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Methane is the central component of natural gas, which is globally one of the most abundant feedstocks. Due to its strong C–H bond, methane activation is difficult, and its conversion into value-added chemicals and fuels has therefore been the pot of gold in the industry and academia for many years. Industrially, halogenation of methane is one of the most promising methane conversion routes, which is why this paper presents a comprehensive review of the literature on methane activation by halogenation. Homogeneous gas phase reactions and their pertinent reaction mechanisms and kinetics are presented as well as microkinetic models for methane reaction with chlorine, bromine, and iodine. The catalysts for non-oxidative and oxidative catalytic halogenation were reviewed for their activity and selectivity as well as their catalytic action. The highly reactive products of methane halogenation reactions are often converted to other chemicals in the same process, and these multi-step processes were reviewed in a separate section. Recent advances in the available computational power have made the use of the ab initio calculations (such as density functional theory) routine, allowing for in silico calculations of energy profiles, which include all stable intermediates and the transition states linking them. The available literature on this subject is presented. Lastly, green processes and the production of fuels as well as some unconventional methods for methane activation using ultrasound, plasma, superacids, and light are also reviewed.

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