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

作　　者：Yanxia Zheng Heng Zhang Lei Wang Suojiang Zhang Shaojun Wang 

机构地区：[1]School of Light Industry and Chemical Engineering, Dalian Polytechnic University, Dalian 116034, China [2]Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China [3]School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China

出　　处：《Frontiers of Chemical Science and Engineering》2016年第1期139-146,共8页化学科学与工程前沿（英文版）

摘　　要：Heteropoly compounds with the general formula Cs1Mo.5X＋H3-o.5xP1.2MOllVO4o （M = Fe, Co, Ni, Cu or Zn） and CslCuyH3_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 main- tained 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 tem- perature-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 CSlCUo.3H2P1.2MO11VO40 catalyst had the best performance for the selective oxidation of methacrolein to methacrylic acid.Heteropoly compounds with the general formula Cs1Mo.5X＋H3-o.5xP1.2MOllVO4o （M = Fe, Co, Ni, Cu or Zn） and CslCuyH3_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 main- tained 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 tem- perature-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 CSlCUo.3H2P1.2MO11VO40 catalyst had the best performance for the selective oxidation of methacrolein to methacrylic acid.

关 键 词：heteropoly compounds transition metals selective oxidation METHACROLEIN 

分 类 号：O643.36[理学—物理化学] TQ426.91[理学—化学]