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Gas-phase selective oxidation of cyclohexanol to cyclohexanone over Au/Mg1-xCuxCr2O4 catalysts: On the role of Cu doping
Journal of Catalysis ( IF 6.5 ) Pub Date : 2020-03-17 , DOI: 10.1016/j.jcat.2020.02.025
Yanan Gao , Emiel J.M. Hensen

The industrial production of cyclohexanone from cyclohexanol would benefit from a selective oxidation catalyst. Herein, Cu doping of MgCr2O4 supports for gold nanoparticles active in gas-phase oxidation of cyclohexanol was investigated. Mg1-xCuxCr2O4 exhibited spinel structures (x ≤ 0.25: MgCr2O4; x = 1: CuCr2O4) onto which 3–4 nm gold nanoparticles could be dispersed. Cu doping led to higher activity. During reaction, surface Cu2+ was reduced to Cu0, resulting in AuCu alloy formation. At low temperature, low-Cu-content catalysts (x ≤ 0.1) showed higher activity than high-Cu-content catalysts, likely because the AuCu alloy with highly diluted Cu was more active for the dehydrogenation step of cyclohexanol. However, Au/Mg0.99Cu0.01Cr2O4 and Au/Mg0.9Cu0.1Cr2O4 showed lower cyclohexanol conversion at high temperature than samples with high Cu content, because O2 activation involving Cu becomes rate-limiting. Stable cyclohexanol conversion and cyclohexanone selectivity were 99.1% and 90.2% (space-time yield of 266 gKetone gAu−1 h−1) for Au/Mg0.25Cu0.75Cr2O4 at 300 °C.



中文翻译:

Au / Mg 1-x Cu x Cr 2 O 4催化剂上环己醇气相选择性氧化为环己酮的研究:Cu掺杂的作用

由环己醇工业生产环己酮将受益于选择性氧化催化剂。在此,研究了在环己醇的气相氧化中具有活性的金纳米颗粒的MgCr 2 O 4载体的Cu掺杂。毫克1-x的Cu X的Cr 2 ö 4展出尖晶石结构(X  :≤0.25 MgCr 2 ö 4 ; X:铜铬= 1 2 ö 4在其上3-4纳米的金纳米颗粒可分散)。铜掺杂导致更高的活性。反应期间,表面Cu 2+还原为Cu 0,从而生成Au铜合金的形成。在低温,低Cu含量催化剂(X  ≤0.1)显示出更高的活性比Cu高含量的催化剂,有可能是因为在Au Cu合金具有高度稀释的Cu是用于环己醇脱氢步骤更加活跃。但是,Au / Mg 0.99 Cu 0.01 Cr 2 O 4和Au / Mg 0.9 Cu 0.1 Cr 2 O 4在高温下的环己醇转化率比高Cu含量的样品低,这是因为涉及Cu的O 2活化成为速率限制。稳定的环己醇转化率和环己酮选择性分别为99.1%和90.2%(时空产率266 gAu / Mg 0.25 Cu 0.75 Cr 2 O 4的 g Au -1  h -1)在300°C下。

更新日期:2020-03-19
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