Ni3V2O8催化性能与X射线光电子能谱分析

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摘要：文章采用微波加热，草酸盐共沉淀法制备了Ni₃V₂O₈催化剂，并对催化剂进行了BET，XRD，H₂-TPR，XPS，TEM和电导等技术表征，分析研究了Ni₃V₂O₈催化剂的丙烷氧化脱氢(ODH)制丙烯催化性能与其表面物种的关系。XRD，TEM和电导实验结果表明本方法制得的Ni₃V₂O₈催化剂晶粒均匀，平均粒径为30 nm，具有p-型半导体性质。TPR和XPS实验结果显示Ni₃V₂O₈催化剂中，晶格氧可以较容易转换成未完全还原氧，使催化剂内各种价态的钒之间易于进行氧化还原反应并形成氧缺位，从而催化剂的表面含有较多未充分还原氧物种O^-和V⁴⁺物种。催化活性结果显示当丙烷的转化率为18.60%，丙烯选择性达到60.02%，在相同转化率条件下，比文献报道的NiO和Ni₃V2O₈共存催化体系中的丙烯选择性高，说明Ni₃V₂O₈催化剂中存在未充分还原的O-和V⁴⁺物种有利于提高丙烯的选择性。

关键词：Ni₃V₂O₈;XPS;氧物种;氧化脱氢;p-型半导体

Abstract：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 showed that pure Ni₃V₂O₈ with nice structure was obtained. TEM experiments results demonstrated that the prepared Ni₃V₂O₈ catalyst at 700 ℃ calcination showed uniform particle with the mean particle size of 30 nm. The surface area of the catalyst was 8.623 m²·g^-1. The diagram of the relationship between electrical conductivity and oxygen partial pressure of Ni₃V₂O₈ showed dσ/dP_O₂＞0, implying that Ni₃V₂O₈ catalyst was a p-type semiconductor. H₂-TPR results showed that only one unsymmetrical reduction peak appeared at 663.5 ℃ within 300-900 ℃ 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%, O^2-₂ 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 Ni₃V₂O₈ 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 O^2-₂). This result further illustrated that Ni₃V₂O₈ 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.

Key words：Ni₃V₂O₈;X-ray photoelectron spectroscopy (XPS);Oxygen species;Oxidative dehydrogenation (ODH);p-type semiconductor

收稿日期: 2007-01-12 修订日期: 2007-04-16

中图分类号:

O657.6

通讯作者: 照日格图 E-mail: zrgt@imnu.edu.cn

引用本文:

徐爱菊^1,2,照日格图^2*,贾美林²,林勤¹. Ni₃V₂O₈催化性能与X射线光电子能谱分析[J]. 光谱学与光谱分析, 2007, 27(10): 2134-2138.
XU Ai-ju^1,2,ZHAORIGETU Bao^2*,JIA Mei-lin²,LIN Qin¹. Study on Performance of Ni₃V₂O₈ Catalyst and Analysis of X-Ray Photoelectron Spectroscopy. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2007, 27(10): 2134-2138.

链接本文:

https://www.gpxygpfx.com/CN/Y2007/V27/I10/2134

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