摘要： With the development of green chemistry, metal-free nano-catalysts have gradually substituted metal-based materials, causing widespread concern among researchers in many fields, especially in cataluminescence sensing, because of their long-term stability, environmental friendliness as well as low costs. Besides the catalysts, the innovations of assistant technologies for cataluminescence are needed to enhance the oxidation reactivity of the gas molecules or catalytic efficiency of sensing materials. Although, there are some groups enhancing the cataluminescence reaction via various assistant technologies, the development of assistant technologies in cataluminescence sensors are still in their infancy, the design, effect mechanism and application are still stimulating challenges. Herein, with photodynamic assistant, fluorinated nanoscale hexagonal boron nitride is first employed as a metal-free catalyst to establish a novel cataluminescence method for detecting CO gases, and the cataluminescence reaction mechanism of CO is also investigated in details. Under the best conditions, the detection limit (3σ) of the CO concentration is 0.005 μg mL-1, which has been largely improved in cataluminescence methods. The realization of detection of CO from theory to practice thorough the method of cataluminescence is beneficial of the practical application of metal-free catalysts to detect CO rather than stay at the possibility to detect CO by the means of theoretical calculation only.