Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (8): 1567-1574.doi: 10.3866/PKU.WHXB201506171

• CATALYSIS AND SURFACE SCIENCE • Previous Articles     Next Articles

Preparation of Nano-Manganite Loaded Titanium Electocatalytic Membrane for the Catalytic Oxidation of Benzyl Alcohol

Wen-Jie. TIAN1,2,Hong. WANG1,2,Zhen. YIN1,3,*(),Ying. YANG1,2,Jian-Xin. LI1,2,*()   

  1. 1 State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic University, Tianjin 300387, P. R. China
    2 School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, P. R. China
    3 School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, P. R. China
  • Received:2015-01-20 Published:2015-08-12
  • Contact: Zhen. YIN,Jian-Xin. LI;
  • Supported by:
    the National Natural Science Foundation of China(21206119, 21303119);Changjiang Scholars and InnovativeResearch Team in University of Ministry of Education of China(IRT13084)


MnOx nanoparticles obtained by the emulsion method were loaded on a microporous tubular titanium membrane to prepare a functional MnOx/Ti electrocatalytic membrane. The effects of calcination temperature on the crystal structure of MnOx as well as the electrochemical properties and catalytic performance to oxidize benzyl alcohol of MnOx/Ti membrane were systematically investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), cyclic voltammetry (CV), chronoamperometry (CA), and other characterization methods. The results indicated that the crystal structure of MnOx was gradually transformed from Birnessite-MnO2 to K0.27MnO2, and finally to α-MnO2 from Mn3O4 with increasing calcination temperature. The α-MnO2 particles in the MnOx/Ti electrocatalytic membrane showed high crystallinity and uniform particle size (less than 30 nm). The superior electrochemical properties and catalytic performance of α-MnO2/Ti membrane obtained at a calcination temperature of 450 ℃ could be attributed to the binding effects between unsaturated coordination atoms of Mn and oxygen vacancies with the Ti substrate. The α-MnO2/Ti membrane obtained at 450 ℃ was used as the anode to assemble an electrocatalytic membrane reactor to oxidize benzyl alcohol. 64% conversion of benzyl alcohol and 79% selectivity to benzaldehyde was achieved under the operating conditions: reaction temperature 25 ℃, aqueous benzyl alcohol solution of 50 mmol·L-1, current density 2 mA·cm-2, and residence time 15 min.

Key words: Porous titanium membrane, Electrocatalytic membrane reactor, Manganite, Benzyl alcohol, Catalytic oxidation