Transition metal-doped heteropoly catalysts for the selective oxidation of methacrolein to methacrylic acid

Yanxia Zheng, Heng Zhang, Lei Wang, Suojiang Zhang, Shaojun Wang

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Front. Chem. Sci. Eng. ›› 2016, Vol. 10 ›› Issue (1) : 139-146. DOI: 10.1007/s11705-015-1548-9
RESEARCH ARTICLE

Transition metal-doped heteropoly catalysts for the selective oxidation of methacrolein to methacrylic acid

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Abstract

Heteropoly compounds with the general formula Cs1M0.5x+H3‒0.5xP1.2Mo11VO40 (M= Fe, Co, Ni, Cu or Zn) and Cs1CuyH3‒2yP1.2Mo11VO40 (y = 0.1, 0.3 or 0.7) were synthesized and then used as catalysts for the selective oxidation of methacrolein to methacrylic acid. The effects of the transition metals on the structure and activity of the catalysts were investigated. FTIR spectra showed that the transition metal-doped catalysts maintained the Keggin structure of the undoped catalysts. X-ray diffraction results indicated that before calcination, the catalysts doped with Fe and Cu had cubic secondary structures, while the catalysts doped with Co, Ni or Zn had both triclinic and cubic phases and the Co-doped catalyst had the highest content of the triclinic form. Thermal treatment can decrease the content of the triclinic phase. NH3 temperature-programmed desorption and H2 temperature-programmed reduction results showed that the transition metals changed the acid and redox properties of the catalysts. The addition of Fe or Cu had positive effects on the activities of the catalyst which is due to the improvement of the electron transfer between the Fe or Cu and the Mo. The effects of the copper content on structure and catalytic activity were also investigated. The Cs1Cu0.3H2P1.2Mo11VO40 catalyst had the best performance for the selective oxidation of methacrolein to methacrylic acid.

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Keywords

heteropoly compounds / transition metals / selective oxidation / methacrolein

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Yanxia Zheng, Heng Zhang, Lei Wang, Suojiang Zhang, Shaojun Wang. Transition metal-doped heteropoly catalysts for the selective oxidation of methacrolein to methacrylic acid. Front. Chem. Sci. Eng., 2016, 10(1): 139‒146 https://doi.org/10.1007/s11705-015-1548-9

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Acknowledgments

The authors gratefully acknowledge the financial support from the “Strategic Priority Research Program” of the Chinese Academy of Sciences (XDA07070600), the National Natural Science Foundation of China (Grant No. 21206179) and the Special Fund of the National Natural Science Foundation of China (Grant No. 21127011).
The authors gratefully acknowledge the financial support from the “Strategic Priority Research Program” of the Chinese Academy of Sciences (XDA07070600), the National Natural Science Foundation of China (Grant No. 21206179) and the Special Fund of the National Natural Science Foundation of China (Grant No. 21127011).

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2014 Higher Education Press and Springer-Verlag Berlin Heidelberg
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