One-Pot Method for Multifunctional Yolk Structured Nanocomposites with N-doped Carbon Shell Using Polydopamine as Precursor
© Zhang et al. 2016
Received: 11 January 2016
Accepted: 13 April 2016
Published: 19 April 2016
Herein, we reported a facile method to prepared uniform yolk like nanocomposites with well-defined N-doped carbon shell (C), in which the cores@SiO2@polydopamine (Pdop) were used as the sacrificed template. Typically, inherited from the functional Au core, the yolk particles presented excellent catalytic activities.
Rattle-type or yolk-shell nanostructures have gained much attention, because they exhibited great potential applications in biomedicine , catalysis [2–4], nano-reactor [5, 6], and lithium-ion battery [7, 8], etc. Among them, the newly emerged Core@N-doped carbon yolk-shell structures have triggered great interest to scientists. Such a N-doped carbon shell functioned as a barrier to prevent the encapsulated nanoparticle from coalescence. Furthermore, the incorporated nitrogen atoms can be considered a tool for tuning the carbon properties, which enlarged the application of the carbon material, including electrodes for oxygen reduction reactions , metal-free catalysis , and CO2 capture [11, 12].
One-pot approach represents a green chemical strategy to simplify the synthesis process of core-shell-shell (CSS) nanostructures, and the template process was the most common and efficient method to fabricate these yolk-carbon shell structured nanomaterials from the CSS nanostructures. Thus, the technology combining the one-pot approach with the template process to obtain the yolk-like structured nanomaterials was highly desired by the scientist. Recently, the extension of the Stöber method for the synthesis of resorcinol-formaldehyde (RF) polymer nanospheres opens a novel pathway for synthetic strategies in the facile preparation of RF based core-shell and core@carbon yolk shell nanospheres. For example, Fuertes and coworkers reported a one-step Stöber method to synthesize RF@silica and carbon capsule structures . Furthermore, Liu et al. reported one-step Stöber approach to produce uniform Au(Ag)-silica-polymer spheres with a core-shell-shell structure as templates for Au(Ag)@void@C yolk-shell nanostructures [14, 15]. Shao synthesized the magnetic rattle-type carbon nanospheres using the similar strategy . These greatly widen the application of the RF Stöber method. However, a lack of nitrogen heteroatoms in RF results in an absence of electroactive nitrogen in the final carbon nanocomposites. Moreover, the strongly carcinogenic phenol/formaldehyde would do harm both to humans and the environment. Therefore, it is desirable to explore new polymer analogues that feature low toxicity, and the presence of heteroatom within a framework to prepare carbon nanocomposites for practical applications.
In contrast with phenol/formaldehyde, dopamine is nontoxic, widespread, and a sustainable resource. It contains carbon and nitrogen atoms and is well-known for its chelating capability with many types of metal ions. More importantly, the presence of nitrogen heteroatoms in carbon nanomaterials can strongly enhance the materials’ electrochemical performance [17–24]. Recently, Au@void@C was synthesized from Au@SiO2@Pdop, which exhibit high catalytic ability and stability in the reduction of 4-nitrophenol . The iron oxide@void@C yolk-shell structure was also designed from the iron oxide@SiO2@Pdop for lithium batteries . More recently, the MnO2@void@C yolk-shell nanorods with manganese oxide core and N-doped carbon shell have been constructed using a facile sol-gel method, which exhibit excellent performance in lithium batteries . However, fabrication of core-silica-polydopamine (carbon precursor) involves multiple steps that are time consuming and energy wasting. Hence, a one-pot, effective, and general approach to synthesize CSS templates for yolk-carbon shell nanostructure production is still strongly needed.
Recently, Lu etc have reported that dopamine can be directly polymerized into monodisperse submicrometer spheres in a mixture containing water, ethanol, and ammonia at room temperature . Inspired by this work, we have presented a one-pot strategy for the preparation yolk like nanocomposite with N-doped carbon shell by the extended Stöber method. By varying the core shape, the spherical, spindle, and wire-like structures were achieved. Typically, inherited from the functional Au core, the yolk particles presented excellent catalytic activities.
TEOS, HAuCl4, and Fe(acac)3 were purchased from Energy Chemical; Dopamine purchased from Alfa Aesar; ammonia solution (25–28 %), ethanol, sodium citrate, polyvinylpyrrolidone (PVP), ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol, AgNO3, and NaCl were purchased from Sinopharm Chemical Reagent Co. (Shanghai, China). All the reagents were used without further purification. Deionized water was used throughout the experiments.
Synthesis of Au Nanoparticles
Briefly, 30 mL of deionized water was magnetic stirred and 4.5 mL of 5 mg.mL-1 HAuCl4 solution was added. The mixed solution was stirred until boiling point was reached. Then, 1 mL of 3.3 wt% sodium citrate solution was added rapidly and the system was refluxed for 30 min. When the resultant colloid was cooled to room temperature, 10 mg PVP was added. The resultant was stirred for 24 h to allow complete adsorption of the polymer on the gold surface. After that, the solution was centrifuged (9500 rpm; 20 min) and the supernatant was removed. The volume of the concentrated colloid was then adjusted to 4 mL by dilution with deionized water.
Synthesis of Au@SiO2@Pdop
Four milliliters of as-prepared gold nanoparticles in water was dispersed in 40 mL ethanol, then 1 mL ammonia aqueous solution (32 wt%) was added, after 5 min stirring, 0.2 mL TEOS was added. After that, the reaction mixture was stirred for 12 h at room temperature. Then, 200 mg dopamine was added and stirred for 24 h again. After that, the brown solid product was collected by centrifugation, washed with water and ethanol several times, and air-dried at 50 °C for 5 h.
Synthesis of Au@void@C yolk-shell
Au@SiO2@Pdop was carbonized under N2 atmosphere at 500 °C for 5 h with a heating rate of 10 °C/min using tube furnace. Then, to remove the SiO2 in Au@SiO2@C, the as-synthesized powder was added into the mixture of deionized water (30 mL) and ammonia (10 mL) and then transferred into a Teflon-lined stainless steel autoclave. The autoclave was maintained at 140 °C for 12 h and cooled to room temperature. The Au@void@C yolk-shell particles was collected by centrifuging and washed with deionized water and ethanol several times and air-dried at 50 °C for 5 h. Then, Au@void@C was obtained.
Synthesis of Cores@void@C yolk shell
The cores were Fe3O4, α-Fe2O3, Ag nanowires (Ag NWs), and CNTs/Fe3O4. Cores@void@C were obtained in a similar manner with the synthesis procedures of Au@void@C. The experimental details are shown in the supporting information.
Catalytic properties of the Au@void@C composites
The reduction of methylene blue (MB) by NaBH4 was chosen as a model reaction for the testing catalytic efficiency of the Au@void@C nanocomposites. A given amount of the magnetic catalysts was added into a solution with MB (5 mL, 50 mg/L). After that, an aqueous solution of NaBH4 (1 mL, 0.4 mol/L) was rapidly injected at room temperature with stirring. The color of the mixture gradually vanished, indicating the reduction of the MB dye. Changes in the concentration of MB were monitored by examining the variations in the maximal UV-Vis absorption at 665 nm. After the catalytic reaction was completed, the nanocatalysts were separated by centrifugation and then repeated for the catalytic reaction. The recyclability of the nanoparticle catalysis was determined by measuring the maximal UV-Vis absorption of MB at the end of each catalytic degradation reaction.
The morphology of cores@void@C was observed using a scanning electron microscope (SEM, Hitachi S-8000, Japan) in a secondary electron scattering mode at 5 kV and a transmission electron microscope (TEM). X-Ray powder diffraction (XRD) patterns of the products were recorded with a Rigaku D/max-γB diffractometer equipped with a rotating anode and a Cu Kα source (l = 0.154 nm). The date of energy-dispersive X-ray spectrometer (EDS) data was obtained on a JEOL JEM 2010 electron microscope at an accelerating voltage of 200 kV. The surface area and mesoporous volume of hollow carbon spheres were measured by nitrogen physisorption measurements (micromeritics, ASAP 2460).
Results and Discussion
In summary, we have developed a versatile one-step methodology to produce yolk-shell structured nanocomposites using dopamine as the carbon source. The Au@void@C yolk-shell nanocomposites showed high catalytic ability and stability in the reduction of methylene blue. Moreover, the other kinds of yolk-shell carbon nanostructures such as magnetic carbon nanotube, Fe3O4, α-Fe2O3, and silver nanowires are obtained by carbonizing the Pdop and selectively etching the middle layer. The variety of advanced materials here presented has considerable interest due to their possible application in catalysis, drug delivery, electrochemistry, selective adsorption, and batteries, etc.
The authors are grateful for the financial support by the National Science Foundation of China (No 21305086), The Natural Science Foundation of Shanghai City (13ZR141830), Research Innovation Program of Shanghai Municipal Education Commission (14YZ138), and the Special Scientific Foundation for Outstanding Young Teachers in Shanghai Higher Education Institutions (ZZGJD13016, ZZGJD13018).
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