Wan Haiqin, Li Dan, Zhu Haiyang, Zhang Yanhua, Dong Lihui, Hu Yuhai, Liu Bin, Sun Keqin, Dong Lin, Chen Yi
Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, PR China.
J Colloid Interface Sci. 2008 Oct 1;326(1):28-34. doi: 10.1016/j.jcis.2008.07.036. Epub 2008 Jul 25.
Dispersion of molybdena on CeO(2), ZrO(2) (Tet), and a mixture of CeO(2) and ZrO(2) (Tet), was investigated by using laser Raman spectroscopy (LRS), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and temperature programmed reduction (TPR). The results indicate that molybdena is dispersed on both individual oxide support and mixed oxide support at the adopted molybdena loadings (0.2 and 0.8 mmol Mo(6+)/100 m(2)) and the structure of the supported molybdena species is intimate association with its loading amount. Two molybdena species are identified by Raman results, i.e. isolated MoO(4)(2-) species at 0.2 mmol Mo(6+)/100 m(2) and polymolybdate species at 0.8 mmol Mo(6+)/100 m(2). IR spectra of ammonia adsorption prove that isolated MoO(4)(2-) species are Lewis acid sites on the Mo/Ce and/or Zr samples, and the polymolybdate species are Brönsted acid sites on the Mo/Ce and/or Zr samples. Moreover, a combination of the Raman, IR and TPR results confirms that at 0.2 mmol Mo(6+)/100 m(2) Ce+Zr, molybdena is preferentially dispersed on the surface of CeO(2) when a mixed oxide support (CeO(2) and ZrO(2)) is present, which was explained in term of the difference of the surface basicity between CeO(2) and ZrO(2) (Tet). Surface structures of the oxide supports were also taken into consideration.
采用激光拉曼光谱(LRS)、傅里叶变换红外光谱(FT - IR)、X射线衍射(XRD)和程序升温还原(TPR)等方法,研究了氧化钼在CeO₂、ZrO₂(四方相)以及CeO₂与ZrO₂(四方相)混合物上的分散情况。结果表明,在所采用的氧化钼负载量(0.2和0.8 mmol Mo⁶⁺/100 m²)下,氧化钼既分散在单一氧化物载体上,也分散在混合氧化物载体上,且负载的氧化钼物种的结构与其负载量密切相关。拉曼光谱结果鉴定出两种氧化钼物种,即在0.2 mmol Mo⁶⁺/100 m²时为孤立的MoO₄²⁻物种,在0.8 mmol Mo⁶⁺/100 m²时为多钼酸盐物种。氨吸附的红外光谱证明,孤立的MoO₄²⁻物种是Mo/Ce和/或Zr样品上的路易斯酸位点,而多钼酸盐物种是Mo/Ce和/或Zr样品上的布朗斯台德酸位点。此外,拉曼光谱、红外光谱和程序升温还原结果相结合证实,当存在混合氧化物载体(CeO₂和ZrO₂)时,在0.2 mmol Mo⁶⁺/100 m² Ce + Zr条件下,氧化钼优先分散在CeO₂表面,这可根据CeO₂和ZrO₂(四方相)表面碱性的差异来解释。同时也考虑了氧化物载体的表面结构。