| Ru@G-CS催化剂的制备及在对苯二甲酸二甲酯加氢反应中的应用 |
| Preparation and application in the hydrogenation of dimethyl terephthalate of Ru@G-CS catalyst |
| 作者 | 单位 | E-mail | | 王彩丽 | 浙江大学化学系, 生物质化工教育部重点实验室, 杭州 310058 | | | 叶柏镛 | 浙江大学化学系, 生物质化工教育部重点实验室, 杭州 310058 | | | 王韩 | 浙江恒逸石化研究院有限公司, 杭州 311200 | | | 王松林 | 浙江恒逸石化研究院有限公司, 杭州 311200 | | | 杨磊 | 浙江恒逸石化研究院有限公司, 杭州 311200 | | | 侯昭胤 | 浙江大学化学系, 生物质化工教育部重点实验室, 杭州 310058
浙江恒逸石化研究院有限公司, 杭州 311200 | zyhou@zju.edu.cn |
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| 摘要: 采用一步热解法制备了一系列氮掺杂石墨烯包覆的Ru基催化剂（Ru@G-CS），并将该催化剂用于对苯二甲酸二甲酯（DMT）加氢制备1，4-环己烷二甲酸二甲酯（DMCD）的反应中。利用粉末X射线衍射、拉曼光谱、N2吸附-脱附、X射线光电子能谱、扫描电子显微镜和透射电子显微镜对催化剂的组成、结构和表面形貌进行了表征。实验发现： Ru@G-CS （1∶4）催化剂具有最高的活性和优异的稳定性，在160℃、2.5 MPa、mDMT/mRu=833的条件下，反应4 h后DMT的转化率可达100%，DMCD的选择性高于98.5%；且该催化剂的活性经10次循环使用后未见明显下降。表征结果表明，氮掺杂石墨烯骨架中的氮原子可以促进Ru的分散，而且与负载的Ru之间存在较强的相互作用，这种电子-结构的协同效应可能是Ru@G-CS （1∶4）催化剂表现出优异的活性和稳定性的主要原因。 |
| 关键词: 对苯二甲酸二甲酯 1,4-环己烷二甲酸二甲酯 加氢 石墨烯 Ru |
| 基金项目: 中央高校基本科研业务费专项资金（No.226-2022-00055）资助。 |
| Abstract: A series of nitrogen-doped graphene-coated Ru-based catalysts (Ru@G-CS) were prepared using glucose, melamine, and RuCl3 as raw materials in a facile one-step pyrolysis method at 700℃ with a varied mass ratio of glucose/melamine in feed. The composition, structure, and surface morphology of these catalysts were characterized with powder X-ray diffraction, Raman spectroscopy, N2 adsorption-desorption, X-ray photoelectron spectroscopy, scanning electron microscope, and transmission electron microscope. Characterization results showed that nitrogen in the graphene skeleton can promote the dispersion of Ru, and there was also a strong interaction between nitrogen and loaded Ru. Ru@G-CS(1:4) catalyst (with the mass ratio of glucose/melamine in feed was 1:4) possesses the highest surface area (429 m2·g-1), biggest pore volume (0.45 cm3·g-1) and highly dispersed Ru particles (about 1 nm) that encapsulated in 1-2 layered graphene film. At the same time, the detected wRu0/wRu4 + (73.6/26.4), ID/IG (1.30) and I2D/IG (0.32) reached their maximum in Ru@G-CS(1:4). These catalysts were tested in dimethyl terephthalate (DMT) hydrogenation to 1,4-cyclohexane dimethyl dicarboxylate (DMCD) under mild conditions and compared with those traditional carriers (HZSM-5, Al2O3, MgO, ZnO) supported Ru catalysts. Ru@G-CS(1:4) exhibited high activity and stability at 160℃, 2.5 MPa H2, mDMT/mRu=833, the detected conversion of DMT reached 100% and the selectivity of DMCD remained higher than 98.5% within 4 h. The calculated turnover frequency of each Ru was 233.4 h-1. More importantly, Ru@G-CS(1:4) could maintain its performance at least in 10 cycles. It was concluded that the electron-structure synergistic effect might be the main reason for the excellent activity and stability of Ru@G-CS(1:4). |
| Keywords: dimethyl terephthalate dimethyl 1,4-cyclohexanedicarboxylate hydrogenation graphene Ru |
| 投稿时间：2023-05-20 修订日期：2023-09-17 |
| 摘要点击次数: 1890 |
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| 王彩丽,叶柏镛,王韩,王松林,杨磊,侯昭胤.Ru@G-CS催化剂的制备及在对苯二甲酸二甲酯加氢反应中的应用[J].无机化学学报,2023,39(11):2091-2102. |
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