Citation: WANG Guan-Nan, CHEN Li-Min, GUO Yuan-Yuan, FU Ming-Li, WU Jun-Liang, HUANG Bi-Chun, YE Dai-Qi. Effect of Chromium Doping on the Catalytic Behavior of Cu/ZrO₂/CNTs-NH₂ for the Synthesis of Methanol from Carbon Dioxide Hydrogenation[J]. Acta Physico-Chimica Sinica, ;2014, 30(5): 923-931. doi: 10.3866/PKU.WHXB201403051 shu

Effect of Chromium Doping on the Catalytic Behavior of Cu/ZrO₂/CNTs-NH₂ for the Synthesis of Methanol from Carbon Dioxide Hydrogenation

1.
1 Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, Guangzhou 510006, P. R. China;
2 College of Environment and Energy, South China University of Technology, Guangzhou 510006, P. R. China

Received Date: 8 January 2014
Available Online: 5 March 2014
Fund Project:

A series of Cu/ZrO₂/CNTs-NH₂ catalysts with various chromium dopings were prepared using a coprecipitation method for the synthesis of methanol by the hydrogenation of CO₂. The impact of the addition of chromium on the catalytic performance of the Cu/ZrO₂/CNTs-NH₂ catalyst was investigated in a fixed-bed plug flow reactor. When the chromium loading was set to 1% of the total amount of Cu²⁺ and Zr⁴⁺, the methanol yield increased to a maximum of 7.78% (reaction conditions: 3.0 MPa, 260 ℃, V(H₂):V(CO₂):V(N₂)=69:23:8 and gaseous hourly space velocity (GHSV)=3600 mL·h^-1·g^-1). The catalysts were characterized by N₂ physisorption, X-ray diffraction (XRD), temperature-programmed desorption of H₂ (H₂-TPD), X-ray photoelectron spectroscopy (XPS), temperature- programmed desorption of CO₂ (CO₂-TPD), differential thermal analysis (DTA), and scanning electron microscopy (SEM). The results of these analyses indicated that the introduction of chromium reduced the size of the Cu nanoparticles, enhanced the dispersion of the Cu species, inhibited the phase transformation and sintering of ZrO₂, increased the specific surface area, enhanced the amount of CO₂ adsorbed, and promoted the conversion of weakly adsorbed CO₂ species to strongly adsorbed CO₂ species. Taken together, these factors lead to a high methanol yield. However, when the chromium loading was greater than 1%, the amount Cu and Zr on the surface, as well as the size of the Cu nanoparticle reduced considerably, which led to a significant reduction in the adsorption of CO₂ species. This effect also facilitated the formation of strongly adsorbed CO₂ species, leading to lower methanol yields.
- CNTs-NH₂,
- Chromium,
- Copper,
- Zirconia,
- Methanol synthesis,
- Carbon dioxide hydrogenation
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Effect of Chromium Doping on the Catalytic Behavior of Cu/ZrO2/CNTs-NH2 for the Synthesis of Methanol from Carbon Dioxide Hydrogenation

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通讯作者: 陈斌, bchen63@163.com

Effect of Chromium Doping on the Catalytic Behavior of Cu/ZrO₂/CNTs-NH₂ for the Synthesis of Methanol from Carbon Dioxide Hydrogenation