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Progress in Chemistry 2022, Vol. 34 Issue (9): 1911-1934 DOI: 10.7536/PC211101 Previous Articles   Next Articles

• Review •

Fabrication of Multifunctional Core-Shell Structured Nanoreactors and Their Catalytic Performances

Hao Chen, Xu Xu, Chaonan Jiao, Hao Yang, Jing Wang(), Yinxian Peng()   

  1. School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology,Zhenjiang 212100, China
  • Received: Revised: Online: Published:
  • Contact: *e-mail: wangjingalice@just.edu.cn (Jing Wang);pyxhx@just.edu.cn (Yinxian Peng)
  • About author:
    †These authors contributed equally to this work.
  • Supported by:
    Discharge Control of Ship Painting and Hazardous Waste Treatment Technology and Equipment Program of the Ministry of Industry and Information Technology of China(MC-202003-Z01-07); Postgraduate Research & Practice Innovation Program of Jiangsu Province(KYCX20_3151)
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With the development of nanotechnology, it has been possible to easily adjust the compositions, morphologies, and sizes of nanomaterials to control their properties. In order to endow nanomaterials with new functions and expand their applications in the fields of materials, chemistry, biology and medicine, it is very meaningful to develop new types of nanomaterials that can achieve multiple functions at the same time. One of the methods for obtaining multifunctional nanomaterials is achieved by coating the surface of simple nanoparticles with functional materials, and the resulting composite structure is called a core-shell structure. The core and shell of the core-shell structure can be composed of the same or different materials. By changing the compositions, structures and surface properties of the core and shell materials, the nanomaterials can be endowed with special optical, electrical, magnetic, catalytic, adsorption and biological activities. The hollow and yolk-shell structure can be formed by the controllable transformation of the core and the shell, in which the inner cavity can be used as a high-performance nanoreactor in various fields of catalysis. In this review, the design and application of core-shell structured nanoreactors with different structures in the field of catalysis are discussed, with emphases on the applications in catalytic degradation of dye pollutants, catalytic hydrogenation, catalytic oxidation, and catalytic cascade reactions. Finally, some prospects are put forward for the future research and development of multifunctional core-shell structured nanoreactors.

Contents

1 Introduction

2 Classification of core-shell structured nanoreactors

2.1 Traditional core-shell structure

2.2 Hollow core-shell structure

3 Application of core-shell nanoreactors in catalytic reactions

3.1 Catalytic degradation of dye pollutants

3.2 Catalytic hydrogenation

3.3 Catalytic oxidation

3.4 Catalytic cascade reaction

4 Conclusion and outlook

Key words: nanoreactor, catalysis, mesoporous silica, noble metal nanoparticles, transition metal oxide
Fig. 1 Various core-shell nanostructures. (a) Traditional core-shell nanostructure, (b) yolk-shell nanostructure formed by partial removal of shell, (c) yolk-shell nanostructure formed by partial removal of core
Fig.2 Various types of spherical core-shell structures. (a) Cores with single or multiple particles, (b) cores with different shapes, (c) shells of various types
Fig. 3 Other shapes of core-shell nanostructures, including (a) nanotubes, (b) nanocubes, (c) dodecahedrons, (d) nanorings
Table 1 Core-shell structured nanoreactors
Schematic diagram Structure Specialty
Core-shell Regular shape and stable performance
Yolk-shell Inner space facilitates the occurrence of various chemical reactions and inner core is easy to be functionalized
Multi-core yolk-shell Multiple small nano-sized catalyst particles in the shell are more advantageous than a relatively large nano-sized catalytic core
Mesoporous shell Very high specific surface area, regular pore structure, narrow pore size distribution, continuously adjustable pore size
Mesoporous multi-shell Pore size of the inner and outer shells is adjustable, which provides favorable conditions for shape-selective catalysis and helps to improve the selectivity
nanotube Large aspect ratio and surface area, the restricted space in the tube will increase the interaction between the substrate molecule and the active sites
Fig. 4 Some common hollow core-shell structures. (a, b) multiple cores single shell, (c) yolk-shell, (d) multi-core yolk-shell, (e) multi shells, (f) single core multi shells, (g, h) multi-cores/shells
Table 2 Core-shell structured nanoreactors for Fischer-Tropsch synthesis reaction
Catalyst Reaction conditions CO conversion
CO (%)		 Hydrocarbon selectivity (mol%) ref
H2/CO T(K) p(MPa) CH4 C2-4 C5+ C5-12 C13+
Ru-PVP@SiO2 YSNs 2.0 423 3.0 20 1.8 3.7 86.9 63.8 23.1 89
WOM-0.45-Ru@SiO2 2.0 483 2.0 25 4.1 13.4 82.7 16.7 66 90
Co@SiO2-5 2.0 513 2.0 30 11.2 9.6 78.7 / / 91
Fe3O4@MnO2@HZSM-5 1.0 593 4.0 69.3 4.0 15.6 80.4 80.4a 0b 92
CoRu@HCS 2.0 493 1.0 18.3 37 14 49 / / 93
Co@HCS@Ru 2.0 493 1.0 12.4 21 8 71 / / 93
Co/SiO2@H-ZSM-5 2.0 533 1.0 11 12 12 76 72a 4b 94
R-Fe@H-ZSM-5 2.0 543 2.0 93 7.5 21.5 71 71a / 95
Fe3O4@H-ZSM-5 1.0 543 2.0 87 16 36.2 47.8 44.6 3.2 96
Co/Nanoβ-Zeolite 2.0 493 1.0 30.2 33.3 33c 26.2d / / 97
Co/TiO2 NTs 2.0 493 1.0 7.65 52.8 0.23 47.0 / / 98
Ru/meso-ZSM-5 1.0 533 2.0 29.6 5.9 14.6 79.5 79a 0.5b 99
Co/SiO2 2.0 493 2.0 80.6 8.7 11.3 80 62.4a / 100
Ru/HB-S 2.0 533 1.0 78.8 10.7 17.4 71.9 71.7a 0.3b 101
Co/NS-MFI 2.0 493 2.0 74 7.9 5.4 81 73.8a 7.2b 102
Co/Ce-meso-Y 1.0 523 2.0 34 11 6.6 82.4 74a 8.6b 103
Fig. 5 (a) Strategy for preparing hollow and yolk-shell HSNs. (b) Hydrogenation of nitrobenzene with different catalysts[110]. Copyright 2020, American Chemical Society
Fig. 6 (a) Multistep self-assembly illustration of preparation of the Gd2O3@Pt@ZIF nanoreactor[114]. (b) UV-vis spectra of the reduction of 4-NP with Gd2O3@ZIF-8 and with Gd2O3@Pt@ZIF-8. (c) The recycling of Gd2O3@Pt@ZIF-8 nanoreactor for the reduction of 4-NP. Copyright 2020, American Chemical Society
Fig. 7 (a) TEM images of a PS-b-P2VP particle with ordered microphase separation structure[120]. (b) UV-Vis spectra of the reduction of 4-nitrophenol using Au@PDA particles as nanoreactors without NIR irradiation at 39.3℃ and under NIR irradiation. (c) Schematic illustration for the synthesis process of PNIPAM/Au@meso-SiO2[124]. (d) Time-dependence conversion curves of reduction of 4-nitrophenol catalyzed by PNIPAM/Au@SiO2 at 30℃ and 50℃. Copyright 2012, American Chemical Society
Table 3 The performances of nanoreactors with different core-shell structures in the hydrogenation of nitroaromatic compounds
Nanostructure Catalyst Reducing
substance		 Reduction conversion Rate constant
k (s-1)		 ref
Yolk-shell Co-N-C@SiO2 nitrobenzene >80%a 12.7 × 10-3 110
Yolk-shell Pt@SiO2-Ph nitrobenzene 99% / 113
Core-shell ZIF-8 Gd2O3@Pt@ZIF-8 4-nitrophenol >99.9%b / 114
Core-shell MOFs UiO-66-NH2@COP@Pd nitrobenzene >92% a 5.2 × 10-3 115
Hollow nanocapsules Pd@SiO2 NACs 4-nitrophenol >99%c / 116
Yolk-shell Pd/N-Cs@SnO2 4-nitrophenol >92%c 1 × 10-3 117
Core-shell Au triangular
nanoplates@SiO2		 4-nitrophenol >90%d 2.6 × 10-3 118
Core-shell Au-coated Fe3O4@SiO2 4-nitrophenol > 90% 7.5 × 10-4 119
Core-shell Au-coated Fe3O4@SiO2
(808 nm radiation)		 4-nitrophenol > 95% 3.4 × 10-3 119
Multi-compartment Au@PDA 4-nitrophenol >89.9% 1.9 × 10-5 120
Megranate-like Pd-silica nanorattles-SO3H 4-methoxy-nitrobenzene >98%c / 129
Megranate-like Ag@mSiO2 4-nitrophenol >90%c 13.8 × 10-3 130
Megranate-like Fe3O4@SiO2-Au@C 4-nitrophenol >95% a 11 × 10-3 19
multi-shelled MSNs Au@MMSNs 4-nitrophenol >95%c / 132
Yolk-shell Au@MgSiO3 4-nitrophenol >97%c 2.5 × 10-3 133
Yolk-shell YS-Au@Ph-PMOs 4-nitrophenol >88%a 5 × 10-3 134
Yolk-shell YS-Au@SiO2 4-nitrophenol / 2 × 10-3 134
Hollow doughnut Ag/Hd-MSN-NH2 4-nitrophenol >97%a 4.1 × 10-3 135
Fig. 8 (a) Schematic illustration for the preparation of multifunctional amphiphilic nanoreactor[141]; (b) Kinetic plots of aerobic oxidation of 4-methoxybenzyl alcohol over different catalysts. Copyright 2018, American Chemical Society; (c) Schematic illustration of the synthetic route to the PIL@SiO2-Pd nanoreactor[143]. Copyright 2015, American Chemical Society; (d) Overall flowchart for the fabrication of the Y@HWS-TiO2 via three sequential steps[146]; (e) Comparison of photocatalytic activity of C-TiO2, Y@S-TiO2, Y@WS-TiO2 and Y@HWS-TiO2 structures in selective oxidation of benzyl alcohol under UV and visible conditions
Fig. 9 (a) Formation of AuPt nanoalloy yolk@shell hollow particles in ordered mesoporous silica microspheres from AuPt@RF@SiO2 aerosol particles[150]. (b) Conversion of styrene and selectivity to styrene oxide at different reaction times. Copyright 2016, American Chemical Society
Fig. 10 TEM images of Co3O4 (a), CeO2@Co3O4 (b), CeO2 (c). (d) Toluene conversion over Co3O4, CeO2@Co3O4, CeO2[156]. Copyright 2020, American Chemical Society. (e) A schematic illustration of the fabrication of Pd/h-NiCoOx and NiCoOx nanosheets[158]. (f) The catalytic activities of h-NiCoOx samples with different Pd loadings. Copyright 2020, American Chemical Society. (g) Schematic illustration for synthesizing PtxRuy/ZrO2 nanocomposites[159]. (h) Toluene conversion as a function of reaction temperature over different catalysts. Copyright 2020, American Chemical Society
Fig. 11 (a) Schematic illustration for preparation of polymersome nanoreactors for cooperative cancer therapy via systemic administration[168]. (b) Time-dependent H2O2 production of G@R-NRs and G@N-NRs. (c) Fe2/3+ release from Fe/G@R-NRs and Fe/G@NNRs in the absence or presence of glucose after 24 h incubation. Copyright 2019, American Chemical Society
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