An Improved Method for the Complete Hydrogenation of Aromatic Compounds under 1 Bar H2 with Platinum Nanowires
An Improved Method for the Complete Hydrogenation of Aromatic Compounds under 1 Bar H2 with Platinum Nanowires
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DOI：
10.1002/cctc.201300394
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发表时间：
2013-10
期刊：
影响因子：
4.5
通讯作者：
Tingting Yu;Jiaqing Wang;Xinming Li;Xueqin Cao;H. Gu
中科院分区：
文献类型：
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作者：
Tingting Yu;Jiaqing Wang;Xinming Li;Xueqin Cao;H. Gu
芳香族化合物的催化氢化形成环己烷衍生物代表了化学的一般合成和工业领域中的具有挑战性的研究领域。尽管用于氢解的均相催化剂的开发最近取得了进展，但非均相体系的性质通常被认为是更有利和良性的，包括其较低的成本、操作简单性以及易于分离和可再循环性。因此，非均相催化剂已用于广泛的工业应用中，包括药物、农用化学品、精细化学品、调味剂、香料和膳食补充剂的生产。然而，由于缺乏活性催化剂，使用目前的钯、钌和铑金属催化剂的芳族化合物的完全氢化仍然需要使用危险的反应条件（即高H2压力）和高能途径（>100 ℃）。工业应用尤其需要高产率、高水平的选择性和生产率、低成本以及安全和环境友好的方法以及其他技术因素。在催化氢化过程中使用定义明确的金属纳米结构材料最近已成为快速增长的研究领域，并且许多研究致力于开发用于芳族化合物和烯烃的氢化以及用于分子物种不催化或催化不良的反应的有效和选择性催化剂。例如，Somorjai和Yang报道了使用铂纳米晶体催化氢化吡咯，并发现活性和选择性严重依赖于纳米晶体的尺寸和形状。Han等人[11]用钯纳米晶体也报道了类似的现象。Gu等人报道了用一维铂纳米线（Pt NW）直接催化氢化硝基芳族化合物，以及羰基化合物与芳族硝基化合物的偶联或在IMPa的初始氢气压力下氢化芳族化合物。因此，开发一种简单、绿色且有效的芳族化合物氢化方法仍然是化学工业相当感兴趣的，并且对合成化学家来说是一个重大挑战。在此，我们报告了一种新的，有效的，方便的，和环境友好的方法来合成环己烷衍生物从相应的芳香族化合物，使用铂纳米线作为催化剂与刘易斯酸助催化剂（例如，AlCl 3）的发展。Pt纳米线催化剂是通过在空气气氛下对FePt纳米线进行酸蚀刻而获得的。（图1、图S1和
The catalytic hydrogenation of aromatic compounds to form cyclohexane derivatives represents a challenging area of research in both the general synthetic and industrial fields of chemistry. Despite recent progress in the development of homogeneous catalysts for hydrogenolysis, the properties of heterogeneous systems are generally considered to be more favorable and benign, including their lower cost, operational simplicity, and ease of separation and recyclability. Consequently, heterogeneous catalysts have been used in a broad range of industrial applications, including the production of pharmaceuticals, agrochemicals, fine chemicals, flavors, fragrances, and dietary supplements. The complete hydrogenation of aromatic compounds using current palladium, ruthenium, and rhodium metal catalysts, however, still requires the use of dangerous reaction conditions (i.e. high H2 pressures) and highly energetic pathways (>100 8C) because of the lack of active catalysts. Industrial applications in particular require high yields, high levels of selectivity and productivity, low costs, and safety and environmentally benign processes among other technical factors. The use of well-defined metal nanostructured materials in catalytic hydrogenation processes has recently become a rapidly growing area of research, and numerous studies have been devoted to the development of efficient and selective catalysts for the hydrogenation of aromatic compounds and olefins, as well as for reactions that are not catalyzed or are poorly catalyzed by molecular species. For example, Somorjai and Yang reported the catalytic hydrogenation of pyrrole using platinum nanocrystals and found that the activity and selectivity were heavily dependent on the size and shape of the nanocrystals. A similar phenomenon was also reported by Han et al. 11] with palladium nanocrystals. Gu et al. reported the direct catalytic hydrogenation of nitroaromatic compounds with one-dimensional platinum nanowires (Pt NWs), together with the coupling of carbonyl compounds with aromatic nitro compounds or the hydrogenation of aromatic compounds under 1 MPa of initial hydrogen pressure. The development of a simple, green, and efficient method for the hydrogenation of aromatic compounds is, therefore, still of considerable interest to the chemical industry and represents a significant challenge to synthetic chemists. Herein, we report the development of a novel, efficient, convenient, and environmentally benign approach to the synthesis of cyclohexane derivatives from the corresponding aromatic compounds using platinum nanowires as a catalyst in conjunction with a Lewis acid co-catalyst (e.g. , AlCl3). Pt NWs catalysts were obtained from the acidic etching of FePt NWs under an air atmosphere. (Figure 1, Figure S1 and