Zhu Haiyang, Shen Mingmin, Wu Yong, Li Xiaowei, Hong Jianming, Liu Bin, Wu Xinglong, Dong Lin, Chen Yi
Key Laboratory of Mesoscopic Chemistry of MOE, College of Chemistry and Chemical Engineering, Center of Modern Analysis, Department of Physics, Nanjing University, Nanjing 210093, China.
J Phys Chem B. 2005 Jun 16;109(23):11720-6. doi: 10.1021/jp050890a.
Raman and FT-IR spectra were employed to investigate the dispersion of molybdena on mixed TiO2 (rutile and anatase, signed as R and A) with different BET surface ratios of rutile/TiO2(R + A). The results showed that (1) molybdena would preferentially disperse on the rutile surface in mixed TiO2; (2) for MoO3/rutile with low molybdena loading (e.g., 0.20 mmol/100 m2 rutile), a dispersed molybdena species existed on the rutile surface in an isolated tetrahedral coordination environment, while for MoO3/rutile with high molybdena loading (e.g. 0.82 mmol/100 m2 rutile), a polymeric molybdena species could be detected on the rutile surface; (3) for the MoO3/anatase sample, a dispersed molybdena species existed on the anatase surface in a polymeric coordination environment; and (4) the formation of the Bronsted acid site on the surface of rutile and anatase should be related to the polymeric molybdena species. All these results have been discussed via the interaction between OH groups of molybdena and OH groups of rutile and anatase, and it seems reasonable to suggest that, for the lower molybdena loading, the different states of the dispersed molybdena species should result from the different dehydration orders of OH groups of the molybdena and surface OH groups of rutile and anatase.
采用拉曼光谱和傅里叶变换红外光谱研究了钼氧化物在具有不同金红石/二氧化钛(金红石+锐钛矿,分别标记为R和A)BET表面比的混合二氧化钛(金红石和锐钛矿)上的分散情况。结果表明:(1)钼氧化物优先分散在混合二氧化钛的金红石表面;(2)对于低钼负载量的三氧化钼/金红石(例如,0.20 mmol/100 m²金红石),在金红石表面存在处于孤立四面体配位环境的分散钼物种,而对于高钼负载量的三氧化钼/金红石(例如0.82 mmol/100 m²金红石),在金红石表面可检测到聚合钼物种;(3)对于三氧化钼/锐钛矿样品,在锐钛矿表面存在处于聚合配位环境的分散钼物种;(4)金红石和锐钛矿表面布朗斯特酸位点的形成应与聚合钼物种有关。所有这些结果都通过钼氧化物的羟基与金红石和锐钛矿的羟基之间的相互作用进行了讨论,似乎有理由认为,对于较低的钼负载量,分散钼物种的不同状态应源于钼氧化物的羟基与金红石和锐钛矿表面羟基的不同脱水顺序。