An atomistic control of chemical bonds formation and cleavage holds the key to making molecular transformations more energy efficient and product selective. However, inherent scaling relations among binding strengths of adsorbates on various catalytic materials often give rise to volcano-shaped relationships between the catalytic activity and the affinity of critical intermediates to the surface. The optimal catalysts should bind the reactants 'just right', i.e., neither too strong nor too weak, which is the Sabatier's principle. It is extremely useful for searching promising catalysts, but also imposes serious constraints on design flexibility. Therefore, how to circumvent scaling constraints is crucial for advancing catalytic science. It has been shown that hot electrons can selectively activate the chemical bonds that are not responsive to phonon excitation, thus providing a rational approach beyond scaling limitation. Another emerging yet effective way to break the scaling constraint is single atom catalysis. Strong interactions of supported single atoms with supports dramatically affect the electronic structure of active sites, which reroutes mechanistic pathways of surface reactions. In my PhD research, we use CO oxidation reaction on metal-based active sites as a benchmark system to tailor mechanistic pathways through those two strategies 1) ultra-fast laser induced nonadiabatic surface chemistry and 2) oxide-supported single metal catalysis, with the aim to go beyond the Sabatier activity volcano in metal catalysis. / Doctor of Philosophy / Catalysis is the process of increasing the chemical reaction rate by lowering down the activation barrier. There are three different types of catalysis including enzyme, homogeneous, and heterogeneous catalysis. Heterogeneous catalytic reactions involve a sequence of elementary steps, e.g., adsorption of reactants onto the solid surface, transformation of adsorbed species, and desorption of the products. However, the existing scaling relations among binding energies of reaction intermediates on various catalytic materials lead to volcano-shaped relationships, which show the reaction activity versus the binding energy of critical intermediates. The optimal catalysts should bind the reaction intermediates neither too strong nor too weak. This is the Sabatier's principle, which provides useful guidance for searching promising catalysts. But it also imposes the constraint on the attainable catalytic performance. How to break the constraint to further improve the catalytic activity is an emerging problem. The recent studies have shown that the hot surface electrons on the metal surfaces induced by the ultra-fast laser can selectively activate the chemical bonds, thus providing a rational approach beyond scaling constraints. Another way to break the scaling constraint is single atom catalysis. The metal oxides are frequently used as the support to stabilize the single metal atoms. The strong interaction between the single metal atoms and the support affects the electronic structure of the catalysts. Thereby catalytic reactions on the single metal atoms catalyst are very different from that on metal surfaces. In my PhD research, we use CO oxidation reaction as a benchmark system, to tailor reaction pathways through those two strategies on 1) Ru(0001) under ultra-fast laser pulse and 2) Ir single metal atoms supported on spinel oxides, to go beyond Sabatier activity volcano in metal catalysis.