Non-equilibrium Theoretical Framework and Universal Design Principles of Oscillation-Driven Catalysis

Abstract: At stationary environmental conditions, a catalyst's reaction rates may be restricted by thermodynamic laws, and certain performances can never be achieved (e.g., catalysts can not change the free energy difference between reactants and products). However, it has been reported that if environments change rapidly, catalysts can be driven away from stationary states and exhibit anomalous performance. We present a general geometric non-equilibrium theory to describe and explain anomalous catalytic behaviors in rapidly oscillating environments that exceed the steady-state restrictions. It leads to a universal design principle of novel catalysts with oscillation-pumped performances. Even though a catalyst at various environmental conditions cannot be described by a single free energy landscape, we propose a novel control-conjugate landscape to encode the reaction rates over a continuous range of control parameters $\lambda$, which is inspired by the exponential form of the Arrhenius law. The control-conjugate landscape significantly simplifies the design principle and makes it applicable to large-amplitude environmental oscillations. The design principle is demonstrated by two examples, (1) inverting a spontaneous reaction to synthesize high-free-energy molecules and (2) speeding up reactions without utilizing low activation barriers. In both examples, catalysts autonomously harness energy from non-equilibrium environments to enable such functionalities.