Balanced Mass Transfer and Active Sites Density in Hierarchical Porous Catalytic Metal-Organic Framework for Enhancing Redox Reaction in Lithium-Sulfur Batteries.

Developing highly efficient catalysts, characterized by controllable pore architecture and effective utilization of active sites, is paramount in addressing the shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs) in lithium-sulfur batteries (LSBs), which, however, remains a formidable challenge. In this study, a hierarchical porous catalytic metal-organic framework (HPC-MOF) with both appropriate porosity and abundant exposed catalytic sites is achieved through time-controlled precise pore engineering. It is revealed that the evolution of the porous structure and catalytic site density is time-dependent during the etching processes. The moderately etched HPC-MOF-M attains heterogeneous pores at various scales, where large apertures ensure fast mass transfer and micropores inherit high-density catalytic sites, enhancing utilization and catalytic kinetics at internal catalytic sites. Capitalizing on these advantages, LSB incorporating the HPC-MOF-M interlayer demonstrates a 164.6% improvement in discharge capability and an 83.3% lower decay rate over long-term cycling at 1.0C. Even under high sulfur loading of 7.1 mg cm-2 and lean electrolyte conditions, the LSB exhibits stable cycling for over 100 cycles. This work highlights the significance of balancing the relationship between mass transfer and catalytic sites through precise chemical regulation of the porous structure in catalytic MOFs, which are anticipated to inspire the development of advanced catalysts for LSBs.

Molten Guest-Mediated Metal-Organic Frameworks Featuring Multi-Modal Supramolecular Interaction Sites for Flame-Retardant Superionic Conductor in All-Solid-State Batteries.

The development of solid-state electrolytes (SSEs) with outstanding comprehensive performance is currently a critical challenge for achieving high energy density and safer solid-state batteries (SSBs). In this study, a strategy of nano-confined in situ solidification is proposed to create a novel category of molten guest-mediated metal-organic frameworks, named MGM-MOFs. By embedding the newly developed molten crystalline organic electrolyte (ML20) into the nanocages of anionic MOF-OH, MGM-MOF-OH, characterized by multi-modal supramolecular interaction sites and continuous negative electrostatic environments within nano-channels, is achieved. These nanochannels promote ion transport through the successive hopping of Li+ between neighbored negative electrostatic environments and suppress anion movement through the chemical constraint of the hydroxyl-functionalized pore wall. This results in remarkable Li+ conductivity of 7.1 × 10-4 S cm-1 and high Li+ transference number of 0.81. Leveraging these advantages, the SSBs assembled with MGM-MOF-OH exhibit impressive cycle stability and a high specific energy density of 410.5 Wh kganode + cathode + electrolyte -1 under constrained conditions and various working temperatures. Unlike flammable traditional MOFs, MGM-MOF-OH demonstrates high robustness under various harsh conditions, including ignition, high voltage, and extended to humidity.

Multimodal Engineering of Catalytic Interfaces Confers Multi-Site Metal-Organic Framework for Internal Preconcentration and Accelerating Redox Kinetics in Lithium-Sulfur Batteries.

The development of highly efficient catalysts to address the shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs) in lithium-sulfur batteries (LSBs) remains a formidable challenge. In this study, a series of multi-site catalytic metal-organic frameworks (MSC-MOFs) were elaborated through multimodal molecular engineering to regulate both the reactant diffusion and catalysis processes. MSC-MOFs were crafted with nanocages featuring collaborative specific adsorption/catalytic interfaces formed by exposed mixed-valence metal sites and surrounding adsorption sites. This design facilitates internal preconcentration, a coadsorption mechanism, and continuous efficient catalytic conversion toward polysulfides concurrently. Leveraging these attributes, LSBs with an MSC-MOF-Ti catalytic interlayer demonstrated a 62 % improvement in discharge capacity and cycling stability. This resulted in achieving a high areal capacity (11.57 mAh cm-2 ) at a high sulfur loading (9.32 mg cm-2 ) under lean electrolyte conditions, along with a pouch cell exhibiting an ultra-high gravimetric energy density of 350.8 Wh kg-1 . Lastly, this work introduces a universal strategy for the development of a new class of efficient catalytic MOFs, promoting SRR and suppressing the shuttle effect at the molecular level. The findings shed light on the design of advanced porous catalytic materials for application in high-energy LSBs.

COVID-19 impacts on cross-border mobility of senior population between Shenzhen and Hong Kong.

The onset of the COVID-19 outbreak led to widespread adoption of mobility intervention policies, which were widely regarded as effective measures to control the spread of the virus. The initial pandemic wave, accompanied by the enforcement of mobility intervention policies, greatly changed human mobility patterns, especially cross-border mobility (CBM). This study investigates the impact of the first wave of the pandemic and related mobility intervention policies on the CBM of the senior population between Shenzhen and Hong Kong. Based on anonymous mobile phone trajectory data from 17 million devices active in Shenzhen spanning December 2019 to May 2020, we consider the implementation of mobility intervention policies during different stages of pandemic in both cities. We adopt interrupted time series (ITS) analysis to explore the causal effects of different mobility intervention policies on the CBM of older people between Hong Kong and Shenzhen. We find that most mobility intervention policies have a significant abrupt or gradual effect on the CBM of older people, especially in the 60-64 age group. As these policies neglect the mobility needs and characteristics among the senior groups, such as visiting relatives or friends and seeking medical treatment across borders, we suggest that more coordinated and integrated policies and measures are required to address the CBM needs of older people in Shenzhen and Hong Kong, especially in the post-pandemic era.

Bilayer Zwitterionic Metal-Organic Framework for Selective All-Solid-State Superionic Conduction in Lithium Metal Batteries.

Solid-state batteries (SSBs) hold immense potential for improved energy density and safety compared to traditional batteries. However, existing solid-state electrolytes (SSEs) face challenges in meeting the complex operational requirements of SSBs. This study introduces a novel approach to address this issue by developing a metal-organic framework (MOF) with customized bilayer zwitterionic nanochannels (MOF-BZN) as high-performance SSEs. The BZN consist of a rigid anionic MOF channel with chemically grafted soft multicationic oligomers (MCOs) on the pore wall. This design enables selective superionic conduction, with MCOs restricting the movement of anions while coulombic interaction between MCOs and anionic framework promoting the dissociation of Li+ . MOF-BZN exhibits remarkable Li+ conductivity (8.76 × 10-4 S cm-1 ), high Li+ transference number (0.75), and a wide electrochemical window of up to 4.9 V at 30 °C. Ultimately, the SSB utilizing flame retarded MOF-BZN achieves an impressive specific energy of 419.6 Wh kganode+cathode+electrolyte -1 under constrained conditions of high cathode loading (20.1 mg cm-2 ) and limited lithium metal source. The constructed bilayer zwitterionic MOFs present a pioneering strategy for developing advanced SSEs for highly efficient SSBs.

Covalent Organic Framework with Multi-Cationic Molecular Chains for Gate Mechanism Controlled Superionic Conduction in All-Solid-State Batteries.

Although solid-state batteries (SSBs) are high potential in achieving better safety and higher energy density, current solid-state electrolytes (SSEs) cannot fully satisfy the complicated requirements of SSBs. Herein, a covalent organic framework (COF) with multi-cationic molecular chains (COF-MCMC) was developed as an efficient SSE. The MCMCs chemically anchored on COF channels were generated by nano-confined copolymerization of cationic ionic liquid monomers, which can function as Li+ selective gates. The coulombic interaction between MCMCs and anions leads to easier dissociation of Li+ from coordinated states, and thus Li+ transport is accelerated. While the movement of anions is restrained due to the charge interaction, resulting in a high Li+ conductivity of 4.9×10-4  S cm-1 and Li+ transference number of 0.71 at 30 °C. The SSBs with COF-MCMC demonstrate an excellent specific energy density of 403.4 Wh kg-1 with high cathode loading and limited Li metal source.

Constructing Heterogeneous Structure in Metal-Organic Framework-Derived Hierarchical Sulfur Hosts for Capturing Polysulfides and Promoting Conversion Kinetics.

Lithium-sulfur batteries (LSBs) are still severely blocked by the shuttle of polysulfides (LiPSs), resulting in low sulfur utilization and decreased lifetime. The optimal design of hosts with tailored porous structures and catalytic sites is expected to address this issue. Herein, a Bi/Bi2O3 heterostructure within the metal-organic framework (MOF)-derived sulfur host with a hierarchical structure was elaborated for both serving as sulfur hosts and promoting the redox reaction kinetics of LiPSs. The shuttle effects of LiPSs can be mitigated by the dual functional Bi/Bi2O3 heterostructure enriched in the outer layer of CAU-17-derived carbonic rods, i.e., the effective redox conversion of LiPSs can be realized at the Bi/Bi2O3 heterointerface by the adsorption of LiPSs over Bi2O3 and subsequently catalytic conversion over Bi. Benefiting from these merits, the fabricated LSBs realized a significantly optimized performance, including a high discharge capacity of 740.8 mAh g-1 after 1000 cycles with an ultralow decay rate of 0.022% per cycle at 1 C, a high areal capacity of 6.6 mAh cm-2 after 100 cycles with a sulfur loading of 8.1 mg cm-2, and good performance in pouch cells as well.

Design of thiol-lithium ion interaction in metal-organic framework for high-performance quasi-solid lithium metal batteries.

Metal-organic frameworks (MOFs) have recently emerged as promising solid electrolytes (SEs) for solid-state batteries (SSBs). Developing MOFs with high-density functional groups may improve the spatial density of hopping sites and facilitate ion transport. Herein we synthesized a new series of ion conductive MOFs, Zr-MA-M (M = Li+, Na+, K+, Zn2+), with high density -SH groups functionalized in small pores and metal ions adsorbed on the thiol groups. Taking advantage of the interaction between S and metal ions, such ion conductors show high ionic conductivity, low interfacial resistance, high lithium ion (Li+) transference number (0.63) and wide electrochemical window up (4.6 V). Moreover, the SSBs assembled with Zr-MA-Li+ based SE exhibit excellent rate performance (106 mA h g-1 at 2C) and remarkable cyclic stability (low decay rate of 0.21‰ per cycle for 700 cycles at 2C). Thus, this study provides a new route for developing high-performance MOF-based SEs via the application of host-guest interaction.

Co3O4 Supraparticle-Based Bubble Nanofiber and Bubble Nanosheet with Remarkable Electrochemical Performance.

Hollow nanostructures based on transition metal oxides (TMOs) with high surface-to-volumetric ratio, low density, and high loading capacity have received great attention for energy-related applications. However, the controllable fabrication of hybrid TMO-based hollow nanostructures in a simple and scalable manner remains challenging. Herein, a simple and scalable strategy is used to prepare hierarchical carbon nanofiber (CNF)-based bubble-nanofiber-structured and reduced graphene oxide (RGO)-based bubble-nanosheet-structured Co3O4 hollow supraparticle (HSP) composites (denoted as CNF/HSP-Co3O4 and RGO/HSP-Co3O4, respectively) by solution self-assembly of ultrasmall Co3O4 nanoparticles (NPs) assisting with polydopamine (PDA) modification. It is proved that the electrochemical performance of Co3O4 NPs can be greatly enhanced by the rationally designed nanostructure of bubble-like supraparticles combined with carbon materials as excellent electrodes for supercapacitors. The favorable structure and composition endow the hybrid electrode with high specific capacitance (1435 F g-1/1360 F g-1 at 1 A g-1/5 mV s-1) as well as fantastic rate capability. The asymmetric supercapacitors achieve an excellent maximum energy density of 51 W h kg-1 and superb electrochemical stability (92.3% retention after 10 000 cycles). This work suggests that the rational design of electrode materials with bubble-like superstructures provides an opportunity for achieving high-performance electrode materials for advanced energy storage devices.

Hierarchical Nanosheets/Walls Structured Carbon-Coated Porous Vanadium Nitride Anodes Enable Wide-Voltage-Window Aqueous Asymmetric Supercapacitors with High Energy Density.

The energy density of aqueous asymmetric supercapacitors (ASCs) is usually limited by low potential windows and capacitances of both anode and cathode. Herein, a facile strategy to fabricate hierarchical carbon-coated porous vanadium nitride nanosheet arrays on vertically aligned carbon walls (CC/CW/p-VN@C) as anode for aqueous ASCs is reported. The potential window of CC/CW/p-VN@C electrode can be stably extended to -1.3 to 0 V (vs Ag/AgCl) with greatly improved specific capacitance (604.8 F g-1 at 1 A g-1), excellent rate capability (368 F g-1 at 60 A g-1), and remarkable electrochemical stability. To construct ASCs, a Birnessite Na0.5MnO2 nanosheet arrays (CC/CW/Na0.5MnO2) cathode is similarly built. Benefiting from the matchable potential windows and high specific capacitances of the rationally designed anode and cathode, aqueous CC/CW/p-VN@C||CC/CW/Na0.5MnO2 ASCs with a wide voltage window of 2.6 V are fabricated. Moreover, the ASCs showcase an ultrahigh energy density up to 96.7 W h kg-1 at a high power density of 1294 W kg-1, and excellent cycling stability (92.5% retention after 10 000 cycles), outperforming most of previously reported ASCs and even comparable to that of organic electrolyte supercapacitors (SCs). This efficient strategy for fabricating 2.6 V aqueous ASCs suggests a promising research system for high energy density SCs.

Fe3O4-Encapsulating N-doped porous carbon materials as efficient oxygen reduction reaction electrocatalysts for Zn-air batteries.

Fe3O4 nanoparticle-encapsulating N-doped porous carbon was synthesized. Owing to the large specific surface area, hierarchical porous structure, and sufficient number of active sites from the graphitic carbon wrapped Fe3O4 NPs as well as the joint effect with Fe-Nx moieties, the as-prepared 2D-Fe3O4@FeNC-700 electrocatalyst exhibits exceptional performance in Zn-air batteries.

Facile and Scalable Fabrication of Nitrogen-Doped Porous Carbon Nanosheets for Capacitive Energy Storage with Ultrahigh Energy Density.

Porous carbon materials are the most commonly used electrode materials for supercapacitors because of their abundant structures, excellent conductivities, and chemical stability. However, the manufacture of carbon materials possessing sizable pores and remarkable wettability with the electrolyte remains challenging. Herein, we developed a facile and industrially scalable method for the production of nitrogen-doped porous carbon nanosheets (PNDC-4) with excellent pore size distribution, large specific surface area (>1200 m2 g-1), high conductivity (>700 S m-1), and superb wettability either in aqueous or organic electrolyte. Particularly, PNDC-4 shows a high capacitance of 387 F g-1 (1 A g-1) in a three-electrode system with 3 M KOH and 80 F g-1 (1 A g-1) in a symmetric two-electrode system with EMIMBF4. The device exhibits an ultrahigh energy density of 81 W h kg-1 at a power density of 1.3 kW kg-1 and can still maintain at 60.8 W h kg-1 when the power density is increased to 266.6 kW kg-1. Moreover, the devices show superb stability that 94% of its initial capacitance is still maintained after 100 000 cycles at 20 A g-1.

When Al-Doped Cobalt Sulfide Nanosheets Meet Nickel Nanotube Arrays: A Highly Efficient and Stable Cathode for Asymmetric Supercapacitors.

Although cobalt sulfide is a promising electrode material for supercapacitors, its wide application is limited by relative poor electrochemical performance, low electrical conductivity, and inefficient nanostructure. Here, we demonstrated that the electrochemical activity of cobalt sulfide could be significantly improved by Al doping. We designed and fabricated hierarchical core-branch Al-doped cobalt sulfide nanosheets anchored on Ni nanotube arrays combined with carbon cloth (denoted as CC/H-Ni@Al-Co-S) as an excellent self-standing cathode for asymmetric supercapacitors (ASCs). The combination of structural and compositional advantages endows the CC/H-Ni@Al-Co-S electrode with superior electrochemical performance with high specific capacitance (1830 F g-1/2434 F g-1 at 5 mV s-1/1 A g-1) and excellent rate capability (57.2%/72.3% retention at 1000 mV s-1/100 A g-1). The corresponding all-solid-state ASCs with CC/H-Ni@Al-Co-S and multilayer graphene/CNT film as cathode and anode, respectively, achieve a high energy density up to 65.7 W h kg-1 as well as superb cycling stability (90.6% retention after 10 000 cycles). Moreover, the ASCs also exhibit good flexibility and stability under different bending conditions. This work provides a general, effective route to prepare high-performance electrode materials for flexible all-solid-state energy storage devices.