Metal organic frameworks (MOFs) are considered as a group of compounds, either metal ions or clusters, harmonized with organic ligands to form one or some dimensional structures. In addition to resilient bonds between inorganic and organic units, reticular synthesis creates MOFs, accurate selection of constituents of which can produce high thermal and chemical stability and crystals of ultrahigh porosity. Other solids have not shown the same accuracy normally used in chemical modification and even the capability of increasing their metrics with no modification of the underlying topology. With shape of building units and chemical compositions multiplying based on specific structures, MOFs might result in compounds that propose a synergistic mixture of features. This study presents up to date advances in both synthesis methods of MOFs and structural characteristics. Furthermore, the use of MOFs in different fields such as the removal of absorption and separation of toxic substances from gas and liquid, catalysts, a variety of sensors, storage of clean energies and environmental applications, medical and biological applications, and optoelectronic equipment is included.

A review on metal-organic frameworks: Synthesis and applications

The sustainable and scalable production of hydrogen through hydrogen evolution reaction (HER) and oxygen through oxygen evolution reaction (OER) in water splitting demands efficient and robust electrocatalysts. Currently, state‐of‐the‐art electrocatalysts of Pt and IrO2/RuO2 exhibit the benchmark catalytic activity toward HER and OER, respectively. However, expanding their practical application is hindered by their exorbitant price and scarcity. Therefore, the development of alternative effective electrocatalysts for water splitting is crucial. In the last few decades, substantial effort has been devoted to the development of alternative HER/OER and water splitting catalysts based on various transition metals (including Fe, Co, Ni, Mo, and atomic Pt) which show promising catalytic activities and durability. In this review, after a brief introduction and basic mechanism of HER/OER, the authors systematically discuss the recent progress in design, synthesis, and application of single atom and cluster‐based HER/OER and water splitting catalysts. Moreover, the crucial factors that can tune the activity of catalysts toward HER/OER and water splitting such as morphology, crystal defects, hybridization of metals with nonmetals, heteroatom doping, alloying, and formation of metals inside graphitic layered materials are discussed. Finally, the existing challenges and future perspectives for improving the performance of electrocatalysts for water splitting are addressed.

Single Atoms and Clusters Based Nanomaterials for Hydrogen Evolution, Oxygen Evolution Reactions, and Full Water Splitting

The oxygen evolution reaction (OER) is a critical electrochemical reaction in water splitting and rechargeable metal–air batteries. It plays a pivotal role in achieving high-efficiency clean-energy production and energy storage in these devices. Transition metal-based bimetallic MOFs (TMB MOFs) with two different metal ions possess specific synergistic effects, which could exhibit OER performance and stability superior to those of the corresponding monometallic MOFs for water oxidation. Benefiting from the diversity of chemical composition and structural type, TMB MOFs can also serve as precursors and templates to obtain alloy-particle-decorated carbon materials with high surface area, or metal compounds such as bimetallic sulfides, phosphides, and hydroxides with atomic-level mixing of heterometallic elements. These materials with high-density active sites exhibit much improved catalytic activity in the water oxidation reaction. This article aims to review the recent progress with TMB MOFs and their derivatives in relation to applications as electrocatalysts in OER, including analysis of the mechanism of the OER process with the assistance of DFT calculations and in situ or operando techniques.

Transition metal-based bimetallic MOFs and MOF-derived catalysts for electrochemical oxygen evolution reaction

Bimetallic metal-organic frameworks (MOFs) have two different metal ions in the inorganic nodes. According to the metal distribution, the architecture of bimetallic MOFs can be classified into two main categories namely solid solution and core-shell structures. Various strategies have been developed to prepare bimetallic MOFs with controlled compositions and structures. Bimetallic MOFs show a synergistic effect and enhanced properties compared to their monometallic counterparts and have found many applications in the fields of gas adsorption, catalysis, energy storage and conversion, and luminescence sensing. Moreover, bimetallic MOFs can serve as excellent precursors/templates for the synthesis of functional nanomaterials with controlled sizes, compositions, and structures. Bimetallic MOF derivatives show exposed active sites, good stability and conductivity, enabling them to extend their applications to the catalysis of more challenging reactions and electrochemical energy storage and conversion. This review provides an overview of the significant advances in the development of bimetallic MOFs and their derivatives with special emphases on their preparation and applications.

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Bimetallic metal–organic frameworks and their derivatives

Electrochemical water splitting is an appealing and promising approach for energy conversion and storage. As a key half-reaction of electricity-driven water splitting, the oxygen evolution reaction (OER) is a sluggish process due to the transfer of four protons and four electrons. Therefore, development of low-cost and robust OER electrocatalysts is of great importance for improving the efficiency of water splitting. Based on the merits of high surface area, rich pore structure, diverse composition and well-defined metal centers, metal-organic frameworks (MOFs) and their derivatives have been widely exploited as OER electrocatalysts. Herein, the current progress on MOFs and their derivatives for OER electrolysis is summarized, highlighting the design principle, synthetic methods and performance for MOF-based materials. In addition, the structure-performance relationships of MOFs and their derivatives toward the OER are discussed, providing valuable insights into rationally developing OER catalysts with high efficiency. The current scientific and technological challenges and future perspectives towards the purpose of sustainable industrial applications are addressed at the end.

Metal–organic frameworks and their derivatives as electrocatalysts for the oxygen evolution reaction

Developing efficient, stable, and low-cost catalysts for oxygen evolution reaction (OER) is highly desired in water splitting and metal–air batteries. Transition metal–organic frameworks (MOFs) have emerged as promising catalysts and have been intensively investigated especially due to their tunable crystalline structure. Unlike traditional strategies of tuning the morphology of well-crystalline MOFs, low-crystalline bimetallic MOFs are constructed via inducing exotic metal ions, and the formation process is revealed by experimental and theoretical methods. The low-crystalline bimetallic MOFs exhibit rich active sites due to local crystallinity and long-range disorder and deliver a small overpotential of 260 mV at 10 mA cm–2, a low Tafel slope of 35 mV dec–1, and a high Faradaic efficiency of 99.5% as oxygen evolution elecctrocatalysts. The work opens up a new avenue for the development of highly efficient earth-abundant catalysts in frontier potential applications.

Low-Crystalline Bimetallic Metal–Organic Framework Electrocatalysts with Rich Active Sites for Oxygen Evolution

Boosting oxygen reduction activity with low-temperature derived high-loading atomic cobalt on nitrogen-doped graphene for efficient Zn-air batteries.

Hierarchical Bimetallic Selenide Nanosheet-Constructed Nanotubes for Efficient Electrocatalytic Water Oxidation

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Low-Crystalline Bimetallic Metal–Organic Framework Electrocatalysts with Rich Active Sites for Oxygen Evolution

Boosting oxygen reduction activity with low-temperature derived high-loading atomic cobalt on nitrogen-doped graphene for efficient Zn-air batteries.

Hierarchical Bimetallic Selenide Nanosheet-Constructed Nanotubes for Efficient Electrocatalytic Water Oxidation