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Effective solvent-free oxidation of cyclohexene to allylic products with oxygen by mesoporous etched halloysite nanotube supported Co2+†
RSC Advances ( IF 3.9 ) Pub Date : 2018-04-19 00:00:00 , DOI: 10.1039/c7ra11245a Cuiping Li 1 , Yue Zhao 1 , Tianwen Zhu 1 , Yan'ge Li 1 , Jiajia Ruan 1 , Guanghui Li 1
RSC Advances ( IF 3.9 ) Pub Date : 2018-04-19 00:00:00 , DOI: 10.1039/c7ra11245a Cuiping Li 1 , Yue Zhao 1 , Tianwen Zhu 1 , Yan'ge Li 1 , Jiajia Ruan 1 , Guanghui Li 1
Affiliation
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One dimensional mesoporous etched halloysite nanotube supported Co2+ is achieved by selective etching of Al2O3 from halloysite nanotube (HA) and immersing the etched HA (eHA) into the Co(NO3)2·6H2O solution consecutively. By facilely tuning the etching time and the weight ratio of Co(NO3)2·6H2O to eHA, the morphology, specific surface area and the supported Co2+ content of the mesoporous material can be tuned. The method for mesoporous material is scaled up and can be extended to other clay minerals. The mesoporous eHA supported Co2+ is used as catalyst for the selective catalytic oxidation of cyclohexene in solvent-free reaction system with O2 as oxidant. The results shows the catalytic activity is dependent on etching time, weight ratio of Co(NO3)2·6H2O to eHA, calcination treatment and reaction time/temperature. Among them, mesoporous eHA supported Co2+ prepared with 18 h etching time and 2 : 1 Co(NO3)2·6H2O/eHA weight ratio without calcination (HA/HCl-18 h/Co2+-2 : 1) demonstrates the highest catalytic activity under 75 °C reaction temperature and 18 h reaction time (58.30% conversion and 94.03% selectivity to allylic products). Furthermore, HA/HCl-18 h/Co2+-2 : 1 has exhibit superior cycling stability with 37.69% conversion and 92.73% selectivity to allylic products after three cycles.
中文翻译：
通过介孔蚀刻埃洛石纳米管负载 Co2+† 有效地将环己烯无溶剂氧化为氧烯丙基产物
通过从埃洛石纳米管(HA)选择性蚀刻Al 2 O 3并将蚀刻的HA (eHA)连续浸入Co(NO 3 ) 2 ·6H 2 O溶液中来实现一维中孔蚀刻埃洛石纳米管负载Co 2+ 。通过方便地调整蚀刻时间和Co(NO 3 ) 2 ·6H 2 O与eHA的重量比，可以调整介孔材料的形貌、比表面积和负载的Co 2+含量。介孔材料的方法规模化，可推广到其他粘土矿物。介孔 eHA 支持 Co 2+用于无溶剂反应体系中以O 2为氧化剂选择性催化氧化环己烯的催化剂。结果表明催化活性取决于蚀刻时间、Co(NO 3 ) 2 ·6H 2 O与eHA的重量比、煅烧处理和反应时间/温度。其中，刻蚀时间为18 h、未煅烧2:1 Co(NO 3 ) 2 ·6H 2 O/eHA重量比(HA/HCl-18 h/Co 2+ )制备的介孔eHA负载Co 2+-2 : 1) 在 75 °C 反应温度和 18 小时反应时间下表现出最高的催化活性（58.30% 的转化率和 94.03% 的烯丙基产物选择性）。此外，HA/HCl-18 h/Co 2+ -2 : 1 具有优异的循环稳定性，三个循环后转化率为 37.69%，对烯丙基产物的选择性为 92.73%。
更新日期：2018-04-19
中文翻译：
通过介孔蚀刻埃洛石纳米管负载 Co2+† 有效地将环己烯无溶剂氧化为氧烯丙基产物
通过从埃洛石纳米管(HA)选择性蚀刻Al 2 O 3并将蚀刻的HA (eHA)连续浸入Co(NO 3 ) 2 ·6H 2 O溶液中来实现一维中孔蚀刻埃洛石纳米管负载Co 2+ 。通过方便地调整蚀刻时间和Co(NO 3 ) 2 ·6H 2 O与eHA的重量比，可以调整介孔材料的形貌、比表面积和负载的Co 2+含量。介孔材料的方法规模化，可推广到其他粘土矿物。介孔 eHA 支持 Co 2+用于无溶剂反应体系中以O 2为氧化剂选择性催化氧化环己烯的催化剂。结果表明催化活性取决于蚀刻时间、Co(NO 3 ) 2 ·6H 2 O与eHA的重量比、煅烧处理和反应时间/温度。其中，刻蚀时间为18 h、未煅烧2:1 Co(NO 3 ) 2 ·6H 2 O/eHA重量比(HA/HCl-18 h/Co 2+ )制备的介孔eHA负载Co 2+-2 : 1) 在 75 °C 反应温度和 18 小时反应时间下表现出最高的催化活性（58.30% 的转化率和 94.03% 的烯丙基产物选择性）。此外，HA/HCl-18 h/Co 2+ -2 : 1 具有优异的循环稳定性，三个循环后转化率为 37.69%，对烯丙基产物的选择性为 92.73%。
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