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In order to achieve global carbon neutrality, much attention needs to be diverted towards CO<jats:sub>2<\/jats:sub> management. Catalytic hydrogenation of CO<jats:sub>2<\/jats:sub> is an exciting opportunity to curb the increasing CO<jats:sub>2<\/jats:sub> and produce value\u2010added products. However, the comprehensive understanding of CO<jats:sub>2<\/jats:sub> hydrogenation is still a matter of discussion due to its complex reaction mechanism and involvement of various species. This review comprehensively discusses three processes: reverse water gas shift (RWGS) reaction, modified Fischer Tropsch synthesis (MFTS), and methanol\u2010mediated route (MeOH) for CO<jats:sub>2<\/jats:sub> hydrogenation to hydrocarbons. Along with analysing the reaction pathways, it is also very important to understand the real\u2010time evolvement of catalytic process and reaction intermediates by employing <jats:italic>in\u2010situ<\/jats:italic> characterization techniques under actual reaction conditions. Subsequently, in second part of this review, we provided a systematic analysis of advancements in <jats:italic>in<\/jats:italic>\u2010<jats:italic>situ<\/jats:italic> techniques aimed to monitor the evolution of catalysts during CO<jats:sub>2<\/jats:sub> reduction process. The section also highlights the key components of <jats:italic>in\u2010situ<\/jats:italic> cells, their working principles, and applications in identifying reaction mechanisms for CO<jats:sub>2<\/jats:sub> hydrogenation. Finally, by reviewing respective achievements in the field, we identify key gaps and present some future directions for CO<jats:sub>2<\/jats:sub> hydrogenation and <jats:italic>in\u2010situ<\/jats:italic> studies.<\/jats:p>","DOI":"10.1002\/cplu.202300511","type":"journal-article","created":{"date-parts":[[2024,6,9]],"date-time":"2024-06-09T22:30:05Z","timestamp":1717972205000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["<i>In\u2010Situ<\/i> Characterization Techniques for Mechanism Studies of CO<sub>2<\/sub> Hydrogenation"],"prefix":"10.1002","volume":"89","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4017-2184","authenticated-orcid":false,"given":"Rasmeet","family":"Singh","sequence":"first","affiliation":[{"name":"Laboratory for Catalysis Engineering School of Chemical and Biomolecular Engineering The University of Sydney  Camperdown New South Wales 2006 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lizhuo","family":"Wang","sequence":"additional","affiliation":[{"name":"Laboratory for Catalysis Engineering School of Chemical and Biomolecular Engineering The University of Sydney  Camperdown New South Wales 2006 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8704-605X","authenticated-orcid":false,"given":"Jun","family":"Huang","sequence":"additional","affiliation":[{"name":"Laboratory for Catalysis Engineering School of Chemical and Biomolecular Engineering The University of Sydney  Camperdown New South Wales 2006 Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,8,8]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.rser.2014.07.093"},{"key":"e_1_2_8_2_1","unstructured":"\u00a0"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1038\/nclimate3231"},{"key":"e_1_2_8_4_2","first-page":"151","volume-title":"Climate change 2014: synthesis report. 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