Robust multifunctional Zr-based metal–organic polyhedra for high proton conductivity and selective CO₂ capture

Abstract

A new stable Zr-based MOP is successfully constructed. Unique cavity and 2D hydrogen-bonding networks endow the MOP with highly selective CO2 capture and excellent proton conduction.

Ultrathin Films of Porous Metal–Organic Polyhedra for Gas Separation

“…Moreover,p revious studies [16] have shown that C 12 RhMOP displays an egligible N 2 adsorption at 77 K( 0.17 and 0.82 N 2 molesp er MOP mol at P/P 0 % 0.1 and P/P 0 % 0.95, respectively) and as ignificant CO 2 per MOP mol at P/P 0 % 0.1 and P/P 0 % 0.95, respectively), making it an interesting candidate for CO 2 /N 2 separation. Multiple C 12 RhMOP monolayer films were thus deposited on the permeable polymer poly[1-(trimethylsilyl)-1-propyne] (PTMSP) to fabricate am ultilayer membrane with the desired MOP film thickness. TheC O 2 /N 2 selectivity of the PTMSP membrane at 1bar and 35 8Cw as significantly increased from 4.1 to 10.1 after 30 deposition cycles of C 12 RhMOP monolayers while keeping high the CO 2 permeance (195 GPU), thereby demonstrating the potential of molecularly thin MOP films for the CO 2 /N 2 separation.…”

“…TheC O 2 /N 2 selectivity of the PTMSP membrane at 1bar and 35 8Cw as significantly increased from 4.1 to 10.1 after 30 deposition cycles of C 12 RhMOP monolayers while keeping high the CO 2 permeance (195 GPU), thereby demonstrating the potential of molecularly thin MOP films for the CO 2 /N 2 separation. We initially prepared ad iluted C 12 RhMOPs olution in DCM (2.8 10 À6 m)t os tudy Langmuir film formation.T hen, 1000-1200 mLo ft he C 12 RhMOPs olution (i.e. the total mass of C 12 RhMOP employed was 0.04 mg) were spreado nt he water subphase.…”

“…We initially prepared ad iluted C 12 RhMOPs olution in DCM (2.8 10 À6 m)t os tudy Langmuir film formation.T hen, 1000-1200 mLo ft he C 12 RhMOPs olution (i.e. the total mass of C 12 RhMOP employed was 0.04 mg) were spreado nt he water subphase. After solvent evaporation (ca.…”

Stabilizing Metal–Organic Polyhedra (MOP): Issues and Strategies

“…The cage molecule showed permanent porosity;t he BETand Langmuir surfacea reas were 1201 and 1675 m 2 g À1 ,r espectively,d eterminedf rom N 2 sorption isotherms at 77 K. The authors revealed that as the number of hydrogen-bonding interactions increased (Fig- . [71] The BET surface area of this cage, calculated from the CO 2 isotherm at 195 K, was 490 m 2 g À1 .T he cage moleculesn ot only retainedt heir crystalline structures on desolvating at 150 8C, but the same stabilityt rend was noted even in water,a cidic, and basic media. The porosity and pH stability of this stable Zr-based MOP further endowed it with selectiveC O 2 capturea nd ah igh proton conductivity of 1.14 10 À3 Scm À1 at 30 8Cand 98 %relative humidity (RH).…”

“…In another report, Xiang et al. synthesized a MOP formulated as [Cp 3 Zr 3 (μ 3 ‐O)(μ 2 ‐OH) 3 ] 2 L 3 ⋅ 4 Na ⋅ 4 H 2 O (L=sulfonate‐containing linker) with SO 3 − decorated on the surface (six SO 3 − per MOP) . The BET surface area of this cage, calculated from the CO 2 isotherm at 195 K, was 490 m 2 g −1 .…”