4.7 Article

Enhanced Methane Combustion Performance over Zinc-Aided Co3O4 by Engineering the Reactivity of Active Oxygen Species

Journal

ENERGY & FUELS
Volume 36, Issue 21, Pages 13168-13178

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.energyfuels.2c02719

Keywords

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Funding

  1. National Natural Science Foundation of China
  2. Natural Science Foundation of Fujian Province
  3. Research Foundation of the Academy of Carbon Neutrality Project of Fujian Normal University
  4. [21872027]
  5. [22272023]
  6. [2020J01148]
  7. [TZH2022-07]

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The insertion of zinc into the Co3O4 matrix and the formation of Co-Zn-O solid solution enhanced the electron richness and oxygen vacancy density of the catalyst, improving its ability to adsorb and activate aerial O2. This resulted in better oxygen transfer and more effective methane combustion.
Engineering the lattice oxygen reactivity and activation of gaseous O2 is vital for boosting methane combustion over Co3O4. Herein, zinc was inserted into the Co3O4 matrix, driven by its slightly larger cationic radius and lower electro-negativity than those of cobalt. The suitable doping of zinc offered the optimum occupation of Zn2+ at the tetrahedral sites, granting more active Co3+ sites. The formation of Co-Zn-O solid solution delivered the lattice disorder and endowed cobalt with richer electrons, which increased the oxygen vacancy density, oxygen storage capacity, migration property of surface lattice oxygen, and reducibility of catalysts, and tuned the surface acid-base properties. Also, the ability to adsorb and activate aerial O2 of catalysts was enhanced, which could realize more effective spillover of O2 to regenerate lattice oxygen. These entire properties allowed the redox cycles to proceed more smoothly on the Co3+-O pair sites for Zn0.6Co2.4O4 compared to its analogues. Consequently, Zn0.6Co2.4O4 manifested more effective methane combustion with its T90 at 380 degrees C while holding outstanding long-term stability.

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