Surface properties are critical in catalytic reactions, with increasing evidence that structural and mechanical factors, alongside electronic properties, play significant roles. Despite progress in catalyst design based on adsorption energy, these approaches often fail in practical applications because adsorption energy alone does not fully capture catalytic efficiency. The reaction barrier, a key factor in both thermodynamic and kinetic aspects, has often been overlooked. In this study, we introduce surface stress work $W_{\mathrm{SS}}$ as a quantitative descriptor for mechanical effects in surface reactions, which simultaneously influences both adsorption energy and reaction barriers. Using first-principles calculations on representative transition metals, we show that $W_{\mathrm{SS}}$ directly affects hydrogen adsorption energy and reaction barriers. Furthermore, we demonstrate that $W_{\mathrm{SS}}$ can be modulated via methods such as alloying, optimizing both adsorption energies and reaction barriers. $\mathrm{Pd}$-$\mathrm{Ni}$ alloys show the most significant improvements. These findings establish a quantitative concept for surface stress work in catalyst design, which applies not only to hydrogen-related reactions but also to oxygen-involving surface processes.

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• Chemical kinetics, dynamics & catalysis
• Chemical reactions
• Electrochemistry
• Interface & surface thermodynamics
• Stress
• Energy applications
• Surfaces
• First-principles calculations