Structure-Function Relationship of Highly Reactive CuOx Clusters on Co₃O₄ for Selective Formaldehyde Sensing at Low Temperatures

Abstract

Designing reactive surface clusters at the nanoscale on metal-oxide supports enables selective molecular interactions in low-temperature catalysis and chemical sensing. Yet, finding effective material combinations and identifying the reactive site remains challenging and an obstacle for rational catalyst/sensor design. Here, the low-temperature oxidation of formaldehyde with CuOₓ clusters on Co₃O₄ nanoparticles is demonstrated yielding an excellent sensor for this critical air pollutant. When fabricated by flame-aerosol technology, such CuOₓ clusters are finely dispersed, while some Cu ions are incorporated into the Co₃O₄ lattice enhancing thermal stability. Importantly, infrared spectroscopy of adsorbed CO, near edge X-ray absorption fine structure spectroscopy and temperature-programmed reduction in H₂ identified Cu⁺ and Cu²⁺ species in these clusters as active sites. Remarkably, the Cu⁺ surface concentration correlated with the apparent activation energy of formaldehyde oxidation (Spearman's coefficient rho = 0.89) and sensor response (0.96), rendering it a performance descriptor. At optimal composition, such sensors detected even the lowest formaldehyde levels of 3 parts-per-billion (ppb) at 75 degrees C, superior to state-of-the-art sensors. Also, selectivity to other aldehydes, ketones, alcohols, and inorganic compounds, robustness to humidity and stable performance over 4 weeks are achieved, rendering such sensors promising as gas detectors in health monitoring, air and food quality control.