Journal Home > Volume 14 , Issue 4
Nano Research 2021, 14(4): 1018-1025 https://doi.org/10.1007/s12274-020-3144-7
Research Article | Issue | Published: 17 October 2020

β-Cyclodextrin polymer networks stabilized gold nanoparticle with superior catalytic activities

Show Author's Information Yong Zhang1,§( ),  Bing Hu1,§,  Xiao-Mei Cao1,  Liang Luo1,  Yu Xiong3,  Zhi-Peng Wang2,  Xin Hong1,  San-Yuan Ding2( )
Key Laboratory of Organo-pharmaceutical Chemistry, Gannan Normal University, College of Chemistry and Chemical Engineering, Ganzhou 341000, China
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
Department of Chemistry, Tsinghua University, Beijing 100084, China

§ Yong Zhang and Bing Hu contributed equally to this work.

Keywords:
β-cyclodextrin polymer, Au nanoparticles, superior catalytic activity, 4-nitrophenol reduction
Topics:
Gold nanoparticlesMetal nanoparticlesNanocatalysts
Cite this article:
Zhang Y, Hu B, Cao X-M, et al. β-Cyclodextrin polymer networks stabilized gold nanoparticle with superior catalytic activities. Nano Research, 2021, 14(4): 1018-1025. https://doi.org/10.1007/s12274-020-3144-7
Download citation
EndNote(RIS)
BibTeX

715

Views

21

Downloads

Citations

14

Crossref

N/A

WoS

15

Scopus

3

CSCD

Abstract Full text Electronic supplementary material About this article

Support materials play a significant role in heterogeneous nanocatalysis. In this work, β-cyclodextrin (β-CD) was used directly as a monomer to construct polymer networks for gold nanoparticles (Au NPs) immobilization. Using the simple nucleophilic substitution reaction, β-CD based polymer networks (β-CDP-N and β-CDP-C) were successfully prepared. Compared to β-CDP-C, the hydroxyl groups and N atoms in β-CDP-N played a synergistic role in immobilizing smaller Au NPs, thus leading to high catalytic activities. Notably, the apparent rate constant (Kapp) value for Au@β-CDP-N in the reduction of 4-nitrophenol to 4-aminophenol is 14.15 × 10−2 s−1, which shows a significant improvement over all previously reported Au NPs with solid supports under similar conditions. Considering the negligible porosity of the β-CDP-N support, we purposed a "capture-catalysis-release" model to explain the high catalytic activity of Au@β-CDP-N. This explanation is supported by the guest-responsive properties of β-CDP-N. Moreover, the Au@β-CDP-N is easily recycled and maintained its high catalytic efficiency after seven successful cycles.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

β-Cyclodextrin polymer networks stabilized gold nanoparticle with superior catalytic activities

Show Author's information Yong Zhang1,§( ), Bing Hu1,§, Xiao-Mei Cao1, Liang Luo1, Yu Xiong3, Zhi-Peng Wang2, Xin Hong1, San-Yuan Ding2( )
Key Laboratory of Organo-pharmaceutical Chemistry, Gannan Normal University, College of Chemistry and Chemical Engineering, Ganzhou 341000, China
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
Department of Chemistry, Tsinghua University, Beijing 100084, China

§ Yong Zhang and Bing Hu contributed equally to this work.

Abstract

Support materials play a significant role in heterogeneous nanocatalysis. In this work, β-cyclodextrin (β-CD) was used directly as a monomer to construct polymer networks for gold nanoparticles (Au NPs) immobilization. Using the simple nucleophilic substitution reaction, β-CD based polymer networks (β-CDP-N and β-CDP-C) were successfully prepared. Compared to β-CDP-C, the hydroxyl groups and N atoms in β-CDP-N played a synergistic role in immobilizing smaller Au NPs, thus leading to high catalytic activities. Notably, the apparent rate constant (Kapp) value for Au@β-CDP-N in the reduction of 4-nitrophenol to 4-aminophenol is 14.15 × 10−2 s−1, which shows a significant improvement over all previously reported Au NPs with solid supports under similar conditions. Considering the negligible porosity of the β-CDP-N support, we purposed a "capture-catalysis-release" model to explain the high catalytic activity of Au@β-CDP-N. This explanation is supported by the guest-responsive properties of β-CDP-N. Moreover, the Au@β-CDP-N is easily recycled and maintained its high catalytic efficiency after seven successful cycles.

Keywords: β-cyclodextrin polymer, Au nanoparticles, superior catalytic activity, 4-nitrophenol reduction

References(63)

[1]
E. Gross,; G. A. Somorjai, Mesoscale nanostructures as a bridge between homogeneous and heterogeneous catalysis. Top. Catal. 2014, 57, 812-821.
DOI Google Scholar
[2]
F. Zaera, Nanostructured materials for applications in heterogeneous catalysis. Chem. Soc. Rev. 2013, 42, 2746-2762.
DOI Google Scholar
[3]
W. J. Stark,; P. R. Stoessel,; W. Wohlleben,; A. Hafner, Industrial applications of nanoparticles. Chem. Soc. Rev. 2015, 44, 5793-5805.
DOI Google Scholar
[4]
L. C. Liu,; A. Corma, Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981-5079.
DOI Google Scholar
[5]
Z. Li,; S. F. Ji,; Y. W. Liu,; X. Cao,; S. B. Tian,; Y. J. Chen,; Z. Q. Niu,; Y. D. Li, Well-defined materials for heterogeneous catalysis: From nanoparticles to isolated single-atom sites. Chem. Rev. 2020, 120, 623-682.
DOI Google Scholar
[6]
S. B. Tian,; M. Hu,; Q. Xu,; W. B. Gong,; W. X. Chen,; J. R. Yang,; Y. R. Zhu,; C. Chen,; J. He,; Q. Liu, et al. Single-atom Fe with Fe1N3 structure showing superior performances for both hydrogenation and transfer hydrogenation of nitrobenzene. Sci. China Mater., in press, .
DOI Google Scholar
[7]
M. Zahmakıran,; S. Özkar, Metal nanoparticles in liquid phase catalysis; from recent advances to future goals. Nanoscale 2011, 3, 3462-3481.
DOI Google Scholar
[8]
S. Schauermann,; N. Nilius,; S. Shaikhutdinov,; H. J. Freund, Nanoparticles for heterogeneous catalysis: New mechanistic insights. Acc. Chem. Res. 2013, 46, 1673-1681.
DOI Google Scholar
[9]
R. J. White,; R. Luque,; V. L. Budarin,; J. H. Clark,; D. J. Macquarrie, Supported metal nanoparticles on porous materials. Methods and applications. Chem. Soc. Rev. 2009, 38, 481-494.
DOI Google Scholar
[10]
S. Navalon,; A. Dhakshinamoorthy,; M. Alvaro,; H. Garcia, Metal nanoparticles supported on two-dimensional graphenes as heterogeneous catalysts. Coord. Chem. Rev. 2016, 312, 99-148.
DOI Google Scholar
[11]
J. Zhang,; C. Y. Zheng,; M. L. Zhang,; Y. J. Qiu,; Q. Xu,; W. C. Cheong,; W. X. Chen,; L. R. Zheng,; L. Gu,; Z. P. Hu, et al. Controlling N-doping type in carbon to boost single-atom site Cu catalyzed transfer hydrogenation of quinoline. Nano Res. 2020, 13, 3082-3087 .
DOI Google Scholar
[12]
S. L. Xu,; S. C. Shen,; Z. Y. Wei,; S. Zhao,; L. J. Zuo,; M. X. Chen,; L. Wang,; Y. W. Ding,; P. Chen,; S. Q. Chu, et al. A library of carbon- supported ultrasmall bimetallic nanoparticles. Nano Res. 2020, 13, 2735-2740.
DOI Google Scholar
[13]
L. Shang,; T. Bian,; B. H. Zhang,; D. H. Zhang,; L. Z. Wu,; C. H. Tung,; Y. D. Yin,; T. R. Zhang, Graphene-supported ultrafine metal nanoparticles encapsulated by mesoporous silica: Robust catalysts for oxidation and reduction reactions. Angew. Chem., Int. Ed. 2014, 53, 250-254.
DOI Google Scholar
[14]
C. T. Wang,; L. Wang,; J. Zhang,; H. Wang,; J. P. Lewis,; F. S. Xiao, Product selectivity controlled by zeolite crystals in biomass hydrogenation over a palladium catalyst. J. Am. Chem. Soc. 2016, 138, 7880-7883.
DOI Google Scholar
[15]
A. Dhakshinamoorthy,; A. M. Asiri,; H. Garcia, Metal organic frameworks as versatile hosts of Au nanoparticles in heterogeneous catalysis. ACS Catal. 2017, 7, 2896-2919.
DOI Google Scholar
[16]
Q. H. Yang,; Q. Xu,; H. L. Jiang, Metal-organic frameworks meet metal nanoparticles: Synergistic effect for enhanced catalysis. Chem. Soc. Rev. 2017, 46, 4774-4808.
DOI Google Scholar
[17]
G. D. Li,; S. L. Zhao,; Y. Zhang,; Z. Y. Tang, Metal-organic frameworks encapsulating active nanoparticles as emerging composites for catalysis: Recent progress and perspectives. Adv. Mater. 2018, 30, 1800702.
DOI Google Scholar
[18]
S. F. Ji,; Y. J. Chen,; S. Zhao,; W. X. Chen,; L. J. Shi,; Y. Wang,; J. C. Dong,; Z. Li,; F. W. Li,; C. Chen, et al. Atomically dispersed ruthenium species inside metal-organic frameworks: Combining the high activity of atomic sites and the molecular sieving effect of MOFs. Angew. Chem., Int. Ed. 2019, 58, 4271-4275.
DOI Google Scholar
[19]
Y. G. Zhang,; S. N. Riduan, Functional porous organic polymers for heterogeneous catalysis. Chem. Soc. Rev. 2012, 41, 2083-2094.
DOI Google Scholar
[20]
S. Y. Ding,; W. Wang, Covalent organic frameworks (COFs): From design to applications. Chem. Soc. Rev. 2013, 42, 548-568.
DOI Google Scholar
[21]
J. S. M. Lee,; A. I. Cooper, Advances in conjugated microporous polymers. Chem. Rev. 2020, 120, 2171-2214.
DOI Google Scholar
[22]
D. J. Cram,; J. M. Cram, Host-guest chemistry. Science 1974, 183, 803-809.
DOI Google Scholar
[23]
G. A. Petsko,; D. Ringe, Protein Structure and Function; New Science Press: Sunderland, MA, 2004.
[24]
X. Y. Zhang,; K. N. Houk, Why enzymes are proficient catalysts: Beyond the Pauling paradigm. Acc. Chem. Res. 2005, 38, 379-385.
DOI Google Scholar
[25]
C. J. Brown,; F. D. Toste,; R. G. Bergman,; K. N. Raymond, Supramolecular catalysis in metal-ligand cluster hosts. Chem. Rev. 2015, 115, 3012-3035.
DOI Google Scholar
[26]
C. M. Hong,; R. G. Bergman,; K. N. Raymond,; F. D. Toste, Self- assembled tetrahedral hosts as supramolecular catalysts. Acc. Chem. Res. 2018, 51, 2447-2455.
DOI Google Scholar
[27]
K. I. Assaf,; W. M. Nau, Cucurbiturils: From synthesis to high- affinity binding and catalysis. Chem. Soc. Rev. 2015, 44, 394-418.
DOI Google Scholar
[28]
J. Meeuwissen,; J. N. H. Reek, Supramolecular catalysis beyond enzyme mimics. Nat. Chem. 2010, 2, 615-621.
DOI Google Scholar
[29]
D. Y. Xia,; P. Wang,; X. F. Ji,; N. M. Khashab,; J. L. Sessler,; F. H. Huang, Functional supramolecular polymeric networks: The marriage of covalent polymers and macrocycle-based host-guest interactions. Chem. Rev. 2020, 120, 6070-6123.
DOI Google Scholar
[30]
A. Alsbaiee,; B. J. Smith,; L. L. Xiao,; Y. H. Ling,; D. E. Helbling,; W. R. Dichtel, Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer. Nature 2016, 529, 190-194.
DOI Google Scholar
[31]
H. Y. Li,; B. Meng,; S. H. Chai,; H. L. Liu,; S. Dai, Hyper-crosslinked β-cyclodextrin porous polymer: An adsorption-facilitated molecular catalyst support for transformation of water-soluble aromatic molecules. Chem. Sci. 2016, 7, 905-909.
DOI Google Scholar
[32]
S. N. Talapaneni,; D. Kim,; G. Barin,; O. Buyukcakir,; S. H. Je,; A. Coskun, Pillar[5]arene based conjugated microporous polymers for propane/methane separation through host-guest complexation. Chem. Mater. 2016, 28, 4460-4466.
DOI Google Scholar
[33]
D. Shetty,; I. Jahovic,; J. Raya,; F. Ravaux,; M. Jouiad,; J. C. Olsen,; A. Trabolsi, An ultra-absorbent alkyne-rich porous covalent polycalix[4]arene for water purification. J. Mater. Chem. A 2017, 5, 62-66.
DOI Google Scholar
[34]
K. Z. Su,; W. J. Wang,; B. B. Li,; D. Q. Yuan, Azo-bridged calix[4] resorcinarene-based porous organic frameworks with highly efficient enrichment of volatile iodine. ACS Sustainable Chem. Eng. 2018, 6, 17402-17409.
DOI Google Scholar
[35]
H. S. Yang,; Y. Du,; S. Wan,; G. D. Trahan,; Y. H. Jin,; W. Zhang, Mesoporous 2D covalent organic frameworks based on shape- persistent arylene-ethynylene macrocycles. Chem. Sci. 2015, 6, 4049-4053.
DOI Google Scholar
[36]
A. Giri,; W. Hussain,; B. SK,; A. Patra, Connecting the dots: Knitting C-phenylresorcin[4] arenes with aromatic linkers for task-specific porous organic polymers. Chem. Mater. 2019, 31, 8440-8450.
DOI Google Scholar
[37]
L. P. Skala,; A. N. Yang,; M. J. Klemes,; L. L. Xiao,; W. R. Dichtel, Resorcinarene cavitand polymers for the remediation of halomethanes and 1,4-dioxane. J. Am. Chem. Soc. 2019, 141, 13315-13319.
DOI Google Scholar
[38]
W. Gong,; Q. Q. Wu,; G. X. Jiang,; G. J. Li, Ultrafine silver nanoparticles supported on a covalent carbazole framework as high-efficiency nanocatalysts for nitrophenol reduction. J. Mater. Chem. A 2019, 7, 13449-13454.
DOI Google Scholar
[39]
J. Szejtli, Introduction and general overview of cyclodextrin chemistry. Chem. Rev. 1998, 98, 1743-1754.
DOI Google Scholar
[40]
A. R. Hedges, Industrial applications of cyclodextrins. Chem. Rev. 1998, 98, 2035-2044.
DOI Google Scholar
[41]
E. M. M. Del Valle, Cyclodextrins and their uses: A review. Process Biochem. 2004, 39, 1033-1046.
DOI Google Scholar
[42]
N. Szaniszló,; É. Fenyvesi,; J. Balla, Structure-stability study of cyclodextrin complexes with selected volatile hydrocarbon contaminants of soils. J. Incl. Phenom. Macrocycl. Chem. 2005, 53, 241-248.
DOI Google Scholar
[43]
M. Sankar,; Q. He,; R. V. Engel,; M. A. Sainna,; A. J. Logsdail,; J. A. Roldan,; D. J. Willock,; N. Agarwal,; C. J. Kiely,; G. J. Hutchings, Role of the support in gold-containing nanoparticles as heterogeneous catalysts. Chem. Rev. 2020, 120, 3890-3938.
DOI Google Scholar
[44]
A. Corma,; H. Garcia, Supported gold nanoparticles as catalysts for organic reactions. Chem. Soc. Rev. 2008, 37, 2096-2126.
DOI Google Scholar
[45]
H. L. Jiang,; T. Akita,; T. Ishida,; M. Haruta,; Q. Xu, Synergistic catalysis of Au@Ag core-shell nanoparticles stabilized on metal- organic framework. J. Am. Chem. Soc. 2011, 133, 1304-1306.
DOI Google Scholar
[46]
Q. Yue,; Y. Zhang,; C. Wang,; X. Q. Wang,; Z. K. Sun,; X. F. Hou,; D. Y. Zhao,; Y. H. Deng, Magnetic yolk-shell mesoporous silica microspheres with supported Au nanoparticles as recyclable high- performance nanocatalysts. J. Mater. Chem. A 2015, 3, 4586-4594.
DOI Google Scholar
[47]
P. Zhang,; C. J. Chen,; X. C. Kang,; L. J. Zhang,; C. Y. Wu,; J. L. Zhang,; B. X. Han, In situ synthesis of sub-nanometer metal particles on hierarchically porous metal-organic frameworks via interfacial control for highly efficient catalysis. Chem. Sci. 2018, 9, 1339-1343.
DOI Google Scholar
[48]
T. Ishida,; N. Kinoshita,; H. Okatsu,; T. Akita,; T. Takei,; M. Haruta, Influence of the support and the size of gold clusters on catalytic activity for glucose oxidation. Angew. Chem., Int. Ed. 2008, 47, 9265-9268.
DOI Google Scholar
[49]
J. He,; S. Razzaque,; S. B. Jin,; I. Hussain,; B. E. Tan, Efficient synthesis of ultrafine gold nanoparticles with tunable sizes in a hyper-cross-linked polymer for nitrophenol reduction. ACS Appl. Nano Mater. 2019, 2, 546-553.
DOI Google Scholar
[50]
J. Wang,; A. H. Liu,; M. R. Li,; W. P. Zhang,; Y. S. Chen,; D. X. Tian,; W. C. Li, Thin porous alumina sheets as supports for stabilizing gold nanoparticles. ACS Nano 2013, 7, 4902-4910.
DOI Google Scholar
[51]
Y. Huang,; Y. Fang,; L. Y. Chen,; A. Lu,; L. N. Zhang, One-step synthesis of size-tunable gold nanoparticles immobilized on chitin nanofibrils via green pathway and their potential applications. Chem. Eng. J. 2017, 315, 573-582.
DOI Google Scholar
[52]
A. T. Ezhil Vilian,; R. Sivakumar,; Y. S. Huh,; J. H. Youk,; Y. K. Han, Palladium supported on an amphiphilic triazine-urea-functionalized porous organic polymer as a highly efficient electrocatalyst for electrochemical sensing of rutin in human plasma. ACS Appl. Mater. Interfaces 2018, 10, 19554-19563.
DOI Google Scholar
[53]
C. Y. Zhou,; C. Lai,; D. L. Huang,; G. M. Zeng,; C. Zhang,; M. Cheng,; L. Hu,; J. Wan,; W. P. Xiong,; M. Wen, et al. Highly porous carbon nitride by supramolecular preassembly of monomers for photocatalytic removal of sulfamethazine under visible light driven. Appl. Catal. B Environ. 2018, 220, 202-210.
DOI Google Scholar
[54]
P. Hervés,; M. Pérez-Lorenzo,; L. M. Liz-Marzán,; J. Dzubiella,; Y. Lu,; M. Ballauff, Catalysis by metallic nanoparticles in aqueous solution: Model reactions. Chem. Soc. Rev. 2012, 41, 5577-5587.
DOI Google Scholar
[55]
G. F. Liao,; Y. Gong,; L. Zhong,; J. S. Fang,; L. Zhang,; Z. S. Xu,; H. Y. Gao,; B. Z. Fang, Unlocking the door to highly efficient Ag-based nanoparticles catalysts for NaBH4-assisted nitrophenol reduction. Nano Res. 2019, 12, 2407-2436.
DOI Google Scholar
[56]
Y. T. Yang,; T. N. Wang,; X. F. Jing,; G. S. Zhu, Phosphine-based porous aromatic frameworks for gold nanoparticle immobilization with superior catalytic activities. J. Mater. Chem. A 2019, 7, 10004-10009.
DOI Google Scholar
[57]
Y. K. Fu,; L. Qin,; D. L. Huang,; G. M. Zeng,; C. Lai,; B. S. Li,; J. F. He,; H. Yi,; M. M. Zhang,; M. Cheng, et al. Chitosan functionalized activated coke for Au nanoparticles anchoring: Green synthesis and catalytic activities in hydrogenation of nitrophenols and azo dyes. Appl. Catal. B Environ. 2019, 255, 117740.
DOI Google Scholar
[58]
L. L. Yang,; H. J. Wang,; J. Wang,; Y. Li,; W. Zhang,; T. B. Lu, A graphdiyne-based carbon material for electroless deposition and stabilization of sub-nanometric Pd catalysts with extremely high catalytic activity. J. Mater. Chem. A 2019, 7, 13142-13148.
DOI Google Scholar
[59]
T. B. Nguyen,; C. P. Huang,; R. A. Doong, Enhanced catalytic reduction of nitrophenols by sodium borohydride over highly recyclable Au@graphitic carbon nitride nanocomposites. Appl. Catal. B Environ. 2019, 240, 337-347.
DOI Google Scholar
[60]
H. X. Fu,; Z. H. Zhang,; W. H. Fan,; S. F. Wang,; Y. Liu,; M. H. Huang, A soluble porous organic polymer for highly efficient organic- aqueous biphasic catalysis and convenient reuse of catalysts. J. Mater. Chem. A 2019, 7, 15048-15053.
DOI Google Scholar
[61]
P. T. Huang,; Y. N. Chen,; K. C. Chen,; S. H. Wu,; C. P. Liu, Confinement of silver nanoparticles in polystyrenes through molecular entanglements and their application for catalytic reduction of 4-nitrophenol. J. Mater. Chem. A 2019, 7, 20919-20925.
DOI Google Scholar
[62]
P. An,; R. Anumula,; C. N. Cui,; Y. Liu,; F. Zhan,; Y. Tao,; Z. X. Luo, A facile method to synthesize water-soluble Pd8 nanoclusters unraveling the catalytic mechanism of p-nitrophenol to p-aminophenol. Nano Res. 2019, 12, 2589-2596.
DOI Google Scholar
[63]
K. Wu,; X. Y. Wang,; L. L. Guo,; Y. J. Xu,; L. Zhou,; Z. Y. Lyu,; K. Y. Liu,; R. Si,; Y. W. Zhang,; L. D. Sun, et al. Facile synthesis of Au embedded CuOx-CeO2 core/shell nanospheres as highly reactive and sinter-resistant catalysts for catalytic hydrogenation of p-nitrophenol. Nano Res. 2020, 13, 2044-2055.
DOI Google Scholar
File
12274_2020_3144_MOESM1_ESM.pdf (3.2 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 18 August 2020
Revised: 19 September 2020
Accepted: 24 September 2020
Published: 17 October 2020
Issue date: April 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature

Acknowledgements

The authors thank the National Natural Science Foundation of China (Nos. 21865003 and 21562003), China Postdoctoral Science Foundation (No. 2018M640114), National Undergraduate Training Programs for Innovation and Entrepreneurship (No. 201910418003) and the Gannan Normal University Innovation Fund (No. YCX19A002) for generous support.

Return