Construction of a CoNiHHTP MOF/PHI Z-Scheme Heterojunction for ppb Level NO2 Photoelectric Sensing with 405 nm Irradiation at RT

Ultrasensitive photoelectric detection of nitrogen dioxide (NO₂) with PHI under visible light irradiation at room temperature (RT) remains an ongoing challenge due to the low charge separation and scarce adsorption sites. In this work, a dimensionally matched ultrathin CoNiHHTP MOF/PHI Z-scheme heterojunction is successfully constructed by taking advantage of the π-π interactions existing between the CoNiHHTP MOF and PHI. The amount-optimized heterojunction possesses a record detection limit of 1 ppb (response = 15.6%) for NO₂ under 405 nm irradiation at RT, with reduced responsive (3.6 min) and recovery (2.7 min) times, good selectivity and reversibility, and long-time stability (150 days) compared with PHI, even superior to others reported at RT. Based on the time-resolved photoluminescence spectra, in situ X-ray photoelectron spectra, and diffuse reflectance infrared Fourier transform spectroscopy results, the resulting sensing performance is attributed to the favorable Z-scheme charge transfer and separation. Moreover, the Ni nodes favorably present in adjacent metal sites between the lamellae contribute to charge transfer and redistribution, whereas Co nodes could act as selective centers for promoted adsorption of NO₂. Interestingly, it is confirmed that the CoNiHHTP MOF/PHI heterojunction could effectively reduce the influence of O₂ in the gas-sensitive reaction due to their unique bimetallic (Co and Ni) nodes, which is also favorable for the improved sensing performances for NO₂. This work provides a feasible strategy to develop promising PHI-based optoelectronic gas sensors at RT.