Although　Zn-based　catalysts　are　widely　used　for　propane　dehydrogenation　(PDH),　the　positively　charged　Zn　is　susceptible　to　reduction　to　metallic　state　under　harsh　conditions,　which　ultimately　leads　to　its　vaporization　and　thus　irreversible　deactivation.　Moreover,　the　understanding　of　the　structure-performance　relationship　of　Zn-based　catalysts　in　PDH　remains　limited.　In　this　work,　the　effect　of　peripheral　P　doping　on　PDH　over　atomically　dispersed　Zn　catalysts　with　different　N/C　coordination　numbers　(Zn1-NnC4-n-P,　n　=　2–4)　is　investigated　by　density　functional　theory　(DFT)　calculations.　The　results　show　that　the　peripherally　P-doped　Zn1-N2C2　catalyst　exhibits　improved　performance　and　stability　compared　to　the　undoped　Zn1-N2C2.　It　is　revealed　that　there　is　a　linear　relationship　between　the　energy　barrier　of　the　first　dehydrogenation　step　of　C3H8　and　the　H　affinity　of　the　active　site.　Furthermore,　the　peripheral　P　doping　contributes　to　the　stabilization　of　the　tetra-coordination　structure　of　Zn　during　catalysis,　which　in　turn　lowers　the　energy　barrier　for　the　second　dehydrogenation　step　of　C3H8.　The　experimental　results　are　in　good　agreement　with　theoretical　predictions.　This　work　provides　useful　insights　for　the　rational　design　of　efficient　SACs　for　PDH　via　doping　strategy.　©　2024　Elsevier　Ltd