In　the　process　of　direct　synthesis　of　ethanol　from　syngas,　rhodium-based　catalysts　continue　becoming　a　hot　topic　because　of　their　high　selectivity　for　C2　oxygen-containing　compounds　such　as　ethanol.　In　this　work,　UiO-66　was　used　as　a　support　to　introduce　the　metal　Ce4+　species　into　the　[Zr6O4(OH)4]　metal　node　of　UiO-66-Zr　to　replace　some　of　the　metal　Zr4+　species　formation　[Zr6−xCexO4(OH)4]　metal　nodes,　so　as　to　accurately　study　the　problem　of　ethanol　activity　sites　for　the　preparation　of　syngas.　The　characterization　results　of　XRD,　TG,　Raman,　BET,　H2-TPR,　XPS,　and　in-situ　DRIFTS　showed　that　with　the　introduction　of　metal　Ce4+　species　at　the　UiO-66　[Zr6O4(OH)4]　node,　-(Zr-O)-Rh-(O-Ce)-sites　were　formed　on　the　catalyst,　and　-(Zr-O)-Rh-(O-Zr)-sites　were　formed　on　the　Rh/UiO-66-Zr　catalyst.　Combined　with　the　evaluation　results　of　the　catalytic　reaction,　the　number　of　ethanol　active　sites　was　significantly　increased.　Because　of　the　interaction　between　Rh　species　and　-(O-Zr)-species　is　stronger　than　Rh　species　with　-(O-Ce)-　sites,　the　potential　difference　of　this　interaction　favors　the　efficient　transport　of　electrons.　On　the　other　hand,　-(Zr-O)-Rh-(O-Ce)-　can　stabilize　the　key　intermediates　for　the　preparation　of　ethanol　from　syngas,　which　can　promote　the　formation　of　ethanol.　©　2022　Science　Press.　All　rights　reserved.