Engineering hierarchical quaternary superstructure of an integrated MOF-derived electrode for boosting urea electrooxidation assisted water electrolysis

Controllable design of the catalytic electrodes with hierarchical superstructures is expected to improve their electrochemical performance.Herein,a self-supported integrated electrode(NiCo-ZLDH/NF)with a unique hierarchical quaternary superstructure was fabricated through a self-sacrificing template strategy from the metal–organic framework(Co-ZIF-67)nanoplate arrays,which features an intriguing well-defined hierarchy when taking the unit cells of the NiCo-based layered double hydroxide(NiCo-LDH)as the primary structure,the ultrathin LDH nanoneedles as the secondary structure,the mesoscale hollow plates of the LDH nanoneedle arrays as the tertiary structure,and the macroscale three-dimensional frames of the plate arrays as the quaternary structure.Notably,the distinctive structure of NiCo-ZLDH/NF can not only accelerate both mass and charge transfer,but also expose plentiful accessible active sites with high intrinsic activity,endowing it with an excellent electrochemical performance for urea oxidation reaction(UOR).Specially,it only required the low potentials of 1.335,1.368 and 1.388 V to deliver the current densities of 10,100 and 200 mA cm^(-2),respectively,much superior to those for typical NiCo-LDH.Employing NiCo-ZLDH/NF as the bifunctional electrode for both anodic UOR and cathodic HER,an energy-saving electrolysis system was further explored which can greatly reduce the needed voltage of 213 mV to deliver the current density of 100 mA cm^(-2),as compared to the conventional water electrolysis system composed of OER.This work manifests that it is prospective to explore the hierarchically nanostructured electrodes and the innovative electrolytic technologies for high-efficiency electrocatalysis.

Water-based synthesis of nanoscale hierarchical metal-organic frameworks:Boosting adsorption and catalytic performance

The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.

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.

Hierarchical Metal-Organic Frameworks with Macroporosity:Synthesis, Achievements,and Challenges

Introduction of multiple pore size regimes into metalorganic frameworks(MOFs)to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases,where interactions with bulky molecules are involved,enlarging the pore size of typically microporous MOF adsorbents or MOF catalysts is crucial for enhancing both mass transfer and molecular accessibility.In this review,we examine the range of synthetic strategies which have been reported thus far to prepare hierarchical MOFs or MOF composites with added macroporosity.These fabrication techniques can be either pre-or post-synthetic and include using hard or soft structural template agents,defect formation,routes involving supercritical CO2,and 3D printing.We also discuss potential applications and some of the challenges involved with current techniques,which must be addressed if any of these approaches are to be taken forward for industrial applications.

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.

Metal–organic framework derived hierarchical porous TiO_2 nanopills as a super stable anode for Na-ion batteries

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.

Multi-Topology Hierarchical Collaborative Hybrid Particle Swarm Optimization Algorithm for WSN

Wireless sensor networks(WSN)are widely used in many situations,but the disordered and random deployment mode will waste a lot of sensor resources.This paper proposes a multi-topology hierarchical collaborative particle swarm optimization(MHCHPSO)to optimize sensor deployment location and improve the coverage of WSN.MHCHPSO divides the population into three types topology:diversity topology for global exploration,fast convergence topology for local development,and collaboration topology for exploration and development.All topologies are optimized in parallel to overcome the precocious convergence of PSO.This paper compares with various heuristic algorithms at CEC 2013,CEC 2015,and CEC 2017.The experimental results show that MHCHPSO outperforms the comparison algorithms.In addition,MHCHPSO is applied to the WSN localization optimization,and the experimental results confirm the optimization ability of MHCHPSO in practical engineering problems.

Ultra-stable and High-rate Lithium Ion Batteries Based on Metal-organic Framework-derived ln2O3 Nanocrystals/Hierarchically Porous Nitrogen-doped Carbon Anode

Exploring electrode materials with attractive specific capacity and prominent cyclic durability is of the essence for promoting lithium ion batteries(LIBs).In2O3 has shown an extraordinary promise for LIBs with advantageous gravimetric capacity(theoretically 965 mA h g-1) and low working voltage.However,In2O3 still suffers from the inherent weaknesses of metal oxides in practical application,especially low conductivity and incorrigible volume expansion upon the cycling process.Here,we demonstrate the architecture of metal-organic framework(MOF)-derived In2O3 nanocrystals/hierarchically porous nitrogen-doped carbon composite(In2O3/HPNC) for ultra-stable LIBs anode.This hierarchically porous structure(micro/meso/macro-pores) with nitrogen doping not only ensures exceptional mechanical strength and accommodates the volume expansion of In2O3 nanocrystals,but also offers electrons and lithium ions efficient interpenetrating pathways to migrate rapidly during charge/discharge processes.Thus,In2O3/HPNC exhibits excellent cyclic stability with a high specific capacity of 623 mA h g-1 over2000 cycles at 1000 mA g-1,corresponding to an ultra-low specific capacity decay of 0.017% per cycle(the best among the ln203-based anode for LIBs),and outstanding rate performance,suggesting a critical step toward achieving long-life and high-rate LIBs in practical devices.

Analytical solution for the stress field of hierarchical defects:multiscale framework and applications

Hierarchical defects are defined as adjacent defects at different length scales.Involved are the two scales where the stress field distribution is interrelated.Based on the complex variable method and conformal mapping,a multiscale framework for solving the problems of hierarchical defects is formulated.The separated representations of mapping function,the governing equations of potentials,and the stress field are subsequently obtained.The proposed multiscale framework can be used to solve a variety of simplified engineering problems.The case in point is the analytical solution of a macroscopic elliptic hole with a microscopic circular edge defect.The results indicate that the microscopic defect aggregates the stress concentration on the macroscopic defect and likely leads to global propagation and rupture.Multiple micro-defects have interactive effects on the distribution of the stress field.The level of stress concentration may be reduced by the coalescence of micro-defects.This work provides a unified method to analytically investigate the influence of edge micro-defects within the scope of multiscale hierarchy.The formulated multiscale approach can also be potentially applied to materials with hierarchical defects,such as additive manufacturing and bio-inspired materials.

Weaving 3D highly conductive hierarchically interconnected nanoporous web by threading MOF crystals onto multi walled carbon nanotubes for high performance Li-Se battery

Lithium-selenium(Li-Se)battery has attracted growing attention.Nevertheless,its practical application is still impeded by the shuttle effect of the formed polyselenides.Herein,we report in-situ hydrothermal weaving the three-dimensional(3 D)highly conductive hierarchically interconnected nanoporous web by threading microporous metal organic framework MIL-68(Al)crystals onto multi-walled carbon nanotubes(MWCNTs).Such 3 D hierarchically nanoporous web(3 D MIL-68(Al)@MWCNTs web)with a very high surface area,a large amount of micropores,electrical conductivity and elasticity strongly traps the soluble polyselenides during the electrochemical reaction and significantly facilitates lithium ion diffusion and electron transportation.Molecular dynamic calculation confirmed the strong affinity of MIL-68(Al)for the adsorption of polyselenides,quite suitable for Li-Se battery.Their hexahedral channels(1.56 nm)are more efficient for the confinement of polyselenides and for the diffusion of electrolytes compared to their smaller triangular channels(0.63 nm).All these excellent characteristics of 3 D MIL-68(Al)@MWCNTs web with suitable confinement of a large amount of selenium and the conductive linkage between MIL-68(Al)host by MWCNTs result in a high capacity of 453 m Ah/g at 0.2 C with 99.5%coulombic efficiency after 200 cycles with significantly improved cycle stability and rate performance.The 3 D MIL-68(Al)@MWCNTs web presents a good performance in Li-Se battery in term of the specific capacity and cycling stability and also in terms of rate performance compared with all the metal-organic framework(MOF)based or MOF derived porous carbons used in Li-Se battery.

Charge-transfer-regulated bimetal ferrocene-based organic frameworks for promoting electrocatalytic oxygen evolution

The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.

Hierarchical Cognition Cycle for Cognitive Radio Networks

Cognitive radio(CR) can bring about remarkable improvement in spectrum utilization.Different cognition cycles have been proposed in recent years.However,most of the existing works only emphasize functional or operational aspects of cognition cycle,regardless of other indispensable aspects and the connection between them.To deal with the emerging situation of "data rich,information vague,knowledge poor" in cognitive radio networks(CRNs),we propose the hierarchical cognition cycle(HCC) as a new transdisciplinary research field in this paper.HCC investigates a fundamental problem,which is how to manage available resources in the complex environment to meet various demands in CRN.A comprehensive theoretical framework of HCC is established in terms of the core,the essence loop,the function loop,the operation loop,and the external loop of HCC.The reduction of uncertainty in CRN is studied and several new metrics in HCC are defined.Furthermore,a few research challenges ahead are presented as well.

基于Robot Framework测试框架的机载娱乐系统自动化测试设计

在对机载娱乐系统软件架构进行分析的基础上,阐明了机载娱乐系统自动化测试的必要性,设计了基于Robot Fra-mework测试框架的自动化分层测试组织结构,明确了自动化测试中测试用例、测试规程、测试结果之间的追踪性,并将设计的测试组织结构在实际项目中进行了应用。实践表明,采用所设计的自动化分层测试组织结构可以较好的满足机载娱乐系统在软件测试过程中的脚本维护、扩展、稳定测试等要求,有利于软件的快速交付。

多级孔MOF的制备及其吸附分离应用研究进展

金属有机框架材料(MOF)因其具有高比表面积、丰富孔隙率、孔径可调的优点,受诸多学者关注,被认为是用于吸附分离的理想吸附剂。但是在实际应用中,大部分微孔MOF材料在吸附过程中的内在传质速率严重受限,而且构建多级孔的方法一般不具有普遍性。本文介绍了调节剂策略、模板策略、后处理策略等构建多级孔MOF的方法,制备了兼具介孔、大孔的多级孔材料,并结合应用场景评价各方法的优缺点,以获得在相对温和条件下构建孔径可调的多级孔MOF的普适性策略。针对多级孔MOF材料在气体吸附分离领域的应用问题,着重剖析了构建多级孔MOF对CO_(2)气体吸附提升的案例,发现多级孔的构建增加了孔径,提高了MOF的比表面积,提供了额外的孔通道,使气体分子的吸附容量和传质速率得到提升,表明多级孔MOF在气体吸附分离方面有优异的性能。最后讨论了多级孔MOF合成和应用存在的问题,并对多级孔MOF面临的合成过程绿色可重复等挑战进行了展望。

北京市与深圳市儿童分级诊疗相关政策对比分析

背景为了解决儿童“看病难”“看病贵”的医疗困境,我国推行了分级诊疗制度。目前国内对儿童分级诊疗相关政策分析的系统研究献见报道。目的作为分级诊疗第一批试点城市,北京市和深圳市社区卫生服务机构(以下简称社区卫生机构)儿童接诊情况差异较大,本研究通过分析两地儿童分级诊疗相关政策,探索政策对社区卫生机构接诊儿童的影响。方法根据研究小组制定的分级诊疗政策研究框架(社区首诊制、双向转诊、医联体、薪酬激励、儿科培训、宣传、农村医疗可及性),在北京市政府、北京市卫生健康委员会、深圳市政府在线、深圳市卫生健康委员会官方网站检索儿童分级诊疗相关政策文件。筛选符合纳入、排除标准的政策,比较两市纳入政策的数量与内容,分析异同点。结果从6953篇政策文件中筛选出35篇符合分级诊疗政策研究框架的政策文件,其中北京市27篇、深圳市8篇。在医联体、薪酬激励、儿科培训方面,两市都有相关政策。在差异性方面北京市在分级诊疗的宣传和农村医疗可及性方面有相关政策,深圳市在社区首诊制和双向转诊制有相关政策。结论通过落实社区首诊制或加大医保支付比例差距方法促进儿童基层首诊、完善双向转诊指征、完善医联体、薪酬激励和儿科培训相关分级诊疗政策可能对改善社区卫生机构接诊儿童现况有重要意义。

晶种辅助蒸气转化Al-SBA-15合成Beta纳米晶团聚体

采用晶种辅助蒸气转化(SASC)策略,将有序介孔分子筛Al-SBA-15颗粒直接转化为Beta纳米晶团聚体(BNA).除规则微孔外,BNA含有2种多级介孔结构.研究了骨架组装与多级孔结构的关系.通过调节热分解条件,将P123胶束选择性分解成碳颗粒并分散于Al-SBA-15介孔中,在颗粒内部构建了均匀的三维纳米空间网格.通过浸渍Beta晶种和四乙基铵阳离子(TEA+)强化分子筛成核,采用蒸气处理方法,将Al-SBA-15无定形孔壁在纳米空间中缓慢转化为Beta纳米晶体.通过调节合成参数,使纳米晶体沿Al-SBA-15孔壁方向规则排列,形成有序介观结构.此外,经高温焙烧去除碳颗粒后,BNA内部生成了穴状介孔.实验结果表明,低的溶剂用量可显著降低传质速度,提高骨架组装质量,从而使BNA酸性增强.优异的多级孔结构和较强的酸性使BNA在大分子反应中具有应用潜力.

Carbon nanocages bridged with graphene enable fast kinetics for dual-carbon lithium-ion capacitors

Lithium-ion capacitors(LICs) combining the advantages of lithium-ion batteries and supercapacitors are considered a promising nextgeneration energy storage device. However, the sluggish kinetics of battery-type anode cannot match the capacitor-type cathode, restricting the development of LICs. Herein, hierarchical carbon framework(HCF) anode material composed of 0D carbon nanocage bridged with 2D graphene network are developed via a template-confined synthesis process. The HCF with nanocage structure reduces the Li^(+) transport path and benefits the rapid Li^(+) migration, while 2D graphene network can promote the electron interconnecting of carbon nanocages. In addition, the doped N atoms in HCF facilitate to the adsorption of ions and enhance the pseudo contribution, thus accelerate the kinetics of the anode. The HCF anode delivers high specific capacity, remarkable rate capability. The LIC pouch-cell based on HCF anode and active HCF(a-HCF) cathode can provide a high energy density of 162 Wh kg^(-1) and a superior power density of 15.8 kW kg^(-1), as well as a long cycling life exceeding 15,000cycles. This study demonstrates that the well-defined design of hierarchical carbon framework by incorporating 0D carbon nanocages and 2D graphene network is an effective strategy to promote LIC anode kinetics and hence boost the LIC electrochemical performance.

Construction of hierarchically porous metal-organic framework particle by a facile MOF-template strategy

Increasing the mass diffusion efficiency is a major challenge in the realm of metal-organic frameworks(MOFs).Construction of hierarchically porous,typically microporous MOF adsorbents or catalysts is crucial for enhancing both mass transfer and molecular accessibility.Many strategies have been proposed for the synthesis of hierarchically porous MOFs(HP-MOFs),with some striking results.In this paper,we proposed a facile and versatile strategy,termed the MOF-Template strategy,for fabricating hierarchical pores in MOF particle.The highly controlled crystalline sizes and morphologies of the unstable Cu-MOFs Cu_(3)(BTC)_(2) and Cu(Qc)_(2) have been exploited in their utilization as sacrificial agents by uniformly dispersing them during the shaping process of ZIF-8.Through a facile treatment with alkaline solution,tunable mesopores and macropores could be easily introduced in the shaped ZIF-8 spheres.This strategy could effectively improve the adsorption kinetics and separation productivity of MOF materials while maintaining high mechanical stability,offering promising prospects for industrial application.

基于科普教育类APP的用户体验要素模型设计研究

“体验式”思潮和游戏化教育观念近年来迅速崛起,为探究促进科普教育类APP用户体验的设计方法和策略,以Garrett用户体验要素模型为理论基础,分析科普教育APP的用户需求,归纳出更具体的设计思路,进一步整理成针对科普教育类APP的用户体验要素模型,并带入案例予以验证,从而为提高科普教育APP的用户黏性与市场竞争力提供一定参考。

CoZn-MOF衍生多级孔取向碳载CoP及其析氢性能

在“双碳”背景下,高效、清洁的氢能源成为代替传统化石能源的重要选择,而电解水产氢是开发氢能源需要攻克的关键技术之一。目前,电解水产氢催化活性较高的催化剂主要以贵金属催化剂为主,然而贵金属价格高昂、资源稀缺严重阻碍了它们在清洁能源领域的大规模应用。因此,开发高效、耐用、廉价和地球资源丰富的电催化剂是实现电解水产氢的迫切需求。本文以无定形的锌钴双金属有机框架为前体,通过酸溶液处理制备了一种具有独特多面体结构的新型骨架材料(ZnCo-MOF),然后通过逐级碳化磷化过程,在保留原有形态的基础上得到了CoP负载的具有规则形貌的多级孔碳(H-CoP/C)。研究表明:多级孔碳作载体不仅能够负载更多活性位点,而且有利于活性位点的暴露、材料的导电性和催化过程中的传质。凭借有利的结构特征、充足的活性位点,所获得的电催化剂H-CoP/C在碱性介质中展现出优异的HER性能,驱动10mA/cm^(2)的电流密度只需168mV的过电位,优于大多数的非贵金属电催化剂。