CO₂ and CH₄ contribute to greenhouse gas emissions, while the production of industrial base chemicals from natural gas resources is emerging as well. Such conversion processes, however, are energy-intensive and introducing a renewable and sustainable electric activation seems optimal, at least for intermediate-scale modular operation. The review thus analyses such valorisation by plasma reactor technologies and heterogeneous catalysis application, largely into higher hydrocarbon molecules, that is ethane, ethylene, acetylene, propane, etc., and organic oxygenated compounds, i.e. methanol, formaldehyde, formic acid and dimethyl ether. Focus is given to reaction pathway mechanisms, related to the partial oxidation steps of CH₄ with O₂, H₂O and CO₂, CO₂ reduction with H₂, CH₄ or other paraffin species, and to a lesser extent, to mixtures' dry reforming to syngas. Dielectric barrier discharge, corona, spark and gliding arc sources are considered, combined with (noble) metal materials. Carbon (C), silica (SiO₂) and alumina (Al₂O₃) as well as various catalytic supports are examined as precious critical raw materials (e.g. platinum, palladium and rhodium) or transition metal (e.g. manganese, iron, cobalt, nickel and copper) substrates. These are applied for turnover, such as that pertinent to reformer, (reverse) water–gas shift (WGS or RWGS) and CH₃OH synthesis. Time-on-stream catalyst deactivation or reactivation is also overviewed from the viewpoint of individual transient moieties and their adsorption or desorption characteristics, as well as reactivity.

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.