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Pd-Co catalysts prepared from palladium-doped cobalt titanate precursors for chemoselective hydrogenation of halonitroarenes
Molecular Catalysis ( IF 3.9 ) Pub Date : 2019-12-10 , DOI: 10.1016/j.mcat.2019.110702
Tatiana M. Bustamante , Robinson Dinamarca , Cecilia C. Torres , Gina Pecchi , Cristian H. Campos

Bimetallic Pd-Co catalysts supported on the mixed oxides CoTiO3-CoO-TiO2 (CTO) were synthesized via the thermal reduction of Pd-doped cobalt titanates PdxCo1-xTiO3 and evaluated for the chemoselective hydrogenation of halonitroarenes to haloarene-amines. The nominal Pd mass percentage of the Pd-Co/CTO systems was varied from 0.0 to 0.50. After the thermal reduction of PdxCo1-xTiO3 at 500 °C for 3 h, Pd was completely reduced and Co was partially reduced, producing a mixture of ionic Co, metallic Co, and TiO2-rutile species to give the supported bimetallic catalysts. The metallic cobalt content increased with the Pd content of the precursor. The catalytic activity toward 4-chloronitrobenzene increased with the Pd content; however, >0.1 mass% Pd decreased the chemoselectivity toward 4-chloroaniline due to the formation of the hydrodehalogenation product—aniline. The 0.1Pd-Co/CTO system was used as a model catalyst to produce haloarene-amine building blocks for linezolid, loxapine, lapatinib, and sorafenib with >98% conversion, 96% chemoselectivity, and no hydrohalogenation products. Finally, recycling tests of the 0.1Pd-Co/CTO catalyst showed loss of activity and selectivity during the third cycle due to catalyst deactivation. Regeneration treatments, every two catalytic cycles, allowed six operation cycles without loss of chemoselectivity and only a slight decrease in catalytic activity during the last cycle.



中文翻译:

由钯掺杂的钛酸钴钴前体制备的Pd-Co催化剂用于卤代硝基芳烃的化学选择性加氢

通过热还原掺杂钯的钛酸钴Pd x Co 1-x TiO 3合成了负载在混合氧化物CoTiO 3 -CoO-TiO 2(CTO)上的双金属Pd-Co催化剂,并评估了卤代硝基芳烃的化学选择性加氢。 -胺。Pd-Co / CTO系统的标称Pd质量百分比在0.0到0.50之间变化。将Pd x Co 1-x TiO 3在500°C下热还原3小时后,Pd完全还原而Co部分还原,生成了离子Co,金属Co和TiO 2的混合物-金红石型,得到负载型双金属催化剂。金属钴含量随前体的Pd含量增加而增加。随着Pd含量的增加,对4-氯硝基苯的催化活性增加; 然而,由于加氢脱卤化产物苯胺的形成,> 0.1质量%的Pd降低了对4-氯苯胺的化学选择性。0.1Pd-Co / CTO系统用作模型催化剂,用于生产利奈唑胺,洛沙平,拉帕替尼和索拉非尼的卤代芳烃胺结构单元,其转化率> 98%,化学选择性为96%,并且没有加氢卤化产物。最后,0.1Pd-Co / CTO催化剂的循环测试表明,由于催化剂失活,在第三次循环中活性和选择性下降。每两个催化循环进行一次再生处理,

更新日期:2019-12-11
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