金属有机框架及其衍生金属氧化物在锂和钠离子电池中的应用

高性能锂和钠离子电池是未来便携电子设备、电动汽车和大规模储能电站的重要组成部分,受到了各行业的广泛关注。目前商用的锂离子电池和研发中的钠离子电池都面临着一些技术瓶颈,主要表现为能量密度低、充放电慢等,导致无法满足市场的需求。具有独特结构、高比表面积的金属有机框架及其衍生金属氧化物可作为电化学储能器件新型电极材料,满足高性能锂和钠离子电池的要求。本文综述了近年来金属有机框架及其衍生金属氧化物作为锂和钠离子电池电极材料的研究进展,同时指出了金属有机框架及其衍生金属氧化物在实际应用中的不足及未来可能的一些改进措施。     

Graphene‐based ternary composites for supercapacitors

The research on electrode materials for supercapacitor application continues to evolve as the request of high‐energy storage system has increased globally due to the demand for energy consumption. Over the past decades, various types of carbon‐based materials have been employed as electrode materials for high‐performance supercapacitor application. Among them, graphene is 1 of the most widely used carbon‐based materials due to its excellent properties including high surface area and excellent conductivity. To exploit more of its interesting properties, graphene is tailored to produce graphene oxide and reduced graphene oxide to improve the dispersibility in water and easy to be incorporated with other materials to form binary composites or even ternary composites. Nowadays, ternary composites have attracted enormous interest as 2 materials (binary composites) cannot satisfy the requirement of the high‐performance supercapacitor. Thus, many approaches have been employed to fabricate ternary composites by combining 3 different types of electroactive materials for high‐performance supercapacitor application. This review focuses on the supercapacitive performance of graphene‐based ternary composites with different types of active materials, ie, conducting polymers, metal oxide, and other carbon‐based materials.     

Room-temperature hydrogen storage performance of metal-organic framework/graphene oxide composites by molecular simulations

Metal-organic framework/graphene oxide (MOF/GO) composites have been regarded as potential room-temperature hydrogen storage materials recently. In this work, the influence of MOF structural properties, GO functional group contents and different amounts of doped lithium (Li⁺) on hydrogen storage performance of different MOF/GO composites were investigated by grand canonical Monte Carlo (GCMC) simulations. It is found that MOF/GO composites based on small-pore MOFs exhibit enhanced hydrogen storage capacity, whereas MOF/GO based on large-pore MOFs show decreased hydrogen storage capacity, which can be ascribed to the novel pores at MOF/GO interface that favors the enhanced hydrogen storage performance due to the increased pore volume/surface area. By integrating the small-pore MOF-1 with GO, the hydrogen storage capacity was enhanced from 9.88 mg/go up to 11.48 mg/g. However, the interfacial pores are smaller compared with those in large-pore MOFs, resulting in significantly reduced pore volume/surface area as well as hydrogen storage capacities of large-pore MOF/GO composite. Moreover, with the increased contents of hydroxyl, epoxy groups as well as carboxyl group modification, the pore volumes and specific surface areas of MOF/GO are decreased, resulting in reduced hydrogen storage performance. Furthermore, the room-temperature hydrogen storage capacities of Li⁺ doped MOF/GO was improved with increased Li⁺ at low loading and decrease with the increased Li⁺ amounts at high loading. This is due to that the introduced Li⁺ effectively increases the accessible hydrogen adsorption sites at low Li⁺ loading, which eventually favors the hydrogen adsorption capacity. However, high Li⁺ loading causes ion aggregation that reduces the accessible hydrogen adsorption sites, leading to decreased hydrogen storage capacities. MOF-5/GO composites with moderate Li⁺ doping achieved the optimum hydrogen storage capacities of approximately 29 mg/g.     

Novel strategies to tailor the photocatalytic activity of metal–organic frameworks for hydrogen generation: a mini-review

This review provides a recompilation of the most important and recent strategies employed to increase the efficiency of metal–organic framework (MOF)-based systems toward the photocatalytic hydrogen evolution (PHE) reaction through specific strategies: tailoring the photocatalytic activity of bare MOFs and guest@MOF composites, formation of heterojunctions based on MOFs and various photocatalysts, and inorganic photocatalysts derived from MOFs. According to the data reported in this mini-review, the most effective strategy to improve the PHE of MOFs relies on modifying the linkers with new secondary building units (SBUs). Although several reviews have investigated the photocatalytic activity of MOFs from a general point of view, many of these studies relate this activity to the physicochemical and catalytic properties of MOFs. However, they did not consider the interactions between the components of the photocatalytic material. This study highlights the effects of strength of the supramolecular interactions on the photocatalytic performance of bare and MOF-based materials during PHE. A thorough review and comparison of the results established that metal–nanoparticle@MOF composites have weak van der Waals forces between components, whereas heterostructures only interact with MOFs at the surface of bare materials. Regarding material derivatives from MOFs, we found that pyrolysis destroyed some beneficial properties of MOFs for PHE. Thus, we conclude that adding SBUs to organic linkers is the most efficient strategy to perform the PHE because the SBUs added to the MOFs promote synergy between the two materials through strong coordination bonds.     

Novel in-situ P-doped metal-organic frameworks derived cobalt and heteroatoms co-doped carbon matrix as high-efficient electrocatalysts

Metal organic frameworks (MOFs) are considered as ideal templates for the synthesis of metal-heteroatom co-doped carbon materials. However, the tedious heteroatoms doping pathways hinders the maximizing of catalytic performances. Herein, we synthesize a series of high-efficient Co and N, P heteroatoms co-doped carbon-based composites by first constructing a novel in-situ P-doped MOF with novel larger N, P-containing ligands and 2-methylimidazole as mixed ligands, and then calcining these MOFs at high temperature. During the pyrolysis process, the generated gases derived from the thermal decomposition of organic ligands are liberated from inner of P-ZIF materials to make the Co–Co₂P@NC-P catalysts become loose and porous. When being used as electrode materials, the optimal Co–Co₂P@NC-P₃-700 catalyst exhibits excellent ORR and OER activity, the ORR performance is superior to the Pt/C catalysts, and the OER performance can be comparable with the commercial RuO₂ catalyst. Moreover, when applied in the assembled primary Zn-air battery, the performances of Co–Co₂P@NC-P₃-700 catalyst can outperform the commercial Pt/C catalysts, exhibiting a high peak power density, specific capacity and a long-term stability. Furthermore, the catalytic active sites of catalysts are carefully investigated in this work.     

Nanoporous metal organic framework materials for smart applications

Abstract

This review is concerned with the recent advances in metal organic framework (MOF) materials. We highlight the unique combination of physicochemical and thermomechanical characteristics associated with MOF-type materials and illustrate emergent applications in three challenging technological sectors: energy, environmental remediation and biomedicine. MOFs represent an exciting new class of nanoporous crystalline solids constituting metal ions/clusters and multifunctional organic linkages, which self-assemble at molecular level to generate a plethora of ordered 3D framework materials. The most intriguing feature of a MOF lies in its exceptionally large surface area, far surpassing those of the best activated carbons and zeolites. Next generation multifunctional materials encompassing MOF based thin films, coatings, membranes and nanocomposites have potential for exploitation in an immense array of unconventional applications and smart devices. We pinpoint the key technological challenges and basic scientific questions to be addressed, so as to fulfil the translational potential for bringing MOFs from the laboratory into commercial applications.     

High electrochemical performance of metal azolate framework-derived ZnO/Co3O4 for supercapacitors

Metal azolate frameworks MAF-6 (Zn, Zn Co, and Co) were fabricated with a facile solution mixture method. Flower-like ZnO/Co₃O₄ was synthesized with MAF-6 as the template in a solvothermal condition of 90°C for 2 hours. The produced materials were characterized by XRD, EDS, SEM, and XPS. MAF-6 and the derived metal oxides acted as the electrode materials of supercapacitors. This study reported that ZnO/Co₃O₄ exhibited the maximal specific capacitance of 830.20 F/g at 1A/g, resulting from the synergy of Zn and Co and the enhanced conductivity. Furthermore, ZnO/Co₃O₄ electrode exhibited prominent rate capacitance, high electrochemical reversibility, and long life (89% capacitance was kept after 1000 cycles at 1 A/g). Given the results of this study, the prepared ZnO/Co₃O₄ electrode can be demonstrated as a potential candidate in the field of renewable energy storage.     

Hydrothermal synthesis of nano-sized MnO2 supported on attapulgite electrode materials for supercapacitors

Among the electrode materials of supercapacitors, transition metal oxides have been widely used because of their low price, high theoretical capacitance and good cycle stability, and MnO₂ is one of the typical representative materials. However, the actual specific capacitance of MnO₂ is low because of its poor conductivity, easy agglomeration in the preparation process and large volume change in the process of repeated charge and discharge. Attapulgite can not only provide a large specific surface area for transition metal oxide materials, but also provide a skeleton on which nano-sized materials can be grown or dispersed. Therefore, the electrochemical performance of electrode materials can be improved by designing nanostructures and compounding a variety of materials with different properties. Herein, a new type of composites electrode material is prepared by simple one-step hydrothermal method. As an electrode material, the ATP-MnO₂ composites exhibited a high specific capacitance of 138.2 F/g at a current density of 0.5 A/g, which was 13.4% higher than that of pure MnO₂ nanoflowers. Under the current density of 3 A/g, the capacitance retention of ATP-MnO₂ composites was 89.4% after 5000 cycles.     

Metal-organic frameworks as highly efficient electrodes for long cycling stability supercapacitors

Among a large variety of energy storage technologies, supercapacitors possess special advantages such as rapid charge/discharge, high power density, safety, and environmental friendliness to meet the requirement of specific applications. The common electrode materials of supercapacitors, including porous carbon, conductive polymers, and metal oxides/hydroxides, have their own benefits and drawbacks in energy density and stability. Owing to the big surface area and controllable porosity, the metal-organic frameworks (MOFs) have been explored as important candidates for supercapacitor applications. This mini-review focuses on the recent advances of MOF-based materials including pristine MOFs, MOFs composite materials, and MOF-derived materials in the development of long cycling life supercapacitors. The devices discussed here mean those with capacitive retention rates of more than 90% after 10,000 cycles and high energy density. In addition, we also describe the fundamental knowledge of supercapacitors, highlight the stabilization mechanism of MOFs, and propose the strategies to enhance the stability of MOF-based supercapacitor electrodes.     

Fabrication and characterization of highly efficient three component CuBTC/graphene oxide/PSF membrane for gas separation application

Metal organic frameworks (MOFs) with marvelous properties have aroused enormous attention for different application especially gas adsorption and separation. In this regard, fabrication of MOF hybrids with carbon based materials is new strategy to upgrade MOF performance. In this study CuBTC (Copper benzene-1,3,5-tricarboxylic acid)/graphene oxide (GO) composite was synthesized and characterized by BET, SEM, TGA, XRD and FT-IR techniques. Then CuBTC and CuBTC/GO composite were incorporated into polysulfone (PSF) polymer to construct mixed matrix membranes (MMMs). The obtained membranes were characterized by SEM, TGA, XRD and tensile tests and their gas permeability was measured. The results were compared to those of CuBTC/PSF MMMs. It was revealed that CuBTC/GO composite as filler showed superior performance relative to CuBTC. For instance, 15 wt% loading of CuBTC/GO in PSF represented outstanding gas separation behavior while the same loading of CuBTC in PSF deteriorated performance of MMM. Well particle dispersion and favorable polymer-filler interaction were responsible for such observed difference. A high H₂/CH₄ and H₂/N₂ selectivity of 80.03 and 70.46 were recorded for CuBTC/GO in PSF (15 wt%) compared to 44.56 and 40.92 for CuBTC in PSF (15 wt%).     

Textile supercapacitors‐based on MnO2/SWNT/conducting polymer ternary composites

This paper describes a simple and fast process for the fabrication of flexible and textile‐based supercapacitors. Symmetric electrodes made up of binder‐free ternary composites of manganese oxide (MnO₂) nanoparticles, single walled carbon nanotubes (SWNT) and a conducting polymer (either polyaniline (PANI) or poly(3,4‐ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS)) were layer‐by‐layer deposited onto cotton substrates by dip coating method. Solid‐state supercapacitor devices were assembled using a gel electrolyte. Specific capacitances of 294 F/g and 246 F/g were obtained for MnO₂/SWNT/PANI and MnO₂/SWNT/PEDOT:PSS ternary nanocomposite supercapacitors, respectively. Power densities for these supercapacitors were 746.5 W/kg and 640.5 W/kg for MnO₂/SWNT/PANI and MnO₂/SWNT/PEDOT:PSS, respectively. Good capacity retention (more than 70%) upon cycling over 1000 times was achieved for both electrode compositions. Supercapacitors demonstrated in this work would be well suited as disposable power sources for wearable and intelligent textiles. Copyright © 2015 John Wiley & Sons, Ltd.     

Gel combustion synthesized NiMoO4 anchored polymer nanocomposites as a flexible electrode material for solid state asymmetric supercapacitors

Recent research has focused on the search for new electrode materials to improve the specific capacitance of supercapacitors. Conductive polymers and metal oxides have been extensively tested as electrode materials for supercapacitors. Incorporating both conductive polymers and metal oxides into a composite provides excellent results for the electrochemical performance of supercapacitors. In this present work, we have fabricated the nanoscale α-NiMoO₄ particles that enwrapped on electronically conducting polymer nanocomposites (PNCs) based on Polyvinyl alcohol (PVA)/Poly(vinyl) pyrrolidone (PVP) for supercapacitor applications. The different concentrations of PVA/PVP with α-NiMoO₄ loaded polymer nanocomposites were developed by using a solution casting method. All the polymer nanocomposites have been subjected to Scanning Electron Microscopy (SEM), Fourier Transforms Infrared (FTIR), X-ray diffraction (XRD), and electrochemical studies. The prepared PNCs surface morphology has been acquired as a non-uniform rod-like structure. The electrochemical performances of the prepared PNCs have been investigated and the resultant value of the maximum specific capacitance is 15.56 F g⁻¹ for 1 wt % of α-NiMoO₄ nanoparticles(NPs) loaded polymer blended electrode at a scan rate of 5 mVs⁻¹. The prepared PNCs exhibit 97.12% of columbic efficiency studied by using two electrode systems at room temperature in an aqueous electrolyte solution of 3 M KOH. From these investigation, it has been revealed that the PVA/PVP/α-NiMoO₄ composites could be portable and flexible electrodes for energy storage applications.     

Estimation of system-level hydrogen storage for metal-organic frameworks with high volumetric storage density

Metal organic framework (MOF) materials have emerged as the adsorbent materials with the highest H₂ storage densities on both a volumetric and gravimetric basis. While measurements of hydrogen storage at the material level (primarily at 77 K) have been published for hundreds of MOFs, estimates of the system-level hydrogen storage capacity are not readily available. In this study, hydrogen storage capacities are estimated at the system-level for MOFs with the highest demonstrated volumetric and gravimetric H₂ storage densities. System estimates are based on a single tank cryo-adsorbent system that utilizes a type-1 tank, multi-layer vacuum insulation, liquid N₂ cooling channels, in-tank heat exchanger, and a packed MOF powder inside the tank. It is found that with this powder-based system configuration, MOFs with ultra-high gravimetric surface areas and hydrogen adsorption amounts do not necessarily provide correspondingly high volumetric or gravimetric storage capacities at the system-level. Meanwhile, attributes such as powder packing efficiency and system cool-down temperature are shown to have a large impact on the system capacity. These results should shed light on the material properties that must to be optimized, as well as highlight the important design challenges for cryo-adsorbent hydrogen storage systems.     

Metal oxide applications in organic-based photovoltaics

Abstract

Organic-based photovoltaics (PV) have attracted increasing attention in recent years and efficiencies exceeding 8% have recently been confirmed. These low cost, lightweight and mechanically flexible devices offer unique advantages and opportunities currently unavailable with crystalline silicon technology. Progress in the field of organic PV has been achieved in part due to the incorporation of transition metal oxides. These offer a wide range of optical and electronic properties, making them applicable in organic-based PV in many capacities. Transparent electrodes can be made from doped metal oxides. The high intrinsic charge carrier mobility of many undoped metal oxides makes them attractive as active materials and charge collectors. Metal oxides can increase the charge selectivity of the electrodes due to the energetic positioning of their valence and conduction bands. Thin films of these materials can manipulate the light distribution inside of organic devices, allowing for improved light harvesting. Metal oxides are stable and can be processed at low temperatures. Consequently, they have been demonstrated as suitable intermediate layer materials in tandem cells. Finally, oxygen-deficient metal oxides can improve the stability of the oxygen- sensitive organic semiconductors. The present work reviews the various applications of metal oxide layers in organic PV devices and summarises the challenges associated with organic/oxide interfaces.     

In situ grown Cu-Based metal-organic framework on copper foam as high-performance electrocatalysts for oxygen evolution reaction

It is of great significance to develop highly efficient and robust oxygen evolution reaction (OER) electrocatalysts derived from earth-abundant and inexpensive elements for future hydrogen economy via electrochemical water splitting. Herein, Cu-based metal-organic framework (MOF) is directly supported on conductive Cu foam (CF) by a simply chemical oxidation of Cu substrate to grow Cu(OH)₂ nanowire arrays, followed by solvothermal treatment to obtain in situ grown Cu-based MOF electrode (MOF [Cu(OH)₂]/CF). The as-prepared 3D electrode shows superior OER activity with a low potential of 330 mV to deliver a current density of 10 mA cm⁻², a Tafel slope of 108 mV dec⁻¹, and excellent durability in alkaline media (1.0 M KOH). After electrolysis, XRD confirms that the initial MOFs have been transformed into CuO species, which are essentially active components for OER performance. This demonstrates that the MOFs can serve as efficient precursors for formation of highly active Cu oxide catalysts towards OER. This work provides a new strategy to develop MOFs-derived electrocatalysts for future clean energy conversion and storage systems.     

Characterisation of metal organic frameworks for adsorption cooling

Silica gel/water adsorption cooling systems suffer from size, performance and cost limitations. Therefore, there is a need for new adsorbent materials that outperform silica gel. Metal organic frameworks (MOFs) are new micro-porous materials that have extraordinary porosity and uniform structure. Due to the lack of published data that characterise MOF/water adsorption, this paper experimentally investigates the adsorption characteristics of HKUST-1 (Cu-BTC (copper benzene-1,3,5-tricarboxylate), C₁₈H₆Cu₃O₁₂) and MIL-100 (Fe-BTC (Iron 1,3,5-benzenetricarboxylate), C₉H₃FeO₆) MOFs compared to silica gel RD-2060. The adsorption characteristics of Silica gel RD-2060, HKUST-1 and MIL-100 were determined using an advanced gravimetric dynamic vapour sorption analyser (DVS). Results showed that HKUST-1 performed better than silica gel RD-2060 with an increase of water uptake of 93.2%, which could lead to a considerable increase in refrigerant flow rate, cooling capacity and/or reducing the size of the adsorption system. However, MIL-100 MOF showed reduced water uptake comparable to silica gel RD-2060 for water chilling applications with evaporation at 5 ⁰C. These results highlight the potential of using MOF materials to improve the efficiency of water adsorption cooling systems.     

Review of selected 100 recent papers for supercapacitors（Mar. 1，2016 to Sep. 30，2016）

该文是一篇近七个月的超级电容器文献评述,我们以“supercapacitor”为关键词检索了Web of Science从2016年3月1日至2016年9月30日上线的超级电容器研究论文,共有997篇,选取了其中100篇加以评论。双电层超级电容器主要研究了新型多孔碳材料、石墨烯等材料可控制备对其性能的影响。赝电容超级电容器的研究主要集中在金属氧化物复合材料、导电聚合物复合材料、杂质原子掺杂碳材料和新型赝电容材料等四个方面。混合型超级电容器包括水系混合型超级电容器和有机系混合型超级电容器两个方面的研究。     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Review of selected 100 recent papers for supercapacitors（Nov. 1, 2015 to Feb. 29, 2016）

该文是一篇近四个月的超级电容器文献评述,我们以“supercapacitor”为关键词检索了Web of Science从2015年11月1日至2016年2月29日上线的超级电容器研究论文,共有830篇,选取了其中100篇加以评论。双电层超级电容器主要研究了新型多孔碳材料、石墨烯等材料可控制备对其性能的影响。赝电容超级电容器的研究主要集中在金属氧化物复合材料、导电聚合物复合材料、杂质原子掺杂碳材料和新型赝电容材料等4个方面。混合型超级电容器包括水系混合型超级电容器和有机系混合型超级电容器两个方面的研究。     

Recent research progress of tin oxide as anode materials for sodium-ion batteries

与锂元素相比,钠元素在地壳中储量丰富、分布均匀又价格低廉,继锂离子电池研究受限后,钠离子电池又重新引起了研究者们的关注。在众多钠离子电池电极材料中,锡基金属氧化物因具有较高的理论比容量（1378 mA·h/g）,近年来备受青睐。据文献可知,不同纳米结构的锡基氧化物材料表现出不同的电化学性能。本文从钠离子电池锡基金属氧化物亟待解决的问题出发,系统地总结了特殊形貌的锡基金属氧化物、低维度纳米结构的锡基氧化物材料的复合化、三维结构的锡基氧化物材料复合化、核壳结构的锡基氧化物材料的复合化、特殊结构的锡基氧化物材料的复合化的纳米结构特征及其电化学性能,并展望了锡基氧化物材料的面临的挑战。