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CoCr2O4在催化氧化四氢萘的可控气氛下化学吸附氧的EPR研究

EPR Study of the Oxygen Adsorbed on CoCr2O4 in Controlled-atmosphere Catalytic Oxidation of Tetralin

  • 摘要: 钴铬氧化物CoCr2O4对四氢萘催化氧化的比活性和得到萘满酮的选择性均高于单组分氧化物CoO和Cr2O3的。用EPR方法对三个催化剂样品表面吸附氧及其在可控气氛下与四氢萘的作用进行了研究。实验表明,CoO和CoCr2O4在50℃下氧气中处理后,得到可归属为化学吸附超氧负离子O2-顺磁信号,该信号在1.33×10-2Pa的室温及低温(157K)下均能稳定存在。CoCr2O4在400℃下抽空至1.33×10-2Pa无O2-顺磁信号。吸附过氧的CoCr2O4催化剂在无气相氧存在,于50℃下与四氢萘作用时,2-的顺磁信号随反应时间延长而渐弱,同时IR检测到羰基信号,表明2-可能是活性氧物种,钴为>2-化学吸附的中心组分。参铬改变了其配位环境,增加了>2-的吸附量。

     

    Abstract: The catalytic activity and selectivity to tetralone of CoCr2O4 catalyst in oxidation of tetralin are higher than that of CoO and Cr2O3.By election paramagentic resonance(EPR),the oxygen adsorbed or desorbed on three catalysts,and the action contacted with tetralin in cotrolled-atmosphere have been investigated respectively.The results of EPR confirm that a signal with 3-g values (2.000~2.085) comes from the species of surface adsorbing oxygen,and that they can be assigned to super-oxide species O2- which is chemisorbed on the samples.It is stable under the conditions of room or 157K temperature and vacuum of 1.33×10-2Pa.The O2- on CoCr2O4 could not be detected under the conditions of 673K and vacuum of 1.33×10-2Pa,neither could O2- on Cr2O3 under all conditions.It was found that the signal intensity of the O2- reduced when CoCr2O4 was contacted with tetralin under conditions of 323K and without oxygen gas.At the same time,the signal (C=0) was given by IR.The results show that the species O2- might be the active species oxygen,and that the cobalt is active position of chemisorbed oxygen.The concentration of O2- is increased and its complex state is changed by addition of chromium.

     

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