锌酞菁基多孔有机聚合物催化CO2与环氧化物的环加成反应
Zinc phthalocyanine-based porous organic polymer for cycloaddition reaction of carbon dioxide and epoxides
钟建交 1罗荣昌2
作者信息
- 1. 惠州凯美特气体有限公司,广东 惠州 516000
- 2. 广东工业大学 轻工化工学院,广东 广州 510006
- 折叠
摘要
以四氨基酞菁锌和均苯三甲醛为原料,通过席夫碱缩合反应,在溶剂热的条件下制备了锌酞菁基多孔有机聚合物(ZnPc-POP).采用FTIR、13CNMR、XPS、TEM和N2 吸附-脱附对其进行了表征,以环氧氯丙烷(ECH)和CO2的环加成反应为模型,以四丁基溴化铵(TBAB)为助催化剂,考察了ZnPc-POP的催化性能、循环使用性和其催化不同环氧化物的底物适用性,并对催化机理进行了探究.结果表明,ZnPc-POP具有丰富的介孔结构(孔容约为0.64 cm3/g,平均孔径约为20 nm)和大的比表面积(171.6 m2/g).ECH在100℃和1.0 MPa CO2条件下生成环状碳酸酯的选择性＞99%,产率为96%,转化频率(TOF)高达533.3 h-1.ZnPc-POP循环使用5次后,其催化活性无明显降低.ZnPc-POP催化不同环氧化物的环加成反应的选择性≥96%.环氧化物中三元环氧原子与ZnPc-POP的Lewis酸位点锌中心发生配位作用而被有效活化,助催化剂TBAB中Br-通过亲核进攻促进环氧化物开环,该双重活化环氧化物开环是CO2环加成反应的控速步骤.
Abstract
Zinc phthalocyanine-based porous organic polymer(denoted as ZnPc-POP)was prepared from Schiff-base condensation reaction of zinc tetraminophthalocyanine and 1,3,5-benzenetricarboxaldehyde under solvothermal conditions,and characterized by FTIR,13CNMR,XPS,TEM and N2 adsorption-desorption.The catalytic performance,recycling ability and substrate applicability of ZnPc-POP were evaluated via cycloaddition reaction of epichlorohydrin(ECH)and CO2 as model and tetrabutylammonium bromide(TBAB)as cocatalyst,and the catalytic mechanism was explored.The results showed that ZnPc-POP exhibited a structure with abundant mesopores(pore volume was about 0.64 cm3/g,average pore size was about 20 nm)and large specific surface area(171.6 m2/g).At 100℃and 1.0 MPa CO2,the selectivity of ECH to produce cyclic carbonate was>99%,the yield reached 96%,and the turnover frequency(TOF)was up to 533.3 h-1.ZnPc-POP showed no significant decrease in the catalytic activity after being recycled for 5 times.The selectivity of the cycloaddition reaction catalyzed by ZnPc-POP with different epoxides as substrates was greater than or equal to 96%.The ternary oxygen atom in the epoxide was activated effectively by coordination with the Lewis acidic zinc center of ZnPc-POP,and the bromine ion in the co-catalyst TBAB promoted the ring-opening of the epoxide through nucleophilic attack.This double activation of epoxide ring-opening was the rate-controlling step of CO2 cycloaddition reaction.
关键词
多孔有机聚合物/锌酞菁/CO2转化/环状碳酸酯/协同效应/催化技术Key words
porous organic polymers/zinc phthalocyanine/CO2 conversion/cyclic carbonates/synergistic effect/catalysis technology引用本文复制引用
基金项目
国家自然科学基金面上项目(21978056)
出版年
2024
NETL
NSTL
万方数据