基于超分子晶体制备超细铂纳米颗粒用于催化加氢硝基苯

doi:10.6023/A20090445

摘要/Abstract

由于纳米催化剂的独特催化活性, 因而开发稳定的超细纳米催化剂的制备方法引起了广大科研工作者们的关注. 然而, 复杂的合成过程和结构的不稳定性已经成为纳米催化剂研究和实际应用的瓶颈. 本工作通过原位还原氯铂酸和十甲基五元瓜环(Me₁₀CB[5])构筑的超分子晶体材料, 成功制备了粒径尺寸约为3.0 nm的超细铂纳米粒子. Me₁₀CB[5]的空间限域效应成功抑制铂纳米颗粒的团聚; 瓜环端口羰基氧与铂纳米粒子表面的相互作用防止铂纳米粒子脱落, 确保催化剂的高稳定性. 该铂纳米催化剂对于温和条件下催化加氢硝基苯反应具有优良的催化活性、高稳定性和高化学选择性. 这项工作为纳米催化剂的制备开辟了一条新途径, 为纳米催化剂在电化学、能源科学和环境保护等许多重要领域的应用提供了基础.

关键词: 超分子晶体, Pt纳米颗粒, 硝基芳烃, 催化加氢

The development of a general synthetic approach for stable ultrafine heterogeneous nanocatalysts has attracted extensive attentions worldwide. However, the complex synthetic process and structure unstability have been recognized as the bottleneck of their investigation and practical application. Herein, a convenient and high selective platinum nanocatalyst was developed based from crystalline supramolecular hybrid solid materials. The macrocyclic decamethylcucurbit[5]uril (Me₁₀CB[5]) and [PtCl₆]^2– anions were firstly self-assembled into cyrstalline supramolecular solid in the presence of different alkali metal ions (Li⁺, Na⁺, K⁺). Then, ultrafine platinum (Pt) nanoparticles (NPs) have been successfully synthesized through in-situ reduction of cyrstalline supramolecular assemblies under mild thermal treatment at H₂atmosphere. Uniform Pt NPs (ca.3.0 nm) are produced and deposited on Me₁₀CB[5] substrate to form M-Pt@Me₁₀CB[5] (M=Li⁺, Na⁺, K⁺) composite materials. The obtained Pt NPs are characterized extensively by a range of physical measurements including X-ray powder diffractions (PXRD), thermogravimetric analyses (TGA), inductively coupled plasma emission spectrometer (ICP), X-ray photoelectron spectroscopy (XPS) and transmission electron microscope (TEM). The morphology and size of Pt NPs can be easily tuned through changing the original supramolecular structures. The different interaction between [PtCl₆]^2– and Me₁₀CB[5] capsulates affects the morphology and size of Pt NPs greatly. Such differences in geometric structures of Pt NPs have a significant impact on their catalytic performance. Moreover, the unique confinement effect provided by the supramolecular assembly as well as the special steric effect offered by macrocyclic Me₁₀CB[5] suppresses the growth of Pt NPs during the reduction process. In addition, the atomic level uniform dispersion of Pt ions in ordered crystalline structure of the supramolecular assembly assures the uniform distribution of the final Pt NPs on the intact Me₁₀CB[5], which acts as both a stabilizer and support. The Pt NPs obtained from Na⁺ and K⁺ constructed supramolecular assemblies exhibit high activity and chemoselectivity in catalytic hydrogenation of substituted nitrobenzenes to corresponding anilines under mild conditions. Meanwhile, the final Pt NPs also show an excellent stability in recycle test without dramatic loss of activity. This work demonstrates a novel, high-performance catalyst for the chemoselective hydrogenation reaction, and opens up a new approach for the preparation of nanocatalysts, which can be used in many other important fields, such as electrochemistry, energy science and environmental protection.

Key words: supramolecular crystalline materials, Pt nanoparticles, nitroarenes, catalytic hydrogenation

引用此文

张晓萌, 李希雅, 熊晚枫, 李红芳, 曹荣. 基于超分子晶体制备超细铂纳米颗粒用于催化加氢硝基苯[J]. 化学学报, 2021, 79(2): 180-185.

Xiaomeng Zhang, Xiya Li, Wanfeng Xiong, Hongfang Li, Rong Cao. Ultrafine Platinum Nanoparticles Derived from Supramolecular Crystal for Catalytic Hydrogenation of Nitroarenes[J]. Acta Chimica Sinica, 2021, 79(2): 180-185.

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图/表 8

Figure 1. 超细Pt纳米颗粒制备流程图

. Schematic illustration of the fabrication of Pt nanoparticles

图2. 两种不同结构的一维链状超分子晶体

Figure 2. One-dimensional chain subunit of supramolecular crystallines

图3. M-Pt@Me10CB[5]复合材料的XRD图

Figure 3. The XRD patterns of the M-Pt@Me10CB[5] composites

图4. (a) Li-Pt@Me10CB[5], (b) Na-Pt@Me10CB[5]和(c) K-Pt@Me10CB[5]的透射电镜图, 相应内插图为Pt纳米颗粒的粒径分布图. (d) K-Pt@Me10CB[5]的能谱以及高分辨透射电镜和选区电子衍射图.

Figure 4. The TEM images of (a) Li-Pt@Me10CB[5], (b) Na-Pt@Me10CB[5] and (c) K-Pt@Me10CB[5]. The inset are the corresponding diameter distribution histogram of the Pt NPs. (d) EDS analysis, high-resolution TEM image and the SAED pattern of the Pt NPs denoted in (c)

图5. K-Pt@Me10CB[5]中Pt 4f光电子能谱图

Figure 5. XPS spectra of Pt 4f in K-Pt@Me10CB[5]

Entry	Catalyst	Pt (mol%)	Solvent	Time/h	Yield/%
1	Blank	0	Ethanol	1.0	Trace
2	K-Pt@Me₁₀CB[5]	0.05	Ethanol	1.0	2.04
3	K-Pt@Me₁₀CB[5]	0.1	Ethanol	1.0	4.4
4	K-Pt@Me₁₀CB[5]	0.3	Ethanol	1.0	31.5
5	K-Pt@Me₁₀CB[5]	0.5	Ethanol	1.0	65.7
6	K-Pt@Me₁₀CB[5]	1.0	Ethanol	1.0	100
7	K-Pt@Me₁₀CB[5]	0.5	Ethanol	1.5	98.2
8	K-Pt@Me₁₀CB[5]	0.5	Ethanol	2.0	100
9	Li-Pt@Me₁₀CB[5]	0.5	Ethanol	1.5	74.9
10	Na-Pt@Me₁₀CB[5]	0.5	Ethanol	1.5	98.9

表1. 超细Pt纳米颗粒催化加氢硝基苯

Table 1. Hydrogenation of nitrobenzene to aniline catalyzed by ultra-small Pt nanoparticles

图6. (a) 催化剂循环稳定性测试和(b) 5次循环使用后Pt纳米颗粒的TEM图

Figure 6. (a) The reusability of catalysts in hydrogenation of nitrobenzene and (b) TEM image for K-Pt@Me10CB[5] after fifth recycles catalysis

Entry	t/h	Con.^b/%	Sel./%
1	2.0	>99	>99
2	2.0	>99	>99
3	1.5	>99	>99
4	2.0	>99	>99
5	2.0	>99	>99
6 ^c	5.0	>99	>94
7 ^d	2.0	>99	85

表2. K-Pt@Me10CB[5]催化不同的芳香硝基化合物

Table 2. Reduction of various nitroarenes catalyzed by K-Pt@Me10CB[5]a

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