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Given the spread of natural gas engines in low-term toward decarbonization and the growing interest in gaseous mixtures as well as the use of hydrogen in Heavy-Duty (HD) engines, appropriate strategies are needed to maximize thermal efficiency and achieve near-zero emissions from these propulsor systems. In this context, some phenomena related to real-world driving operations, such as engine cut-off or misfire, can lead to inadequate control of the Air-to-Fuel ratio, key factor for Three-Way Catalyst (TWC) efficiency. Goal of the present research activity is to investigate the performance of a bio-methane-fueled HD engine and its Aftertreatment System (ATS), consisting of a Three-Way Catalyst, at different Air-to-Fuel ratio. An experimental test bench characterization, in different operating conditions of the engine workplan, was carried out to evaluate the catalyst reactivity to a defined pattern of the Air-to-Fuel ratio.