CO₂ Conversion in Cu–Pd Based DisorderedNetwork Metamaterials with Ultrasmall Mode Volumes

Plasmons can drive chemical reactions by directly exciting intramolecular transitions. However, strong coupling of plasmons to single molecules remains a challenge as ultrasmall mode volumes are required. In the presented work, we propose Cu–Pd plasmonic network metamaterials as scalable platforms for plasmon-assisted catalysis. Due to the absence of translational symmetry, these networks provide a unique plasmonic environment featuring a large local density of optical states and an unparalleled density of hotspots that effectively localizes light in mode volumes <i>V</i> < 8 × 10^–24 m³. Catalytic performance tests during CO₂ conversion reveal production rates of up to 4.3 × 10² mmol g^–1 h^–1 and altered reaction selectivity under light illumination. Importantly, we show that the selectivity of the catalytic process can be tuned by modifying the network’s chemical composition, offering a versatile approach to optimize reaction pathways.