Oxygen Vacancy-rich Porous Co₃O₄ Nanosheets toward Boosted NO Reduction by CO and CO Oxidation: Insights into the Structure–Activity Relationship and Performance Enhancement Mechanism

Oxygen vacancy-rich porous Co₃O₄ nanosheets (OV-Co₃O₄) with diverse surface oxygen vacancy contents were synthesized via facile surface reduction and applied to NO reduction by CO and CO oxidation. The structure-activity relationship between surface oxygen vacancies and catalytic performance was systematically investigated. By combining Raman, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and O₂-temperature programmed desorption, it was found that the efficient surface reduction leads to the presence of more surface oxygen vacancies and thus distinctly enhance the surface oxygen amount and mobility of OV-Co₃O₄. The electron transfer towards Co sites was promoted by surface oxygen vacancies with higher content. Compared with the pristine porous Co₃O₄ nanosheets, the presence of more surface oxygen vacancies is beneficial for the catalytic performance enhancement for NO reduction by CO and CO oxidation. The OV-Co₃O₄ obtained in 0.05 mol L⁻¹ NaBH₄ solution (Co₃O₄-0.05) exhibited the best catalytic activity, achieving 100% NO conversion at 175 °C in NO reduction by CO and 100% CO conversion at 100 °C in CO oxidation, respectively. Co₃O₄-0.05 exhibited outstanding catalytic stability and resistance to high gas hour space velocity in both reactions. Combining in situ DRIFTS results, the enhanced performance of OV-Co₃O₄ for NO reduction by CO should be attributed to the promoted formation and transformation of dinitrosyl species and -NCO species at lower and higher temperatures. The enhanced performance of OV-Co₃O₄ for CO oxidation is due to the promotion of oxygen activation ability, surface oxygen mobility, as well as the enhanced CO₂ desorption ability. The results indicate that the direct regulation of surface oxygen vacancies could be an efficient way to evidently enhance the catalytic performance for NO reduction by CO and CO oxidation.