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.

Sunlight-powered reduction of CO₂ to fuels and chemicals is a promising strategy to close the carbon loop and facilitate the energy transition. In this research, we demonstrate that Au nanoparticles supported on TiO₂ are an efficient plasmonic catalyst for the sunlight-powered reverse water-gas shift (rWGS) reaction. A maximum CO production rate of 429 mmol ⋅ g_Au⁻¹ ⋅ h⁻¹ with a selectivity of 98 % and an apparent quantum efficiency of 4.7 % were achieved using mildly concentrated sunlight (1.44 W ⋅ cm⁻² equals 14.4 sun). The CO production rate showed an exponential increase with increasing light intensity, suggesting that the process is mainly promoted by a photothermal effect. Thermal reference experiments with the same catalysts promoted CH₄ formation, dropping the CO selectivity to 70 %. Thus, mildly concentrated sunlight can efficiently and selectively enhance the promotion of the rWGS reaction without using external heating.