Two‐Dimensional Conjugated Metal‐Organic Frameworks with Large Pore Apertures and High Surface Areas for NO2 Selective Chemiresistive Sensing

Abstract The emergence of two‐dimensional conjugated metal–organic frameworks (2D c ‐MOFs) with pronounced electrical properties (e.g., high conductivity) has provided a novel platform for efficient energy storage, sensing, and electrocatalysis. Nevertheless, the limited availability of suitable ligands restricts the number of available types of 2D c ‐MOFs, especially those with large pore apertures and high surface areas are rare. Herein, we develop two new 2D c ‐MOFs (HIOTP‐ M , M =Ni, Cu) employing a large p‐π conjugated ligand of hexaamino‐triphenyleno[2,3‐b:6,7‐b′:10,11‐b′′]tris[1,4]benzodioxin (HAOTP). Among the reported 2D c ‐MOFs, HIOTP‐Ni exhibits the largest pore size of 3.3 nm and one of the highest surface areas (up to 1300 m 2 g −1 ). As an exemplary application, HIOTP‐Ni has been used as a chemiresistive sensing material and displays high selective response (405 %) and a rapid response (1.69 min) towards 10 ppm NO 2 gas. This work demonstrates significant correlation linking the pore aperture of 2D c ‐MOFs to their sensing performance.