Subsurface Single-atom Catalyst Enabled by Mechanochemical Synthesis for Oxidation Chemistry.

Single-atom catalysts have garnered significant attention due to their exceptional atom utilization and unique properties. However, the practical application of these catalysts is often impeded by challenges such as sintering-induced instability and poisoning of isolated atoms due to strong gas adsorption. In this study, we employed the mechanochemical method to insert single Cu atoms into the subsurface of Fe2O3 support. By manipulating the location of single atoms at the surface or subsurface, catalysts with distinct adsorption properties and reaction mechanisms can be achieved. It was observed that the subsurface Cu single atoms in Fe2O3 remained isolated under both oxidation and reduction environments, whereas surface Cu single atoms on Fe2O3 experienced sintering under reduction conditions. The unique properties of these subsurface single-atom catalysts call for innovations and new understandings in catalyst design.

Structure-Function Relationship of Highly Reactive CuOx Clusters on Co3 O4 for Selective Formaldehyde Sensing at Low Temperatures.

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 Co3 O4 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 Co3 O4 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 ρ = 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°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.

Cascade NH3 Oxidation and N2O Decomposition via Bifunctional Co and Cu Catalysts.

The selective catalytic oxidation of NH3 (NH3-SCO) to N2 is an important reaction for the treatment of diesel engine exhaust. Co3O4 has the highest activity among non-noble metals but suffers from N2O release. Such N2O emissions have recently been regulated due to having a 300× higher greenhouse gas effect than CO2. Here, we design CuO-supported Co3O4 as a cascade catalyst for the selective oxidation of NH3 to N2. The NH3-SCO reaction on CuO-Co3O4 follows a de-N2O pathway. Co3O4 activates gaseous oxygen to form N2O. The high redox property of the CuO-Co3O4 interface promotes the breaking of the N-O bond in N2O to form N2. The addition of CuO-Co3O4 to the Pt-Al2O3 catalyst reduces the full NH3 conversion temperature by 50 K and improves the N2 selectivity by 20%. These findings provide a promising strategy for reducing N2O emissions and will contribute to the rational design and development of non-noble metal catalysts.

A novel inhibition mechanism of aniline on nitrification: Aniline degradation competes dissolved oxygen with nitrification.

Aniline is a toxic aromatic amine and an inhibitor of nitrification. This study explored the inhibition effect and underlying mechanism. After sludge acclimation, 540 mg/L aniline was removed in 24 h and almost all ammonia released from aniline was oxidized to nitrate. However, nitrification never started until no aniline left. The cellular adenosine triphosphate (cATP) concentration of acclimated sludge reduced only by 2% after aniline exposure. Neither transmembrane transport of ammonia nor ammonia monooxygenase (AMO) activity was affected by aniline. Growing initial aniline concentration did not deteriorate the specific nitrification rate (NR). These all revealed that the toxicity of aniline only play a minor role in inhibition. Competition for dissolved oxygen (DO) was proposed to be another possible inhibition mechanism. The oxygen affinity constant (Ks) of aniline degraders and ammonia-oxidizing bacteria (AOB) was calculated to be 0.894 mg/L and 1.274 mg/L respectively, suggesting the former possessed much stronger oxygen affinity (P < 0.01). With aniline and ammonium as initial substrates, increasing aeration intensity advanced nitrification and increased the NR. Max NR of 0.63 mgN/(gMLSS·h) was achieved at the highest aeration intensity of 1000 mL/min. This study brings one step closer to better removal of aniline and derived nitrogen pollutants.