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 and tunable compositions and structures. In this Review, we present engineering principles promoting the electro-/photochemical performance of MOF-based materials for ECS by component design and nanostructuring. Through the discussion of the engineering strategies of pristine MOFs, MOF composites, and their derivatives for ECS, the superiority and composition–structure–activity relationships of the engineered MOF-based materials with advanced components and nanostructures will be clarified. Finally, we provide a concluding discussion on the challenges and direction of future development in this emerging area of MOF-based materials for ECS.

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The excessive depletion of fossil fuels and consequent energy crisis combining environmental issues calls for inexhaustible, clean and renewable energy sources and environmental-friendly energy technologies, such as solar energy and...

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Transition‐metal phosphides have flourished as promising candidates for oxygen evolution reaction (OER) electrocatalysts. Herein, it is demonstrated that the electrocatalytic OER performance of CoP can be greatly improved by constructing a hybrid CoP/TiOx heterostructure. The CoP/TiOx heterostructure is fabricated using metal–organic framework nanocrystals as templates, which leads to unique hollow structures and uniformly distributed CoP nanoparticles on TiOx. The strong interactions between CoP and TiOx in the CoP/TiOx heterostructure and the conductive nature of TiOx with Ti3+ sites endow the CoP–TiOx hybrid material with high OER activity comparable to the state‐of‐the‐art IrO2 or RuO2 OER electrocatalysts. In combination with theoretical calculations, this work reveals that the formation of CoP/TiOx heterostructure can generate a pathway for facile electron transport and optimize the water adsorption energy, thus promoting the OER electrocatalysis.

Trogtalite CoSe2 nanobuds encapsulated into boron and nitrogen codoped graphene (BCN) nanotubes (CoSe2@BCN‐750) are synthesized via a concurrent thermal decomposition and selenization processes. The CoSe2@BCN‐750 nanotubes deliver an excellent storage capacity of 580 mA h g−1 at current density of 100 mA g−1 at 100th cycle, as the anode of a sodium ion battery. The CoSe2@BCN‐750 nanotubes exhibit a significant rate capability (100–2000 mA g−1 current density) and high stability (almost 98% storage retention after 4000 cycles at large current density of 8000 mA g−1). 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 CoSe2, into BCN tubes, enables the observed excellent adsorption energy of Na+ ions in high energy storage devices, which supports the experimental results.

Metal–organic frameworks (MOFs), featuring porous crystalline structures with coordinated metal nodes and organic linkers, have recently found increasing interest in diverse applications. By virtue of their versatile and highly tunable compositions and structures, constructing hollow architectures will further endow MOFs with enhanced properties and designability, exceeding the molecular scale. MOFs could be considered as promising building units to fabricate complex hollow nanocomposites with faster mass transport, multiple active components, more exposed active sites, and better compatibility than bulk MOFs. To construct a promising blueprint for hollow pristine MOFs, this review provides a comprehensive overview for structural design strategies and applications of hollow pristine MOFs. We will highlight the merits, challenges and future potential by structuring and applying MOFs in sensing, separation, storage, catalysis, environmental remediation, photochemical and electrochemical energy conversion. This review might pave a new avenue for future development of novel pristine hollow MOFs.

The development of advanced energy conversion systems such as fuel cells and electrolyzers with desirable efficiency and durability is of great significance in order to power society in a sustainable way, which highly depends on the fabrication of electrocatalysts with desirable electrochemical performance. Multi‐scale design of electrocatalysts from the atomic scale to device‐scale is crucial to achieve optimal overall electrochemical performance in terms of activity, selectivity, and durability. Benefitting from their highly diverse and tunable structures and compositions, metal–organic frameworks (MOFs) are promising platforms to design and synthesize electrocatalysts at multiple scales for energy electrocatalysis. Herein, the fundamental principles and recent progress in multi‐scale design of MOF‐derived materials from the aspects of active sites, interfaces, pore structures, and morphologies are summarized. Moreover, precise control of these variables, to meet the requirements of specific energy‐related reactions including oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, CO2 reduction reaction (CO2RR), and N2 reduction reaction is critically discussed. Furthermore, challenges and future research directions in multi‐scale design and fabrication of MOF‐derived electrocatalysts for real‐world energy conversion applications are provided.