Gas Adsorption-Driven Electronic Modulation in WO3@Cu3(HHTP)2 Heterostructure: Mechanistic Origin of Selective Drift
Mohammad Jamir Ahemad1, Eunyoung Lee1,2, Chanyoung Kim1,3
1Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), Wanju, Jeollabuk-do, Republic of Korea.
Abstract:
Formaldehyde is a ubiquitous indoor air pollutant whose carcinogenicity, high toxicity, and volatility pose severe health risks even at trace concentrations. Nevertheless, realizing ultra-low detection limits with high selectivity under ambient-temperature conditions using a single chemiresistive semiconductor remains an enduring challenge. A heterointerface-engineered WO3@Cu3(HHTP)2 nanocomposite is developed, integrating the high surface reactivity of WO3 with the intrinsic conductivity and ordered π-conjugated framework of the 2D conductive metal-organic framework (cMOF) Cu3(HHTP)2. Synergistic interfacial orbital hybridization between W 5d (WO3) and O 2p π-orbitals (cMOF) induces pronounced electronic structure modulation, promoting enhanced charge transport and gas-solid interfacial reaction kinetics. DFT calculations reveal that HCHO preferentially adsorbs at phenolic O sites in the cMOF and O-vacancy sites on WO3, inducing localized charge redistribution and suppressing mid-gap defect states. This adsorption-driven Fermi level shift correlates directly with the experimentally observed resistance drop under HCHO exposure. The WO3@Cu3(HHTP)2 sensor exhibits an ultralow detection limit (∼48 ppb), rapid response/recovery, minimal baseline drift, and exceptional selectivity under mixed gas environments at room temperature. These findings establish a clear mechanistic link between interfacial electronic structure tuning and enhanced sensing performance, offering a generalizable strategy for designing next-generation VOC sensors via surface modification of metal oxides with cMOFs.
