Fundamental Design of Non-noble Intermetallic Compound Surface Chemistry in Thermal Driven and Microwave Driven Reactions

This dissertation focuses on the rational design and mechanistic understanding of intermetallic compounds (IMCs) and their application in selective hydrogenation and non-equilibrium, microwave-driven methane pyrolysis for CO2-free hydrogen production. The first part of this work establishes IMCs as a tunable platform for controlling surface chemistry and hydrogenation kinetics through electronic modulation. By systematically studying both late and early transition-metal IMCs, the effects of d–p state hybridization and surface redox properties are identified as key factors governing hydrogenation kinetics. The second part explores a novel approach to methane pyrolysis driven by microwave energy. This study demonstrates that non-equilibrium “hot phonons” generated under microwave irradiation can directly activate methane, enabling hydrogen production without CO2 emissions while simultaneously forming valuable carbon nanostructures. Experimental and theoretical analyses reveal that phonon–electron coupling facilitates bond cleavage and energy localization beyond conventional thermal limits. Together, these studies provide a unified understanding of how tailored electronic structures and non-equilibrium energy carriers can be harnessed to design efficient and sustainable catalytic systems. The insights gained offer guiding principles for developing next-generation catalysts that integrate structural precision with alternative energy inputs for selective and carbon-neutral chemical transformations.