Interfacial interactions between support and active species are crucial for the catalytic oxidation of chlorinated volatile organic compounds (CVOCs), yet whether stronger interactions always yield superior performance remains unresolved. Herein, a pure-phase Ce10W22O81 support with thermally stable oxygen vacancies (Ov) was synthesized. These Ov, originating from WO7 pentagonal bipyramid-induced lattice distortion, were governed in concentration by the pre-calcination temperature. After loading RuOx–ZrOx, the Ov-mediated interfacial interactions were examined in 1,2-dichloroethane (DCE) oxidation. The moderate interfacial interaction in the RuOx–ZrOx/Ce10W22O81-600 catalyst induced abundant Lewis (L) acid–base sites and an appropriate redox capacity, enabling a cascade pathway (DCE → vinyl chloride → acetaldehyde → acetate) that balanced dechlorination and deep oxidation, thereby delivering 90% conversion at 277 °C, 64 h stability, and complete suppression of polychlorinated by-products (PCBs). Conversely, the Ce10W22O81 supports pre-calcined at 700–800 °C contained more Ov, inducing a stronger interfacial interaction that generated excess interfacial Ov and highly active RuOx species. These excess Ov provided abundant adsorption sites for chlorine (Cl) species, causing metal–chlorine accumulation, while the highly active RuOx advanced the Deacon reaction and facilitated in-situ Cl2 activation at high temperatures, synergistically intensifying intermediate chlorination, competing with deep oxidation, producing PCBs, and ultimately lowering high-temperature mineralization efficiency. In contrast, toluene oxidation activity increased monotonically with enhanced interfacial interaction, highlighting the distinct behavior of Cl-containing systems. This work reveals that interfacial interaction strength does not linearly correlate with catalytic performance in Cl-containing systems, providing a basis for designing Cl-resistant catalysts that suppress PCBs formation during CVOCs oxidation.
The electrochemical conversion of CO2 to CO in membrane electrode assembly (MEA) electrolyzers using gas diffusion electrodes (GDEs) offers a sustainable and scalable pathway for carbon utilization. Here, we present a one-step atomic layer deposition (ALD) approach to prepare ZnO-based GDEs with tunable loadings and high selectivity toward CO. Increasing the number of ALD cycles raises the ZnO loading but progressively reduces the pore accessibility within the GDE. An optimal balance is achieved at 200 ALD cycles, delivering a peak CO faradaic efficiency (FECO) of 88% and a full-cell energy efficiency of 38% at −100 mA cm−2. Crucially, the scalability of ALD is demonstrated through stable long-term testing, achieving 85% FECO in a 5 cm2 MEA after 30 h, and 80% FECO in a 100 cm2 MEA after 24 h. These results establish ALD as an effective and versatile strategy for fabricating high-performance ZnO electrodes for CO2 electrolysis.
