CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190, China
b.
School of Nanoscience and Technology, University of Chinese Academy of Sciences, Beijing 100049, China
c.
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150080, China
d.
Sino-Danish Center for Education and Research, Sino-Danish College, University of Chinese Academy of Sciences, Beijing 100049, China
Received Date:
12 May 2020 Available Online:
15 September 2020
Fund Project:
Project supported by the Strategic Priority Research Program of Chinese Academy of Sciences (No. XDB36000000), National Key Basic Research Program of
China (No. 2016YFA0200700), National Natural Science Foundation of China (Nos. 21890381, 21721002), Frontier Science Key Project of Chinese Academy of Sciences (No. QYZDJ-SSW-SLH038), and K.C.Wong Education Foundation
Abstract:
Two-dimensional nanomaterials have received extensive attention because of their unique physicochemical properties. However, bottom-up synthesis of two-dimensional (2D) stable nanomaterials still remains great challenge. In this work, a novel 2D metal-organic (Cu-BDT) nanosheet is constructed at room temperature by coordinative self-assembly, namely, using monovalent copper ion as the metal precursor and 1,4-benzenedithiol as organic ligand. As-synthesized Cu-BDT nanosheets are fully characterized by various techniques including powder-diffraction of X-rays (P-XRD), Fourier transform infrared spectrometer (FT-IR), Raman spectra (Raman), scanning electron microscopy (SEM), transmission electron microscope (TEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectrometer (ICP-OES) and contact angle test. The catalytic result verifies that the Cu-BDT nanosheet surfaces possess abundant active sites and good hydrophobicity, which facilitate oxidation of sulfides into sulfoxide compounds.
Figure 1.
(a) Scheme of the formation and structure of Cu-BDT. (b) Cu-BDT solid powder image and Tyndall light scattering of Cu-BDT nanosheets in ethanol solution. (c) The XRD patterns of Cu-BDT reported in the literature and synthesized in this paper. (d) FT-IR and (e) Raman spectra of BDT and Cu-BDT.
Figure 2.
The (a) SEM and (b) TEM images of Cu-BDT nanosheets, the inset shows Cu-BDT nanosheets are hydrophobic. (c) Elemental mapping images of Cu-BDT nanosheets. (d) AFM image and corresponding height profile of Cu-BDT nanosheets.
a Reaction conditions: substrate (6 mmol), catalyst (5 mg), Isopropanol (5 mL), H2O2 (1 mL), 50 ℃, reaction time: 6 h. b Conversion for specific products were determined by gas chromatography. c Selectivity＝yield/conversion, mol%. d TON was calculated by the mole number of converted (TON＝yield/mole number of total Cu). e, f The same conditions, just reaction time is 7 h and 24 h respectively.
Figure 5.
(a) Effect of time on oxidation reaction. (b) Effect of oxidant large amount on methy p-tolylsulfide oxidation reaction. (c) Methy p-tolylsulfide oxidation conversion and ln(Ct/C0) versus the reaction time. (d) 4-chlorothioanisol oxidation conversion and ln(Ct/C0) versus the reaction time.
图 6.
a) 催化氧化4-甲基茴香硫醚的循环测试. (b) 五个催化循环后Cu-BDT纳米片的扫描电镜图. (c) Cu-BDT纳米片反应前后的XRD. (d) Cu-BDT纳米片反应前后的铜2p的XPS谱图.
Figure 6.
(a) The recycle test of methy p-tolylsulfide oxidation. (b) SEM image of Cu-BDT nanosheets after 5 recyclable tests. (c) The XRD of Cu-BDT nanosheets before and after reaction. (d) XPS spectra of Cu 2p before and after reaction.
Niu, L.-Y.; Coleman, J. N.; Zhang, H.; Shin, H.; Chhowalla, M.; Zheng, Z.-J. Small2016, 12, 272. doi: 10.1002/smll.201502207
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Doherty, S.; Knight, J. G.; Carroll, M. A.; Ellison, J. R.; Hobson, S. J.; Stevens, S.; Hardacre, C.; Goodrichb, P. Green Chem.2015, 17, 1559. doi: 10.1039/C4GC01770F
Figure 1
(a) Scheme of the formation and structure of Cu-BDT. (b) Cu-BDT solid powder image and Tyndall light scattering of Cu-BDT nanosheets in ethanol solution. (c) The XRD patterns of Cu-BDT reported in the literature and synthesized in this paper. (d) FT-IR and (e) Raman spectra of BDT and Cu-BDT.
Figure 2
The (a) SEM and (b) TEM images of Cu-BDT nanosheets, the inset shows Cu-BDT nanosheets are hydrophobic. (c) Elemental mapping images of Cu-BDT nanosheets. (d) AFM image and corresponding height profile of Cu-BDT nanosheets.
Figure 5
(a) Effect of time on oxidation reaction. (b) Effect of oxidant large amount on methy p-tolylsulfide oxidation reaction. (c) Methy p-tolylsulfide oxidation conversion and ln(Ct/C0) versus the reaction time. (d) 4-chlorothioanisol oxidation conversion and ln(Ct/C0) versus the reaction time.
图 6
a) 催化氧化4-甲基茴香硫醚的循环测试. (b) 五个催化循环后Cu-BDT纳米片的扫描电镜图. (c) Cu-BDT纳米片反应前后的XRD. (d) Cu-BDT纳米片反应前后的铜2p的XPS谱图.
Figure 6
(a) The recycle test of methy p-tolylsulfide oxidation. (b) SEM image of Cu-BDT nanosheets after 5 recyclable tests. (c) The XRD of Cu-BDT nanosheets before and after reaction. (d) XPS spectra of Cu 2p before and after reaction.
a Reaction conditions: substrate (6 mmol), catalyst (5 mg), Isopropanol (5 mL), H2O2 (1 mL), 50 ℃, reaction time: 6 h. b Conversion for specific products were determined by gas chromatography. c Selectivity＝yield/conversion, mol%. d TON was calculated by the mole number of converted (TON＝yield/mole number of total Cu). e, f The same conditions, just reaction time is 7 h and 24 h respectively.
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