Superblackbody Metasurface Activates CO2 Vibrational Mode for Enhanced Selectivity in CO2 Reduction.

Thermal activation of reactants is a key initial step in catalysis, which can occur either by temperature-driven activation of surface adsorbates or by radiation-driven excitation above the surface. Here, two configurations of five-bilayer Ni/SiO2 thermal metasurfaces are engineered to provide superblackbody near-field emission within the CO2 asymmetric stretching band of 4.3 μm wavelength, with broadband and narrowband absorption, respectively. Thermal dipole simulations show that the broadly absorbing cylindrical array drives edge-guided resonances with a near-uniform rim field, whereas the narrowly emitting cuboid array with higher absorptivity shows corner field localization due to higher field interior confinement. Both metasurfaces have high near-field intensities in excess of blackbody radiation by up to ×2. Experimentally, the wideband metasurface achieves a higher CO production rate and >50% higher CO/CH4 selectivity. In situ-diffused reflectance Fourier transform spectroscopy indicates reduced buildup of carbonate intermediates and adsorbed CO on the wideband metasurface relative to the narrowband metasurface, indicating faster CO desorption and suppressed methanation. Density functional theory simulations support the observation by showing that gas CO2 bond stretching can eliminate the kinetic energy barrier to CO2 chemisorption and promote CO2 dissociation toward CO formation. Minimizing CO adsorbate stretching suppresses hydrogenation pathways that proceed through formate intermediate and subsequent methanation. Overall, the engineering of the metasurface thermal dipole-induced field coupling with confinement or radiative channels, modulated by emission spatial distribution, can independently activate reactant molecules above the surface while favoring the surface for desorption of products. This shows a physically driven approach to catalysis by decoupling the surface activation and desorption counteractions.