Distinguishing between photothermal and non-thermal contributions is essential in plasmon catalysis. Use of a tailored optical temperature sensor based on fiber Bragg gratings enabled us to obtain an accurate temperature map of an illuminated plasmonic catalyst bed with high spatiotemporal resolution. Its importance for quantification of the photothermal and non-thermal contributions to plasmon catalysis is demonstrated using a Ru/Al₂O₃ catalyst. Upon illumination with LEDs, we measured temperature differences exceeding 50 °C in the top 0.5 mm of the catalyst bed. Furthermore, we discovered differences between the surface temperature and the temperature obtained via conventional thermocouple measurements underneath the catalyst bed exceeding 200 °C at 2.6 W cm⁻² light intensity. This demonstrates that accurate multi-point temperature measurements are a prerequisite for a correct interpretation of catalysis results of light-powered chemical reactions obtained with plasmonic catalysts.

Plasmonic CO₂ methanation using γ-Al₂O₃-supported Ru nanorods was carried out under continuous-flow conditions without conventional heating, using mildly concentrated sunlight as the sole and sustainable energy source (AM 1.5, irradiance 5.5–14.4 kW·m⁻² = 5.5–14.4 suns). Under 12.5 suns, a CO₂ conversion exceeding 97% was achieved with complete selectivity towards CH₄ and a stable production rate (261.9 mmol·g^{−1 Ru·h−1}) for at least 12 h. The CH₄ production rate showed an exponential increase with increasing light intensity, suggesting that the process was mainly promoted by photothermal heating. This was confirmed by the apparent activation energy of 64.3 kJ·mol⁻¹, which is very similar to the activation energy obtained for reference experiments in dark (67.3 kJ·mol⁻¹). The flow rate influence was studied under 14.4 suns, achieving a CH₄ production plateau of 264 µmol min⁻¹ (792 mmol·g^{−1 Ru·h−1}) with a constant catalyst bed temperature of approximately 204^◦C.