A First-Principles Study of Formaldehyde Adsorption on the Surface of ZnO [202¯1] High Index Polar Facet

High-sensitivity detection of formaldehyde is critically important for environmental protection and public health. Zinc oxide (ZnO) is a widely used core material for chemiresistive gas sensors; however, its conventional low-index facets suffer from a limited number of active sites, creating a bottleneck for further sensitivity enhancement. To overcome this limitation, this study pioneers the application of the highly reactive ZnO [202¯1] high-index polar surface for formaldehyde detection. By leveraging its unique stepped atomic configuration and unprecedented density of coordination-unsaturated active sites, we systematically investigate the formaldehyde adsorption behavior and the underlying sensing mechanism using first-principles calculations based on density functional theory (DFT). The pristine ZnO [202¯1] surface exhibits intrinsic metallic character. At a coverage of 1 monolayer (ML), the most stable G1 configuration achieves an adsorption energy of −1.54 eV per CH2O molecule. Within a 2 × 1 supercell, formaldehyde adopts both associative and dissociative adsorption modes. At a lower coverage, formaldehyde forms a stable bidentate structure through dual C–O and Zn–O bonding interactions. Electronic structure analysis reveals significant orbital hybridization and interfacial charge redistribution upon adsorption. Notably, associative adsorption opens a bandgap of 0.04 eV at the Fermi level, inducing a metal-to-semiconductor transition. In contrast, dissociative adsorption results in pronounced n-type doping, thereby elucidating the microscopic origin of the resistivity decrease observed in ZnO-based sensors. Overall, this work highlights the structural advantages of high-index facets and demonstrates for the first time the superior formaldehyde adsorption capability of the ZnO [202¯1] facet, providing robust theoretical guidance for the rational design of next-generation, high-performance gas-sensing materials.