采用价键分析和周期密度泛函理论相结合的方法,研究了具有M1晶相结构的MoVTeNbO复合氧化物催化剂中各活性中心的d电子性质.通过分析各活性中心配对出现的d电子和氧缺位的可能分布,得到了最可能高效完成丙烷选择氧化反应的M-M-Te(M=Mo或V)活性中心组合.此外,根据各活性中心对骨架稳定的贡献,说明了稳定的M1相骨架主要来自MoO6八面体中赤道面上的强共价Mo-O键,而VO6八面体的贡献较小.通常被认为稳定M1相的Nb物种主要以离子键的形式存在于五边形孔道中,因而Nb5+作为一种模板离子,诱导五边形孔道乃至M1晶相结构的生成.
参考文献
| [1] | 杨汉培,范以宁,许波连,陈懿.丙烷选择氧化用BiCeVMoO复合氧化物催化剂中Ce组分的作用[J].催化学报,2003(04):265-269. |
| [2] | 金燕仙,黄传敬,应方,翁维正,万惠霖.丙烷选择氧化制丙烯醛VTeO/SiO2催化剂的反应性能与结构表征[J].厦门大学学报（自然科学版）,2005(06):796-800. |
| [3] | 朱百春,李洪波,盛世善,杨维慎,林励吾.Mo-V-Te-Nb-O催化剂上丙烷选择氧化制丙烯酸Ⅰ.催化剂的制备条件及稳定性[J].催化学报,2004(04):277-281. |
| [4] | Ushikubo T;Oshima K;Kayou A;Hatano M .[J].Studies in Surface Science and Catalysis,1997,112:473. |
| [5] | Bart J C J;Giordano N .[J].Journal of Catalysis,1980,64:356. |
| [6] | Botella P;Lopez Nieto J M;Solsona B .[J].Journal of Molecular Catalysis A:Chemical,2002,184:335. |
| [7] | DeSanto P;Buttrey D J;Grasselli R K;Lugmair CqVolpe A F Toby B H Vogt T .[J].Zeitschrift für Kristallographie,2004,219:152. |
| [8] | Vallar S;Goreaud M .[J].Journal of Solid State Chemistry,1997,129:303. |
| [9] | Brown I D;Altermatt D .[J].Acta Crystallographica Section B:Structural Science,1985,41:244. |
| [10] | Grasselli R K;Buttrey D J;DeSanto P;Burrington J D Lugmair C Q Volpe A F Weingand T .[J].Catalysis Today,2004,91-92:251. |
| [11] | Perdew J P;Burke K;Ernzerhof M .[J].Physical Review Letters,1996,77:3865. |
| [12] | Clark S J;Segall M D;Pickard C J;Hasnip P J Probert M J Refson K Payne M C .[J].Zeitschrift für Kristallographie,2005,220:567. |
| [13] | Baca M;Millet JMM .Bulk oxidation state of the different cationic elements in the MoVTe(Sb)NbO catalysts for oxidation or ammoxidation of propane[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,2005(1/2):67-77. |
| [14] | Canadell E;Provost J;Guesdon A;Borel M M Leclaire A .[J].Chemistry of Materials,1997,9:68. |
| [15] | Baca M;Pigamo A;Dubois J L;Millet J M M .[J].Catalysis Communications,2005,6:215. |
| [16] | Baca M;Aouine M;Dubois JL;Millet JMM .Synergetic effect between phases in MoVTe(Sb)NbO catalysts used for the oxidation of propane into acrylic acid[J].Journal of Catalysis,2005(1):234-241. |
| [17] | Garcia-Gonzalez E.;Nieto JML.;Botella P.;Gonzalez-Calbett JM. .On the nature and structure of a new MoVTeO crystalline phase[J].Chemistry of Materials,2002(10):4416-4421. |
| [18] | Hofmann R;Gruehn R .[J].ZAnorg AIIg Chem,1991,602:105. |
| [19] | Pyrz W D;Blom D A;Shiju N R;Guliants V V Vogt T Buttrey D J .[J].Catalysis Today,2009,142:320. |
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