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Revealing the Dynamic Formation Process and Mechanism of Hollow Carbon Spheres: from Bowl to Sphere’s Shape Xin Liu, Pingping Song, Jiahui Hou, Bo Wang, Feng Xu, and Xueming Zhang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b04634 • Publication Date (Web): 30 Dec 2017 Downloaded from http://pubs.acs.org on January 3, 2018
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Revealing the Dynamic Formation Process and Mechanism of
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Hollow Carbon Spheres: from Bowl to Sphere’s Shape
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Xin Liu, Pingping Song, Jiahui Hou, Bo Wang, Feng Xu and Xueming Zhang*
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Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, 35 Qinghua
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East Road, Haidian District, Beijing, P. R. China, 100083.
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*Corresponding author
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E-mail: xm_zhang@bjfu.edu.cn (Xueming Zhang). Tel. and Fax: +86-01062336189.
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ABSTRACT
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Hollow carbon spheres are attracting great attention due to their great potential utilizations in
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drug delivery, energy storage and catalysis. However, the formation process and mechanism of
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the hollow carbon spheres were still unclear. Herein, we chose glucose as carbon precursor,
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double surfactants PEO–PPO–PEO triblock copolymers and sodium oleate as soft template, the
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synthesis process of hollow carbon spheres was investigated in the coupling of soft templating
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method and hydrothermal carbonization system by regulating the reaction time. A dynamic
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formation process of the hollow carbon spheres was identified based on the results from SEM and
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TEM images, in which it experienced three evolution stages including hollow carbon bowls,
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capsules and spheres. In addition, the formation mechanism was also presumed: During the
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synthesis process, the double surfactant interacted with each other to act as the soft template, and
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the glucose underwent hydration, polymerization and aromatization stages. When the
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concentration of aromatic compounds reached the critical supersaturation, the nucleation took
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place from a point and extended outward gradually along the interface to widen and thicken the
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carbon shell, resulting in different morphologies’ hollow structured carbon particles were formed
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successively by controlling the reaction time. Furthermore, the resultant hollow structured carbon
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particles were stable and uniform, and we made preliminary explorations on their biochemical
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and electrochemical performance.
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KEYWORDS: hollow carbon spheres, glucose, soft templating method, hydrothermal
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carbonization
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INTRODUCTION 2
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Hollow carbon spheres (HCSs) have attracted increasing attention in recent years. Owing to
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their unique structure and properties such as encapsulation ability, high surface-to-volume ratio,
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surface functionality, excellent thermal and chemical stabilities1-3, they have been widely studied
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for adsorption/separation, catalysis, drug delivery, synthesis template, micro-reactor, energy
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storage and conversion applications4-10.
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Much effort has been devoted to the synthesis of HCSs by various approaches. The most
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commonly and widely used method is the template-assisted methods11-13. Generally, the
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template-assisted methods can be divided into hard templating method and soft templating
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method according to the types of core templates used. In the hard templating method, some
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specially prepared rigid particles are employed as core templates. When the carbon shells around
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the cores are generated, the templates are generally sacrificed by high temperature, dissolution, or
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acid/alkaline etching, resulting in the formation of the hollow carbon structure14. This method has
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the advantages of better control of the morphology and the size of products, while it generally
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includes the drawbacks of multi-steps, time-consuming and non-environmentally friendly 15-18. In
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comparison, the soft templating method, based on the self-assemble of the precursor molecules
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and the colloidal systems as the core-template, is more convenient. Organic additives, block
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copolymers, surfactants, nanoemulsion droplets or gas bubbles always act as the core-templates,
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which can be easily consumed or removed in the subsequent process, such as pyrolysis or
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extraction19,20. However, the precursors in the soft-template method usually tend to polymerize at
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low temperatures. Additionally, many carbon precursors are highly dependent on fossil-based
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compounds or carbonaceous polymers (ie. benene, phenol, ethylene, resorcinol, formaldehyde,
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dihydroxybenzoic acid, cokes, polystyrene, polyacrylonitrile)13,21-23, which are generally 3
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corrosive, toxic or expensive.
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Considering the environmental concern and economic value, it is preferable to prepare HCSs
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from renewable resources in a highly efficient and environmental friendly way24,25. Hydrothermal
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carbonization (HTC), as a facile, low-cost and environmentally friendly technique, is used for
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preparation of functional carbon materials, and the obtained carbon materials are considered as
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sustainable alternatives to traditional carbons6,24,25. The hydrothermal carbonization process has a
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couple of merits, including the use of renewable resources (either from isolated carbohydrates or
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crude plants), facile instrumentation and techniques, and a high energy and atom economy7,26.
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However, the main problems of HTC carbons are their intrinsic low porosity and conductivity6,27,
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and it has been reported that the template-assisted methods is a powerful tool to generate the
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porous materials28,29. Notably, coupling the template-assisted method with the hydrothermal
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carbonization process has shown powerful capability in controlling the synthesis of various
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carbonaceous nanostructures with special morphology and property7,29,30.
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In a previous study by Sun and Li4, monodisperse colloidal carbon microspheres were prepared
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from aqueous glucose solutions by hydrothermal synthesis, and encapsulated noble-metal
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nanoparticles were also obtained by this procedure. In addition, in Wang et al. work17, the
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formation of carbon structure was investigated based on the hydrothermal treatment of glucose on
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amino-functionalized surfaces of silica-based templates, in which the templates were inversely
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replicated. After heat treatment and aqueous hydrofluoric acid treatment, the well-developed
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porous shell hollow carbon spheres were obtained and they were applicable to catalyst supports.
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Recently, Wang et al.23 used PEO-PPO-PEO triblock copolymers (P123) and sodium oleate (SO)
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as double surfactants and 2,4-dihydroxybenzoic acid and hexamethylenetetramine as the polymer 4
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precursors to synthesize uniform hollow polymer spheres (HPSs) based on hydrothermal
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treatment. Moreover, PtCo bimetallic nanoparticles within the hollow carbon spheres
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((PtCo@HCS-500) were prepared, which showed outstanding catalytic performance in the
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hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF).
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Although some researches focused on the synthesis of hollow carbon spheres and their
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potential utilizations, few studies aimed at investigating their formation process and mechanism,
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especially under the coupling of soft templating method and hydrothermal carbonization system.
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Therefore, further investigation into the evolution states and forming mechanism of hollow
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carbon spheres is required. In this paper, Glucose, an inexpensive, nontoxic and sustainable
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carbon-rich biomass material, was chosen as the carbon precursor. The biocompatible and
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commercially available double surfactants PEO-PPO-PEO triblock copolymers (P123) and
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sodium oleate (SO) were used as the soft template. Since no hazardous chemicals involved in the
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synthesis process, and the coupling of soft templating method and hydrothermal carbonization
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approach was simple and facile, it was believed that our study met the concept of sustainable and
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green chemistry. A dynamic formation process of the hollow carbon spheres was studied by
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regulating the reaction time. Depending on the reaction time, this process experienced the
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dynamic formation of hollow carbon bowls (HCBs), capsules (HCCs), and spheres (HCSs). The
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formation mechanism of hollow carbon structures has also been assumed, which would be
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valuable for illustrating the hollow carbon spheres growth in the hydrothermal carbonization and
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soft templating method synergistic system. Additionally, the resultant hollow structured carbon
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particles (HCPs) were stable and uniform, and their performances in potential applications for
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biomedical materials and supercapacitors were simultaneously evaluated. 5
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EXPERIMENTAL SECTION
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Chemicals
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The PEO–PPO–PEO triblock copolymers (P123) was purchased from Aldrich. Sodium oleate
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(SO) and glucose were purchased from Beijing Ouhe Technology Co., Ltd and Sinopharm
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Chemical Reagent
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polytetrafluoroethylene (PTFE) were supplied from Beijing Lanyi Chemical Products Co., Ltd.
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All the chemicals above were analytical grade and used without further purification.
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Synthesis of hollow carbon spheres (HCSs)
Co.,
Ltd,
respectively.
Other
chemicals including graphite
and
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Typically, 0.016 mol glucose was dissolved in 40 mL deionized water. Then, 20 mL of an
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aqueous solution containing 0.12 mmol SO and 0.0075 mmol P123 was added. After stirring for
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30 min at room temperature, the solution was transferred into a 75 mL autoclave and
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hydrothermal treated at 160 °C for different reaction times (3, 6, 12, 18 and 24 h). Then the dark
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brown products were collected after centrifugation and washed several times with deionized
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water, and dried at 60 °C overnight. Based on the different morphologies of the obtained particles,
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we named them as hollow carbon bowls (HCBs), capsules (HCCs), and spheres (HCSs),
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separately. And all of these were collectively called the hollow structured carbon particles
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(HCPs).
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Synthesis of carbonized hollow carbon spheres (CHCSs)
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The HCSs sample was undergone a temperature-programmed calcination, in which the specific 6
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program was set as follows. The HCSs were heated to 200 °C and maintained for 30 min, then
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calcined to 600 °C and held for 1 h, subsequently the HCSs were further heated to 900 °C and
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kept for 1 h. Whole process was performed under N2 atmosphere with a heating rate of 5 °C/min.
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The obtained black powder was named as carbonized hollow carbon spheres (CHCSs).
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Characterization
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Scanning electron microscopy (SEM) micrographs were taken with a MERLIN VP compact field
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emission scanning electron microscope (ZEISS, Germany) using an accelerating voltage of 15 kV.
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Transmission electron microscopy (TEM) and high resolution transmission electron microscopy
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(HRTEM) micrographs were recorded on JEM-2100F (JEOL, Japan) operating at 100 kV with an
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energy dispersive X-ray spectrometer (EDX). The dynamic light scattering (DLS) and zeta
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potential measurements were measured with a zeta meter (Zeta Master, Malvern Instruments,
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UK). The crystal structure of samples was recorded on an X-ray diffractometer (Smartlab, Rigaku,
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Japan) with Cu Kα radiation (λ=0.154 nm). The Raman spectra were performed on a Raman
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Spectrometer (JY HR-800, HORIBA Ltd., France) at room temperature. Fourier-transform
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infrared (FT-IR) spectra were measured by a Perkin Elmer Spotlight 400 imaging system (Perkin
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Elmer, UK). Surface tension measurements were obtained on a contact angle meter SL200KS
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(Kino, USA). The thermogravimetric analysis (TGA) was carried out using a TG-DTA 7300
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analyzer (SⅡ, Japan) from 20 to 900 °C in N2 flow of 50 mL/min at a heating rate of 10 °C/min.
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The N2 adsorption−desorption isotherms and pore size distribution analysis were performed by
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using a physisorption analyser (SSA-7000, Builder, China).
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Cytotoxicity evaluation
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The cytotoxicity of HCBs was evaluated by a cell counting kit-8 (CCK-8) assay. Mouse
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fibroblast-cells (L929) were seeded at a density of 4 × 103 cells per well in 180 mL culture
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medium and incubated for 24 h. Then, the cells were treated with different concentrations of
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HCBs solution at 37 °C in a humidified incubator with 5% CO2 for 24 h. Then, 20 µL of CCK-8
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solution was added to each well and incubated for 1 h at 37 °C. The absorbance value was
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measured with an infinite M200 microplate spectrophotometer (Tecan, Switzerland) at 450 nm
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wavelength. The cell viability was expressed as percentage of absorbance relative to control, and
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the control was obtained in the absence of HCBs.
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Electrochemical characterization
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The electrode material was a mixture of the active material, graphite and PTFE with the mass
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ratio of 85:10:5. At room temperature, alcohol was added to the electrode material and stirred
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continuously to form homogeneous slurry8. Then the slurry was coated on the nickel foam and
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pressed under 10 MPa for 5min. After being dried to evaporate the solvent, the working electrode
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was obtained.
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The electrochemical measurements were performed by using two-electrode test system
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consisting of two symmetric CHCSs-based electrodes in 6 M KOH electrolyte. All the
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electrochemical measurements were carried on Autolab 302N electrochemical workstation
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(Metrohm Ltd, Switzerland) at room temperature. The cyclic voltammetry (CV) was obtained in
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the voltage range between 0 and 1 V at scan rates from 10 to 200 mV/s. Galvanostatic
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charge−discharge (GCD) measurements were carried out at current density from 0.1 to 5 A/g in
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the voltage range between 0 and 1 V. The Nyquist plot was performed at open circuit potential
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over the frequency range from 0.01 to 100 KHz with an amplitude of 5 mV, and it could be fitted
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to an equivalent circuit including an electrolyte resistance (Rs), charge transfer resistance (Rct),
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Warburg element (Zw) and pseudocapacitance (Cp)31.
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The specific capacitance of the symmetric supercapacitor was determined from the GCD measurements using the equation: ଶ୍×∆୲
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C୫ = ∆×୫
(1)
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where I (A) is the discharge current, ∆t (s) is the discharge time, ∆V (V) is the voltage change
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(excluding the iR drop) within the discharge time, and m (g) is the mass of the active materials on
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the two electrodes.
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The energy density (E, Wh/kg) and power density (P, W/kg) derived from the GCD curves were calculated by the following equations: (∆)మ
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E = C୫ × ଼×ଷ.
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P = ∆୲
(2) (3)
The controlled experiment with the pure graphite as the active material was tested according to
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the above method.
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RESULTS AND DISCUSSION
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Our research aimed at revealing the formation process and synthesis mechanism of the hollow
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carbon spheres (HCSs) using glucose as the carbon precursor and coupling both the soft
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templating method and hydrothermal carbonization process. The double surfactants
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PEO-PPO-PEO triblock copolymers (P123) and sodium oleate (SO) were chosen as the soft
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template. The P123 is known to have strong interaction with ionic surfactants, leading to the 9
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formation of mixed micelles in aqueous media32. As shown in the Figure S1, the dynamic light
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scattering (DLS) results showed the sizes of SO and P123 micelles in H2O were around 150 nm
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and 25 nm, respectively. When mixing the P123 with SO in the solution, the micelle size
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dramatically decreased to 3.5 nm. It was also noted that the critical micelle concentration of
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mixed micelles was less than that from pure SO (Figure S2), which confirmed the formation of
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P123/SO micelles due to the strong interaction between P123 and SO.
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Figure 1. (a−e) TEM and (f−j) SEM images of the HCPs prepared with different reaction times.
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To understand the formation and evolution process of the HCSs, we characterized the physical
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morphology and structure of the HCPs obtained at different reaction times from 3 to 24 h by
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TEM and SEM images (Figure 1). The images in Figures 1a and 1f revealed that the bowl-like
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HCPs began to take shape even though the thin shell did not have enough mechanical strength to
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retain the plump structure (3 h). For the samples synthesized for 6h (Figures 1b and 1g), the
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morphology of bowl-like HCPs were more regular, but deflated structure and fragments still
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existed. When the reaction time prolonged to 12 h (Figures 1c and 1h), HCBs with diameter
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around at 400 nm and shell thickness of about 60 nm formed eventually, which became more
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uniform and monodisperse. After 18 h reaction, the HCCs with an opening formed as shown in
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Figures 1d and 1i, the average diameter was between 500 and 550 nm and shell thickness was in
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the range of 80-100 nm. Finally, the uniform HCSs with diameter of 550-600 nm and shell
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thickness of about 180 nm were formed after hydrothermal treatment for 24 h as shown in
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Figures 1e and 1j. Obviously, we could conclude that the diameter of hollow void first increased
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and then decreased and shell thickness increased with the increase of the reaction time, which
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indicated that the swelling of the nanoemulsion template and the polymerization in the core kept
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happening during the hydrothermal carbonization process.
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Figure 2. TEM and SEM images of the corresponding morphologies synthesized with different molar ratios of P123
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and SO: (a) 0:16 (without P123), (b) 0.5:16, (c) 2:16, (d) 4:16, (e) 1:0 (without SO).
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Figure 3. TEM and SEM images of the corresponding morphologies synthesized with different amounts of glucose (a)
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and (c): 0.008 mol, (b) and (d): 0.032 mol.
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In order to investigate the effect of different molar ratios of P123 and SO and amounts of
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glucose on the morphologies of HCSs, some contrast experiments were also carried out as shown
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in Figures 2 and 3. It was clearly noted that many small spherical carbon particles with around
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180 nm diameter and some large HCCs were formed with the absence of P123 in the reaction
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system (Figures 2a and 2f). However, when only the P123 was added, the carbon particles with a
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wide size distribution from 80 nm to 2 µm could be obtained (Figures 2e and 2j). As the ratios of
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P123 to SO were 0.5:16 (Figures 2b and 2g) and 1:16 (Figures 1c and 1h), the relatively regular
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HCBs formed, which indicated the P123 interacted with SO and served as morphology controller.
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The successive increasing of P123 (2:16) resulted in the formation of larger HCBs with uneven
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shell thickness as shown in Figures 2c and 2h. However, too much P123 (Figures 2d and 2i) led
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to the formation of much bigger bowl-like HCPs and the size distribution was very broad, which
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might be attributed to the instability of the emulsions in hydrothermal process23.Therefore, it
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could be concluded that the optimal molar ratio between P123 and SO was 1:16 in our study.
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What’s more, we also adjusted the amount of carbon precursor (glucose) as shown in Figure 3.
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When the amount of glucose was reduced to 0.008 mol, the deflated HCBs were formed with 300
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nm in average diameter and 80 nm in shell thickness (Figures 3a and 3c). With increasing of
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glucose to 0.032 mol, the HCSs formed with uneven size and shell thickness as depicted in
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Figures 3b and 3d.
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Figure 4. FT-IR spectra of the glucose, HCBs and HCSs.
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The FT-IR spectra corresponding to HCBs, HCSs and glucose raw material are shown in
245
Figure 4. It was clear that nearly no differences between HCBs and HCSs samples were observed.
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The bands at approximately 2900 cm-1 corresponded to stretching vibrations of aliphatic C-H33.
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And the band at 1000–1460 cm-1 were assigned to C-O stretching vibrations in hydroxyl, ester or
248
ether and O-H bending vibrations34. Notably, the intensities of the bands corresponding to the
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hydroxyl groups (3000–3700 and 1000–1450 cm-1)35 in the samples became weaker compared
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with the raw glucose, and new vibration band of C=O groups appeared at 1707 cm-1, which was
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attributed to the dehydration reactions. Meanwhile, the new vibration peaks at 1615, 1510, and
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1450 cm-1 unambiguously indicated the existence of benzene ring structure in the samples36,37,
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and the bands at 875–750 cm-1 were assigned to aromatic C-H out-of-plane bending vibrations38.
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Based on the above analysis, it was demonstrated that the aromatization of glucose occurred
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during hydrothermal treatment. Additionally, the zeta-potential of HCSs was negative value
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(-18.4 mV), which also confirmed the hydrophilic groups attached to the carbon framework39.
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The presence of hydrophilic groups would greatly improve the stability of HCPs for enhancing 13
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their dispersions in aqueous media, and be beneficial for the introduction of additional functional
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groups or materials during hydrothermal reaction or post functionalization, resulting in further
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improvement in the physical and chemical properties of HCPs7, 40,41.
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Scheme 1. Schematic illustration of the formation process of HCSs.
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A possible mechanism and formation process of HCSs were proposed as illustrated in Scheme
264
1. Firstly, the SO and P123 as the double surfactants formed mixed micelles due to the
265
hydrophobic interaction between the alkyl chains of SO and PO blocks in P123 in aqueous
266
media23, 42. As the temperature increased and time prolonged, the oleate would convert to oleic
267
acid and form oleic acid emulsion core43. Meanwhile, the glucose interacted with
268
PEO–PPO–PEO triblock copolymer template through the hydrogen bond between hydroxyl
269
groups and EO repeating units20, 44, and the glucose underwent dehydration reactions and led to
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the formation of soluble products, such as furfural-like compounds (i.e. 5-hydroxymethyl furfural,
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furfural) and some organic acids (i.e. formic, acetic and lactic acids)4, 38, 45. These acids lowered
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the pH of the system and acted as the catalysts for the subsequent further dehydration and
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degradation reaction26,29,36. In addition, the PPO segments became more hydrophobic led to the
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swelling of the nanoemulsion and the PEO segments contributed to their stability during this
275
stage18, 44. The subsequent reaction stage has been denoted as the “polymerization” stage, which
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may be induced by the intermolecular dehydration, fragmentation, aldol condensation and
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resulted in the formation of soluble polymers. Subsequently, the aromatization of polymers
278
occurred. When the concentration of aromatic compounds reached its critical supersaturation, a
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burst nucleation took place and grew towards the interface of the emulsion droplets and water,
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leading to the formation of carbon shell. Based on the SEM and TEM images from different
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reaction time, the nucleation started from a point and extended outward gradually along the
282
interface to widen and thicken the carbon shell until the final size and morphology were achieved.
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And a dynamic formation process of hollow carbon spheres was identified, which experienced
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three evolution stages including hollow carbon bowls, capsules and spheres.
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Figure 5. Cell viability of L929 cells in the presence of different concentration of HCBs.
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To explore the potential application of the HCPs in biochemical application, the cell counting
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kit-8 (CCK-8) assay was used to evaluate the cytotoxicity of the HCPs to living cells. As shown 15
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in Figure 5, take the HCBs as an example, the L929 cell viabilities against samples were
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estimated to be greater than 80% after 24 h incubation with the concentration ranged from 10 to
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1000 µg/ mL, which indicated the excellent biocompatibility, low toxicity and safety in vitro and
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in vivo applications of the as-prepared products46-47. Additionally, the HCPs had quite uniform
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shell thickness and easily controlled void size, also possessed appropriate surface functional
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groups, which may be helpful in realizing identical behavior in biochemistry and clinical
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diagnostics prospects36, 48.
296 297
Figure 6. (a) TEM images of CHCSs and (b-d) Element mapping overlap, C and O elements in CHCSs.
298
The carbonized hollow carbon spheres (CHCSs) were obtained by a temperature-programmed
299
calcination of HCSs as depicted in the experimental. As shown in Figure 6a, the original
300
morphology of HCSs were still remained after high-temperature treatment. The elemental
301
mapping images (Figures 6b-6d) showed that all the expected elements, including carbon and
302
oxygen elements, could be detected and matched well with CHCSs’ structure. In order to
303
investigate whether the soft template core in the HCSs was removed after hydrothermal process
304
or not, the pure oleic acid, P123 and HCSs were analysed by thermogravimetric (TG) analysis
305
(Figure S3). It was shown that the onset of thermal degradation of pure oleic acid and P123 was
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around 200 °C, which was higher than the hydrothermal process (160 °C). Moreover, the
307
maximum rate of weight loss was observed at the second pyrolysis stage, in which over 96%
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weight was pyrolyzed between 200 and 400 oC. Therefore, it was tentatively concluded that the
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soft template core was still retained after hydrothermal process, while it was completely removed
310
in
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adsorption–desorption isotherms and pore size distribution of CHCSs are shown in Figure S4.
312
According to the International Union of Pure and Applied Chemistry (IUPAC) classification, the
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N2 adsorption–desorption isotherms of the CHCSs (Figure. S4a) were identified as type I,
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supporting the microporous nature of the interconnected microporous carbon framework49. The
315
CHCSs displayed a specific BET surface area of 871.02 m2/g and a pore volume of 0.59 cm3/g,
316
respectively. As shown in Figure S4b, the pore size distribution concentrated in micropores region,
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the existence of micropores was beneficial for increasing the effective contact area between
318
electrolyte ion and electrode49,50. On the contrary, if the pores are too small to allow easy access
319
of electrolyte ions, they will not contribute to double-layer capacitance and will weaken the
320
ability to store charge51. Additionally, the hollow core in CHCSs can further shorten the ion
321
diffusion distance and accelerate the ion response rate18.
the
temperature-programmed
carbonization
process23.
322 323
Figure 7. (a) Raman spectra and (b) XRD pattern of CHCSs and HCSs.
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The Raman spectra of CHCSs and HCSs (Figure 7a) showed two distinct peaks at 1587 cm-1
325
(G-band) and 1341 cm-1 (D-band), which were attributed to in-plane vibrations of crystalline
326
graphite and disordered amorphous carbon, respectively52. Both the D band and G band of HCSs
327
displayed a broad shape and relative low intensity, indicating the high content of amorphous
328
carbon. While the D band and G band of CHCSs showed sharper and high intensity peaks, which
329
indicated the improved graphitization degree after calcination53. The IG/ID intensity ratio of
330
CHCSs was calculated to be 1.04, indicating that the CHCSs was partially graphitized54. In
331
addition, the weak broad 2D peak observed at ~2800 cm-1 was scribed to the second-order zone
332
boundary phonons55. This kind of carbons with partial graphitization is highly desirable for the
333
application as electrode materials56. Figure 7b showed the XRD patterns of CHCSs and HCSs.
334
Before the carbonization, the XRD pattern of HCSs showed a broad peak at 2θ = 21.30°, which
335
was attributed to highly disordered and low crystallined carbon atoms. After carbonization, two
336
obvious broad diffraction peaks (around at 24° and 44°) were observed in the XRD pattern of
337
CHCSs, which were assigned to the stacking carbon layer structure (002) and ordered graphitic
338
carbon structure (100), suggesting the carbonization degree increased after carbonization process
339
and coincided with the Raman result57,58. Additionally, an obvious increase in the intensity at the
340
low-angle region of the XRD pattern also demonstrates a high porosity in the sample as
341
mentioned above49,59.
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Figure 8. (a) CV curves at various sweep rates and (b) GCD curves at different current densities for CHCSs.
344
The electrochemical performance of the CHCSs was measured with symmetric two-electrode
345
system in 6 M KOH solution. Obviously, comparing with the pure graphite electrode (Figure S5),
346
the performance of CHCSs electrode has been improved significantly. The cyclic voltammetry
347
(CV) curves in Figure 8a showed nearly symmetrical rectangular shapes in the range from 10 to
348
200 mV/s and displayed a more rectangular shape at a low scan rate. The existence of Equivalent
349
Series Resistance (Figure S6) and pore structure may cause the slight deviation of the CV
350
curves53. The galvanostatic charge/discharge (GCD) profiles (Figure 8b) exhibited nearly linearly
351
symmetric triangular shape and the columbic efficiency can still reach up to 94% when the
352
current density was 1 A/g, indicating electrode’s charge–discharge process was highly reversible.
353
The slight curvature shown on the lines might be ascribed to a certain degree of pseudocapacitive
354
behavior of the electrode due to the existence of the oxygen-containing groups as revealed in the
355
EDX and FT-IR results60. The specific capacitance of CHCSs was calculated as 116 F/g at 0.1 A/g,
356
and the CHCSs displayed an energy density of 4.03 Wh/kg and a power density of 25.1 W/kg
357
under the same condition. These results indicated an efficient double layer and fast ion transport
358
within the working electrodes was formed and the CHCSs possessed the potential in 19
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supercapacitor application.
360 361
CONCLUSION
362
In summary, the formation process and mechanism of hollow carbon spheres were investigated
363
based on the coupling the soft templating method with hydrothermal carbonization process.
364
During this process, the double surfactant interacted with each other, resulting in forming mixed
365
micelles and acting as the soft template. Glucose underwent dehydration reactions and led to the
366
formation of soluble products, such as furfural-like compounds and some organic acids. These
367
acids lowered the pH of the system and acted as the catalysts for the subsequent further
368
dehydration and degradation reaction. Then the soluble derivatives went through polymerization
369
and aromatization stages. When the concentration of aromatic compounds reached its critical
370
supersaturation, a burst nucleation took place from a point and extended outward gradually along
371
the interface to widen and thicken the carbon shell until the final size and morphology were
372
achieved. By regulating the reaction time, a dynamic formation process of hollow carbon spheres
373
was identified, in which it experienced three evolution stages including hollow carbon bowls,
374
capsules and spheres. Furthermore, the resultant hollow structured carbon particles were stable
375
and uniform, and showed good performance in potential applications for biochemistry materials
376
and supercapacitors.
377 378
379
ACKNOWLEDGMENT
We are grateful for the financial support of this research from the Fundamental Research Funds 20
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for the Central Universities (No. 2016JX03), National Key Research and Development Program
381
of China (2017YFD0601004) and Natural Science Foundation of China (No. 31470606).
382 383
384 385
Note
The authors declare no conflict of interest including any financial, personal or other relationships with other people or organizations.
386 387
ASSOCIATED CONTENT
388
Supporting Information
389
The size distribution and surface tension measurements of the P123, SO and P123/SO
390
micelle/emulsion in H2O. The TG and DTG curves of P123, oleic acid and HCSs. N2
391
adsorption-desorption isotherms and pore size distribution of CHCSs. Some supplementary
392
electrochemical results for pure graphite and CHCSs electrodes. The Supporting Information is
393
available free of charge on the ACS Publications website.
394 395
AUTHOR INFORMATION
396
Corresponding Author
397
*Tel. /Fax: +86-01062336189. E-mail: xm_zhang@bjfu.edu.cn.
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REFERENCES
401
(1) Zhou, W.; Xiao, X.; Cai, M.; Yang, L. Polydopamine-coated, nitrogen-doped, hollow
402
carbon-sulfur double-layered core-shell structure for improving lithium-sulfur batteries. Nano
403
Lett. 2014, 14 (9), 5250-5256, DOI: 10.1021/nl502238b.
404
(2) Liang, J.; Yu, X. Y.; Zhou, H.; Wu, H. B.; Ding, S.; Lou, X. W. Bowl-like SnO2@carbon
405
hollow particles as an advanced anode material for lithium-ion batteries. Angew. Chem., Int. Ed.
406
2014, 53 (47), 12803-12807, DOI: 10.1002/anie.201407917.
407
(3) Liang, J.; Hu, H.; Park, H.; Xiao, C.; Ding, S.; Paik, U.; Lou, X. W. Construction of hybrid
408
bowl-like structures by anchoring NiO nanosheets on flat carbon hollow particles with enhanced
409
lithium
410
10.1039/c5ee01125f.
411
(4) Sun, X.; Li, Y. Colloidal carbon spheres and their core/shell structures with noble-metal
412
nanoparticles. Angew. Chem., Int. Ed. 2004, 43 (5), 597-601, DOI: 10.1002/anie.200352386.
413
(5) Gröger, H.; Kind, C.; Leidinger, P.; Roming, M.; Feldmann, C. Nanoscale hollow spheres:
414
microemulsion-based synthesis, structural characterization and container-type functionality.
415
Materials 2010, 3 (8), 4355-4386, DOI: 10.3390/ma3084355.
416
(6) Wang, J.; Nie, P.; Ding, B.; Dong, S.; Hao, X.; Dou, H.; Zhang, X. Biomass derived carbon
417
for energy storage devices. J. Mater. Chem. A 2017, 5 (6), 2411-2428, DOI: 10.1039/c6ta08742f.
418
(7) Hu, B.; Wang, K.; Wu, L.; Yu, S. H.; Antonietti, M.; Titirici, M. M. Engineering carbon
419
materials from the hydrothermal carbonization process of biomass. Adv. Mater. 2010, 22 (7),
420
813-828, DOI: 10.1002/adma.200902812.
storage
properties.
Energy
Environ.
Sci.
2015,
22
ACS Paragon Plus Environment
8
(6),
1707-1711,
DOI:
Page 23 of 31 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
421
(8) Fang, B.; Kim, J. H.; Kim, M.; Kim, M.; Yu, J. S. Hierarchical nanostructured hollow
422
spherical carbon with mesoporous shell as a unique cathode catalyst support in proton exchange
423
membrane fuel cell. Phys. Chem. Chem. Phys. 2009, 11 (9), 1380-1387, DOI: 10.1039/b816629c.
424
(9) Arif, A. F.; Kobayashi, Y.; Balgis, R.; Ogi, T.; Iwasaki, H.; Okuyama, K. Rapid
425
microwave-assisted synthesis of nitrogen-functionalized hollow carbon spheres with high
426
monodispersity. Carbon 2016, 107, 11-19, DOI: 10.1016/j.carbon.2016.05.048.
427
(10) Arif, A. F.; Kobayashi, Y.; Schneider, E. M.; Hess, S. C.; Balgis, R.; Izawa, T.; Iwasaki, H.;
428
Taniguchi, S.; Ogi, T.; Okuyama, K.; Stark, W. J. Selective Low-Energy Carbon Dioxide
429
Adsorption Using Monodisperse Nitrogen-Rich Hollow Carbon Submicron Spheres. Langmuir
430
2017, DOI: 10.1021/acs.langmuir.7b01353.
431
(11) Wang, D.; Yu, Y.; He, H.; Wang, J.; Zhou, W.; Abruna, H. D. Template-free synthesis of
432
hollow-structured Co3O4 nanoparticles as high-performance anodes for lithium-ion batteries. ACS
433
nano 2015, 9 (2), 1775-1781, DOI: 10.1021/nn400731g.
434
(12) Liu, J.; Wickramaratne, N. P.; Qiao, S. Z.; Jaroniec, M. Molecular-based design and
435
emerging applications of nanoporous carbon spheres. Nat. Mater. 2015, 14 (8), 763-774, DOI:
436
10.1038/nmat4317.
437
(13) Li, S.; Pasc, A.; Fierro, V.; Celzard, A. Hollow carbon spheres, synthesis and applications–a
438
review. J. Mater. Chem. A 2016, 4 (33), 12686-12713, DOI: 10.1039/c6ta03802f.
439
(14) Valle-Vigón, P.; Sevilla, M.; Fuertes, A. B. Synthesis of uniform mesoporous carbon
440
capsules by carbonization of organosilica nanospheres. Chem. Mater. 2010, 22 (8), 2526-2533,
441
DOI: 10.1021/cm100190a.
442
(15) Li, Y.; Shi, J. Hollow-structured mesoporous materials: chemical synthesis, functionalization 23
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 24 of 31
443
and applications. Adv. Mater. 2014, 26 (20), 3176-3205, DOI: 10.1002/adma.201305319.
444
(16) Cheng, W.; Tang, K.; Qi, Y.; Sheng, J.; Liu, Z. One-step synthesis of superparamagnetic
445
monodisperse porous Fe3O4 hollow and core-shell spheres. J. Mater. Chem. 2010, 20 (9),
446
1799-1805, DOI: 10.1039/b919164j.
447
(17) Ikeda, S.; Tachi, K.; Ng, Y. H.; Ikoma, Y.; Sakata, T.; Mori, H.; Harada, T.; Matsumura, M.
448
Selective Adsorption of Glucose-Derived Carbon Precursor on Amino-Functionalized Porous
449
Silica for Fabrication of Hollow Carbon Spheres with Porous Walls. Chem. Mater. 2007, 19 (17),
450
4335-4340, DOI: 10.1021/cm0702969.
451
(18) Li, Y.; Tan, H.; Salunkhe, R. R.; Tang, J.; Shrestha, L. K.; Bastakoti, B. P.; Rong, H.; Takei,
452
T.; Henzie, J.; Yamauchi, Y.; Ariga, K. Hollow carbon nanospheres using an asymmetric triblock
453
copolymer structure directing agent. Chem. Commun. 2016, 53 (1), 236-239, DOI:
454
10.1039/c6cc07360c.
455
(19) Ramasamy, E.; Chun, J.; Lee, J. Soft-template synthesized ordered mesoporous carbon
456
counter electrodes for dye-sensitized solar cells. Carbon 2010, 48 (15), 4563-4565, DOI:
457
10.1016/j.carbon.2010.07.030.
458
(20) Meng, Y.; Gu, D.; Zhang, F.; Shi, Y.; Yang, H.; Li, Z.; Yu, C.; Tu, B.; Zhao, D. Ordered
459
Mesoporous Polymers and Homologous Carbon Frameworks: Amphiphilic Surfactant Templating
460
and
461
10.1002/ange.200501561.
462
(21) Cao, C.; Wei, L.; Su, M.; Wang, G.; Shen, J. “Spontaneous bubble-template” assisted
463
metal–polymeric framework derived N/Co dual-doped hierarchically porous carbon/Fe3O4
464
nanohybrids: superior electrocatalyst for ORR in biofuel cells. J. Mater. Chem. A 2016, 4 (23),
Direct
Transformation.
Angew.
Chem.
2005,
117
24
ACS Paragon Plus Environment
(43),
7215-7221,
DOI:
Page 25 of 31 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
465
9303-9310, DOI: 10.1039/c6ta03125k.
466
(22) zhang, H.; Li, X. Interface-mediated fabrication of bowl-like and deflated ballon-like hollow
467
carbon
468
10.1016/j.jcis.2015.04.027.
469
(23) Wang, G. H.; Hilgert, J.; Richter, F. H.; Wang, F.; Bongard, H. J.; Spliethoff, B.;
470
Weidenthaler, C.; Schuth, F. Platinum-cobalt bimetallic nanoparticles in hollow carbon
471
nanospheres for hydrogenolysis of 5-hydroxymethylfurfural. Nat. Mater. 2014, 13 (3), 293-300,
472
DOI: 10.1038/nmat3872.
473
(24)
474
Natural-Precursor-Derived
475
10.1021/acs.chemrev.5b00566.
476
(25) Abbasi, T.; Abbasi, S. A. Biomass energy and the environmental impacts associated with its
477
production and utilization. Renewable Sustainable Energy Rev. 2010, 14 (3), 919-937, DOI:
478
10.1016/j.rser.2009.11.006.
479
(26) Sevilla, M.; Fuertes, A. B. Chemical and structural properties of carbonaceous products
480
obtained by hydrothermal carbonization of saccharides. Chemistry 2009, 15 (16), 4195-4203,
481
DOI: 10.1002/chem.200802097.
482
(27) White, R. J.; Budarin, V.; Luque, R.; Clark, J. H.; Macquarrie, D. J. Tuneable porous
483
carbonaceous materials from renewable resources. Chem. Soc. Rev. 2009, 38 (12), 3401-3418,
484
DOI: 10.1039/b822668g.
485
(28) Yan, H. Soft-templating synthesis of mesoporous graphitic carbon nitride with enhanced
486
photocatalytic H2 evolution under visible light. Chem. Commun. 2012, 48 (28), 3430-3432, DOI:
nanospheres.
Bazaka,
K.;
J.
Colloid
Jacob,
M.
V.;
Nanocarbons.
Interface
Ostrikov,
Sci.
K.
Chem. Rev.
2015,
K.
452,
Sustainable
2016, 116
25
ACS Paragon Plus Environment
(1),
141-147,
Life
DOI:
Cycles
of
163-214, DOI:
ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 26 of 31
487
10.1039/c2cc00001f.
488
(29) Deng, J.; Li, M.; Wang, Y. Biomass-derived carbon: synthesis and applications in energy
489
storage and conversion. Green Chem. 2016, 18 (18), 4824-4854, DOI: 10.1039/c6gc01172a.
490
(30) Gao, Z.; Zhang, Y.; Song, N.; Li, X. Biomass-derived renewable carbon materials for
491
electrochemical
492
10.1080/21663831.2016.1250834.
493
(31) Zhao, Q.; Wang, X.; Wu, C.; Liu, J.; Wang, H.; Gao, J.; Zhang, Y.; Shu, H. Supercapacitive
494
performance of hierarchical porous carbon microspheres prepared by simple one-pot method. J.
495
Power Sources 2014, 254, 10-17, DOI: 10.1016/j.jpowsour.2013.12.091.
496
(32) Ganguly, R.; Aswal, V.; Hassan, P.; Gopalakrishnan, I.; Kulshreshtha, S. Effect of SDS on
497
the self-assembly behavior of the PEO-PPO-PEO triblock copolymer (EO)20 (PO)70 (EO)20. J.
498
Phys. Chem. B 2006, 110 (20), 9843-9849, DOI: 10.1021/jp0607061.
499
(33) Zhang, Z.; Qin, M.; Jia, B.; Zhang, H.; Wu, H.; Qu, X. Facile synthesis of novel bowl-like
500
hollow carbon spheres by the combination of hydrothermal carbonization and soft templating.
501
Chem. Commun. 2017, 53 (20), 2922-2925, DOI: 10.1039/c7cc00219j.
502
(34) Wu, L. M.; Tong, D. S.; Li, C. S.; Ji, S. F.; Lin, C. X.; Yang, H. M.; Zhong, Z. K.; Xu, C. Y.;
503
Yu, W. H.; Zhou, C. H. Insight into formation of montmorillonite-hydrochar nanocomposite
504
under
505
10.1016/j.clay.2015.06.015.
506
(35) Lian, P.; Wang, J.; Cai, D.; Ding, L.; Jia, Q.; Wang, H. Porous SnO2@C/graphene
507
nanocomposite with 3D carbon conductive network as a superior anode material for lithium-ion
508
batteries. Electrochim. Acta 2014, 116, 103-110, DOI: 10.1016/j.electacta.2013.11.007.
energy
hydrothermal
storage.
conditions.
Mater.
Appl.
Res.
Clay
Lett.
2016,
Sci.
26
ACS Paragon Plus Environment
2016,
5
(2),
119,
69-88,
116-125,
DOI:
DOI:
Page 27 of 31 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
509
(36) Sun, X.; Li, Y. Hollow carbonaceous capsules from glucose solution. J. Colloid Interface Sci.
510
2005, 291 (1), 7-12, DOI: 10.1016/j.jcis.2005.04.101.
511
(37) Möller, M.; Harnisch, F.; Schröder, U. Hydrothermal liquefaction of cellulose in subcritical
512
water—the role of crystallinity on the cellulose reactivity. RSC Adv. 2013, 3 (27), 11035-11044,
513
DOI: 10.1039/c3ra41582a.
514
(38) Sevilla, M.; Fuertes, A. B. The production of carbon materials by hydrothermal
515
carbonization of cellulose. Carbon 2009, 47 (9), 2281-2289, DOI: 10.1016/j.carbon.2009.04.026.
516
(39) Liu, X.; Pang, J.; Xu, F.; Zhang, X. Simple approach to synthesize amino-functionalized
517
carbon dots by carbonization of chitosan. Sci. Rep. 2016, 6, 31100, DOI: 10.1038/srep31100.
518
(40) Cao, X.; Ro, K. S.; Chappell, M.; Li, Y.; Mao, J. Chemical Structures of Swine-Manure
519
Chars Produced under Different Carbonization Conditions Investigated by Advanced Solid-State
520
13
521
10.1021/ef101342v.
522
(41) Falco, C.; Perez Caballero, F.; Babonneau, F.; Gervais, C.; Laurent, G.; Titirici, M. M.;
523
Baccile, N. Hydrothermal carbon from biomass: structural differences between hydrothermal and
524
pyrolyzed carbons via
525
10.1021/la202361p.
526
(42) Zhou, T.; Zhou, Y.; Ma, R.; Zhou, Z.; Liu, G.; Liu, Q.; Zhu, Y.; Wang, J. In situ formation of
527
nitrogen-doped carbon nanoparticles on hollow carbon spheres as efficient oxygen reduction
528
electrocatalysts. Nanoscale 2016, 8 (42), 18134-18142, DOI: 10.1039/c6nr06716f.
529
(43) Chen, C.; Wang, H.; Han, C.; Deng, J.; Wang, J.; Li, M.; Tang, M.; Jin, H.; Wang, Y.
530
Asymmetric Flasklike Hollow Carbonaceous Nanoparticles Fabricated by the Synergistic
C Nuclear Magnetic Resonance (NMR) Spectroscopy. Energy Fuels 2011, 25 (1), 388-397, DOI:
13
C solid state NMR. Langmuir
2011, 27 (23), 14460-14471, DOI:
27
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 28 of 31
531
Interaction between Soft Template and Biomass. J. Am. Chem. Soc. 2017, 139 (7), 2657-2663,
532
DOI: 10.1021/jacs.6b10841.
533
(44) Wei, J.; Zhou, D.; Sun, Z.; Deng, Y.; Xia, Y.; Zhao, D. A Controllable Synthesis of Rich
534
Nitrogen-Doped Ordered Mesoporous Carbon for CO2 Capture and Supercapacitors. Adv. Funct.
535
Mater. 2013, 23 (18), 2322-2328, DOI: 10.1002/adfm.201202764.
536
(45) Yao, C.; Shin, Y.; Wang, L. Q.; Windisch, C. F.; Samuels, W. D.; Arey, B. W.; Wang, C.;
537
Risen, W. M.; Exarhos, G. J. Hydrothermal dehydration of aqueous fructose solutions in a closed
538
system. J. Phys. Chem. C 2007, 111 (42), 15141-15145, DOI: 10.1021/jp0741881.
539
(46) Wang, S.; Shang, L.; Li, L.; Yu, Y.; Chi, C.; Wang, K.; Zhang, J.; Shi, R.; Shen, H.;
540
Waterhouse, G. I. Metalang, K.; Z W. D.; Arey, B. W.; Wang, C.; Risen, W. M.; Exarhos, G. J.
541
Hydrothermal dehydration of ar Conformal Phototherapy. Adv. Mater. 2016, 28 (38), 8379-8387,
542
DOI: 10.1002/adma.201602197.
543
(47) Chen, D.; Wang, C.; Jiang, F.; Liu, Z.; Shu, C.; Wan, L. J. In vitro and in vivo
544
photothermally enhanced chemotherapy by single-walled carbon nanohorns as a drug delivery
545
system. J. Mater. Chem. B 2014, 2 (29), 4726-4732, DOI: 10.1039/c4tb00249k.
546
(48) Chen, Y.; Xu, P.; Wu, M.; Meng, Q.; Chen, H.; Shu, Z.; Wang, J.; Zhang, L.; Li, Y.; Shi, J.
547
Colloidal RBC-Shaped, Hydrophilic, and Hollow Mesoporous Carbon Nanocapsules for Highly
548
Efficient
549
10.1002/adma.201400303.
550
(49) Luo, H.; Yang, Y.; Mu, B.; Chen, Y.; Zhang, J.; Zhao, X. Facile synthesis of microporous
551
carbon for supercapacitors with a LiNO3 electrolyte. Carbon 2016, 100, 214-222, DOI:
552
10.1016/j.carbon.2016.01.004.
Biomedical
Engineering.
Adv.
Mater.
2014,
28
ACS Paragon Plus Environment
26
(25),
4294-4301,
DOI:
Page 29 of 31 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
553
(50) Raymundo-Piñero, E.; Kierzek, K.; Machnikowski, J.; Béguin, F. Relationship between the
554
nanoporous texture of activated carbons and their capacitance properties in different electrolytes.
555
Carbon 2006, 44 (12), 2498-2507, DOI: 10.1016/j.carbon.2006.05.022.
556
(51) Sharma, P.; Bhatti, T. S. A review on electrochemical double-layer capacitors. Energy
557
Convers. Manage. 2010, 51 (12), 2901-2912, DOI: 10.1016/j.enconman.2010.06.031.
558
(52) Zhang, L.; You, T.; Zhou, T.; Zhou, X.; Xu, F. Interconnected hierarchical porous carbon
559
from lignin-derived byproducts of bioethanol production for ultra-high performance
560
supercapacitors.
561
10.1021/acsami.6602774.
562
(53) Hao, P.; Zhao, Z.; Tian, J.; Li, H.; Sang, Y.; Yu, G.; Cai, H.; Liu, H.; Wong, C.; Umar, A.
563
Hierarchical porous carbon aerogel derived from bagasse for high performance supercapacitor
564
electrode. Nanoscale 2014, 6 (20), 12120-12129, DOI: 10.1039/c4nr03574g.
565
(54) Zhang, W.; Jiang, X.; Zhao, Y.; Carne-Sanchez, A.; Malgras, V.; Kim, J.; Kim, J. H.; Wang,
566
S.; Liu, J.; Jiang, J. S.; Yamauchi, Y.; Hu, M. Hollow carbon nanobubbles: monocrystalline MOF
567
nanobubbles and their pyrolysis. Chem. Sci. 2017, 8 (5), 3538-3546, DOI: 10.1039/c6sc04903f.
568
(55) Zhu, Y.; Murali, S.; Cai, W.; Li, X.; Suk, J. W.; Potts, J. R.; Ruoff, R. S. Graphene and
569
graphene oxide: synthesis, properties, and applications. Adv. Mater. 2010, 22 (35), 3906-3924,
570
DOI: 10.1002/adma.201001068.
571
(56) Li, Z.; Xu, Z.; Tan, X.; Wang, H.; Holt, C. M.; Stephenson, T.; Olsen, B. C.; Mitlin, D.
572
Mesoporous nitrogen-rich carbons derived from protein for ultra-high capacity battery anodes
573
and supercapacitors. Energy Environ. Sci. 2013, 6 (3), 871-878, DOI: 10.1039/c2ee23599d.
574
(57) Yun, Y. S.; Park, M. H.; Hong, S. J.; Lee, M. E.; Park, Y. W.; Jin, H. J. Hierarchically porous
ACS
Appl.
Mater.
Interfaces
2016,
29
ACS Paragon Plus Environment
8
(22),
13918-13925,
DOI:
ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
575
carbon nanosheets from waste coffee grounds for supercapacitors. ACS Appl. Mater. Interfaces
576
2015, 7 (6), 3684-3690, DOI: 10.1021/am5081919.
577
(58) Tang, J.; Liu, J.; Salunkhe, R. R.; Wang, T.; Yamauchi, Y. Nitrogen-doped hollow carbon
578
spheres with large mesoporous shells engineered from diblock copolymer micelles. Chem.
579
Commun. 2016, 52 (3), 505-508, DOI: 10.1039/c5cc07610b.
580
(59) Zhu, Y.; Murali, S.; Stoller, M. D.; Ganesh, K.; Cai, W.; Ferreira, P. J.; Pirkle, A.; Wallace, R.
581
M.; Cychosz, K. A.; Thommes, M. Carbon-based supercapacitors produced by activation of
582
graphene. science 2011, 332 (6037), 1537-1541, DOI: 10.1126/science.1200770.
583
(60) Xu, X.; Zhou, J.; Nagaraju, D. H.; Jiang, L.; Marinov, V. R.; Lubineau, G.; Alshareef, H. N.;
584
Oh, M. Flexible, Highly Graphitized Carbon Aerogels Based on Bacterial Cellulose/Lignin:
585
Catalyst-Free Synthesis and its Application in Energy Storage Devices. Adv. Funct. Mater. 2015,
586
25 (21), 3193-3202, DOI: 10.1002/adfm.201500538.
30
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TOC graph “For Table of Contents Use Only”
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Synopsis: The dynamic formation process from bowl to sphere’s shape and mechanism of hollow
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