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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.

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Fig. 1: Spatially controlled signal generation in a hydrogel.
Fig. 2: Simulations of light-induced diffusion in the hydrogel.
Fig. 3: Experimental and simulated catalytic activity on local irradiation.
Fig. 4: Enhanced catalysis under non-equilibrium conditions.

Data availability

The data that support the findings of this study are available from the corresponding author on reasonable request.


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The research was financially supported by the China Science Council (R.C.) and the Italian Ministry of Education and Research (L.J.P., grant no. 2017E44A9P). T. Carofiglio is acknowledged for preparation of the masks. J. Czescik is acknowledged for providing the substrate HPNPP. M. Troiani is acknowledged for contributing to the synthesis of compound A.

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Authors and Affiliations



R.C. and L.J.P. designed the experiments. R.C. carried out all experiments. S.N. performed preliminary experiments. L.J.P. wrote the kinetic models and performed the simulations. R.C. and L.J.P. wrote the manuscript.

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Correspondence to Leonard J. Prins.

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Supplementary Information

Supplementary Methods, Figs. 1–37, Tables 1–17, Scheme 1 and refs. 1–2.

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Chen, R., Neri, S. & Prins, L.J. Enhanced catalytic activity under non-equilibrium conditions. Nat. Nanotechnol. 15, 868–874 (2020).

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