Metal-organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability and richness of their structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple and selective heterogeneous interactions and activations in these MOF-based nanocatalysts. Pyrolysis of MOF-nanoparticle composites forms highly porous N- or P-doped graphitized MOF-derived nanomaterials that are increasingly used as efficient catalysts especially in electro- and photocatalysis. This review first briefly summarizes this background of MOF nanoparticle catalysis and then comprehensively reviews the fast-growing literature reported during the last years. The major parts are catalysis of organic and molecular reactions, electrocatalysis, photocatalysis, and views of prospects. Major challenges of our society are addressed using these well-defined heterogeneous catalysts in the fields of synthesis, energy, and environment. In spite of the many achievements, enormous progress is still necessary to improve our understanding of the processes involved beyond the proof-of-concept, particularly for selective methane oxidation, hydrogen production, water splitting, CO2 reduction to methanol, nitrogen fixation, and water depollution.

State of the Art and Prospects in Metal-Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis.

More than 95% (in volume) of all of today’s chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic rese...

Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives

The study of hydrogen evolution reaction and oxygen evolution reaction electrocatalysts for water electrolysis is a developing field in which noble metal-based materials are commonly used. However, the associated high cost and low abundance of noble metals limit their practical application. Non-noble metal catalysts, aside from being inexpensive, highly abundant and environmental friendly, can possess high electrical conductivity, good structural tunability and comparable electrocatalytic performances to state-of-the-art noble metals, particularly in alkaline media, making them desirable candidates to reduce or replace noble metals as promising electrocatalysts for water electrolysis. This article will review and provide an overview of the fundamental knowledge related to water electrolysis with a focus on the development and progress of non-noble metal-based electrocatalysts in alkaline, polymer exchange membrane and solid oxide electrolysis. A critical analysis of the various catalysts currently available is also provided with discussions on current challenges and future perspectives. In addition, to facilitate future research and development, several possible research directions to overcome these challenges are provided in this article.

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Recent Progresses in Electrocatalysts for Water Electrolysis

Metal-organic frameworks and their derivatives as bifunctional electrocatalysts

Due to their significance in energy-conversion applications, the development of efficient non-noble electrocatalysts for the oxygen reduction reaction (ORR) to accelerate the sluggish cathodic reaction for fuel cells and metal–air batteries has attracted extensive attention. Metal–organic frameworks (MOF), a family of crystalline organic–inorganic porous materials constituted by ligands and metal struts, have been identified as a promising platform for preparing efficient ORR catalysts. In this review, the progress and current developments of MOF derivatives as non-noble ORR catalysts are summarized. Beginning with an introduction of the general principles in fabricating efficient non-noble ORR catalysts, the MOF-directed synthesis in the fabrication of non-noble catalysts with finely controlled local electronic structures, extrinsic structures and interface properties is reviewed and discussed. The construction of special local electronic structures and morphologies under the guidelines of general principles is presented in detail. Particularly, the superiority of MOFs, as compared to other precursors, in the controlled immobilization of favourable factors into resulting catalysts is highlighted. Finally, prospects and future perspectives of MOF utilization in fabricating non-noble ORR catalysts are proposed.

Metal–organic frameworks: a promising platform for constructing non-noble electrocatalysts for the oxygen-reduction reaction

Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

Given that combined merits of both compositions and novel structures play important roles in energy storage of electrode materials, we herein use [CH3NH3][NixCo1-x(HCOO)3] as self-sacrificed precursors to synthesize structure-controlled hollow nickel cobalt phosphides microcubes. The as-obtained hollow NiCoP-2 displays the highest specific capacity of 629 C g−1 at 1 A g−1 and superior cycling stability with 81.3% capacitance retention at 6 A g−1 after 8000 cycles. Moreover, the asymmetric supercapacitor composed of NiCoP-2 and commercial active carbon (YP-80F) presents the remarkable battery storage performance in terms of outstanding specific capacitance (121.5 F g−1 at 1 A g−1), excellent cycling durability (90.1% capacitance retention after 10,000 cycles) and high energy density of 43.2 Wh kg−1 at a power density of 801.6 W kg−1. The attractive performance can be ascribed to superiority of the transition metal phosphides, hollow structures, as well as synergism between Ni and Co.

Template synthesis of structure-controlled 3D hollow nickel-cobalt phosphides microcubes for high-performance supercapacitors.

N-doped porous carbon-encapsulated Fe nanoparticles as efficient electrocatalysts for oxygen reduction reaction

The exploitation of efficient and stable non-noble-metal bifunctional electrocatalysts is key to the development of hydrogen production technology. Although some progress has been made in the synth...

MOF-Derived Hierarchical CoSe2 with Sheetlike Nanoarchitectures as an Efficient Bifunctional Electrocatalyst.

Transition metal oxides as electrode materials for LIBs are constrained by tremendous volume changes, self-aggregation and poor conductivity. Therefore, it is extremely imperative and necessary to develop a new electrode material with high capacity and long-term cycles. In this paper, yolk–shell Co-V2O3-24 nanospheres assembled with nanosheets were designed and synthesized through a one-step solvothermal treatment and calcination process. The results show that the anion plays a significant role in morphology induction during the solvothermal reactions. As an anode material, Co-V2O3-24 displayed an outstanding reversible specific capacity of 986.2 mA h g−1 at 0.5 A g−1 after 630 cycles with a high capacity retention rate. Even when tested at 5 A g−1 after 2200 cycles, the specific capacity of 457.6 mA h g−1 can be retained, which indicates that Co-V2O3-24 has excellent rate performance and cycle stability. The outstanding lithium storage properties mainly benefit from the novel 3D hierarchical structure, Co doping and abundant electrochemical active sites.

Aihua Zhao

Papers

Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

Template synthesis of structure-controlled 3D hollow nickel-cobalt phosphides microcubes for high-performance supercapacitors.

N-doped porous carbon-encapsulated Fe nanoparticles as efficient electrocatalysts for oxygen reduction reaction

MOF-Derived Hierarchical CoSe2 with Sheetlike Nanoarchitectures as an Efficient Bifunctional Electrocatalyst.

Synthesis of cobalt-doped V2O3 with a hierarchical yolk–shell structure for high-performance lithium-ion batteries