Guest-tuned proton conductivity of a porphyrinylphosphonate-based hydrogen-bonded organic framework

Abstract

A porous porphyrin-based hydrogen-bonded organic framework (HOF) was constructed, and its proton conductivity was improved through a two-step guest-tuned strategy. After regulation, the proton conductivity of the HOF reaches 1.59 × 10−1 S cm−1 at 80 °C and 99% RH.

A proton conductive hydrogen-bonded framework incorporating 18-crown-6-ether and dicarboxy-o-terphenyl moieties

“…To date, some HOFs are reported to show proton conductivity. [26][27][28][29][30][31][32] However, proton conductive HOFs based on crown ethers are hitherto unknown.…”

Hydrogen-bonded organic frameworks: design, applications, and prospects

“…It is worth noting that HOF materials have made breakthroughs in the application of proton conductivity. Wang et al reported the preparation and proton conductivity of a 3D porous porphyrin-based HOF material [(NiH 4 TPPP) (Me 2 NH 2 ) DMF) (H 2 O) 4 synthesized from nickel phosphate-based porphyrin (NiH 8 TPPP),denoted as UPC-H5 131. The proton conductivity of the crystal was different depending on the relative humidity and temperature.…”

Hybrid Nafion Membranes of Ionic Hydrogen-Bonded Organic Framework Materials for Proton Conduction and PEMFC Applications

“…In the past 2 decades, crystalline materials, such as metal–organic frameworks (MOFs), covalent organic frameworks (COFs), or hydrogen-bonded organic frameworks (HOFs), have attracted extensive attention because of their unlimited structural diversity and functional tunability. − Due to the ability to custom-design the ligands with carrier molecules, tailor pore environments, and understand proton-transport pathways at the molecular level, crystalline materials provide a new platform for proton-conducting materials. − However, most of these crystalline materials focus on the conduction of crystals, the research studies on PEMs and PEMFCs are rare. ,− Owing to the unique characteristics such as rich hydrogen-bonding network and solution machinability, crystalline HOFs render a promising platform for proton conductivity and PEM materials. − The ligands used to construct single-component HOFs such as −COOH and −NH 2 can use their own functional groups to form hydrogen bonds, − but these traditional HOFs connected by weak hydrogen bonds have poor stability and, in most cases, the structures collapse under medium and high temperature conditions. Different from single-component HOFs, ionic two-component HOFs (also known as charge-assisted hydrogen bond frameworks) showed good stability due to the various hydrogen bond types and electrostatic interactions.…”

“…Different from single-component HOFs, ionic two-component HOFs (also known as charge-assisted hydrogen bond frameworks) showed good stability due to the various hydrogen bond types and electrostatic interactions. Most of the two-component HOFs are based on guanidinium–sulfonate, amidinium–carboxylate, or ammonium–sulfonate. ,− In recent years, some HOFs have shown promising proton conductivity, ,, but there is no report about the application of HOF materials in PEMFCs so far.…”

“…Most of the two-component HOFs are based on guanidinium−sulfonate, amidinium−carboxylate, or ammonium− sulfonate. 40,45−47 In recent years, some HOFs have shown promising proton conductivity, 29,39,41 but there is no report about the application of HOF materials in PEMFCs so far.…”