High Proton Conductivity of the UiO-66-NH₂-SPES Composite Membrane Prepared by Covalent Cross-Linking

Abstract

A sulfonated poly­(ethersulfone) (SPES)–metal–organic framework (MOF) film with excellent proton conductivity was synthesized by anchoring UiO-66-NH2 to the main chain of the aromatic polymer through the Hinsberg reaction. The chemical bond was formed between the amino group in MOFs and the −SO2Cl group in chlorosulfonated poly­(ethersulfones) to conduct protons in the proton channel of the membrane, making the membrane have excellent proton conductivity. UiO-66-NH2 is successfully prepared as a result of the consistency of the experimental and simulated powder X-ray diffraction (PXRD) patterns of MOFs. The existence of absorption peaks of characteristic functional groups in Fourier transform infrared (FTIR) spectra proved the successful preparation of SPES, PES–SO2Cl, and a composite film. The results of the AC impedance test indicate that the composite film with a 3% mass fraction has the best proton conductivity of 0.215 S·cm–1, which is 6.2 times higher than that of the blended film without a chemical bond at 98% RH and 353 K. To our knowledge, there are rarely any reports on the preparation of a composite membrane by directly linking MOFs and the membrane matrix with chemical bonds. This work provides a good way to synthesize the highly conductive proton exchange film.

Chlorosulfonated Polyphenylene Ether Metal–Organic Framework Nanomaterial Composite Proton Exchange Membranes for Fuel Cells

“…In the interior of the IL-MOF, the imino and water molecules of the IL can also form hydrogen bonds to achieve proton conduction . In cross-linked membranes, because sulfonimide itself is acidic and can produce protons, abundant hydrogen bond network is formed between sulfonic acid group, amino group, and uncoordinated water molecule in MOF-SO 2 –PPO- X and IL-MOF-SO 2 –PPO-3. In the hydrogen bond network, proton jumps between H 3 O + and −SO 3 – through the formation of hydrogen bonds to achieve proton transfer (Figure ).…”

A highly selective and high-performance sulfonated poly(ether ether ketone)-based hybrid membrane enabled by complexed UiO-66-NH2 and sulfonated graphitic carbon nitride for vanadium flow batteries

“…† Among the various component ratios of UiO-66-NH 2 /s-g-C 3 N 4 , SPEEK/NF-1 : 1 shows a better tensile strength and modulus of 37.8 MPa and 1.72 GPa, respectively. This is mainly due to the acid-base interaction that offers an enhanced entanglement between SPEEK and nano-llers, and the nanosheet structure plays a supporting and anchoring role, 24 thus meeting the requirements of the VFB system. 23,29,36 To understand the interaction between NF and SPEEK, ATR-FTIR is used to analyze the structural changes.…”

“…[20][21][22][23] As a stabilized MOF derivative, the covalently bonded UiO-66-NH 2 onto the SPES backbone provides an excellent conductivity for the UiO-66-NH 2 -SPES composite as compared with the blended one. 24 Through polymerization of p-styrenesulfonate sodium into UiO-66-NH 2 , the prepared hybrid S-UiO nanollers signicantly enhance the proton conductivity and VO 2+ resistance of the SPEEK/S-UiO membranes contributed by their strong electrostatic interactions. 25 Aer the introduction of GO tethered UiO-66-NH 2 into the Naon matrix, the UiO-66-NH 2 @GO/Naon membrane shows excellent conductivity and long-term stability due to the structural advantages of GO@UiO-66-NH 2 .…”

Sensitive determination of 4,6-dinitro-o-cresol based on a glassy carbon electrode modified with Zr-UiO-66 metal–organic framework entrapped FMWCNTs

“…35,36 In these applications, it is used either in composite form 37 or in the form of covalent linkage. 38 Owing to the presence of the –NH 2 functional group, it is an excellent coupling matrix for FMWCNTs which can further be tailored for specific targeted applications.…”