One-Pot, Room-Temperature Conversion of CO₂ into Porous Metal-Organic Frameworks

The conversion of CO₂ into functional materials under ambient conditions is a major challenge to realize a carbon-neutral society. Metal-organic frameworks (MOFs) have been extensively studied as designable porous materials. Despite the fact that CO₂ is an attractive renewable resource, the synthesis of MOFs from CO₂ remains unexplored. Chemical inertness of CO₂ has hampered its conversion into typical MOF linkers such as carboxylates without high energy reactants and/or harsh conditions. Here, we present a one-pot conversion of CO₂ into highly porous crystalline MOFs at ambient temperature and pressure. Cubic [Zn₄O(piperazine dicarbamate)₃] is synthesized via in situ formation of bridging dicarbamate linkers from piperazines and CO₂ and shows high surface areas (∼2366 m² g^-1) and CO₂ contents (>30 wt %). Whereas the dicarbamate linkers are thermodynamically unstable by themselves and readily release CO₂, the formation of an extended coordination network in the MOF lattices stabilizes the linker enough to demonstrate stable permanent porosity.