Selective oxidation of benzene to phenol in the liquid phase over copper-substituted LaFeO3 perovskite oxide as catalyst

Rajib Mistri
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Abstract

Abstract Selective oxidation of benzene to phenol is done in the liquid phase over copper-substituted LaFeO3 perovskite oxides as catalyst using H2O2 as oxidant under mild reaction conditions. Among the different copper-substituted perovskite catalysts synthesized by a novel solution combustion method, the LaFe0.90Cu0.10O3 catalyst showed highest activity (∼56 % with 100 % selectivity of phenol) and also gives better activity than the corresponding catalyst made via incipient wetness impregnation of 10 at % Cu over combustion-synthesized LaFeO3. XRD analysis revealed formation of the perovskite phase as the predominant one. The greater activity of the combustion-made catalyst has been attributed to the occurrence of a peculiar poorly-defined structure having substitutional copper ion sites on top of the LaFeO3 particle as observed in HRTEM analysis. Much less occurrence of this phase in the impregnated catalyst, where copper is primarily present as dispersed CuO crystallites, explains its comparatively lower activity in the oxidation reaction. The effect of catalyst recycling shows negligible change of activity for the combustion-made catalyst whereas the analogous impregnated catalyst shows considerable decrease in activity in recycling. This explained to be due to the essentially intact poorly-defined structure in the former and leaching of the finely dispersed CuO crystallites from the latter catalyst during cycling.
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在铜取代的LaFeO3钙钛矿氧化物催化下,苯在液相中选择性氧化为苯酚
摘要在温和的反应条件下,以铜取代的LaFeO3钙钛矿氧化物为催化剂,以H2O2为氧化剂,在液相中选择性地将苯氧化为苯酚。在新型溶液燃烧法合成的不同铜取代钙钛矿催化剂中,LaFe0.90Cu0.10O3催化剂的活性最高(~ 56 %,苯酚选择性为100 %),并且比燃烧合成的LaFeO3催化剂在 % Cu下初始湿浸渍10得到的相应催化剂的活性更好。XRD分析表明,钙钛矿相的形成是主要的。燃烧制催化剂的更大活性归因于在HRTEM分析中观察到的LaFeO3颗粒顶部出现了一种特殊的不明确结构,具有取代的铜离子位点。在浸渍催化剂中,铜主要以分散的CuO晶的形式存在,这就解释了它在氧化反应中相对较低的活性。催化剂再循环对燃烧制催化剂活性的影响可以忽略不计,而类似的浸渍催化剂在再循环中活性明显降低。这是由于前者的结构基本完整,结构不明确,而后者的催化剂在循环过程中浸出了精细分散的CuO晶体。
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