Enhanced catalytic activity under non-equilibrium conditions.

The development of non-equilibrium synthetic systems provides access to innovative materials with life-like properties. Non-equilibrium systems require a continuous input of energy to retain their functional state, which makes for a fundamental difference to systems that operate at thermodynamic equilibrium. Kinetic asymmetry in the energy consumption pathway is required to drive systems out of equilibrium. This understanding has permitted chemists to design dissipative synthetic molecular machines and high-energy materials. Here we show that kinetic asymmetry also emerges at the macroscopic level by demonstrating that local energy delivery in the form of light to a hydrogel containing gold nanoparticles installs a non-equilibrium steady state. The instalment and maintenance of the macroscopic non-equilibrium state is facilitated by the gel matrix in which motion is governed by diffusion rather than convection. The non-equilibrium state is characterized by a persistent gradient in the surface composition of the nanoparticles embedded in the gel, which affects the fluorescent and catalytic properties of the system. We show that the overall catalytic performance of the system is enhanced under these non-equilibrium conditions. In perspective it will be possible to develop out-of-equilibrium matrices in which functional properties emerge as a result of spatially controlled energy delivery and spatially controlled chemistries.