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Sharp Fluorescence Nanofiber Network of Cdse/Cds Core-Shell

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Sharp Fluorescence Nanofiber Network of Cdse/Cds Core-Shell ESEARCH ARTICLE R ScienceAsia 46 (2020): 595–601 doi: 10.2306/scienceasia1513-1874.2020.082 Sharp fluorescence nanofiber network of CdSe/CdS core-shell nanoplatelets in polyvinylpyrrolidone Dongni Hana, Lanlan Yangb, Zhongyi Hua, Zhonglin Dua, Yao Wanga, Ze Yuana, Qiao Wanga, b a, Mikhail Artemyev , Jianguo Tang ∗ a Institute of Hybrid Materials, National Center of International Joint Research for Hybrid Materials Technology, National Base of International Science & Technology Cooperation on Hybrid Materials, Qingdao University, Qingdao 266071 China b Research Institute for Physical Chemical Problems of the Belarusian State University, Minsk 220006 Belarus ∗Corresponding author, e-mail: [email protected] Received 5 Jun 2020 Accepted 31 Aug 2020 ABSTRACT: In this work, a novel nanofiber network of colloidal semiconductor CdSe/CdS nanoplatelets (NPLs)/polyvinylpyrrolidone (PVP) with characteristics of porous membranes has successfully been fabricated via the electrospinning technique, in which NPLs and PVP were used as fluorescence agent and fiber matrix, respectively. Firstly, the CdSe core NPLs with quasi 2D geometry was synthesized, and the epitaxial growth of the CdS shells was performed by the atomic layer deposition (c-ALD) method at room temperature. CdSe/CdS core-shell NPLs with a narrow, ca. 20 nm photoluminescence band were blended with PVP dissolved in ethanol-trichloroethylene mixture; and hybrid polymer-NPLs fibers were obtained through the electrospinning technique. The final nanofiber network exhibits the excellent optical properties of the NPLs, which has potential for separation and absorption of pollutants and isolation of microorganisms. KEYWORDS: semiconductor nanoplatelets, polymer, electrospinning, hybrid materials, fluorescence nanofiber network INTRODUCTION velop sensing applications [10]. However, spherical CdSe QDs suffer from the size sensitivity to broaden In recent years, microporous membranes have at- spectra and to shift emission wavelengths with the tracted the attentions for separation and absorp- change of their diameter scale and distribution [11]. tion of pollutants and for isolation of microorgan- Whereas, CdSe nanoplatelets (NPLs) have zero size isms [1]. The latest publications [2] indicated deviation along their normal direction along which the possibility that this structure can be fabricated the quantum confinement occurs [12]. Therefore, from nanofiber networks, with the advantages of CdSe NPLs demonstrate narrower absorption and controllable porous size from tens of nanometers emission bands. As compared to QDs, CdSe NPLs to micrometers [3]. In the past decade, there are can potentially exhibit weaker Coulomb interaction publications on the methodology, whereas [4], it between carriers, which allows for more efficient is not possible to know the degree of pollution, charge injection without affecting confinement and harmfulness or toxicity through this kind of porous recombination regimes [13, 14]. structure. Thus, it is necessary to design a structure Electrospinning is an effective and low-cost that can impart this microporous structure to sense technology for preparing polymer fibers with di- these dangerous matters. Thus, fluorescence sens- ameter range from tens of nanometers to a few ing is ideal strategy to meet this task [5]. micrometers [15, 16]. The high surface-to-volume Colloidal semiconductor quantum dots (QDs) ratio of electrospun fibers has encouraged exten- are the promising next-generation units for the ap- sively on tissue engineering scaffolds, energy stor- plication advantages of cost-effective production, age, sensors and drug delivery [17–20]. The sen- superior color purity, high quantum yield (QY), and sitive 2,4-dinitrotoluene fluorescence sensors based precisely tunable emission wavelength through the on porous electrospun fibres and porous mem- whole visible to the near infrared range [6–9]. Such branes prepared from pyrene-doped poly (methyl advantages have encouraged much efforts to de- methacrylate), polyvinyl chloride, polystyrene, and www.scienceasia.org 596 ScienceAsia 46 (2020) co-polymers from these polymers have been success- range of 200–2300 nm using a glass cuvette with a fully developed [21] 1 mm 1 mm optical path. Photoluminescence (PL) So far, there are just few studies on QD- spectra× and fluorescent optical microscopic pho- s/polymer composite fibers by direct mixing method tographs were measured with Cary Eclipse fluores- [22, 23]. And recently, the ultrafine fibers of the cent spectrometer and OLYMPUS BX41 universal mi- QDs doped in polymer hosts illustrated successes croscope with a UV lamp emitting in the wavelength of electrospinning method for electronic and op- range of 340–380 nm, respectively. The morpholo- toelectronic devices [24, 25]. Reports indicated gies of NPLs and hybrid fibers were characterized that there are two methods to introduce QDs into by transmission electron microscopy (TEM, JEM- polymer fibers, i.e. in situ formation method and 2000 Ex) and scanning electron microscopy (SEM, direct blending [26]. Although the in situ for- Tescan-Vage3). Fourier transform infrared (FTIR) mation method has a precise control of the size spectra were recorded on a Nicolet 5700 infrared 1 distribution, the formation process usually leads to spectrophotometer in the range of 4000–400 cm− . increases of surface defects resulting in poor optical Preparation of CdSe and CdSe CdS NPLs properties [27]. The QDs/polymer direct mixing / method can solve the problems mentioned above Twenty mmol of Cd(OAc)2 2 (H2O) was dissolved and achieve ultrafine fibers with excellent optical in 50 ml of methanol and· mixed with 45 mmol properties and narrow size distribution [28, 29]. of myristic acid dissolved separately in 300 ml of Herein, novel hybrid luminescent nanofiber methanol. The white precipitate was filtered out network based on the CdSe/CdS core- from the solution and washed with methanol three shell NPLs/polyvinylpyrrolidone (PVP) was times to remove the excess precursors. The fi- demonstrated. The NPLs have been introduced into nal Cd(myr)2 powder was dried under vacuum at the PVP solution by addition of trichloroethylene to 40 °C overnight. Then, Cd(myr)2 (140 mg), Se the polymer solution. Compared with similar work powder (24 mg) and 1-ODE (15 ml) were intro- in the past, this new type of network was doped duced into a three-neck round-bottom flask and with NPLs that have high quantum yield (QY) degassed under vacuum at 100 °C for 30 min with and extremely narrow full-width at half-maximm stirring. After degassing, the reaction mixture was (FWHM). The different novel hybrid luminescent heated up to 240 °C under nitrogen atmosphere. nanofiber network maintains sharp fluorescence as When the temperature reached 195 °C, 80 mg of usual after electrospinning. This work provided a Cd(OAc)2 2 (H2O) were rapidly added into the new hybrid nanofiber network with great potential reaction mixture.· After the temperature reached applications for sensing and detecting. 240 °C, the reaction mixture was stirred for 8 min, then 2 ml of OA were added and the solution cooled MATERIALS AND METHODS down to 80 °C. To overgrow CdSe core NPLs with Materials CdS shell by ADL method [30], 1 ml of CdSe cores in 4 ml hexane dissolved in 3 ml hexane, and the Cadmium acetate dehydrate (Cd(OAc)2 2 H2O, first monolayer was deposited by adding 12.5 µl of · 99.99%), ammonium sulfide ((NH4)2S, 40%), (NH4)2S in 5 ml NMF and vigorously stirring until myristic acid, selenium powder (Se, 99.99%), complete the phase transfer of NPLs from hexane 1-octadecene (1-ODE, 90%), oleylamine (OAm, to NMF phase. The S-coated CdSe NPLs were pre- 80–90%), oleic acid (OA, 90%), and PVP (Mw cipitated from NMF by adding a mixture of toluene = 1 300 000 g/mol) were purchased from Al- and acetonitrile, centrifuged at 10 000 rpm and re- addin, Shanghai, China. Methanol, hexane, dispersed in 5 ml of NMF.Then, the monolayer of Cd isopropanol, ethanol, trichloroethylene (C2HCl3), was deposited by introducing 1.5 ml of 0.25 M solu- toluene, and acetonitrile were from Sinopharm tion of Cd(OAc) 2 (H O) in NMF, the mixture was Chemical Reagent Co., Ltd, Shanghai, China. N- 2 2 stirred for 3 min,· after which the CdSe/CdS core- methylformamide (NMF, 99%) was from Macklin, shell NPLs were precipitated by adding the mix- Shanghai, China. All chemicals were used as re- ture of toluene and acetonitrile (toluene:acetonitrile ceived and without further purification. = 1:1, v/v). To further increase the CdS shell thickness, the above procedure was repeated three Characterization times and the final core-shell NPLs with different UV-vis absorption of NPLs solution was recorded by thickness were dispersed in trichloroethylene with PerkinElmer Lambda 750S spectrophotometer in the the addition of OAm. www.scienceasia.org ScienceAsia 46 (2020) 597 Fig. 3 TEM images of CdSe core and CdSe/CdS core- shell NPLs: (a) core CdSe NPLs, (b) CdSe/1CdS NPLs, Fig. 1 Schematic diagram of the electrospinning process. (c) CdSe/2CdS NPLs. ( a ) C d S e C d S e / 1 C d S C d S e / 2 C d S ) t i n u . b r u . a a ( / t y i t i n s U n e y t r n a I r t i L b P r A 400 500 600 700 800 W a v e l e n g t h / n m Fig. 2 (a) Absorption and photoluminescence spectra of CdSe core and CdSe/CdS core-shell NPLs with 1 ml and 2 ml thick CdS shell in hexane; (b) sample picture of CdSe core and CdSe/CdS core-shell NPLs. The photolumines- Fig. 4 SEM images of nanofiber network with different cence spectra are obtained by excitation at 460 nm. NPLs contents: (a) 0 wt%, (b) 1 wt%, (c) 3 wt%, (d) 5 wt%. Fabrication of NPLs/PVP hybrid nanofiber network RESULTS AND DISCUSSION To prepare the polymer solution, 10 g PVP was Fig. 2(a) shows the absorption and emission spec- dissolved in the mixture of ethanol and C2HCl3 tra of as-prepared CdSe core, CdSe/1CdS and Cd- (ethanol:C2HCl3 = 2:1, v/v) and stirred for 12 h Se/2CdS core-shell NPLs in hexane solutions at the to obtain a homogeneous solution of 10 wt% PVP room temperature.
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