多基团功能化氧化石墨烯协同催化CO2环加成反应
Synergistic Effects in Multi-group Functionalized Graphene Oxide for CO2 Cycloaddition Reaction
作者单位E-mail
兰东辉 湖南工程学院化学化工学院, 环境催化与废弃物再生化湖南省重点实验室, 湘潭 431000
南昌航空大学, 江西省持久性污染物控制与资源循环利用重点实验室, 南昌 330063 
donghuilan@hnu.edu.cn 
唐婷 湖南工程学院化学化工学院, 环境催化与废弃物再生化湖南省重点实验室, 湘潭 431000  
代威力 南昌航空大学, 江西省持久性污染物控制与资源循环利用重点实验室, 南昌 330063  
谭年元 湖南工程学院化学化工学院, 环境催化与废弃物再生化湖南省重点实验室, 湘潭 431000  
伍水生 湖南工程学院化学化工学院, 环境催化与废弃物再生化湖南省重点实验室, 湘潭 431000  
区泽堂 湖南工程学院化学化工学院, 环境催化与废弃物再生化湖南省重点实验室, 湘潭 431000 pctau@hkbu.edu.hk 
易兵 湖南工程学院化学化工学院, 环境催化与废弃物再生化湖南省重点实验室, 湘潭 431000 bingyi2004@126.com 
摘要: 基于氢键给体、阴离子和胺协同催化CO2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2.49 mmol·g-1。F-GO在无溶剂和无助剂条件下可高效催化CO2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。
关键词: 催化  环加成  氧化石墨烯  功能化  二氧化碳  协同
基金项目: 湖南省自然科学基金(No.2018JJ3099)、江西省持久性污染物控制与资源循环利用重点实验室开放基金(No.ES201880047)、国家自然科学基金(No.21772035)和湖南省环境催化与废弃物再生化重点实验室(湖南工程学院)开放基金资助项目
Abstract: Based on the synergetic effects among hydrogen bond donors, halide anions and suitable amines for the CO2 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 non-toxic, 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 CO2 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 CO2 cycloaddition reaction over F-GO. In addition, F-GO is a water-tolerant and stable catalyst for the cycloaddition reaction, and there was no significant loss of catalytic activity after six runs.
Keywords: catalysis  cycloaddition  graphene oxide  functional  carbon dioxide  synergistic
投稿时间:2018-10-12 修订日期:2018-12-24
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兰东辉,唐婷,代威力,谭年元,伍水生,区泽堂,易兵.多基团功能化氧化石墨烯协同催化CO2环加成反应[J].无机化学学报,2019,35(3):442-448.
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