Recent Progress in Covalent Organic Frameworks for Cathode Materials.

Covalent organic frameworks (COFs) are constructed from small organic molecules through reversible covalent bonds, and are therefore considered a special type of polymer. Small organic molecules are divided into nodes and connectors based on their roles in the COF's structure. The connector generally forms reversible covalent bonds with the node through two reactive end groups. The adjustment of the length of the connector facilitates the adjustment of pore size. Due to the diversity of organic small molecules and reversible covalent bonds, COFs have formed a large family since their synthesis in 2005. Among them, a type of COF containing redox active groups such as -C=O-, -C=N-, and -N=N- has received widespread attention in the field of energy storage. The ordered crystal structure of COFs ensures the ordered arrangement and consistent size of pores, which is conducive to the formation of unobstructed ion channels, giving these COFs a high-rate performance and a long cycle life. The voltage and specific capacity jointly determine the energy density of cathode materials. For the COFs' cathode materials, the voltage plateau of their active sites' VS metallic lithium is mostly between 2 and 3 V, which has great room for improvement. However, there is currently no feasible strategy for this. Therefore, previous studies mainly improved the theoretical specific capacity of the COFs' cathode materials by increasing the number of active sites. We have summarized the progress in the research on these types of COFs in recent years and found that the redox active functional groups of these COFs can be divided into six subcategories. According to the different active functional groups, these COFs are also divided into six subcategories. Here, we summarize the structure, synthesis unit, specific surface area, specific capacity, and voltage range of these cathode COFs.

Universal Synthesis of Half-Metallic Diatomic Catalysts for Efficient Oxygen Reduction Electrocatalysis.

Developing efficient and low-cost noble-free metal electrocatalysts is an urgent requirement. Herein, a one-step, solid-state template-assisted method for fabricating isolated half-metallic diatomic M, Zn─N─C (M═Fe, Co, and Ni) catalysts is reported. In particular, the fabricated Fe, Zn─N─C structure exhibits superior oxygen reduction reaction capabilities with a half-wave potential of 0.867 V versus RHE. The Mossbauer spectra reveal that the Fe, Zn─N─C half-metallic diatomic catalyst has a large proportion of the D2 site (ferrous iron with a medium spin state). Density functional theory (DFT) reveals that in Fe, Zn─N─C structures, the zinc sites play a unique role in accelerating the protonation process of O2 in ORR. In assembled zinc-air batteries, a maximum power density of 138 mW cm-2 and a capacity of 748 mAh g zn-1 can be obtained. This work fabricates a series of efficient M, Zn─N─C diatomic electrocatalysts, and the developed solid-state reaction method can hopefully apply in other energy conversion and storage fields.

High entropy alloy nanoparticles encapsulated in graphitised hollow carbon tubes for oxygen reduction electrocatalysis.

High entropy alloys (HEAs) with a tunable alloy composition and fascinating synergetic effects between various metals have attracted significant attention in the field of electrocatalysis, but their potential is limited by inefficient and unscalable fabrication methodologies. This work proposes a novel solid-state thermal reaction method to synthesise HEA nanoparticles encapsulated in an N-doped graphitised hollow carbon tube. This facile method is simple and efficient and involves no use of organic solvents during the fabrication process. The synthesized HEA nanoparticles are confined by the graphitised hollow carbon tube, which is possibly beneficial for preventing the aggregation of alloy particles during the oxygen reduction reaction (ORR). In a 0.1 M KOH solution, the HEA catalyst FeCoNiMnCu-1000(1 : 1) exhibits an onset and half-wave potential of 0.92 V and 0.78 V (vs. RHE), respectively. We assembled a Zn-Air battery with FeCoNiMnCu-1000 as a catalyst for the air electrode, and a power density of 81 mW cm-2 and a long-term durability of >200 h were achieved, which is comparable to the performance of the state-of-the-art catalyst Pt/C-RuO2. This work herein offers a scalable and green method for synthesising multinary transition metal-based HEAs and highlights the potential of HEA nanoparticles as electrocatalysts for energy storage and conversion.

Tuning Metal-Organic Framework (MOF) Topology by Regulating Ligand and Secondary Building Unit (SBU) Geometry: Structures Built on 8-Connected M6 (M = Zr, Y) Clusters and a Flexible Tetracarboxylate for Propane-Selective Propane/Propylene Separation.

Topology evolution originating from variations of linker and SBU (Secondary Building Unit) geometries could largely enrich the chemistry of metal-organic frameworks (MOFs). Here we report the synthesis and characterization of three MOF structures built on the same organic linker, N,N,N',N'-Tetrakis(4-carboxyphenyl)-1,4-phenylenediamine (tcppda) and similar 8-connected M6 (M = Zr or Y) clusters. The three compounds, HIAM-402, HIAM-403, and HIAM-311, feature 4,8-connected sqc, scu, and flu topology, respectively. Detailed structural analysis revealed that different geometries of the inorganic M6 SBUs as well as the organic linker have led to the formation of distinct MOF nets. In particular, HIAM-402 features exceptional framework stability and high porosity and acts as a propane-selective adsorbent for the discrimination of propane and propylene. Its balanced adsorption selectivity (Spropane/propylene = 1.43) and capacity (Qpropane = 133.3 cm3/g, 298 K and 1 bar) endow it with the capability of separating propane and propylene mixtures and one-step production of highly pure propylene (purity >99.9%), as validated by column breakthrough measurements, with the presence of moisture or propyne. Ab initio calculations further confirm that the propane-selective behavior of HIAM-402 is a result of its higher binding energy toward propane compared to that of propylene.

A Robust Ca-Based Microporous Metal-Organic Framework for Thermodynamic Separation of Hexane Isomers.

Adsorptive separation of alkane isomers, especially the efficient separation of mono- and dibranched alkanes, remains challenging in the petrochemical industry. We report here the discrimination of alkane isomers through a thermodynamically driven mechanism by a highly stable calcium-based metal-organic framework. This newly developed 3D structure is built on a tetracarboxylate linker, featuring 1D channels with optimal pore dimensions to discriminate alkane isomers.

Facile synthesis of hierarchical MoS2/ZnS @ porous hollow carbon nanofibers for a stable Li metal anode.

Lithium metal is considered as an ideal anode candidate for next generation Li battery systems since its high capacity, low density, and low working potential. However, the uncontrollable growth of Li dendrites and infinite volume expansion impede the commercialized applications of Li-metal anodes. In this work, we rationally designed and constructed a hierarchical porous hollow carbon nanofiber decorated with diverse metal sulfides (MS-ZS@PHC). This composite scaffold has three advantages: First, the synergistic effect of multiple-size lithiophilic phases (nano ZnS and micro MoS2) can regulate Li ions nuclei and grow up homogenously on the scaffold. Second, the enlarged interplanar spacing of MoS2 microsphere on the fibers can provide abundant channels for Li ions transportation. Third, the porous scaffold can confine the volume expansion of Li metal anode during cycling. Therefore, in a symmetrical cell, the MS-ZS@PHC host presents a homogenous Li plating/stripping behavior and runs steadily for 1100 h at 5 mA cm-2 with a capacity of 5 mAh cm-2 and even for 700 h at 10 mA cm-2 with a capacity of 1 mAh cm-2. A full cell using MS-ZS@PHC /Li composite as anode and coupled with LiFePO4 as cathode delivers an excellent cyclic and rate performances.

Random Occupation of Multimetal Sites in Transition Metal-Organic Frameworks for Boosting the Oxygen Evolution Reaction.

Developing robust oxygen evolution reaction (OER) electrocatalysts with excellent performance is essential for the conversion of renewable electricity to clean fuel. Herein, we present a facile concept for the synthesis of efficient high-entropy metal-organic frameworks (HEMOFs) as electrocatalysts in a one-step solvothermal synthesis. This strategy allows control of the microstructure and corresponding lattice distortion by tuning the metal ion composition. As a result, the OER activity was improved by optimizing the coordination environment of the metal catalytic center. The optimized Co-rich HEMOFs exhibited a low overpotential of 310 mV at a current density of 10 mA cm-2 , better than a RuO2 catalyst tested under the same conditions. The finding of lattice distortion of the HEMOFs provides a new strategy for developing high-performance electrocatalysts for energy conversion.

Metal organic framework-coated gold nanorod as an on-demand drug delivery platform for chemo-photothermal cancer therapy.

Chemo-photothermal therapy based on nanoparticles has emerged as a promising strategy for cancer treatment. However, its therapeutic efficacy and application potential are largely subjected to the uncontrollability and biotoxicity of functional nanoplatforms. Herein, a novel biocompatible and biodegradable metal organic framework (MOF), which was constructed by growing crystalline zeolitic imidazolate framework-8 on gold nanoroad (Au@ZIF-8), was designed and fabricated for efficient drug loading and controlled release. Owing to the large surface area and guest-matching pore size of ZIF-8, doxorubicin (DOX) was successfully loaded into the Au@ZIF-8 with a high drug loading efficiency of ~ 37%. Under NIR light or weakly acidic environment, the ZIF-8 layer was quickly degraded, which resulted in an on-demand drug release in tumour site. More importantly, under the irradiation of near infrared (NIR) laser, highly efficient cancer treatment was achieved in both in vitro cell experiment and in vivo tumour-bearing nude mice experiment due to the synergistic effect of photothermal (PTT) therapy and chemotherapy. In addition, the in vivo study revealed the good biocompatibility of Au@ZIF-8. This work robustly suggested that Au@ZIF-8 could be further explored as a drug delivery system for chemo-photothermal synergistic therapy.

Defect-rich honeycomb-like nickel cobalt sulfides on graphene through rapid microwave-induced synthesis for ultrahigh rate supercapacitors.

Nickel cobalt sulfides (NCS) are regarded as potential energy storage materials due to the versatile valent states and rich electrochemical activity, but their sluggish synthesis process and inferior rate performance hinder them from large-scale application. Herein, microwave-induced strategy has been employed for efficient synthesis of honeycomb-like NCS/graphene composites, which are explored as ultrahigh rate battery-type electrodes for supercapacitors. Due to the internal heat mechanism, the synthesis time of NCS by microwave could be shortened from hours to minutes. Density functional theory was simulated to uncover the interfacial effect between NCS and graphene, and the resulted Schottky barrier is in favor of enhancing redox activity and capacity. Ultimately, the obtained defect-rich nickel cobalt sulfides/graphene with thermal treatment (NCS/G-H) could exhibit a high specific capacitance of 1186 F g-1 at 1 A g-1 and sustain 89.8% capacity even after the increase of current density over 20 times, which is much superior to bare NCS and NCS/graphene. Furthermore, the assembled NCS/G-H hybrid supercapacitor delivers supreme energy density of 46.4 Wh kg-1, and retains outstanding long-term stability of 89.2% after 10 k cycles. These results indicate that the synthesized NCS/G-H by time-saving microwave-induced liquid process could be served as high rate materials for supercapacitors.

Al-based metal organic framework derived self-assembled carbon nanosheets as innovative anodes for Li- and Na-ion batteries.

Functional modification and structural design of carbon electrode materials are considered as a cost-effective method to improve their electrochemical performance. In this study, a solvothermal method is applied to realize self-assembly of the metal-organic framework. After simple carbonization and acid treatment, carbon nanosheets with 2D adjustable defective sub-units are successfully prepared for the first time. It is found that carbonization temperature has a significant effect on the carbon skeleton structure. The optimal nanostructures with large specific surface area and appropriate pore size distribution make self-assembled carbon nanosheets having excellent Li/Na-ion storage properties. In addition, the adjustable carbon skeleton structure can effectively avoid irreversible damage when charge-discharge cycles. For Li-ion batteries, a specific capacity of 825 mAh g-1 is achieved after 100 cycles at 100 mA g-1, while for Na-ion batteries a specific capacity of 193 mAh g-1 is observed after 100 cycles at 100 mA g-1. Moreover, for Na-ion batteries, even at a high rate of 1000 mA g-1 the material delivers a specific capacity of 109.5 mAh g-1 after 3500 cycles.

High-performance supercapacitors based on hierarchically porous carbons with a three-dimensional conductive network structure.

Clews of polymer nanobelts (CsPNBs) have the advantages of inexpensive raw materials, simple synthesis and large output. Novel clews of carbon nanobelts (CsCNBs) have been successfully prepared by carbonizing CsPNBs and by KOH activation subsequently. From the optimized process, CsCNBs*4, with a specific surface area of 2291 m2 g-1 and a pore volume of up to 1.29 cm3 g-1, has been obtained. Fundamentally, the CsCNBs possess a three-dimensional conductive network structure, a hierarchically porous framework, and excellent hydrophilicity, which enable fast ion diffusion through channels and a large enough ion adsorption/desorption surface to improve electrochemical performance of supercapacitors. The product exhibits a high specific capacitance of 327.5 F g-1 at a current density of 0.5 A g-1 in a three-electrode system. The results also reveal a high-rate capacitance (72.2% capacitance retention at 500 mV s-1) and stable cycling lifetime (95% of initial capacitance after 15 000 cycles). Moreover, CsCNBs*4 provides a high energy density of 29.8 W h kg-1 at a power density of 345.4 W kg-1 in 1 M tetraethylammonium tetrafluoroborate/acetonitrile (TEABF4/AN) electrolyte. These inspiring results imply that this carbon material with a three-dimensional conductive network structure possesses excellent potential for energy storage.

Microwave-assisted rapid preparation of hollow carbon nanospheres@TiN nanoparticles for lithium-sulfur batteries.

Highly conductive titanium nitride (TiN) has a strong anchoring ability for lithium polysulfides (LiPSs). However, the complexity and high cost of fabrication limit their practical applications. Herein, a typical structure of hollow carbon nanospheres@TiN nanoparticles (HCNs@TiN) was designed and successfully synthesized via a microwave reduction method with the advantages of economy and efficiency. With unique structural and outstanding functional behavior, HCN@TiN-S hybrid electrodes display not only a high initial discharge capacity of 1097.8 mA h g-1 at 0.1C, but also excellent rate performance and cycling stability. After 200 cycles, a reversible capacity of 812.6 mA h g-1 is still retained, corresponding to 74% capacity retention of the original capacity and 0.13% decay rate per cycle, which are much better than those of HCNs-S electrodes.

Evolving mechanism of organotemplate-free hierarchical FAU zeolites with house-of-card-like structures.

Hierarchical FAU zeolites with house-of-card-like (HCL) structures were synthesized through a one-pot organotemplate-free route in the Na2O-Al2O3-SiO2-H2O system. The structure details and formation mechanism of HCL zeolites were determined by the combination of electron crystallography and synthesis chemistry. The results revealed that the unique HCL morphology was attributed to large solution viscosity, and the evolution process obeyed a skeleton crystal growth model due to the limited vortexing effect, which was different from those of the HCL zeolites obtained using organic templates.

A Universal Strategy To Prepare Sulfur-Containing Polymer Composites with Desired Morphologies for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are probably the most promising candidates for the next-generation batteries owing to their high energy density. However, Li-S batteries face severe technical problems where the dissolution of intermediate polysulfides is the biggest problem because it leads to the degradation of the cathode and the lithium anode, and finally the fast capacity decay. Compared with the composites of elemental sulfur and other matrices, sulfur-containing polymers (SCPs) have strong chemical bonds to sulfur and therefore show low dissolution of polysulfides. Unfortunately, most SCPs have very low electron conductivity and their morphologies can hardly be controlled, which undoubtedly depress the battery performances of SCPs. To overcome these two weaknesses of SCPs, a new strategy was developed for preparing SCP composites with enhanced conductivity and desired morphologies. With this strategy, macroporous SCP composites were successfully prepared from hierarchical porous carbon. The composites displayed discharge/charge capacities up to 1218/1139, 949/922, and 796/785 mA h g-1 at the current rates of 5, 10, and 15 C, respectively. Considering the universality of this strategy and the numerous morphologies of carbon materials, this strategy opens many opportunities for making carbon/SCP composites with novel morphologies.

Nitrogen-doped graphitic hierarchically porous carbon nanofibers obtained via bimetallic-coordination organic framework modification and their application in supercapacitors.

Herein, N-doped graphitic hierarchically porous carbon nanofibers (NGHPCF) were prepared by electrospinning the composite of bimetallic-coordination metal-organic frameworks and polyacrylonitrile, followed by a pyrolysis and acid wash process. Control over the N content, specific surface area, and degree of graphitization of NGHPCF materials has been realized by adjusting the Co/Zn metal coordination content as well as the pyrolysis temperature. The obtained NGHPCF with a high specific surface area (623 m2 g-1) and nitrogen content (13.83 wt%) exhibit a high capacitance of 326 F g-1 at 0.5 A g-1. In addition, the capacitance of 170 F g-1 is still maintained at a high current density (40 A g-1); this indicates a high capacitance retention capability. Furthermore, a superb energy density (9.61 W h kg-1) is obtained with a high power density (62.4 W kg-1) using an organic electrolyte. These results fully illustrate that the prepared NGHPCF binder-free electrodes are promising candidates for high-performance supercapacitors.

Facile Synthesis of Nitrogen and Oxygen Co-Doped Clews of Carbon Nanobelts for Supercapacitors with Excellent Rate Performance.

Facile synthesis of carbon materials with high heteroatom content, large specific surface area (SSA) and hierarchical porous structure is critical for energy storage applications. In this study, nitrogen and oxygen co-doped clews of carbon nanobelts (NCNBs) with hierarchical porous structures are successfully prepared by a carbonization and subsequent activation by using ladder polymer of hydroquinone and formaldehyde (LPHF) as the precursor and ammonia as the activating agent. The hierarchical porous structures and ultra-high SSA (up to 2994 m² g−1) can effectively facilitate the exchange and transportation of electrons and ions. Moreover, suitable heteroatom content is believed to modify the wettability of the carbon material. The as-prepared activated NCNBs-60 (the NCNBs activated by ammonia at 950 °C for 60 min) possess a high capacitance of 282 F g−1 at the current density of 0.25 A g−1, NCNBs-45 (the NCNBs are activated by ammonia at 950 °C for 45 min) and show an excellent capacity retention of 50.2% when the current density increase from 0.25 to 150 A g−1. Moreover, the NCNBs-45 electrode exhibits superior electrochemical stability with 96.2% capacity retention after 10,000 cycles at 5.0 A g−1. The newly prepared NCNBs thus show great potential in the field of energy storage.

Conducting polymer-coated MIL-101/S composite with scale-like shell structure for improving Li-S batteries.

Lithium-sulfur batteries are regarded as a promising energy storage system. However, they are plagued by rapid capacity decay, low coulombic efficiency, a severe shuttle effect and low sulfur loading in cathodes. To address these problems, effective carriers are highly demanded to encapsulate sulfur in order to extend the cycle life. Herein, we introduced a doped-PEDOT:PSS-coated MIL-101/S multi-core-shell structured composite. The unique structure of MIL-101, large specific area and conductive shell ensure high dispersion of sulfur in the composite and minimize the loss of polysulfides to the electrolyte. The doped-PEDOT:PSS-coated sulfur electrodes exhibited an increase in initial capacity and an improvement in rate characteristics. After 192 cycles at the current density of 0.1C, a doped-PEDOT:PSS-coated MIL-101/S electrode maintained a capacity of 606.62 mA h g-1, while the MIL-101/S@PEDOT:PSS electrode delivered a capacity of 456.69 mA h g-1. The EIS measurement revealed that the surface modification with the conducting polymer provided a lower resistance to the sulfur electrode, which resulted in better electrochemical behaviors in Li-S battery applications. Test results indicate that the MIL-101/S@doped-PEDOT:PSS is a promising host material for the sulfur cathode in the lithium-sulfur battery applications.

Facile Synthesis of Ultrahigh-Surface-Area Hollow Carbon Nanospheres and their Application in Lithium-Sulfur Batteries.

Hollow carbon nanospheres (HCNs) with specific surface areas up to 2949 m2 g-1 and pore volume up to 2.9 cm3 g-1 were successfully synthesized from polyaniline-co-polypyrrole hollow nanospheres by carbonization and CO2 activation. The cavity diameter and wall thickness of HCNs can be easily controlled by activation time. Owing to their large inner cavity and enclosed structure, HCNs are desirable carriers for encapsulating sulfur. To better understand the effects of pore characteristics and sulfur contents on the performances of lithium-sulfur batteries, three composites of HCNs and sulfur are prepared and studied in detail. The composites of HCNs with moderate specific surface areas and suitable sulfur content present a better performance. The first discharge capacity of this composite reaches 1401 mAh g-1 at 0.2 C. Even after 200 cycles, the discharge capacity remains at 626 mAh g-1 .

Facile synthesis of high-surface-area nanoporous carbon from biomass resources and its application in supercapacitors.

It is critical for nanoporous carbons to have a large surface area, and low cost and be readily available for challenging energy and environmental issues. The pursuit of all three characteristics, particularly large surface area, is a formidable challenge because traditional methods to produce porous carbon materials with a high surface area are complicated and expensive, frequently resulting in pollution (commonly from the activation process). Here we report a facile method to synthesize nanoporous carbon materials with a high surface area of up to 1234 m2 g-1 and an average pore diameter of 0.88 nm through a simple carbonization procedure with carefully selected carbon precursors (biomass material) and carbonization conditions. It is the high surface area that leads to a high capacitance (up to 213 F g-1 at 0.1 A g-1) and a stable cycle performance (6.6% loss over 12 000 cycles) as shown in a three-electrode cell. Furthermore, the high capacitance (107 F g-1 at 0.1 A g-1) can be obtained in a supercapacitor device. This facile approach may open a door for the preparation of high surface area porous carbons for energy storage.

Photocatalytic Performance of a Novel MOF/BiFeO3 Composite.

In this study, MOF/BiFeO3 composite (MOF, metal-organic framework) has been synthesized successfully through a one-pot hydrothermal method. The MOF/BiFeO3 composite samples, pure MOF samples and BiFeO3 samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and by UV-vis spectrophotometry. The results and analysis reveal that MOF/BiFeO3 composite has better photocatalytic behavior for methylene blue (MB) compared to pure MOF and pure BiFeO3. The enhancement of photocatalytic performance should be due to the introduction of MOF change the surface morphology of BiFeO3, which will increase the contact area with MB. This composing strategy of MOF/BiFeO3 composite may bring new insight into the designing of highly efficient photocatalysts.