Ma Jinyi, Wu Yong, Pan Qin, Wang Xiangdong, Li Xiaoyong, Li Qiujuan, Xu Xiaoshuai, Yao Yuan, Sun Yang
Department of Applied Chemistry, School of Chemistry, Xi'an Jiaotong University, No. 28, Xianning West Road, Xi'an 710049, China.
Xixian New District Xingyi Advanced Materials Technology Co., Ltd., Room 1046, 1st Floor, Hongdelou, Building No. 20, Science and Technology Innovation Port, Western China, Fengxi New City, Xixian New District, Xi'an 712000, China.
Nanomaterials (Basel). 2023 Jan 20;13(3):433. doi: 10.3390/nano13030433.
The Baeyer-Villiger Oxidation (BVO) of ketones and aldehydes produce lactones and formates, while aerobic carboxylation of aldehydes manufactures carboxylic acids, both having high added value. This work prepared a series of Al-containing silicates modified with organic ligands and SnO nanoparticles, which were then employed as catalyst in BVO and carboxylation. Characterizations revealed the morphology of the synthesized catalyst was changed from micron-sized thin sheets to smaller blocks, and then to uniform nanoparticles (size of 50 nm) having the doped SnO nanoparticles with a size of 29 nm. All catalysts showed high BET surface areas featuring silt-like mesopores. In determining the priority of BVO and carboxylation, an influence evaluation of the parameters showed the order to be substrate > oxidant > solvent > catalyst. Cyclic aliphatic ketones were suitable for BVO, but linear aliphatic and aromatic aldehydes for carboxylation. Coordination of ()-binaphthol or doping of Sn into catalyst showed little influence on BVO under -CPBA, but the Sn-doped catalyst largely increased BVO under (NH)SO and HO. Calculations revealed that the catalyst containing both Al and Sn could give BVO intermediates lower energies than the Sn-beta zeolite model. The present system exhibited merits including wider substrate scope, innocuous catalytic metal, greener oxidant, as well as lower catalyst cost.
酮和醛的拜耳-维利格氧化反应（BVO）生成内酯和甲酸酯，而醛的有氧羧化反应生成羧酸，二者均具有高附加值。本工作制备了一系列用有机配体和SnO纳米颗粒改性的含铝硅酸盐，然后将其用作BVO和羧化反应的催化剂。表征结果显示，合成催化剂的形态从微米级薄片变为较小的块状，然后变为尺寸为50 nm的均匀纳米颗粒，其中掺杂了尺寸为29 nm的SnO纳米颗粒。所有催化剂均具有较高的BET表面积，呈现出类似淤泥的中孔。在确定BVO和羧化反应的优先顺序时，对参数的影响评估表明顺序为底物>氧化剂>溶剂>催化剂。环状脂肪酮适用于BVO，而直链脂肪醛和芳香醛适用于羧化反应。（）-联萘酚的配位或Sn掺杂到催化剂中对在间氯过氧苯甲酸（-CPBA）作用下的BVO影响较小，但Sn掺杂的催化剂在硫酸铵（(NH)SO）和过氧化氢（HO）作用下大幅提高了BVO的效率。计算表明，同时含有Al和Sn的催化剂能使BVO中间体的能量低于Sn-β沸石模型。本体系具有底物范围更广、催化金属无毒、氧化剂更绿色以及催化剂成本更低等优点。
