Proton conductivity as a function of the metal center in porphyrinylphosphonate-based MOFs

The rational design of metal-organic frameworks (MOFs) is highly important for the development of new proton conductors. Porphyrinylphosphonate-based MOFs, providing the directed tuning of physical and chemical properties of materials through the modification of a macrocycle, are potentially high-co...

Full description

Saved in:
Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2021-05, Vol.5 (19), p.6549-656
Main Authors: Enakieva, Yulia Yu, Zhigileva, Ekaterina A, Fitch, Andrew N, Chernyshev, Vladimir V, Stenina, Irina A, Yaroslavtsev, Andrey B, Sinelshchikova, Anna A, Kovalenko, Konstantin A, Gorbunova, Yulia G, Tsivadze, Aslan Yu
Format: Article
Language:English
Subjects:
Carrier density
Chemical properties
Conduction
Conductors
Crystal structure
Crystallography
Dehydration
Material properties
Metal-organic frameworks
Nickel
Palladium
Porphyrins
Protons
Relative humidity
Synchrotrons
Thermal stability
Water chemistry
Zinc
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The rational design of metal-organic frameworks (MOFs) is highly important for the development of new proton conductors. Porphyrinylphosphonate-based MOFs, providing the directed tuning of physical and chemical properties of materials through the modification of a macrocycle, are potentially high-conducting systems. In this work the synthesis and characterization of novel anionic Zn-containing MOF based on palladium( ii ) meso -tetrakis(3-(phosphonatophenyl))porphyrinate, IPCE-2Pd , are reported. Moreover, the proton-conductive properties and structures of two anionic Zn-containing MOFs based on previously described nickel( ii ) and novel palladium( ii ) porphyrinylphosphonates, IPCE-2M (M = Ni( ii ) or Pd( ii )), are compared in details. The high proton conductivity of 1.0 × 10 −2 S cm −1 at 75 °C and 95% relative humidity (RH) is revealed for IPCE-2Ni , while IPCE-2Pd exhibits higher hydrolytic and thermal stability of the material (up to 420 °C) simultaneously maintaining a comparable value of conductivity (8.11 × 10 −3 S cm −1 at 95 °C and 95% RH). The nature of the porphyrin metal center is responsible for the features of crystal structure of materials, obtained under identical reaction conditions. The structures of IPCE-2Pd and its dehydrated derivative IPCE-2Pd-HT are determined from the synchrotron powder diffraction data. The presence of phosphonic groups in compared materials IPCE-2M affords a high concentration of proton carriers that together with the sorption of water molecules leads to a high proton conductivity. New porphyrinylphosphonate MOFs possessing high proton conductivity (up to 10 −2 S cm −1 ) together with superior chemical and thermal stability are described.
ISSN:1477-9226
1477-9234
DOI:10.1039/d1dt00612f