To strategically address these challenges, a comprehensively integrated catalyst and reaction engineering approach has been developed in this dissertation, which systematically combines i) innovative catalyst design strategies, ii) dynamic reactor operations, and iii) advanced in situ/operando characterization methodologies. We first optimized the protective TiOx overlayer on Ni/TiO2 catalysts, which protected Ni from sintering and enriched the oxygen species by slightly reducing exposed active Ni sites, finally balancing DRM conversion and stability.

We optimized the ZrO2-supported NiZn alloy catalysts by varying the Ni/Zn ratio, NiZn loading, and reduction temperature. The optimized NiZn catalysts with NiZn intermetallic outperformed the Ni-rich NiZn alloy regarding their stability and coke resistance. A reversible phase transformation between the NiZn intermetallic and Ni3ZnC0.7 under DRM conditions mitigated the coke deposition.

Thirdly, we designed La2O3 supported multi-metallic catalysts consisting of equal molar Fe, Co, Ni, Cu and Mo. The synergistic effects of the multi-metals balanced the elemental steps of carbon formation and removal, leading to a coke-free DRM reaction. Besides, transient-periodic reaction conditions combined with a series of in situ/operando methodologies (X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and reflectance infrared Fourier transform spectroscopy (DRIFTS)) by modulating inputs (temperature and concentration/partial pressure) of the reactor dynamically in step changes, pulses, or periodically to check the response of the catalyst were applied, which significantly contributed to the structure, intermediates and reaction model discovery.