The utilization of fossil fuels has enabled an unprecedented era of prosperity and advancement of well- being for human society. However， the associated increase in anthropogenic carbon dioxide（CO2） emissions can negatively affect global temperatures and ocean acidity. Moreover， as a limited resource， the depletion of fossil fuels will ultimately force one to seek alternative carbon sources to maintain a sustainable development. Using green hydrogen obtained from the water electrolysis process carried out using electricity generated from renewable sources， the hydrogenation of captured CO2 to methanol not only efficiently utilizes the excess effluent CO2 from industrial gaseous waste， but also produces a clean and renewable chemical feedstock of methanol， the core of which is to develop highly efficient and stable catalysts for methanol formation. In this review， we discuss the reaction mechanism and structure-activity relationship of common heterogeneous catalysts for CO2 hydrogenation to methanol which has attracted great attention in the past decades. We also review the latest development in the design and synthesis of heterogeneous catalysts（Cu-based catalyst， noble metal catalyst and bimetallic catalysts， oxide catalyst and other novel catalysts） for methanol synthesis through the direct hydrogenation of CO2. Moreover， the opportunities and challenges in this field are also prospected.
