多基团功能化氧化石墨烯协同催化CO_2环加成反应
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摘要
基于氢键给体、阴离子和胺协同催化CO_2环加成反应的设计思想,以廉价、无毒、富含三级胺的六次甲基四胺为前驱体,采用原位固载的方法制得了硅羟基、季铵盐和三级胺功能化的氧化石墨烯(GO)。随后,利用正溴丁烷进一步季铵化合成多阳离子季铵盐功能化的GO(F-GO)无金属多相催化剂。采用红外光谱、元素分析和光电子能谱分析了催化剂表面的组成和含量,证明多阳离子化的策略有利于提高GO表面离子液体的固载量,所制备的F-GO表面季铵盐和三级胺负载量分别为2.23和2.49mmol·g~(-1)。F-GO在无溶剂和无助剂条件下可高效催化CO_2和环氧丙烷环加成反应,碳酸丙烯酯收率可达99.2%(100℃,2 MPa,4 h)。此外,F-GO材料具有较好的耐水性和稳定性,循环6次后活性几乎不变。
Based on the synergetic effects among hydrogen bond donors, halide anions and suitable amines for the CO_2 cycloaddition reaction, the multi-functionalized graphene oxide(containing silanol group, quaternary ammonium salt and tertiary amine) were synthesized by a "in-situ approach". Hexamethylenetetramine that is nontoxic, cheap and rich in tertiary amine was used as precursor for quaternary ammonium salt. Then, further quaternization was conducted by adding halohydrocarbon for the formation of multi-cationic quaternary ammonium salt functionalized graphene oxide(F-GO) heterogeneous catalysts. As characterized by X-ray photoelectron spectroscopy and elemental analysis, the loading of quaternary ammonium salt and tertiary amine was up to 2.23 and 2.49 mmol·g~(-1), respectively. The "multi-cationic approach" is proved to be beneficial to improve the amount of ionic liquids and catalytic activity. The F-GO was used as metal-free heterogeneous catalyst for the synthesis of cyclic carbonates through the cycloaddition of CO_2 towards propylene epoxide under mild conditions without solvent and co-catalyst. The yield of propylene carbonate was up to 99.2%(100 ℃, 2 MPa, 4 h). The synergetic effects was investigated by comparing the catalytic activity of F-GO functionalized with different groups. A plausible mechanism was proposed for the CO_2 cycloaddition reaction over F-GO. In addition, F-GO is a watertolerant and stable catalyst for the cycloaddition reaction, and there was no significant loss of catalytic activity after six runs.
Based on the synergetic effects among hydrogen bond donors, halide anions and suitable amines for the CO_2 cycloaddition reaction, the multi-functionalized graphene oxide(containing silanol group, quaternary ammonium salt and tertiary amine) were synthesized by a "in-situ approach". Hexamethylenetetramine that is nontoxic, cheap and rich in tertiary amine was used as precursor for quaternary ammonium salt. Then, further quaternization was conducted by adding halohydrocarbon for the formation of multi-cationic quaternary ammonium salt functionalized graphene oxide(F-GO) heterogeneous catalysts. As characterized by X-ray photoelectron spectroscopy and elemental analysis, the loading of quaternary ammonium salt and tertiary amine was up to 2.23 and 2.49 mmol·g~(-1), respectively. The "multi-cationic approach" is proved to be beneficial to improve the amount of ionic liquids and catalytic activity. The F-GO was used as metal-free heterogeneous catalyst for the synthesis of cyclic carbonates through the cycloaddition of CO_2 towards propylene epoxide under mild conditions without solvent and co-catalyst. The yield of propylene carbonate was up to 99.2%(100 ℃, 2 MPa, 4 h). The synergetic effects was investigated by comparing the catalytic activity of F-GO functionalized with different groups. A plausible mechanism was proposed for the CO_2 cycloaddition reaction over F-GO. In addition, F-GO is a watertolerant and stable catalyst for the cycloaddition reaction, and there was no significant loss of catalytic activity after six runs.
引文
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[2] Lan D H, Au C T, Yin S F, et al. Chinese J. Catal., 2016,37(6):826-845
[3] Dai Z F, Meng X J, Xiao F S, et al. ChemSusChem, 2017,10:1186-1192
[4] Zhou Z, Yang L, Duan C Y, et al. J. Am. Chem. Soc., 2015,137:15066-15069
[5] Song Q W, Zhou Z H, He L N. Green Chem., 2017,19:3707-3728
[6] GU Wei(顾巍), YAN Ming(严铭), SHI Wei-Dong(施伟东),et al. Chinese J. Inorg. Chem.(无机化学学报), 2017,33(3):493-500
[7] Meng X L, Nie Y, Zhang S J, et al. ACS Sustainable Chem.Eng., 2017,5(4):3081-3086
[8] Xu B H, Wang J Q, Zhang S J, et al. Green Chem., 2015,17:108-122
[9] Xie Y, Zhang Z, Han B X, et al. Angew. Chem. Int. Ed.,2007,119:7393-7396
[10]Luo R C, Zhou X T, Ji H B, et al. Carbon, 2015,82:1-11
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[12]Lan D H, Au C T, Yin S F, et al. Carbon, 2015,93:22-31
[13]Zhang W H, He P P, Li Y X, et al. Appl. Catal. A, 2016,509:111-117
[14]Zhang F, Jiang H Y, Li X Y, et al. ACS Catal., 2014,4:394-401
[15]Lan D H, Au C T, Yin S F, et al. Carbon, 2016,100:81-89
[16]Zhang N, Yu B, Hu C W, et al. J. CO2Util., 2017,22:9-14
[17]Liu M S, Lan J W, Sun J M, et al. J. Catal., 2017,347:138-147
[18]Sun J, Cheng W G, Zhang S J, et al. Catal. Today, 2009,148:361-367
[19]Dai W L, Chen L, Yin S F, et al. Catal. Lett., 2010,135:295-304
[20]Yi Z Q, Au C T, Yin S F, et al. Sci. China Chem., 2017,60(7):990-996
[21]Wang L, Zhang G Y, Kodama K, et al. Green Chem., 2016,18:1229-1233
[22]Liu X F, Song Q W, Zhang S, et al. Catal. Today, 2016,263:69-74