Doping effects of B in ZrO2 on structural and catalytic properties of Ru/B-ZrO2 catalysts for benzene partial hydrogenation
Doping effects of B in ZrO2 on structural and catalytic properties of Ru/B-ZrO2 catalysts for benzene partial hydrogenation
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ZrO2中B的掺杂对Ru/B-ZrO2苯部分加氢催化剂结构和催化性能的影响
DOI：
10.1016/j.jcat.2013.12.022
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发表时间：
2014-03
影响因子：
7.3
通讯作者：
Baoning Zong
中科院分区：
文献类型：
--
作者：
Gongbing Zhou;Yan Pei;Zheng Jiang;Kangnian Fan;Minghua Qiao;Bin Sun;Baoning Zong
以氧氯化锆和硼酸为前驱体，制备了不同B/Zr比的B掺杂ZrO 2（B-ZrO 2）样品。在掺杂B后，它们的晶相保持为四相ZrO 2;然而，在标称B/Zr摩尔比为1/10的情况下，B-ZrO 2（1/10）上的刘易斯酸位点的量从ZrO 2上的46.1 μ molNH 3g − 1增加到100.6 μ molNH 3g − 1。采用化学还原法制备了Ru/B-ZrO 2催化剂，并利用光谱技术对其电子结构进行了系统表征.结果表明，负载在B-ZrO 2上的Ru纳米粒子具有相似的尺寸、化学状态和微观结构。在苯部分加氢反应中，苯的转化率与载体上酸中心的数量成线性关系，而在Ru/B-ZrO_2（1/15）催化剂上，环己烯的选择性呈现火山式变化，最高可达88%。动力学分析表明，酸中心的存在不同程度地提高了苯生成环己烯和环己烯生成环己烷的反应速率常数。结果k1/k2比值从3.7 × 10−2l mol−1（Ru/ZrO 2）增加到4.8 × 10−2l mol−1（Ru/B-ZrO 2（1/15）），然后下降到4.1 × 10−2l mol−1（Ru/B-ZrO 2（1/10）），这解释了相对于酸量的环己烯选择性的火山演化。
The B-doped ZrO2(B-ZrO2) samples with different B/Zr ratios were synthesized using zirconium oxychloride and boric acid as the precursors. Their crystallographic phase retained as tetragonal ZrO2after the doping of B; however, the amount of the Lewis acid sites increased from 46.1 μmolNH3g−1on ZrO2to 100.6 μmolNH3g−1on B-ZrO2(1/10) with the nominal B/Zr molar ratio of 1/10. The Ru/B-ZrO2catalysts were then prepared by chemical reduction, and their electronic and structural properties were systematically characterized by spectroscopic techniques. It is identified that the Ru nanoparticles (NPs) supported on these B-ZrO2samples exhibited similar size, chemical state, and microstructure. In the partial hydrogenation of benzene, the turnover frequency of benzene was linearly proportional to the amount of the acid sites on the supports, whereas the selectivity toward cyclohexene displayed a volcanic evolution passing through a maximum of 88% on the Ru/B-ZrO2(1/15) catalyst. Kinetic analysis indicated that the acid sites improved the rate constants of the benzene to cyclohexene step (k1) and the cyclohexene to cyclohexane step (k2) to different degrees. The resultingk1/k2ratio increased from 3.7 × 10−2l mol−1(Ru/ZrO2) to 4.8 × 10−2l mol−1(Ru/B-ZrO2(1/15)), and then declined to 4.1 × 10−2l mol−1(Ru/B-ZrO2(1/10)), which explained the volcanic evolution of the selectivity toward cyclohexene with respect to the acid amount.
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影响因子：
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作者：
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通讯作者：
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影响因子：
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通讯作者：
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影响因子：
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作者：
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