Symmetry-Differentiated Oxygen-Vacancy Motifs Regulate Au–CeO x Interfaces for Selective Photocatalytic Ethane Production from CO 2

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Abstract
Steering CO2 photoreduction toward C2 hydrocarbons remains challenging because of the sluggish multielectron/proton-transfer kinetics and the high energetic demand for C-C coupling. Herein, we report a flame-spray-pyrolysis strategy to construct Au-CeOx nanostructures featuring coexisting symmetric oxygen vacancies (Ce-Ov-Ce) and symmetry-broken oxygen vacancy (Au-Ov-Ce) motifs at the Au-CeOx interface. The symmetric Ce-Ov-Ce sites provide favorable adsorption environments for CO2 activation, whereas the symmetry-broken Au-Ov-Ce sites induce interfacial electron redistribution and promote electron enrichment. The cooperative interaction between these two vacancy configurations shifts the reaction route from *CO desorption toward deep hydrogenation and *CH3-mediated C-C coupling. As a result, the optimized Au-CeOx-SAOv catalyst achieves a C2H6 production rate of 2581 μmol gAu-1 h-1 with a selectivity of 88.14% and an electron utilization rate of 41.22 mmol gAu-1 h-1 in photocatalytic CO2 reduction with H2O. Mechanistic studies suggest that the symmetry-broken Au-Ov-Ce sites stabilize hydrogenated C1 intermediates and lower the energetic requirement for coupling two *CH3 species. This work establishes symmetry-differentiated oxygen-vacancy engineering as an effective strategy for directing multielectron CO2 photoreduction toward C2 hydrocarbons.
Funding Information
  • Shanghai Municipal Youth Science and Technology Star Project (25010701100)
  • Science and Technology Major Project of Inner Mongolia Autonomous Region of China (2019ZD023)
  • Science and Technology Major Project of Inner Mongolia Autonomous Region of China (2021ZD0028)
  • Science and Technology Commission of Shanghai Municipality (2018SHZDZX03)
  • Science and Technology Commission of Shanghai Municipality (20DZ2250400)
  • Science and Technology Commission of Shanghai Municipality (22230780200)
  • Science and Technology Commission of Shanghai Municipality (25520750100)
  • National Key Research and Development Program of China (2023YFB3507100)
  • National Natural Science Foundation of China (22408229)
  • National Natural Science Foundation of China (22461142136)
  • National Natural Science Foundation of China (22572051)
  • National Natural Science Foundation of China (5257330)
  • China Northern Rare Earth (Group) ?unveiled the list of commanding? project (BFXT-2023-D-0043)

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