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.

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.

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.

Bioinspired urchin-like murray carbon nanostructure with protection shell for advanced lithium-sulfur batteries

Commercial application of lithium-sulfur(Li-S) batteries is hindered by the insulating nature of sulfur and the dissolution of polysulfides. Here, a bioinspired 3D urchin-like N-doped Murray's carbon nanostructure(N-MCN) with interconnected micro-meso-macroporous structure and a polydopamine protection shell has been designed as an effective sulfur host for high-performance Li-S batteries. The advanced 3D hierarchically porous framework with the characteristics of the generalized Murray's law largely improves electrolyte diffusion, facilitates electrons/ions transfer and provides strong chemisorption for active species, leading to the synergistic structural and chemical confinement of polysulfides. As a result,the obtained P@S/N-MCN electrode with high areal sulfur loading demonstrates high capacity at high current densities after long cycles. This work reveals that following the generalized Murray's law is feasible to design high-performance sulfur cathode materials for potentially practical Li-S battery applications.

Integration of enzyme immobilization and biomimetic catalysis in hierarchically porous metal-organic frameworks for multi-enzymatic cascade reactions

Multiple enzymes-induced biological cascade catalysis is indispensable in biotechnology and industrial processes. Nevertheless,the drawbacks of most natural enzymes, including poor stability and recyclability and sensitivity to the environment, have hindered their broader application. Here, we report a facile strategy to prepare a biomimetic cascade reaction system by combining the advantages of enzyme immobilization and biomimetic catalysis in a one-pot reaction system based on the hierarchically porous metal-organic frameworks(HP-MOFs). The hierarchically porous zirconium-porphyrin-based MOF(HPPCN-222(Fe)) synthesized by modulator-induced strategy possessed tunable hierarchical porous and peroxidase-like activity,permitting them to act as not only an efficient immobilization matrix for glucose oxidase(GOx) but also peroxidase mimics to catalyze the cascade for glucose detection. A stable, anti-interference and reusable colorimetric biosensor for glucose detection was successfully established through GOx@HP-PCN-222(Fe) on the basis of the artificial tandem catalysis. Moreover, the GOx@HP-PCN-222(Fe)-fabricated electrode was available for glucose detection by electrochemical method. This work provides a potentially universal method to design functional multi-enzymatic cascade reaction systems by integrating the merits of enzyme encapsulation and biomimetic catalysis in HP-MOFs.

Metal oxyacid salts-confined pyrolysis towards hierarchical porous metal oxide@carbon(MO@C)composites as lithium-ion battery anodes

Transition metal oxides(TMOs)have been thought of potential anodic materials for lithium-ion batteries(LIBs)owing to their intriguing properties.However,the limited conductivity and drastic volume change still hinder their practical applications.Herein,a metal oxyacid salts-confined pyrolysis strategy is proposed to construct hierarchical porous metal oxide@carbon(MO@C,MO=MoO_(2),V_(2)O_(5),WO_(3))composites for solving the aforementioned problems.A water-evaporation-induced self-assembly mechanism has been put forward for fabricating the MO@polyvinyl pyrrolidone(PVP)@SiO_(2)precursors.After the following pyrolysis and etching process,small MO nanoparticles can be successfully encapsulated in the hierarchical porous carbon framework.Profiting from the synergistic effect of MO nanoparticles and highly conductive carbon framework,MO@C composites show excellent electrochemical properties.For example,the as-obtained MoO_(2)@C composite exhibits a large discharge capacity(1513.7 mAh·g^(−1)at 0.1 A·g^(−1)),good rate ability(443.5 mAh·g^(−1)at 5.0 A·g^(−1)),supernal long-lived stability(669.1 mAh·g^(−1)after 1000 cycles at 1.0 A·g^(−1)).This work will inspire the design of novel anode materials for high-performance LIBs.