Metal-organic frameworks as catalysts and biocatalysts for methane oxidation: The current state of the art

As the main component of natural and shale gas, seabed clathrates, and biogas, methane (CH4) is an abundant C1 resource for added-value chemicals. CH4 is of critical importance to society as a universal and renewable (biogas) fuel, but it is also a potent greenhouse gas that causes global warming and climate change. Given such a multifaceted occurrence and uses of CH4, the research on its chemical transformations with environmental and sustainability significance represents a frontier direction of modern chemistry that can address many societal challenges. Metal-organic frameworks (MOFs) and derived materials received outstanding attention because of unique features such as structural versatility and tunability, low density, high porosity, and giant specific surface area, which all contributed to their auspicious applications in heterogeneous catalysis. With regard to methane, MOFs are unique and very promising materials for CH4 storage, separation, sensing, and various types of catalytic transformations. The main goal of this work consisted in surveying all the existing literature on the heterogeneous selective oxidation of methane catalyzed by MOFs, aiming at describing the current state of the art and highlighting other aspects, challenges, and perspectives closely relevant to this research area. This review thus focuses on the application of MOFs and their bioinspired or biomimetic analogs (bioMOFs) as heterogeneous catalysts for the selective oxidation of methane. The review is divided into logical sections: (i) methane sources, (ii) current status in methane oxidation, (iii) natural biochemical and enzymatic methane oxidation reactions and their relevance for inspiring the design of advanced catalysts as bioMOFs, (iv) methane oxidation reactions mediated by enzyme-mimicking bioMOFs, (v) MOFs as porous supports for catalytically active species and their catalytic use in methane oxidation, and (vi) computational chemistry toward unveiling MOF-catalyzed methane oxidation mechanisms and predicting prospective catalytic systems. This study will contribute to the advancement and future development of new MOF-based catalytic systems for various methane reactions as a frontier direction of modern chemistry and sustainable catalysis.(c) 2023 Elsevier B.V. All rights reserved.