The regulation of electron transfer is crucial for enhancing the catalytic efficiency of catalysts. Currently, CO selective reduction of NO_x (CO-SCR) catalysts with surface synergistic oxygen vacancies (SSOVs) or alloyed components exhibit superior performance but face challenges of reduced activity and stability in oxygen-rich environments. Here, we demonstrate a strategy that combines PtCo alloys (0.01% Pt; 0.04% Co) with SSOVs in cerium zirconium oxide solid solution to interactively modulate the electronic structure, resulting in a significant enhancement of both the activity and stability of the catalyst under oxygen-rich conditions. This catalyst achieved over 85% NO conversion at 300 °C and 5% O₂, while maintaining approximately 100% N₂ selectivity during 20 h-stability testing, surpassing the performance of the monometallic catalysts. This enhancement arises from the synergistic electronic effects of alloying and SSOVs, which generate negatively charged Pt that facilitates NO adsorption and dissociation, while concurrently producing electron-deficient SSOVs that weaken O₂ chemisorption and promote the formation of moderate reactive oxygen species. Moreover, the preferential adsorption of CO on Co sites alleviates competitive adsorption.

The gas-phase dehydrogenation of 1,6-hexanediol (1,6-HDO) to ε-caprolactone (ε-CL) over the high-performance Cu-based catalysts is highly desirable, but with grand challenges, because the Cu nanoparticles (NPs) are easy to be sintered with the low Hüttig temperature (< 150 °C vs. > 250 °C of reaction temperature). Herein, we report a highly efficient silica-encapsulated nano-Cu catalyst (Cu@SiO₂/SiO₂) prepared via a complexation–impregnation method for the dehydrogenation of 1,6-HDO, exhibiting a 1,6-HDO conversion of 95.3% and ε-CL selectivity of 80.0% at 270 °C. The catalyst also has the outstanding thermal stability (without sintering up to 270 °C for 100 h on stream), which can be attributed to the effective encapsulation of the SiO₂ shell. In addition, the reaction network of 1,6-HDO dehydrogenation is proved. Finally, the pyridine-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in-situ X-ray photoelectron spectroscopy (XPS) reveal that the Cu⁰ species favor the conversion of 1,6-HDO to ε-CL. The synergistic effect of Cu⁺ and Cu⁰ benefits the conversion of ε-CL to 2-methylcyclopentanone (2-MCPN). This study is beneficial for designing the high-performance Cu-based catalysts for 1,6-HDO to ε-CL, understanding the reaction network of 1,6-HDO dehydrogenation over the Cu-based catalysts, and offering a strong foundation for the large-scale production of ε-CL.