Xu Ai-ju, Zhaorigetu Bao, Jia Mei-lin, Lin Qin
School of Metallurgical and Ecological Engineering, University of Science Technology Beijing, Beijing 100083, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2007 Oct;27(10):2134-8.
Ni3V2O8 catalyst was prepared by oxalate co-precipitation method with microwave heating in this paper. In order to study the relationship between the catalytic performance and the surface species, the catalyst was characterized by XRD, BET, H2-TPR, XPS, TEM and conductivity measurement. The surface property of Ni3V2O8 was studied by XPS and the catalytic performance of the oxidative dehydrogenation of propane to propylene was also investigated. The results of XRD showedthat pure Ni3V2O8 with nice structure was obtained. TEM experiments results demonstrated that the prepared Ni3V2O8 catalyst at 700 degrees C calcination showed uniform particle with the mean particle size of 30 nm. The surface area of the catalyst was 8.623 m2 x g(-1). The diagram of the relationship between electrical conductivity and oxygen partial pressure of Ni3V2O8 showed dsigma/dPO2, >0, implying that Ni3V2O8 catalyst was a p-type semiconductor. H2-TPR results showed that only one unsymmetrical reduction peak appeared at 663.5 degreesC within 300-900 degrees C region over Ni3V2O8 catalyst and no obvious shoulder peak was observed. It could also be found that the ratio of non complete reduction oxygen species was about 33.59% (O(-) 27.55%, O2(2-) 6.04%) from the O(1s) XPS result and more V4+ species existed on the Ni3V2O8 catalyst surface. The TPR and XPS results illustrated that the transformation of the lattice oxygen to non-complete reduction oxygen in NiV2O8 catalyst might promote the oxidation-reduction reaction between different valence vanadium and promoted the oxygen vacancy formation. This then led to abundant non-complete reduction oxygen O(-) and V4+ species formation on the surface of Ni3V2O8 catalyst. The active result of oxidative dehydrogenation of propane to propylene showed that the 60.02% propylene selectivity could be reached at 18.60% propane conversion. Compared with the reported results over the coexistent NiO and Ni3V2O8 system from the literature, pure Ni3V2O8 catalyst system in this present paper showed higher propylene selectivity than the coexistent NiO and Ni3V2O8 system under the same propane conversion condition, suggesting that the performance of propane to propene is correlated to the oxidation-reduction of V4+ / V5+ couple and non complete reduction oxygen species (O(-) or O2(2-)). This result further illustrated that NiV2O8 was active phase for oxidative dehydrogenation of propane to propylene. Combining the active and characterization results, it was found that catalytic activity was correlated to the surface non-complete reduction O(-) and V4+ species, which was beneficial to improving the propylene selectivity.
本文采用草酸盐共沉淀法并通过微波加热制备了Ni3V2O8催化剂。为了研究催化性能与表面物种之间的关系,采用XRD、BET、H2-TPR、XPS、TEM和电导率测量等手段对催化剂进行了表征。通过XPS研究了Ni3V2O8的表面性质,并考察了丙烷氧化脱氢制丙烯的催化性能。XRD结果表明,获得了结构良好的纯Ni3V2O8。TEM实验结果表明,在700℃煅烧制备的Ni3V2O8催化剂颗粒均匀,平均粒径为30nm。催化剂的比表面积为8.623 m2·g-1。Ni3V2O8的电导率与氧分压关系图显示dsigma/dPO2>0,这意味着Ni3V2O8催化剂是一种p型半导体。H2-TPR结果表明,在300-900℃范围内,Ni3V2O8催化剂仅在663.5℃出现一个不对称还原峰,未观察到明显的肩峰。从O(1s)XPS结果还可以发现,非完全还原氧物种的比例约为33.59%(O-为27.55%,O2(2-)为6.04%),Ni3V2O8催化剂表面存在更多的V4+物种。TPR和XPS结果表明,NiV2O8催化剂中晶格氧向非完全还原氧的转变可能促进了不同价态钒之间的氧化还原反应,并促进了氧空位的形成。这进而导致在Ni3V2O8催化剂表面形成大量的非完全还原氧O-和V4+物种。丙烷氧化脱氢制丙烯的活性结果表明,在丙烷转化率为18.60%时,丙烯选择性可达60.02%。与文献报道的共存NiO和Ni3V2O8体系的结果相比,本文的纯Ni3V2O8催化剂体系在相同丙烷转化条件下表现出比共存NiO和Ni3V2O8体系更高的丙烯选择性,这表明丙烷制丙烯的性能与V4+/V5+偶的氧化还原以及非完全还原氧物种(O-或O2(2-))有关。该结果进一步表明NiV2O8是丙烷氧化脱氢制丙烯的活性相。结合活性和表征结果发现,催化活性与表面非完全还原的O-和V4+物种相关,这有利于提高丙烯选择性。