Ling‐I HungSouvik PalTing‐Ting HsuShih‐Ting TsengTai‐Lin WuPamela Berilyn SoYu‐Tzu ChangSue‐Lein WangYao‐Ting WangTeng‐Hao ChenChen‐Wei ChanHsin‐Tsung ChenDUN-YEN KANGChia‐Her Lin2025-05-062025-05-062025-04-22https://www.scopus.com/record/display.uri?eid=2-s2.0-105000291562&origin=resultslisthttps://scholars.lib.ntu.edu.tw/handle/123456789/728930The application of ultramicroporous materials for CO2 separation is limited by the rarity of materials exhibiting stability and rapid scale-up characteristics. In this study, we propose a rational approach to enhance the structural stability and durability of the pillared layer structure. Through the topotactic replacement of protons with metal ions in the parent 4,4′-bipyridine (bpy)-pillared zincophosphate, we observed the formation of edge-sharing dimers of ZnO4N and PO4, as well as the insertion of (VOH2O)2+ into the zinc phosphate layers. This resulted in the modified bpy-pillared bimetal phosphate, [(VOH2O)(ZnPO4)2(bpy)]⋅4H2O (denoted as NTHU-16 or VZn-bpy-w), which exhibits exceptional structural stability in a wide pH range (pH 2-12) and boiling water. Additionally, a rapid scale-up process reduced the synthesis time of VZn-bpy-w from 48 hours to just 3 hours, significantly increasing efficiency. The vanadyl groups, with easily displaced coordinated water, enhance the strength of the inorganic sheets and create available metal sites for the adsorption and separation of CO2. This combined strategy of structural enhancement and rapid synthesis offers a new pathway for engineering stable, porous metal phosphates and designing novel organic-inorganic hybrid materials with potential applications in CO2 separation.CO2 separationmixed-matrix membranescale-upultramicroporouszincophosphate[SDGs]SDG6[SDGs]SDG13journal article10.1002/chem.202500136