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However, the fundamentals of their effects are usually difficult to access. Herein, we unravel mechanistic and kinetic aspects of the role of alkali metals in CO<jats:sub>2<\/jats:sub> hydrogenation over Fe\u2010based catalysts through state\u2010of\u2010the\u2010art characterization techniques, spatially resolved steady\u2010state and transient kinetic analyses. The promoters affect electronic properties of iron in iron carbides. These carbide characteristics determine catalyst ability to activate H<jats:sub>2<\/jats:sub>, CO and CO<jats:sub>2<\/jats:sub>. The Allen scale electronegativity of alkali metal promoter was successfully correlated with the rates of CO<jats:sub>2<\/jats:sub> hydrogenation to higher hydrocarbons and CH<jats:sub>4<\/jats:sub> as well as with the rate constants of individual steps of CO or CO<jats:sub>2<\/jats:sub> activation. The derived knowledge can be valuable for designing and preparing catalysts applied in other reactions where such promoters are also used.<\/jats:p>","DOI":"10.1002\/anie.202116517","type":"journal-article","created":{"date-parts":[[2022,3,4]],"date-time":"2022-03-04T16:38:46Z","timestamp":1646411926000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":125,"title":["Identifying Performance Descriptors in CO<sub>2<\/sub> Hydrogenation over Iron\u2010Based Catalysts Promoted with Alkali Metals"],"prefix":"10.1002","volume":"61","author":[{"given":"Qingxin","family":"Yang","sequence":"first","affiliation":[{"name":"Leibniz-Institut f\u00fcr Katalyse e. V.  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