Because of the increasing energy demand of the growing human population, the world is facing a crisis of depleting fossil fuels as well as huge amounts of CO₂ emissions being put into the environment. Therefore, to combat these two major issues, catalytic CO₂ hydrogenation is introduced which utilizes the abundant CO₂ in the atmosphere and at the same time generates clean fuel and chemicals. Metal organic frameworks (MOFs) are a very attractive catalyst for the conversion of CO₂ into CH₄ due to their high surface area, tunable chemical composition, high porosity, and well-ordered structures. They are also photoresponsive materials. This review discusses the various strategies and modifications implemented to further ameliorate the thermal, photo-, and photothermal catalytic performance of MOFs. Initially, three main catalytic approaches, namely thermal catalysis, photocatalysis, and photothermal catalysis, are thoroughly discussed to understand the mechanism and the differences between them with their characteristics and limitations. Then, a comprehensive review was carried out on various strategies employed to augment the performance of MOFs for CO₂ methanation, such as metal addition and incorporation, MOF templating, surface sensitization, formation of heterojunctions, and organic linker modifications via functionalization. Comparisons between MOF-based catalyst and traditional catalyst were carried out to elucidate the beneficial properties of MOFs toward CO₂ methanation. The selectivity control for CH₄ production was then extensively reviewed in terms of operating parameters, type of catalyst, and reactor. Finally, the mechanism, pathways, intermediates, and adsorbed species involved for CO₂ methanation are thoroughly discussed with the help of diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) analysis and Density Functional Theory (DFT) calculations. Therefore, it is clear that metal organic frameworks are highly promising porous crystalline materials for CO₂ methanation reaction and have countless possibilities for further enhancement and development to maximize the production of renewable CH₄.

中文翻译：

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通过光/热加氢提高二氧化碳甲烷化金属有机骨架性能的当前趋势和方法：综述

由于人口不断增长的能源需求的不断增加，世界正面临消耗化石燃料以及大量的CO危机₂排放量被投入到环境中。因此，为了解决这两个主要问题，引入了催化 CO ₂加氢，它利用大气中丰富的 CO ₂同时产生清洁的燃料和化学品。金属有机框架 (MOF) 是一种非常有吸引力的催化剂，用于将 CO ₂转化为 CH ₄由于其高表面积、可调化学成分、高孔隙率和有序结构。它们也是光响应材料。本综述讨论了为进一步改善 MOF 的热、光和光热催化性能而实施的各种策略和修改。首先，深入讨论了三种主要的催化方法，即热催化、光催化和光热催化，以了解其机理和它们之间的差异及其特点和局限性。然后，对用于提高 MOF 对 CO ₂性能的各种策略进行了全面审查甲烷化，例如金属添加和掺入、MOF 模板化、表面敏化、异质结的形成以及通过官能化进行的有机连接体修饰。对基于 MOF 的催化剂和传统催化剂进行了比较，以阐明 MOF 对 CO ₂甲烷化的有益特性。然后在操作参数、催化剂类型和反应器方面广泛审查了 CH ₄生产的选择性控制。最后，CO ₂涉及的机制、途径、中间体和吸附物种在漫反射红外傅里叶变换光谱 (DRIFTS) 分析和密度泛函理论 (DFT) 计算的帮助下，对甲烷化进行了彻底的讨论。因此，很明显，金属有机骨架是用于CO ₂甲烷化反应的非常有前途的多孔结晶材料，并且具有进一步增强和开发以最大化可再生CH ₄的生产的无数可能性。