Oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are three key reactions for the development of green and sustainable energy systems. Efficient electrocatalysts for these reactions are highly desired to lower their overpotentials and promote practical applications of related energy devices. Metal–organic frameworks (MOFs) have recently emerged as precursors to fabricate carbon-based electrocatalysts with high electrical conductivity and uniformly distributed active sites. In this review, the current progress of MOF-derived carbon-based materials for ORR/OER/HER electrocatalysis is presented. Materials design strategies of MOF-derived carbon-based materials are firstly summarized to show the rich possibilities of the morphology and composition of MOF-derived carbon-based materials. A wide range of applications based on these materials for ORR, OER, HER and multifunctional electrocatalysis are discussed, with an emphasis on the required features of MOF-derived carbon-based materials for the electrocatalysis of corresponding reactions. Finally, perspectives on the development of MOF-derived carbon-based materials for ORR, OER and HER electrocatalysis are provided.

MOF-derived electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions

As a new class of crystalline porous materials, metal-organic frameworks (MOFs) have received great attention owing to their unique advantages of ultrahigh surface area, large pore volume and versatile applications. Developing different strategies to control the morphology and size of MOFs is very important for their practical applications. Recently, micro/nanosized MOFs have been regarded as promising candidates for electrode materials with excellent performances, which not only bridge the gap between fundamental MOF science and forward-looking applications, but also provide an opportunity to make clear the relationship between morphologies and properties. This review focuses on the design and fabrication of one-, two- and three-dimensional MOFs at micro/nanoscale, and their direct applications in batteries, supercapacitors and electrocatalysis. A discussion on challenges and future prospects of the synthesis and electrochemical applications of micro/nanoscaled MOF materials is presented.

Synthesis of micro/nanoscaled metal-organic frameworks and their direct electrochemical applications.

Metal-organic frameworks (MOFs) are a class of distinctive porous crystalline materials constructed by metal ions/clusters and organic linkers. Owing to their structural diversity, functional adjustability, and high surface area, different types of MOF-based single metal sites are well exploited, including coordinately unsaturated metal sites from metal nodes and metallolinkers, as well as active metal species immobilized to MOFs. Furthermore, controllable thermal transformation of MOFs can upgrade them to nanomaterials functionalized with active single-atom catalysts (SACs). These unique features of MOFs and their derivatives enable them to serve as a highly versatile platform for catalysis, which has actually been becoming a rapidly developing interdisciplinary research area. In this review, we overview the recent developments of catalysis at single metal sites in MOF-based materials with emphasis on their structures and applications for thermocatalysis, electrocatalysis, and photocatalysis. We also compare the results and summarize the major insights gained from the works in this review, providing the challenges and prospects in this emerging field.

Metal-Organic Framework-Based Catalysts with Single Metal Sites.

Metal–organic frameworks (MOFs), an emerging class of porous materials, have shown intriguing and promising properties in a wide range of applications due to their versatile structures, large surface areas, tunable porosity and tailorable chemistry. In recent years one of the most active research fields is to explore energy applications of MOF-based materials. In this review, we present a critical overview on the recent progress of the use of MOF-based materials for gaseous fuel storage, chemical hydrogen storage, solar and electrochemical energy storage and conversion. The challenges and opportunities towards advanced energy technologies with the MOF-based materials are discussed.

Metal–organic frameworks as a platform for clean energy applications

The local coordination environment of catalysts has been investigated for an extended period to obtain enhanced catalytic performance. Especially with the advancement of single-atom catalysts (SACs), research on the coordination environment has been advanced to the atomic level. The surrounding coordination atoms of central metal atoms play important roles in their catalytic activity, selectivity and stability. In recent years, remarkable improvements of the catalytic performance of SACs have been achieved by the tailoring of coordination atoms, coordination numbers and second- or higher-coordination shells, which provided new opportunities for the further development of SACs. In this review, the characterization of coordination environment, tailoring of the local coordination environment, and their related adjustable catalytic performance will be discussed. We hope this review will provide new insights on further research of SACs.

https://link.springer.com/content/pdf/10.1007/s12274-020-2755-3.pdf

Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance

As emerging crystalline porous organic-inorganic hybrid materials, metal-organic frameworks (MOFs) have been widely used as sacrificial precursors for the synthesis of carbon materials, metal/metal compounds, and their composites with tunable and controllable nanostructures and chemical compositions for electrochemical energy applications. Herein, recent progress of MOF-derived nanomaterials for various electrochemical energy storage and conversion applications including Li-ion batteries, Li-S batteries, Na-ion batteries, supercapacitors, water splitting, and oxygen reduction reaction is reviewed. Structural and compositional design of MOF-derived nanomaterials is systematically summarized, which may hopefully offer inspirations and guidances for future development of MOF-derived nanomaterials for more efficient and more durable electrochemical energy applications.

Metal-organic framework-derived materials for electrochemical energy applications

Metal–organic frameworks (MOFs) have emerged as desirable cross-functional platforms for electrochemical and photochemical energy conversion and storage (ECS) systems owing to their highly ordered ...

Metal–Organic Framework-Based Materials for Energy Conversion and Storage

Highly exposed ruthenium-based electrocatalysts from bimetallic metal-organic frameworks for overall water splitting

The excessive depletion of fossil fuels and consequent energy crisis combined with environmental issues call for inexhaustible, clean and renewable energy sources and environmentally friendly energy technologies, such as solar energy and novel electrochemical energy conversion and storage devices. Developing supporting platforms for energy conversion and storage ameliorating mass transfer and electron transfer has stepped into the center of the energy research arena. Covalent organic frameworks (COFs) are emerging crystalline porous materials linked via covalent bonding possessing flexible molecular design and synthetic strategies, high conjugated and modifiable structures, large surface area and porosity. Due to these merits, COFs have shown promising perspectives in energy applications including photocatalysis, electrocatalysis, supercapacitors, metal-ion/sulfur batteries, etc. This critical review imparts a comprehensive summary of the fast-developing COF field in terms of molecular design and subsequent synthetic strategies to prepare COFs with highly conjugated and modifiable structures and their applications in energy conversion and storage. Furthermore, challenges and perspectives according to previous contributions are also discussed for developing more efficient energy conversion and storage COF materials. It is anticipated that this review could boost further research enthusiasm for COF-based materials in energy applications.

Covalent organic framework-based materials for energy applications

Trogtalite CoSe nanobuds encapsulated into boron and nitrogen codoped graphene (BCN) nanotubes (CoSe@BCN-750) are synthesized via a concurrent thermal decomposition and selenization processes. The CoSe@BCN-750 nanotubes deliver an excellent storage capacity of 580 mA h g at current density of 100 mA g at 100th cycle, as the anode of a sodium ion battery. The CoSe@BCN-750 nanotubes exhibit a significant rate capability (100–2000 mA g current density) and high stability (almost 98% storage retention after 4000 cycles at large current density of 8000 mA g). The reasons for these excellent storage properties are illuminated by theoretical calculations of the relevant models, and various possible Na ion storage sites are identified through first-principles calculations. These results demonstrate that the insertion of heteroatoms, B–C, N–C as well as CoSe, into BCN tubes, enables the observed excellent adsorption energy of Na ions in high energy storage devices, which supports the experimental results.

Tianjie Qiu

Papers

Metal-organic framework-derived materials for electrochemical energy applications

Metal–Organic Framework-Based Materials for Energy Conversion and Storage

Highly exposed ruthenium-based electrocatalysts from bimetallic metal-organic frameworks for overall water splitting

Covalent organic framework-based materials for energy applications

Encapsulating Trogtalite CoSe2 Nanobuds into BCN Nanotubes as High Storage Capacity Sodium Ion Battery Anodes