Zhu, Y.F.Yuwono, J.A.Wilson, M.Xie, B.Kumar, P.Amal, R.Scott, J.Lovell, E.C.2025-10-142025-10-142025Applied Catalysis B: Environmental, 2025; 379:125736-1-125736-110926-33731873-3883https://hdl.handle.net/2440/147782Current C₂₊ hydrocarbon production from fossil fuel feedstocks will in-time be replaced by alternate synthesis methods involving cleaner energy strategies. One approach is to incorporate direct sunlight during catalytic C₂₊ synthesis via the modified Fisher Tropsch synthesis (CO₂-FTS) reaction. Light-driven studies targeting C₂₊ products from CO₂ under high-pressure conditions are scarce. Herein, we demonstrate that direct visible light illumination can selectively boost hydrocarbon synthesis by a K-promoted Fe catalyst during the high pressure (23 bar), thermal catalytic CO₂-FTS reaction. Visible light illumination imparts carrier-induced benefits to amplify CO activation and hydrocarbon synthesis. Visible light illumination modifies the surface charge of Fe. This promotes CO adsorption and C-O bond lengthening over the K-Fe catalysts, and dissociation to *C. The lightenhanced *C production boosted Fe carbide formation which facilitates FTS. Concurrently, *C hydrogenation leads to hydrocarbon synthesis. The findings offer new insight into the cascading impact of light within dynamic catalytic systems arising from the interdependence between catalyst activation and performance.en© 2025 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).Light-assisted thermal catalysis; CO2 Fischer Tropsch synthesis; Catalyst activation; Solar fuel synthesisJournal article10.1016/j.apcatb.2025.125736746608Yuwono, J.A. [0000-0002-0915-0756]