Metal organic framework (MOF) in aqueous energy devices

Aqueous energy devices are under the spotlight of current research due to their safety, low cost and ease of handling. Metal-organic frameworks (MOFs) and their derivatives have spurred extensive exploration as they provide a library of new electrode materials. The rich and structural flexibilities (such as metal nodes, ligands, pore structure) endow MOFs and MOFs-derivatives with vast opportunities for various energy devices. In this review, we discuss the correlation between MOF structural parameters and electrochemical performance for aqueous energy devices in the scope of zinc-based batteries (Zn-ion, Zn-alkaline and Zn-air batteries), potassium-ion batteries and supercapacitors. For each energy device, the effect of determinative factors and structural modulating strategies of MOFs and derivatives are highlighted. Finally, we summarize the challenges and provide our perspective about MOFs and derivatives for future aqueous energy devices.     

Hollow Metal–Organic‐Framework Micro/Nanostructures and their Derivatives: Emerging Multifunctional Materials

Hollow metal–organic framework (MOF) micro/nanostructures and their derivatives are attracting a great amount of research interest in recent years because their hierarchical porous structures not only provide abundant, easily accessed metal sites but also endow 3D channels for rapid mass transport. As a result, they demonstrate significant advantages in many applications including catalysis, gas sensors, batteries, supercapacitors, and so on. Nevertheless, studies on hollow MOFs and their derivatives are still at the beginning of this field, and the relationship between their structures and application performances is not yet reviewed comprehensively. Herein, the synthetic strategies and practical applications of hollow micro/nanostructured MOFs and their derivatives are summarized, and their corresponding prospects are also discussed.     

MOF‐Derived Metal Oxide Composites for Advanced Electrochemical Energy Storage

Over the past two decades, metal–organic frameworks (MOFs), a type of porous material, have aroused great interest as precursors or templates for the derivation of metal oxides and composites for the next generation of electrochemical energy storage applications owing to their high specific surface areas, controllable structures, and adjustable pore sizes. The electrode materials, which affect the performance in practical applications, are pivotal components of batteries and supercapacitors. Metal oxide composites derived from metal–organic frameworks possessing high reversible capacity and superior rate and cycle performance are excellent electrode materials. In this Review, potential applications for MOF‐derived metal oxide composites for lithium‐ion batteries, sodium‐ion batteries, lithium–oxygen batteries, and supercapacitors are studied and summarized. Finally, the challenges and opportunities for future research on MOF‐derived metal oxide composites are proposed on the basis of academic knowledge from the reported literature as well as from experimental experience.     

新型超级电容器电极材料

超级电容器以其高功率、长周期使用寿命、环保等独特性能受到人们的广泛关注。决定超级电容器电荷存储的最关键因素是电极材料的特性。首先简要介绍了电容器的电荷储存机理。其次详细介绍了金属有机骨架材料(MOFs)、共价有机骨架材料(COFs)、二维过渡金属碳(氮)化物(MXenes)、金属氮化物(MN)、黑磷(BP)和有机分子电极材料等有望获得高能量密度和功率密度的新兴电极材料,以及最新制作的对称/非对称超级电容器的能量、电容、功率、循环性能和倍率性等参数。研究表明,COFs有望成为新一代廉价、绿色、可持续、多功能的储能装置的有机电极候选材料,其电化学性能仍有很大的提高空间。重点介绍了MOFs、COFs、MN、BP及近年来新型有机电极材料在超级电容器中的应用。最后,对超级电容器未来的发展和关键技术的挑战进行了展望。     

Carbon Necklace Incorporated Electroactive Reservoir Constructing Flexible Papers for Advanced Lithium–Ion Batteries

Metal–organic frameworks (MOFs) and their derivatives with well‐defined structures and compositions show great potential for wide applications such as sensors, catalysis, energy storage, and conversion, etc. However, poor electric conductivity and large volume expansion are main obstacles for their utilization in energy storage, e.g., lithium–ion batteries and supercapacitors. Herein, a facile strategy is proposed for embedding the MOFs, e.g., ZIF‐67 and MIL‐88 into polyacrylonitrile fibers, which is further used as a template to build a 3D interconnected conductive carbon necklace paper. Owing to the unique structure features of good electric conductivity, interconnected frameworks, electroactive reservoir, and dual dopants, the obtained flexible electrodes with no additives exhibit high specific capacities, good rate capability, and prolonged cycling stability. The hollow dodecahedral ZIF‐67 derived carbon necklace paper delivers a high specific capacity of 1200 mAh g^?1 and superior stability of more than 400 cycles without capacity decay. Moreover, the spindle‐like MIL‐88 derived carbon necklace paper shows a high reversible capacity of 980 mAh g^?1. Their unique 3D interconnected structure and outstanding electrochemical performance pave the way for extending the MOF‐based interweaving materials toward potential applications in portable and wearable electronic devices.     

Metal‐Layer Assisted Growth of Ultralong Quasi‐2D MOF Nanoarrays on Arbitrary Substrates for Accelerated Oxygen Evolution

Controlled growth of metal–organic frameworks (MOFs) nanocrystals on requisite surfaces is highly desired for myriad applications related to catalysis, energy, and electronics. Here, this challenge is addressed by overlaying arbitrary surfaces with a thermally evaporated metal layer to enable the well‐aligned growth of ultralong quasi‐2D MOF nanoarrays comprising cobalt ions and thiophenedicarboxylate acids. This interfacial engineering approach allows preferred chelation of carboxyl groups in the ligands with the metal interlayers, thereby making possible the fabrication and patterning of MOF nanoarrays on substrates of any materials or morphologies. The MOF nanoarrays grown on porous metal scaffolds demonstrate high electrocatalytic capability for water oxidation, exhibiting a small overpotential of 270 mV at 10 mA cm^?2, or 317 mV at 50 mA cm^?2 as well as negligible decay of performance within 30 h. The enhanced performance stems from the improved electron and ion transport in the hierarchical porous nanoarrays consisting of in situ formed oxyhydroxide nanosheets in the electrochemical processes. This approach for mediating the growth of MOF nanoarrays can serve as a promising platform for diverse applications.     

Rare-Earth–Modified Metal–Organic Frameworks and Derivatives for Photo/Electrocatalysis

Metal–organic frameworks (MOFs) and their derivatives have attracted much attention in the field of photo/electrocatalysis owing to their ultrahigh porosity, tunable properties, and superior coordination ability. Regulating the valence electronic structure and coordination environment of MOFs is an effective way to enhance their intrinsic catalytic performance. Rare earth (RE) elements with 4f orbital occupancy provide an opportunity to evoke electron rearrangement, accelerate charged carrier transport, and synergize the surface adsorption of catalysts. Therefore, the integration of RE with MOFs makes it possible to optimize their electronic structure and coordination environment, resulting in enhanced catalytic performance. In this review, progress in current research on the use of RE-modified MOFs and their derivatives for photo/electrocatalysis is summarized and discussed. First, the theoretical advantages of RE in MOF modification are introduced, with a focus on the roles of 4f orbital occupancy and RE ion organic coordination ligands. Then, the application of RE-modified MOFs and their derivatives in photo/electrocatalysis is systematically discussed. Finally, research challenges, future opportunities, and prospects for RE-MOFs are also discussed.     

Metal–Organic Framework‐Derived Materials for Sodium Energy Storage

Recently, sodium‐ion batteries (SIBs) are extensively explored and are regarded as one of the most promising alternatives to lithium‐ion batteries for electrochemical energy conversion and storage, owing to the abundant raw material resources, low cost, and similar electrochemical behavior of elemental sodium compared to lithium. Metal–organic frameworks (MOFs) have attracted enormous attention due to their high surface areas, tunable structures, and diverse applications in drug delivery, gas storage, and catalysis. Recently, there has been an escalating interest in exploiting MOF‐derived materials as anodes for sodium energy storage due to their fast mass transport resulting from their highly porous structures and relatively simple preparation methods originating from in situ thermal treatment processes. In this Review, the recent progress of the sodium‐ion storage performances of MOF‐derived materials, including MOF‐derived porous carbons, metal oxides, metal oxide/carbon nanocomposites, and other materials (e.g., metal phosphides, metal sulfides, and metal selenides), as SIB anodes is systematically and completely presented and discussed. Moreover, the current challenges and perspectives of MOF‐derived materials in electrochemical energy storage are discussed.     

2D Metal–Organic Frameworks (MOFs) for High‐Performance BatCap Hybrid Devices

Two identical layered metal–organic frameworks (MOFs) (CoFRS and NiFRS) are constructed by using flexible 1,10‐bis(1,2,4‐triazol‐1‐yl)decane as pillars and 1,4‐benzenedicarboxylic acid as rigid linkers. The single‐crystal structure analysis indicates that the as‐synthesized MOFs possess fluctuant 2D networks with large interlayer lattices. Serving as active electrode elements in supercapacitors, both MOFs deliver excellent rate capabilities, high capacities, and longstanding endurances. Moreover, the new intermediates in two electrodes before and after long‐lifespan cycling are also examined, which cannot be identified as metal hydroxides in the peer reports. After assembled into battery‐supercapacitor (BatCap) hybrid devices, the NiFRS//activated carbon (AC) device displays better electrochemical results in terms of gravimetric capacitance and cycling performance than CoFRS//AC devices, and a higher energy‐density value of 28.7 Wh kg^?1 compared to other peer references with MOFs‐based electrodes. Furthermore, the possible factors to support the distinct performances are discussed and analyzed.     

Layered Transition Metal Dichalcogenide-Based Nanomaterials for Electrochemical Energy Storage

The rapid development of electrochemical energy storage (EES) systems requires novel electrode materials with high performance. A typical 2D nanomaterial, layered transition metal dichalcogenides (TMDs) are regarded as promising materials used for EES systems due to their large specific surface areas and layer structures benefiting fast ion transport. The typical methods for the preparation of TMDs and TMD-based nanohybrids are first summarized. Then, in order to improve the electrochemical performance of various kinds of rechargeable batteries, such as lithium-ion batteries, lithium–sulfur batteries, sodium-ion batteries, and other types of emerging batteries, the strategies for the design and fabrication of layered TMD-based electrode materials are discussed. Furthermore, the applications of layered TMD-based nanomaterials in supercapacitors, especially in untraditional supercapacitors, are presented. Finally, the existing challenges and promising future research directions in this field are proposed.     

Emerging 2D Copper-Based Materials for Energy Storage and Conversion: A Review and Perspective

2D materials have shown great potential as electrode materials that determine the performance of a range of electrochemical energy technologies. Among these, 2D copper-based materials, such as Cu–O, Cu–S, Cu–Se, Cu–N, and Cu–P, have attracted tremendous research interest, because of the combination of remarkable properties, such as low cost, excellent chemical stability, facile fabrication, and significant electrochemical properties. Herein, the recent advances in the emerging 2D copper-based materials are summarized. A brief summary of the crystal structures and synthetic methods is started, and innovative strategies for improving electrochemical performances of 2D copper-based materials are described in detail through defect engineering, heterostructure construction, and surface functionalization. Furthermore, their state-of-the-art applications in electrochemical energy storage including supercapacitors (SCs), alkali (Li, Na, and K)-ion batteries, multivalent metal (Mg and Al)-ion batteries, and hybrid Mg/Li-ion batteries are described. In addition, the electrocatalysis applications of 2D copper-based materials in metal–air batteries, water-splitting, and CO₂ reduction reaction (CO₂RR) are also discussed. This review also discusses the charge storage mechanisms of 2D copper-based materials by various advanced characterization techniques. The review with a perspective of the current challenges and research outlook of such 2D copper-based materials for high-performance energy storage and conversion applications is concluded.     

Recent Progress in Some Amorphous Materials for Supercapacitors

A breakthrough in technologies having “green” and sustainable energy storage conversion is urgent, and supercapacitors play a crucial role in this area of research. Owing to their unique porous structure, amorphous materials are considered one of the best active materials for high‐performance supercapacitors due to their high specific capacity, excellent cycling stability, and fast charging rate. This Review summarizes the synthesis of amorphous materials (transition metal oxides, carbon‐based materials, transition metal sulfides, phosphates, hydroxides, and their complexes) to highlight their electrochemical performance in supercapacitors.     

Design of Hollow Nanostructures for Energy Storage,Conversion and Production

Hollow nanostructures have shown great promise for energy storage, conversion, and production technologies. Significant efforts have been devoted to the design and synthesis of hollow nanostructures with diverse compositional and geometric characteristics in the past decade. However, the correlation between their structure and energy‐related performance has not been reviewed thoroughly in the literature. Here, some representative examples of designing hollow nanostructure to effectively solve the problems of energy‐related technologies are highlighted, such as lithium‐ion batteries, lithium‐metal anodes, lithium–sulfur batteries, supercapacitors, dye‐sensitized solar cells, electrocatalysis, and photoelectrochemical cells. The great effect of structure engineering on the performance is discussed in depth, which will benefit the better design of hollow nanostructures to fulfill the requirements of specific applications and simultaneously enrich the diversity of the hollow nanostructure family. Finally, future directions of hollow nanostructure design to solve emerging challenges and further improve the performance of energy‐related technologies are also provided.     

Synergistic effects from graphene and carbon nanotubes enable flexible and robust electrodes for high-performance supercapacitors

Flexible and lightweight energy storage systems have received tremendous interest recently due to their potential applications in wearable electronics, roll-up displays, and other devices. To manufacture such systems, flexible electrodes with desired mechanical and electrochemical properties are critical. Herein we present a novel method to fabricate conductive, highly flexible, and robust film supercapacitor electrodes based on graphene/MnO(2)/CNTs nanocomposites. The synergistic effects from graphene, CNTs, and MnO(2) deliver outstanding mechanical properties (tensile strength of 48 MPa) and superior electrochemical activity that were not achieved by any of these components alone. These flexible electrodes allow highly active material loading (71 wt % MnO(2)), areal density (8.80 mg/cm(2)), and high specific capacitance (372 F/g) with excellent rate capability for supercapacitors without the need of current collectors and binders. The film can also be wound around 0.5 mm diameter rods for fabricating full cells with high performance, showing significant potential in flexible energy storage devices.     

An overview of the applications of graphene-based materials in supercapacitors

Due to their unique 2D structure and outstanding intrinsic physical properties, such as extraordinarily high electrical conductivity and large surface area, graphene-based materials exhibit great potential for application in supercapacitors. In this review, the progress made so far for their applications in supercapacitors is reviewed, including electrochemical double-layer capacitors, pseudo-capacitors, and asymmetric supercapacitors. Compared with traditional electrode materials, graphene-based materials show some novel characteristics and mechanisms in the process of energy storage and release. Several key issues for improving the structure of graphene-based materials and for achieving better capacitor performance, along with the current outlook for the field, are also discussed.     

Redox Tuning in Crystalline and Electronic Structure of Bimetal–Organic Frameworks Derived Cobalt/Nickel Boride/Sulfide for Boosted Faradaic Capacitance

The development of efficient electrode materials is a cutting‐edge approach for high‐performance energy storage devices. Herein, an effective chemical redox approach is reported for tuning the crystalline and electronic structures of bimetallic cobalt/nickel–organic frameworks (Co‐Ni MOFs) to boost faradaic redox reaction for high energy density. The as‐obtained cobalt/nickel boride/sulfide exhibits a high specific capacitance (1281 F g^?1 at 1 A g^?1), remarkable rate performance (802.9 F g^?1 at 20 A g^?1), and outstanding cycling stability (92.1% retention after 10 000 cycles). An energy storage device fabricated with a cobalt/nickel boride/sulfide electrode exhibits a high energy density of 50.0 Wh kg^?1 at a power density of 857.7 W kg^?1, and capacity retention of 87.7% (up to 5000 cycles at 12 A g^?1). Such an effective redox approach realizes the systematic electronic tuning that activates the fast faradaic reactions of the metal species in cobalt/nickel boride/sulfide which may shed substantial light on inspiring MOFs and their derivatives for energy storage devices.     

Secondary‐Component Incorporated Hollow MOFs and Derivatives for Catalytic and Energy‐Related Applications

Their highly functional nature has endowed metal–organic frameworks (MOFs) with diverse applications. On this basis, a higher demand has been proposed for the preparation of novel‐structured MOFs. Hollow MOFs have been intensively studied and exhibited versatile properties, and among the various methods, secondary‐component incorporation has been proved promising in the design and preparation of complex structures with requisite properties. Herein, the synthesis and applications of secondary component incorporated MOFs and their derivatives are systematically reviewed. Two main methodologies, preincorporation and postmodification, are discussed in detail, and the role of the secondary component is demonstrated. Based on these introductions, the applications of those materials, including chemical catalysis, electrocatalysis, and energy storage applications, are summarized. Finally, a personal outlook for the future opportunities and challenges in this field is given.     

Hollow Functional Materials Derived from Metal–Organic Frameworks: Synthetic Strategies,Conversion Mechanisms,and Electrochemical Applications

Hollow materials derived from metal–organic frameworks (MOFs), by virtue of their controllable configuration, composition, porosity, and specific surface area, have shown fascinating physicochemical properties and widespread applications, especially in electrochemical energy storage and conversion. Here, the recent advances in the controllable synthesis are discussed, mainly focusing on the conversion mechanisms from MOFs to hollow‐structured materials. The synthetic strategies of MOF‐derived hollow‐structured materials are broadly sorted into two categories: the controllable synthesis of hollow MOFs and subsequent pyrolysis into functional materials, and the controllable conversion of solid MOFs with predesigned composition and morphology into hollow structures. Based on the formation processes of hollow MOFs and the conversion processes of solid MOFs, the synthetic strategies are further conceptually grouped into six categories: template‐mediated assembly, stepped dissolution–regrowth, selective chemical etching, interfacial ion exchange, heterogeneous contraction, and self‐catalytic pyrolysis. By analyzing and discussing 14 types of reaction processes in detail, a systematic mechanism of conversion from MOFs to hollow‐structured materials is exhibited. Afterward, the applications of these hollow structures as electrode materials for lithium‐ion batteries, hybrid supercapacitors, and electrocatalysis are presented. Finally, an outlook on the emergent challenges and future developments in terms of their controllable fabrications and electrochemical applications is further discussed.     

In Situ Coupling of CoP Polyhedrons and Carbon Nanotubes as Highly Efficient Hydrogen Evolution Reaction Electrocatalyst

Hydrogen evolution reaction (HER) from water electrolysis is an attractive technique developed in recent years for cost‐effective clean energy. Although considerable efforts have been paid to create efficient catalysts for HER, the development of an affordable HER catalyst with superior performance under mild conditions is still highly desired. In this work, metal–organic frameworks (MOFs)‐templated strategy is proposed for in situ coupling of cobalt phosphide (CoP) polyhedrons nanoparticles and carbon nanotubes (CNTs). Due to the synergistic catalytic effect between CoP polyhedrons and CNTs, the as‐prepared CoP–CNTs hybrids show excellent HER performance. The resultant CoP–CNTs demonstrate excellent HER activity in 0.5 m H₂SO₄ with Tafel slope of 52 mV dec^?1, small onset overpotential of ≈64 mV, and a low overpotential of ≈139 mV at 10 mA cm^?2. Additionally, the catalyst also manifests superior durability in acid media. Considering the structure diversity of MOFs, the strategy presented here can be extended for synthesizing other well‐defined metal phosphides–CNTs hybrids, which may be used in the fields of catalysis, energy conversion and storage.