Ultrafine Platinum Nanoparticles Derived from Supramolecular Crystal for Catalytic Hydrogenation of Nitroarenes

doi:10.6023/A20090445

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (2): 180-185.DOI: 10.6023/A20090445 Previous Articles Next Articles

Article

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

张晓萌^a, 李希雅^a, 熊晚枫^b, 李红芳^a^,^b^,^*(), 曹荣^a^,^b

a 福州大学化学学院福州 350108
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002

投稿日期:2020-09-24 发布日期:2020-10-27
通讯作者: 李红芳
作者简介:
* E-mail: hongfangli@fjirsm.ac.cn
基金资助:
国家自然科学基金(21520102001); 中国科学院前沿科学重点项目(QYZDJ-SSW-SLH045)

Ultrafine Platinum Nanoparticles Derived from Supramolecular Crystal for Catalytic Hydrogenation of Nitroarenes

Xiaomeng Zhang^a, Xiya Li^a, Wanfeng Xiong^b, Hongfang Li^a^,^b^,^*(), Rong Cao^a^,^b

a College of Chemistry, Fuzhou University, Fuzhou 350108, China
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Received:2020-09-24 Published:2020-10-27
Contact: Hongfang Li
Supported by:
National Natural Science Foundation of China (NSFC)(21520102001); Key Research Program of Frontier Science, Chinese Academy of Sciences(QYZDJ-SSW-SLH045)

1. Supporting Information-A20090445.pdf(336KB)

Abstract

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

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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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Fig. & Tab. 8

. Schematic illustration of the fabrication of Pt nanoparticles

Figure 2. One-dimensional chain subunit of supramolecular crystallines

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

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)

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

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

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

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

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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

Ultrafine Platinum Nanoparticles Derived from Supramolecular Crystal for Catalytic Hydrogenation of Nitroarenes

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