An In Situ One‐Pot Synthetic Approach towards Multivariate Zirconium MOFs

Abstract

Chemically highly stable MOFs incorporating multiple functionalities are of great interest for applications under harsh environments.H erein, we presented af acile onepot synthetic strategy to incorporate multiple functionalities into stable Zr-MOFs from mixed ligands of different geometry and connectivity.V ia our strategy,tetratopic tetrakis(4-carboxyphenyl)porphyrin (TCPP) ligands were successfully integrated into UiO-66 while maintaining the crystal structure, morphology,a nd ultrahigh chemical stability of Integrating multi-functionality into metal-organic frameworks (MOFs) has attracted growing attention as it plays ac ritical role in realizing the potential of MOFs for aw ide range of applications.[1] To date,tremendous efforts have been made to develop strategies to incorporate multiple functionalities into MOFs.[2] Among them, mixed-ligand strategies have been extensively studied owing to the straightforward synthesis and preservation of the structural integrity of MOFs.[3] Remarkably,Y aghi and co-workers reported the synthesis of multifunctional MOFs,s o-called multivariate (MTV)-MOFs by mixing ligands and successfully introduced up to eight functionalities into MOF-5.[4] However,m ixedligand strategies generally require the use of ligands of the same geometry and connectivity (e.g.ligand derivatives) that are "indistinguishable" during the formation of MOFs to prevent generating mixed phases,w hich greatly limits the variety of ligand and functionality that can be incorporated into the MOF.I na ddition to the functionality,t he excellent stability is another prerequisite for practical applications of MOFs,especially for those under harsh conditions,inorder to guarantee the integrity of the framework. Although there have been af ew reported examples of MOFs containing mixed ligands of different symmetry and connectivity,t hose MOFs are mostly based on M 2+ metal species,w hich suffer from poor stability under harsh chemical conditions and thus their applications are severely restricted. Herein, we show that through one-pot thermodynamically controlled synthesis, multiple functionalities can be integrated into aZ r-MOF without forming separate domains even when mixing ligands of different size,s ymmetry,a nd connectivity.T he multifunctionalized Zr-MOFs obtained maintain the crystal structure,morphology,and stability of the parent MOF.Owing to the excellent stability of the parent MOF,our multi-functionalized Zr-MOFs exhibit high stability under harsh chemical environments.T herefore,o ur strategy goes beyond the limit of conventional mixed-ligand strategies and expands the diversity of functionality for stable MOFs modification, holding great potentials for exploring the applications of MOFs extensively.In recent years,Z r-MOFs have been intensively investigated owing to their considerably improved stability compared to common Zn/Cu/Cd-based MOFs.[5] Thev ersatile symmetry and connectivity of the Zr 6 cluster make it compatible with many different kinds of organic ligands to form MOFs.H owev...

In-situ incorporation of Copper(II) porphyrin functionalized zirconium MOF and TiO2 for efficient photocatalytic CO2 reduction

“…According to the diffraction patterns shown in Fig. S9 (online), it can be found that pristine UiO-66 matches well with previous reports, demonstrating the crystalline structure of UiO-66 is perfectly preserved after the introduction of CuTCPP into the MOF [12]. The XRD of TiO 2 fairly conforms to the HR-TEM for plane of anatase ( Fig.…”

“…In contrast, the color of CuTCPP & UiO-66 can be hardly washed away. Associating with previous study [12], it is thereby ascertained that the primary portion of CuTCPP displays steady coordination mofde in the CTU structure.…”

“…TCPP and CuTCPP were synthesized according to our previous work [22]. Generally, CTU was synthesized according to the litera-ture using a solvothermal method [12]. 30 mg ZrCl 4 , 30 mg BDC, 10 mg CuTCPP and 0.5 g benzoic acid were added to 2 mL DMF.…”

“…Moreover, the crystal structure and morphology of UiO-66 can be perfectly maintained after the mixed ligands, CuTCPP and BDC, jointly coordinating with Zr 6 SBUs to build a new MOF, CuTCPP & UiO-66 (CTU) [9][10][11]. It is worth noting that chemically implanting CuTCPP into UiO-66 is of great value in photocatalytic applications, since it is able to prevent CuTCPP from aggregation and self-quenching of the excited states as well as formation of catalytically inactive dimers, and therefore provide a consistent enhancement in light absorption for the actualization of an ameliorated photocatalytic ability than that of mere UiO-66 [12]. Actually, functionalized MOFs have already been explored as multifarious precursors in photo-assistant utilizations, such as hydrogen generation, degradation of organic pollutants, and CO 2 reduction [11,[13][14][15].…”

Recent Progress in the Development of Composite Membranes Based on Polybenzimidazole for High Temperature Proton Exchange Membrane (PEM) Fuel Cell Applications

“…These interesting compounds have been studied for possible different applications such as fuel cells [ 187 ], pervaporation [ 188 ], nanofiltration [ 189 ], gas separation [ 190 ], desammonia adsorption [ 191 ], and organocatalysis [ 192 ]. The introduction of MOFs into organic polymer results in the enhanced thermal chemical stability of the formed composites under harsh conditions, making them suitable for industrial application [ 193 ]. For elaboration of these membranes, polymers such as perfulorosulfonic acid [ 194 ], sulfonated poly (ether ether ketone) [ 195 ], and poly(vinyl alcohol) [ 196 ] have been used.…”