing types ended up in one distinct sub-cluster from the otherwise summer-sowing type, where the autumn- sowing types are most likely derived from. The division into 20 sub-clusters explained 7.3% of the genetic variation, next to 9.7% present among the seven clusters, 81.1% residing among landraces within sub-clusters, and 1.9% within the landraces. The distribution pattern of genetic diversity among the sub-clusters of each cluster was uneven, with two HSuM sub-clusters （Central China） and some South China sub-clusters showing significantly higher level of genetic diversity.

High-performance all-solid-state polymer electrolyte with fast conductivity pathway formed by hierarchical structure polyamide 6 nanofiber for lithium metal battery

The utilization of all-solid-state electrolytes is considered to be an effective way to enhance the safety performance of lithium metal batteries.However,the low ionic conductivity and poor interface compatibility greatly restrict the development of all-solid-state battery.In this study,a composite electrolyte combining the electrospun polyamide 6(PA6)nanofiber membrane with hierarchical structure and the polyethylene oxide(PEO)polymer is investigated.The introduction of PA6 nanofiber membrane can effectively reduce the crystallinity of the polymer,so that the ionic conductivity of the electrolyte can be enhanced.Moreover,it is found that the presence of finely branched fibers in the hierarchical structure PA6 membrane allows the polar functional groups(C=O and N-H bonds)to be fully exposed,which provides sufficient functional sites for lithium ion transport and helps to regulate the uniform deposition of lithium metal.Moreover,the hierarchical structure can enhance the mechanical strength(9.2 MPa)of the electrolyte,thereby effectively improving the safety and cycle stability of the battery.The prepared Li/Li symmetric battery can be stably cycled for 1500 h under 0.3 mA cm^(-2) and 60℃.This study demonstrates that the prepared electrolyte has excellent application prospects in the next generation all-solid-state lithium metal batteries.

Hierarchical Carbon Microtube@Nanotube Core-Shell Structure for High-Performance Oxygen Electrocatalysis and Zn-Air Battery

Zinc-air batteries(ZABs)hold tremendous promise for clean and efficient energy storage with the merits of high theoretical energy density and environmental friendliness.However,the performance of practical ZABs is still unsatisfactory because of the inevitably decreased activity of electrocatalysts when assembly into a thick electrode with high mass loading.Herein,we report a hierarchical electrocatalyst based on carbon microtube@nanotube core-shell nanostructure(CMT@CNT),which demonstrates superior electrocatalytic activity for oxygen reduction reaction and oxygen evolution reaction with a small potential gap of 0.678 V.Remarkably,when being employed as air-cathode in ZAB,the CMT@CNT presents an excellent performance with a high power density(160.6 mW cm^−2),specific capacity(781.7 mAhgZn^−1)as well as long cycle stability(117 h,351 cycles).Moreover,the ZAB performance of CMT@CNT is maintained well even under high mass loading(3 mg cm−2,three times as much as traditional usage),which could afford high power density and energy density for advanced electronic equipment.We believe that this work is promising for the rational design of hierarchical structured electrocatalysts for advanced metal-air batteries.

Research on the hierarchical structure of the metropolitan system and economic development of the provincial capital urban circle in Shandong

Regional development is the trend for future urbanization,and the urban circle is a highly efficient economic spatial pattern of regional development.This study selects statistical data of urban area population,GDP,and the output value of tertiary industry for seven cities in China- Jinan,Zibo,Tai'an,Laiwu,Dezhou,Liaocheng,and Binzhou- in the Shandong provincial capital urban circle from 2005 to 2009.It uses the principles and Zipf model,rank-size rule,and Lotka logarithmic model to analyze and study the hierarchical structure of the metropolitan system and economic development of the Shandong provincial capital urban circle.Based on the above research,this paper provides references for decisionmaking on enhancement of the metropolitan system structure,improvement in core city primacy index,the optimal adjustment of industrial structure and the optimal allocation of essential resources.