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.     

Novel MOF‐Derived Co@N‐C Bifunctional Catalysts for Highly Efficient Zn–Air Batteries and Water Splitting

Metal–organic frameworks (MOFs) and MOF‐derived materials have recently attracted considerable interest as alternatives to noble‐metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N‐C materials (C‐MOF‐C2‐T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C‐MOF‐C2‐900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N‐doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO₂, respectively. Primary Zn–air batteries based on C‐MOF‐900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h g_Zn^–1 under 10 mA cm^–2. Rechargeable Zn–air batteries based on C‐MOF‐C2‐900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm^–2), along with an excellent cycling stability with no increase in polarization even after 120 h – outperform their counterparts based on noble‐metal‐based air electrodes. The resultant rechargeable Zn–air batteries are used to efficiently power electrochemical water‐splitting systems, demonstrating promising potential as integrated green energy systems for practical applications.     

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.     

Carbon‐Based Metal‐Free Catalysts for Energy Storage and Environmental Remediation

Owing to their high earth‐abundance, eco‐friendliness, high electrical conductivity, large surface area, structure tunability at the atomic/morphological levels, and excellent stability in harsh conditions, carbon‐based metal‐free materials have become promising advanced electrode materials for high‐performance pseudocapacitors and metal–air batteries. Furthermore, carbon‐based nanomaterials with well‐defined structures can function as green catalysts because of their efficiency in advanced oxidation processes to remove organics in air or from water, which reduces the cost for air/water purification and avoids cross‐contamination by eliminating the release of heavy metals/metal ions. Here, the research and development of carbon‐based catalysts in supercapacitors and batteries for clean energy storage as well as in air/water treatments for environmental remediation are reviewed. The related mechanistic understanding and design principles of carbon‐based metal‐free catalysts are illustrated, along with the challenges and perspectives in this emerging field.     

Enhanced Chemisorption and Catalytic Effects toward Polysulfides by Modulating Hollow Nanoarchitectures for Long‐Life Lithium–Sulfur Batteries

Hollow nanostructures with intricate interior and catalytic effects hold great promise for the construction of advanced lithium–sulfur batteries. Herein, a double‐shelled hollow polyhedron with inlaid cobalt nanoparticles encapsulated by nitrogen‐doped carbon (Co/NC) nanodots (Co‐NC@Co₉S₈/NPC) is reported, which is acquired by using imidazolium‐based ionic‐polymer‐encapsulated zeolitic imidazolate framework‐67 as a core‐shelled precursor. The Co/NC nanodots promote redox kinetics and chemical adsorbability toward polysulfides, while the interconnected double shells serve as a nanoscale electrochemical reaction chamber, which effectively suppresses the polysulfide shuttling and accelerates ion/electron transport. Benefiting from structural engineering and reaction kinetics modulation, the Co‐NC@Co₉S₈/NPC‐S electrode exhibits high cycling stability with a low capacity decay of 0.011% per cycle within 2000 cycles at 2 C. The electrode still shows high rate performance and cyclability over 500 cycles even in the case of high sulfur loading of 4.5 mg cm^?2 and 75 wt% sulfur content. This work provides one type of new hollow nanoarchitecture for the development of advanced Li–S batteries and other energy storage systems.     

Programmable Self‐Assembling 3D Architectures Generated by Patterning of Swellable MOF‐Based Composite Films

The integration of swellable metal–organic frameworks (MOFs) into polymeric composite films is a straightforward strategy to develop soft materials that undergo reversible shape transformations derived from the intrinsic flexibility of MOF crystals. However, a crucial step toward their practical application relies on the ability to attain specific and programmable actuation, which enables the design of self‐shaping objects on demand. Herein, a chemical etching method is demonstrated for the fabrication of patterned composite films showing tunable self‐folding response, predictable and reversible 2D‐to‐3D shape transformations triggered by water adsorption/desorption. These films are fabricated by selective removal of swellable MOF crystals allowing control over their spatial distribution within the polymeric film. Upon exposure to moisture, various programmable 3D architectures, which include a mechanical gripper, a lift, and a unidirectional walking device, are generated. Remarkably, these 2D‐to‐3D shape transformations can be reversed by light‐induced desorption. The reported strategy offers a platform for fabricating flexible MOF‐based autonomous soft mechanical devices with functionalities for micromanipulation, automation, and robotics.     

Coordination‐Induced Interlinked Covalent‐ and Metal–Organic‐Framework Hybrids for Enhanced Lithium Storage

Covalent organic frameworks (COF) or metal–organic frameworks have attracted significant attention for various applications due to their intriguing tunable micro/mesopores and composition/functionality control. Herein, a coordination‐induced interlinked hybrid of imine‐based covalent organic frameworks and Mn‐based metal–organic frameworks (COF/Mn‐MOF) based on the Mn? N bond is reported. The effective molecular‐level coordination‐induced compositing of COF and MOF endows the hybrid with unique flower‐like microsphere morphology and superior lithium‐storage performances that originate from activated Mn centers and the aromatic benzene ring. In addition, hollow or core–shell MnS trapped in N and S codoped carbon (MnS@NS‐C‐g and MnS@NS‐C‐l) are also derived from the COF/Mn‐MOF hybrid and they exhibit good lithium‐storage properties. The design strategy of COF–MOF hybrid can shed light on the promising hybridization on porous organic framework composites with molecular‐level structural adjustment, nano/microsized morphology design, and property optimization.     

Three‐Dimensional Self‐Supported Metal Oxides for Advanced Energy Storage

The miniaturization of power sources aimed at integration into micro‐ and nano‐electronic devices is a big challenge. To ensure the future development of fully autonomous on‐board systems, electrodes based on self‐supported 3D nanostructured metal oxides have become increasingly important, and their impact is particularly significant when considering the miniaturization of energy storage systems. This review describes recent advances in the development of self‐supported 3D nanostructured metal oxides as electrodes for innovative power sources, particularly Li‐ion batteries and electrochemical supercapacitors. Current strategies for the design and morphology control of self‐supported electrodes fabricated using template, lithography, anodization and self‐organized solution techniques are outlined along with different efforts to improve the storage capacity, rate capability, and cyclability.     

MOF‐Based Hierarchical Structures for Solar‐Thermal Clean Water Production

Solar‐thermal water evaporation, as a promising method for clean water production, has attracted increasing attention. However, solar water evaporators that exhibit both high water vapor generation ability and anti‐oil‐fouling ability have not been reported. Here, a unique metal–organic‐framework‐based hierarchical structure, referred to as MOF‐based hierarchical structure (MHS), is rationally designed and prepared, which simultaneously displays a high solar absorption and a superhydrophilic and underwater superoleophobic surface property. As a proof‐of‐concept application, a device prepared from the MHS can achieve a high solar‐thermal water evaporation rate of 1.50 kg m^?2 h^?1 under 1 sun illumination. Importantly, the MHS also possesses an excellent anti‐oil‐fouling property, ensuring its superior water evaporation performance even in oil‐contaminated water. The high solar‐thermal water evaporation rate and anti‐oil‐fouling property make the MHS a promising material for the solar‐thermal water production.     

A Dual‐Function Na2SO4 Template Directed Formation of Cathode Materials with a High Content of Sulfur Nanodots for Lithium–Sulfur Batteries

The sulfur content in carbon–sulfur hybrid using the melt‐diffusion method is normally lower than 70 wt%, which greatly decreases the energy density of the cathode in lithium–sulfur (Li‐S) batteries. Here, a scalable method inspired by the commercialized production of Na₂S is used to prepare a hierarchical porous carbon–sulfur hybrid (denoted HPC‐S) with high sulfur content (≈85 wt%). The HPC‐S is characterized by the structure of sulfur nanodots naturally embedded in a 3D carbon network. The strategy uses Na₂SO₄ as the starting material, which serves not only as the sulfur precursor but also as a salt template for the formation of the 3D carbon network. The HPC‐S cathode with such a high sulfur content shows excellent rate performance and cycling stability in Li–S batteries because of the sulfur nanoparticles, the unique carbon framework, and the strong interaction between them. The production method can also be readily scaled up and used in practical Li–S battery applications.     

Web‐Like Interconnected Carbon Networks from NaCl‐Assisted Pyrolysis of ZIF‐8 for Highly Efficient Oxygen Reduction Catalysis

The oxygen reduction reaction (ORR) is under intense research due to its significance in energy storage and conversion processes. Recent studies show that interconnected and hierarchically porous structures can further enhance ORR kinetics as well as catalyst durability, but their preparation can be quite time and/or chemical consuming. Here, a simple approach is reported to prepare such complex structures by pyrolyzing composites containing NaCl and ZIF‐8. The templating effect of molten NaCl connects ZIF‐8 particles into web‐like carbon networks. During ORR activity measurements, it achieves a 0.964 V onset potential and a 38 mV dec^?1 Tafel slope, which are comparable to those of the benchmark Pt/C (0.979 V and 40 mV dec^?1). Due to the metal‐free feature, this catalyst exhibits a 16 mV shift in half‐wave potential after a 10 000‐cycle durability test, which is only 60% of that of Pt/C. The catalyst is also tested in Zn–air batteries and the assemblies are able to work at above 1.2 V for 140 h, which triples the life held by those with Pt/C. This study demonstrates a facile strategy to prepare metal‐free ORR catalysts with interconnectivity and hierarchical porosity, and proves their great potentials in ORR catalysis and Zn–air batteries.     

Self‐Template‐Directed Metal–Organic Frameworks Network and the Derived Honeycomb‐Like Carbon Flakes via Confinement Pyrolysis

Metal–organic frameworks (MOFs) have become a research hotspot since they have been explored as convenient precursors for preparing various multifunctional nanomaterials. However, the preparation of MOF networks with controllable flake morphology in large scale is not realized yet. Herein, a self‐template strategy is developed to prepare MOF networks. In this work, layered double‐metal hydroxide (LDH) and other layered metal hydroxides are used not only as a scaffold but also as a self‐sacrificed metal source. After capturing the abundant metal cations identically from the LDH by the organic linkers, MOF networks are in situ formed. It is interesting that the MOF network‐derived carbon materials retain the flake morphology and exhibit a unique honeycomb‐like macroporous structure due to the confined shrinkage of the polyhedral facets. The overall properties of the carbon networks are adjustable according to the tailored metal compositions in LDH and the derived MOFs, which are desirable for target‐oriented applications as exemplified by the electrochemical application in supercapacitors.     

Single Tungsten Atoms Supported on MOF‐Derived N‐Doped Carbon for Robust Electrochemical Hydrogen Evolution

Tungsten‐based catalysts are promising candidates to generate hydrogen effectively. In this work, a single‐W‐atom catalyst supported on metal–organic framework (MOF)‐derived N‐doped carbon (W‐SAC) for efficient electrochemical hydrogen evolution reaction (HER), with high activity and excellent stability is reported. High‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) and X‐ray absorption fine structure (XAFS) spectroscopy analysis indicate the atomic dispersion of the W species, and reveal that the W₁N₁C₃ moiety may be the favored local structure for the W species. The W‐SAC exhibits a low overpotential of 85 mV at a current density of 10 mA cm^?2 and a small Tafel slope of 53 mV dec^?1, in 0.1 m KOH solution. The HER activity of the W‐SAC is almost equal to that of commercial Pt/C. Density functional theory (DFT) calculation suggests that the unique structure of the W₁N₁C₃ moiety plays an important role in enhancing the HER performance. This work gives new insights into the investigation of efficient and practical W‐based HER catalysts.     

Optimization of Microporous Carbon Structures for Lithium–Sulfur Battery Applications in Carbonate‐Based Electrolyte

Developing appropriate sulfur cathode materials in carbonate‐based electrolyte is an important research subject for lithium‐sulfur batteries. Although several microporous carbon materials as host for sulfur reveal the effect, methods for producing microporous carbon are neither easy nor well controllable. Moreover, due to the complexity and limitation of microporous carbon in their fabrication process, there has been rare investigation of influence on electrochemical behavior in the carbonate‐based electrolyte for lithium‐sulfur batteries by tuning different micropore size(0–2 nm) of carbon host. Here, we demonstrate an immediate carbonization process, self‐activation strategy, which can produce microporous carbon for a sulfur host from alkali‐complexes. Besides, by changing different alkali‐ion in the previous complex, the obtained microporous carbon exhibits a major portion of ultramicropore (<0.7 nm, from 54.9% to 25.8%) and it is demonstrated that the micropore structure of the host material plays a vital role in confining sulfur molecule. When evaluated as cathode materials in a carbonate‐based electrolyte for Li‐S batteries, such microporous carbon/sulfur composite can provide high reversible capacity, cycling stability and good rate capability.