Integrated Full‐Spectrum Solar Energy Catalysis for Zero‐Emission Ethylene Production from Bioethanol

Abstract Ethylene, a hydrocarbon (C 2 H 4 ), is one of the widely used products in the chemical industry. A traditional dehydration method of ethanol to ethylene relies strongly on high‐temperature and high‐pressure process with significant energy consumption. In this regard, producing ethylene from bioethanol through dehydration is a promising and sustainable approach, but, this process under mild conditions results in low yields and poor selectivity. Herein, an integrated solar energy catalytic system driven by only sun energy under ambient conditions is established for the first time for bioethanol dehydration using oxygen‐vacancy‐abundant (O v ) WO 3 coupled with a thin layer of carbon coating (C L ) (WO 3− x @C). A record‐high ethylene selectivity of 98.1% is achieved driven by full solar spectrum without any external power, featuring zero pollution emission nature. In this process, O v acts as a solid acid center, which is the key to initiate the dehydration of ethanol to ethylene via a solar thermal process, while the C L promotes solar thermal synergy, ensuring the high reaction temperature and hot carriers transmission simultaneously. In‐situ infrared spectroscopy and thermodynamic calculations demonstrate a novel proton hydrogen‐mediated catalytic process over WO 3− x @C. This work provides a new opportunity of using full‐spectrum solar energy for catalytic generation of value‐added chemicals.