An ultrastable zirconium-phosphonate framework as bifunctional catalyst for highly active CO₂chemical transformation

Abstract

A zirconium-phosphonate network, as a bifunctional catalyst for carbon dioxide (CO)/epoxide coupling reaction, exhibits very high activity that is superior to most documented metal-organic framework (MOF)-based catalysts. Furthermore, it possesses extraordinary tolerance to extremely harsh conditions, such as aqua regia. This paper describes the use of metal phosphonate as a new MOF applied to CO transformation.

Improving MOF stability: approaches and applications

“…Sun's group selected tetraphenylsilane tetrakis-4phosphonic acid as the ligand and constructed a zirconiumphosphonate network that displayed distinctive tolerance to aqueous solutions with a wide range of pH values (1-12) and concentrated acids. 77 As for phenolate-based MOFs, the relatively high pK a of the phenolate ligands can afford stronger M-O bonds with Zr 4+ ions in comparison to carboxylate linkers. Lin's group demonstrated the fabrication of a series of zirconium polyphenolate-(metallo)porphyrin MOFs, in which the highly stable 5-membered rings generated by the chelating effect of polyphenols greatly improved the stability of resultant MOFs (Fig.…”

Synthesis of Some Di‐ and Tetraphosphonic Acids by Suzuki Cross‐Coupling

“…Metal organophosphonates constitute a unique class of porous materials, which recently received tremendous attention in material science . For instance, porous metal organic frameworks (MOFs) or proton‐conducting membranes (PCMs) for fuel cells based on metal organophosphonates are thermally more stable and hydrolytically less sensitive than their carboxylate counterparts , . Up to the early 2000s, most metal‐organophosphonates possessed highly dense pillared‐layered and lamellar structures because their syntheses relied on structurally flexible alkylphosphonate linkers .…”

Phosphonates Meet Metal−Organic Frameworks: Towards CO2 Adsorption

“…primarily CO 2 , N 2 , and water vapor . To this end, phosphonate based zirconium MOFs offer advantage not only because of their enhanced hydrolytic and chemical stability but also the free −OH group on the phosphonate which serves as an additional adsorption site for CO 2 leading to selectivity ,…”