Chem. J. Chinese Universities ›› 2023, Vol. 44 ›› Issue (1): 20220665.doi: 10.7503/cjcu20220665
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YANG Jiye1, SUN Dayin1, WANG Yan1, GU Anqi1, YE Yilan1, DING Shujiang2(), YANG Zhenzhong1()
Received:
2022-10-10
Online:
2023-01-10
Published:
2022-11-26
Contact:
DING Shujiang, YANG Zhenzhong
E-mail:dingsj@mail.xjtu.edu.cn;yangzhenzhong@tsinghua.edu.cn
Supported by:
CLC Number:
TrendMD:
YANG Jiye, SUN Dayin, WANG Yan, GU Anqi, YE Yilan, DING Shujiang, YANG Zhenzhong. Progresses in Template Synthesis and Applications of Hollow Materials[J]. Chem. J. Chinese Universities, 2023, 44(1): 20220665.
Fig.1 Synthesis of the Janus hollow spheres of PCL⁃PDEAEMA(A)[13] and polystyrene⁃sulfonated polystyrene gel(B)[14](A) Copyright 2015, the Royal Society of Chemistry; (B) Copyright 2019, the Royal Society of Chemistry.
Fig.2 SEM and TEM images of the representative titania hollow spheres with tunable shell thickness and cavity size(A)[15], preparation of the composite capsules and the corresponding hollow spheres of PANi and silica(B)[16] and formation of the double⁃shelled hollow sphere against sPS⁃PS⁃sPS sandwiched hollow sphere template(C)[17](A) Copyright 2003, John Wiley and Sons; (B) Copyright 2003, John Wiley and Sons; (C) Copyright 2005, John Wiley and Sons.
Fig.3 Schematic preparation of a multifunctional Janus hollow sphere of N x C@mSiO2(A)[18], illustrative synthesis of the thermally responsive Janus porous hollow sphere of PNIPAM⁃cPVBC⁃PEO(B)[19], and schematic synthesis of the snowman⁃like hollow sphere with dually Janus features(C)[20](A) Copyright 2018, American Chemical Society; (B) Copyright 2020, the Royal Society of Chemistry; (C) Copyright 2010, American Chemical Society.
Fig.4 Illustrative synthesis of the IL/PNIPAM magnetic Janus hollow sphere(A)[24] and illustrative synthesis of the Janus coral⁃like porous sphere by stepwise de⁃alloying of the AlSi10 alloy sphere and subsequential modification(B)[25](A) Copyright 2019, John Wiley and Sons; (B) Copyright 2016, American Chemical Society.
Fig.5 Schematic synthesis of the Janus hollow sphere by emulsion interfacial self⁃organized sol⁃gel process(A)[34], schematic illustration of the biomimetic synthesis of JHS(B)[35], schematic synthesis of the Janus macroporous hollow sphere by using Pickering emulsion template(C)[36] and schematic synthesis of the jellyfish⁃like Janus hollow sphere by two⁃step emulsion interfacial polymerization(D)[37](A) Copyright 2011, the Royal Society of Chemistry; (B) Copyright 2015, American Chemical Society; (C) Copyright 2012, Elsevier; (D) Copyright 2020, American Chemical Society.
Fig.6 Schematic synthesis of the silica hollow sphere by W/O inverse emulsion template(A)[38] and schematic formation of the tadpole⁃like nanotube and the corresponding Janus one(B)[39](A) Copyright 2013, Springer Nature; (B) Copyright 2021, the Royal Society of Chemistry.
Fig.7 Schematic fluoride⁃induced self⁃transformation of TiO2 toward hollow structures in different ion environments(A)[45] and formation of Janus microgels and microshells(B)[56](A) Copyright 2021, Elsevier; (B) Copyright 2010, American Chemical Society.
Fig.8 TEM image(A), STEM image(B) and line scanning of the PtFe(0.9)⁃C(C), LSV polarization curves of the sample(D), mass activity, specific activity, and electrochemical surface area measured at 0.9 V and half⁃wave potential versus commercial Pt/C(E)[60], TEM and EDS images of the PtFe‐HNC(F—H), LSV curves(I) and MA and SA results before and after durability test of the PtFe‐HNC/C(J)[61]
Fig.9 SEM images of the NiCo2O4⁃450⁃Vo at two magnifications(A, B), TEM image of the NiCo2O4⁃ 450⁃Vo(C), LSVs of different catalysts in O2⁃saturated 0.1 mol/L KOH(D), chronoamperometric curves(normalized to initial current) of the NiCo2O4⁃450⁃Vo and Pt/C at 0.6 V vs. RHE(E)[62]
Fig.10 TEM image(A) and HR⁃TEM images(B, C) of the NHCP⁃1000, ORR polarization curves of the NC, NHCP⁃1000 and commercial 20%(mass fraction) Pt/C in O2 saturated 0.1 mol/L KOH solution at 1600 r/min with a scanning rate of 10 mV/s(D), Jk at 0.75 V versus the RHE of NHCP at varied pyrolysis temperature(E)[63], SEM(F), TEM(G) and AFM(H) images of the h⁃N⁃CF⁃800, durability of the catalysts before and after 5000 cycles(I), chronoamperometric test of the h⁃N⁃CF⁃800 in O2 purged 0.1 mol/L KOH electrolyte(J)[64]
Fig.11 Schematic synthesis(A), SEM(B) and TEM(C) images of the hollow Fe⁃N/C⁃800[65], synthesis of the Pt@Fe⁃NC catalyst(D), LSV plots of the Pt/C and Pt@Fe⁃NC(E), mass activity and specific activities of the Pt/C and Pt@Fe⁃NC at 0.9 V versus RHE(F)[66]
Fig.12 Synthesis of the Cu/Co93Cu7@NC NCs catalyst(A)[67], TEM image of the Pt@GB(B)[68], synthesis of the Fe x @N/HCS(C, D), TEM images(E, F), HR⁃TEM image(G) and elemental mapping(H—I) of the Fe20@N/HCS catalyst[69](A) Copyright 2022, Elsevier; (B) Copyright 2014, John Wiley and Sons; (C—I) Copyright 2020, John Wiley and Sons.
Fig.13 SEM(A)and STEM(B) images of PCNSs, rate capability of p⁃PCNS⁃M⁃70 electrode over 100 cycles at various current rates(C)[72], TEM (D) and zoom⁃in images(E) of the reduced hollow TiO2 nanospheres, cycling performance of TiO2-x /sulfur composite cathode at a current rate of C/5(F)[73], SEM(G) and TEM(H) micrographs of 3S⁃TiO2⁃HMS, cycling performance at the current rate of 1 C between 1.0 and 3.0 V(I)[75]
Fig.14 Fluorescence microscopy images of the PDEAEMA⁃EP@silica⁃PEO Janus hollow sphere in the n⁃hexane/water mixture at varied pHs(A)[77], separation of n⁃hexane/water emulsion by thermoresponsive PNIPAM⁃cPVBC⁃PEO Janus cage column(B)[19] and adsorption of paraffin/toluene and modified lipophilic silica particles by PAM/PDVB Janus cage(C)[36](A) (i) pH=4, (ii) pH=10, (iii) pH=4, n-hexane dyed with dil-C18; the insert schematics in i-iii illustrate the different wettability of interior/exterior surface in Janus hollow sphere, (iv) polarizing optical image; inset is the SEM image of the Janus hollow sphere after loading wax inside the cavity at pH=10. (B)(i) (1) The PNIPAM-cPVBC-PEO Janus cage column at 40 ℃, (2) feeding the SDS stabilized n-hexane/water emulsion into the column, (3) n-hexane was captured inside the Janus cage while water eluted, (4) n-hexane was released from the cage when cooling down to 25 ℃; (ii) CLSM image of the SDS stabilized n-hexane/water emulsion; (iii) CLSM image of the eluted water phase; (iv) CLSM image of n-hexane released from the cage at 25 ℃. (C)(i) Fluorescence microscopy image of the PAM/PDVB Janus cages with paraffin/toluene preferentially absorbed inside the cavity; (ii) SEM image of the PAM/PDVB Janus cage after the mixture of paraffin wax (Tm: 52 ℃) and the modified lipophilic silica particles were absorbed inside the cavity, the microsphere was sliced in order to observe the internal structure.(A) Copyright 2022, American Chemical Society; (B) Copyright 2020, the Royal Society of Chemistry; (C) Copyright 2012, Elsevier.
Fig.15 CLSM images of the cells after uptaking the FITC⁃labeled Janus nanocage(A), CLSM images of the HeLa cells after uptaking the DOX@RGO@mSiO2⁃PEG Janus nanocage for 12 h(B), viabilities of the HeLa cells under different treatments(C)[30], CLSM images(D) and cell viabilities(E) after treating the cancer cells with DOX⁃loaded multi⁃shelled hollow spheres[79](A) The nuclei displayed blue after staining with DAPI, the FITC-labeled Janus nanocages displayed green; (B) the nucleus displayed blue after staining with DAPI, the RGO@mSiO2-PEG Janus nanocages displayed red after loading DOX; (D) CLSM images after treating the cancer cells(MCF7 cell line) with the DOX-loaded H-SMON(single-shelled hollow microporous organic network), DH-SMON(double-shelled hollow microporous organic network), and TH-SMON(triple-shelled hollow microporous organic network) for 1 h(scale bar=10 μm); (E) cell viabilities of the cancer cells(MCF7 cell line) after the treatment with DOX-loaded H-SMON, DH-SMON, and TH-SMON for 2 d.
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