Superprotonic Conductivity in a Metalloporphyrin-Based SMOF (Supramolecular Metal-Organic Framework)

Nanomaterials (Basel). 2024 Feb 21;14(5):398. doi: 10.3390/nano14050398.

Abstract

Metal-organic frameworks and supramolecular metal-organic frameworks (SMOFs) exhibit great potential for a broad range of applications taking advantage of the high surface area and pore sizes and tunable chemistry. In particular, metalloporphyrin-based MOFs and SMOFs are becoming of great importance in many fields due to the bioessential functions of these macrocycles that are being mimicked. On the other hand, during the last years, proton-conducting materials have aroused much interest, and those presenting high conductivity values are potential candidates to play a key role in some solid-state electrochemical devices such as batteries and fuel cells. In this way, using metalloporphyrins as building units we have obtained a new crystalline material with formula [H(bipy)]2[(MnTPPS)(H2O)2]·2bipy·14H2O, where bipy is 4,4'-bipyidine and TPPS4- is the meso-tetra(4-sulfonatephenyl) porphyrin. The crystal structure shows a zig-zag water chain along the [100] direction located between the sulfonate groups of the porphyrin. Taking into account those structural features, the compound was tested for proton conduction by complex electrochemical impedance spectroscopy (EIS). The as-obtained conductivity is 1 × 10-2 S·cm-1 at 40 °C and 98% relative humidity, which is a remarkably high value.

Keywords: SMOF; metalloporphyrins; proton conductivity; solid-state electrochemical devices.

Grants and funding

This research was funded by MINISTERIO DE CIENCIA, INNOVACIÓN Y UNIVERSIDADES MCIN/AEI/10.13039/501100011033, grant number PID2019-107468RB-C21, GOBIERNO VASCO/EUSKO JAURLARITZA, grant number IT1546-22 and THE EUROPEAN COMMISSION RESEARCH and INNOVATION H2020-MSCA-RISE-2017, grant number 778412 INDESMOF project and grant number PID2021-122940OB-C31 EVOLMOF project.