Article

pubs.acs.org/cm

Variation in Crystalline Phases: Controlling the Selectivity between

Silicon and Silicon Carbide via Magnesiothermic Reduction using
Silica/Carbon Composites
Jihoon Ahn,† Hee Soo Kim,∥ Jung Pyo,† Jin-Kyu Lee,⊥ and Won Cheol Yoo*,∥
†
Department of Chemistry, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-747, Republic of Korea
∥
Department of Applied Chemistry, Hanyang University, Ansan 426-791, Republic of Korea
⊥
LG Chem., 188 Munji-ro, Yuseong-gu, Daejeon 305-738, Republic of Korea
*
S Supporting Information
Downloaded from pubs.acs.org by IOWA STATE UNIV on 01/28/19. For personal use only.

ABSTRACT: Magnesiothermic reduction of various types of

silica/carbon (SiO2/C) composites has been frequently used
to synthesize silicon/carbon (Si/C) composites and silicon
carbide (SiC) materials, which are of great interest in the
research areas of lithium-ion batteries (LIBs) and nonmetal
oxide ceramics, respectively. Up to now, however, it has not
been comprehensively understood how totally different crystal
phases of Si or SiC can result from the compositionally
Chem. Mater. 2016.28:1526-1536.

identical parent materials (SiO2/C) via magnesiothermic

reduction. In this article, we propose a formation mechanism
of Si and SiC by magnesiothermic reduction of SiO2/C; SiC is formed at the interface between SiO2 and carbon when silicon
intermediates, mainly in situ-formed Mg2Si, encounter carbon through diffusion. Otherwise, Si is formed, which is supported by
an ex situ reaction between Mg2Si and carbon nanosphere that results in SiC. In addition, the resultant crystalline phase ratio
between Si and SiC can be controlled by manipulating the synthesis parameters such as the contact areas between silica and
carbon of parent materials, reaction temperatures, heating rates, and amount of the reactant mixtures used. The reasons for the
dependence on these synthesis parameters could be attributed to the modulated chance of an encounter between silicon
intermediates and carbon, which determines the destination of silicon intermediates, namely, either thermodynamically preferred
SiC or kinetic product of Si as a final product. Such a finding was applied to design and synthesize the hollow mesoporous shell
(ca. 3−4 nm pore) SiC, which is particularly of interest as a catalyst support under harsh environments.

■ INTRODUCTION
Magnesiothermic reduction is defined as a reaction where
with carbon.17 For example, Si@skeletal structures provided by
carbon hollow shells with void spaces can afford the volume
vaporized or liquefied magnesium at elevated temperatures expansion of Si anode materials, enhance the electron
reduces various metal oxides (e.g., SiO2, ZrO2, TiO2, and transferring efficiency due to high electrical conductivity of
GeO2).1−4 Especially, the reduction of SiO2 to form Si has carbon, and reduce the instability by which SEI layer forms on
obtained popularity since Bao et al. reported that the three- the carbon surface instead of Si surface.17 Therefore, designed
dimensionally structured Si replicas could be produced from structures of SiO2/C composites that are pseudomorphically
parent SiO2 diatom by magnesiothermic reduction.5 transformed to Si/C materials via magnesiothermic reduction
Magnesiothermic reduction has been widely employed in have received considerable attention in the field of LIBs.16,18−24
many applications due to the powerfulness of the reduction At the same time, magnesiothermic reduction can also be
process that produces pseudomorphically transformed Si used to produce metal carbide ceramic materials with
structures.6−11 Among them, researchers working on Li-ion controlled structural features, such as SiC from SiO2/C
batteries (LIBs) have shown tremendous enthusiasm in composites.25−29 This carbide material has a very strong
employing magnesiothermic reduction because Si is known to covalent bond between Si and carbon, thus exhibiting
have the largest theoretical capacity (3580 mAh g−1 at room outstanding mechanical strengths and chemical stabilities. For
temperature), making it promising as an anode material of example, SiC has a hardness of 9 on Mohs scale, which is nearly
LIBs.12−16 the same as a diamond,30 and is hardly attacked by
When looking inside the characteristics of Si as an anode concentrated acids and bases, as well as high temperature.31
material, it has critical problems such as volume expansion
during cycling, low intrinsic electrical conductivity, and Received: December 31, 2015
continuous formation of solid electrolyte interphase (SEI) Revised: February 1, 2016
layer. Hence, Si is frequently used as a form of hybrid structure Published: February 7, 2016

© 2016 American Chemical Society 1526 DOI: 10.1021/acs.chemmater.5b05037

Chem. Mater. 2016, 28, 1526−1536
Chemistry of Materials Article

In addition, magnesiothermic reduction is a much less energy suggested. Silicon intermediates, mainly in situ-formed Mg2Si,
consuming process in the production of SiC from SiO2/C have a crucial role for determining the resultant crystalline
composites as it is usually performed around 500 °C or above, phase: when the silicon intermediates encounter carbon, SiC is
compared to the conventional carbothermal reaction that formed; otherwise, Si is formed. The proof-of-concept was
requires at least 1200 °C.32 In addition, SiC is a semiconductor achieved by a designed reaction between Mg2Si and carbon
with a wide bandgap.33 Therefore, formation of SiC with nanopshere. In addition, we have tried to determine the
controlled morphology and porosity from designed SiO2/C synthesis parameters that affect the formation of either Si or
composites via magnesiothermic reduction is attractive in areas SiC. First, the effect of different contact areas of SiO2 with
of electronic devices and catalyst supports under harsh carbon on the formation of different crystalline phases under
environments.34 the same experimental conditions is elucidated. For this
The reason for the wide use of magnesiothermic reduction in purpose, three different types of SiO2/C composites were
the synthesis of Si/C and SiC is that the field of the SiO2/C designed. These include SiO2 within mesoporous carbon with
composites has already been matured as they are used as around 2 nm pore size, SiO2 inside hollow carbon shell, and
intermediate materials in the preparation of SiO2 templated SiO2 particles on the chunk of carbon. The results from the
carbon replicas. For example, carbon molecular sieves of CMK three different models revealed that the contact area influences
series, reported by Ryoo and co-workers, were synthesized via the crystalline phases of the products. Furthermore, the
nanocasting of carbonaceous material in the parent mesoporous resultant crystalline phases also depend on the reaction
SiO2 with pore sizes less than 10 nm.35,36 Zhao’s group had conditions such as the reaction temperatures, heating rates,
employed triconstituent coassembly of ordered mesostructured and amount of the reactants used. The underlying reasons of
SiO2/C composites to form mesoporous carbon.36 Also, three variation in the crystalline phase could be accounted for by a
dimensionally ordered mesoporous carbon (3DOmC) was solid-state diffusion limited process that produces thermody-
successfully synthesized through nanocasting of carbon namically more stable SiC and its dependence on the reaction
materials into a close-packed SiO2 nanoparticle array with temperature. Moreover, material preparation based on the
sizes ranging from 10 to 40 nm.37,38 In addition, hollow carbon understandings of the reaction mechanism is demonstrated.
sphere was also prepared through an introduction of carbon Hollow mesoporous SiC nanoparticles could be synthesized
shell onto a SiO2 nanoparticle template and seubsequent since the formation of SiC occurs only in the restricted regions
etching of SiO2 template.39 Thus, various types of SiO2/C where sufficient contact between SiO2 and carbon is attained.
composites with diverse sizes can readily be designed and
fabricated for synthesizing carbon replica using SiO2 preform.
On reviewing the previous studies on the synthesis of Si/C
■ EXPERIMENTAL SECTION
Materials and Reagents. Aluminum(III) chloride hexahydrate
or SiC materials through magnesiothermic reduction of SiO2/C (AlCl3·6H2O, 99%), phenol (≥99%), paraformaldehyde (95%),
composites, the fact that compositionally equivalent parent resorcinol (98%), oxalic acid (98%), pluronic P123, magnesium
SiO2/C materials could be used to synthesize both Si/C silicide (≥99%), and aqueous formaldehyde solutions (37 wt %) were
purchased from Sigma-Aldrich. TEOS (≥96%) was purchased from
materials and SiC materials cannot be easily rationalized. A TCI Chemicals. Sodium hydroxide (NaOH), 28−30% aqueous
representative case of this problem is given as follows. When solutions of ammonia (NH4OH), and 38−40% concentrated HCl
initial utilization of magnesiothermic reduction method using solutions were purchased from Samchun Chemical (Korea). Absolute
SiO2/C composites was conducted by Stucky and co-workers, ethanol was purchased from J. T. Baker. Magnesium powder (100−
the resultant crystalline phase was of SiC instead of Si/C 200 mesh) was purchased from Alfa-Aesar. L-lysine (99%) was
composite.27 A triconsituent mixture of tetraethylorthosilicate purchased from Acros Organics. Cetyltrimethylammonium bromide
(TEOS), phenol-formaldehyde (PF) resin and F127 nonionic (CTAB, 99%) was purchased from Daejung Chemicals (Korea).
surfactant, and close-packed polystyrene sphere array were used Furfuryl alcohol was purchased from JUNSEI (Japan). Deionized (DI)
water purified with a Milli-Q purification system was used for all the
to prepare three dimensionally ordered macroporous SiO2/C
experiments
framework with mesopores on the wall, which was Reaction between Mg2Si and Carbon Nanosphere. Purchased
pseudomorphically transformed to macro-/mesoporous SiC. pristine Mg2Si and synthetic carbon nanospheres were used. In order
Meanwhile, when a similar approach to prepare SiO2/C to synthesize carbon nanosphere, resorcinol (0.76 g), formaldehyde
composites using triconsituent coassembly of TEOS, PF resin (0.88 g), and aqueous ammonia solution (0.7 g) were dissolved in 200
and F127 was employed using the magnesiothermic reduction mL of DI water.43 The solution was allowed to react with stirring at
by the Zhao’s group, small Si nanoparticles of sizes around 3 room temperature for 24 h, then aged in 90 °C oven for 24 h without
nm embedded inside carbon framework were successfully stirring. Colloidal products were collected and washed by repeated
produced, which were used as anode materials for LIBs.18 centrifugation. Finally, collected products were carbonized at 800 °C
in a N2 atmosphere for 3 h and carbon nanospheres of the size of 328
Unfortunately, no proper explanation is available, which ± 27 nm were finally synthesized. To perform the reaction between
comprehensively addresses the differences in the systems that Mg2Si and carbon nanospheres, 76 mg of Mg2Si and 24 mg of carbon
yield Si or SiC from the compositionally identical parent nanospheres were mixed together using mortar and pestle. Pelletized
system. Only limited explanations on the respective cases of Si mixture was then annealed at 750 °C for 5 h with heating rate of 10
or SiC formation were provided.25,40−42 °C/min in Ar atmosphere. To remove remaining Mg2Si and formed Si,
With respect to the previous studies in the literature, it is the result product was immersed in 1 M HCl for 5 h. After
noteworthy that the size of SiO2 within carbon framework, in purification, it was immersed in 2 M NaOH at 75 °C for 16 h.
other words, the contact area of SiO2 with the carbon Synthesis of Mesoporous SiO2 Containing Carbon (mSiO2−
C). In order to prepare mSiO2−C, mesoporous SiO2 nanoparticles
framework, and a few other experimental conditions seem were initially synthesized.44 Subsequently, 420 g of DI water, 200 g of
crucial for the determination of the final product (either Si or absolute ethanol, 2.22 g of CTAB, 6 g of aqueous ammonia solution,
SiC). and 4.08 g of TEOS were allowed to react for 16 h to produce
In this study, a possible formation mechanism of Si and SiC mesoporous SiO2 nanoparticles. Colloidal product of the mixture was
via magnesiothermic reduction of SiO2/C composites is washed by repeated centrifugation. The product was dried at 80 °C

1527 DOI: 10.1021/acs.chemmater.5b05037

Chem. Mater. 2016, 28, 1526−1536
Chemistry of Materials Article

under reduced pressure and then calcined at 600 °C for 3 h in a muffle L-lysine molecules on the SiO2 surface. Mixture of furfuryl alcohol (12
furnace to remove the remaining CTAB in the mesopores. Mesopores g) and oxalic acid (0.06 g) as a carbon source was infiltrated into the
of the SiO2 template were filled with phenol-paraformaldehyde resin close-packed SiO2 particles at least two times in order to complete the
by a gas-phase polymerization. In a cosolvent of 20 mL of ethanol and infiltration. Furfuryl alcohol infiltrated close-packed SiO2 particles were
20 mL of DI water, 2 g of SiO2 template was mixed with 2 g of transferred to an oven kept at 80 °C for 24 h for polymerization. The
aluminum(III) chloride hexahydrate. Under sonication of the mixture, polymer/close-packed SiO2 composites were then carbonized at 800
Al ions were adsorbed on the pore wall. After drying at 80 °C under °C for 3 h, resulting in the composites of close-packed SiO2@three
reduced pressure, the product was calcined at 700 °C for 3 h ina muffle dimensionally ordered mesoporous carbon (SiO2@3DOmC).
furnace. Then, 200 mg of calcined product, 95 mg of phenol, and 100 Typical Reduction Procedure. Fifty milligrams of SiO2/C
mg of paraformaldehyde were sealed in glass container. The container composite and 31 mg of magnesium were ground together. The
was then heated at 100 °C for 12 h in an oven to allow gas-phase molar ratio of magnesium was around 2.1:1. The mixture was placed in
polymerization. Finally, it was carbonized at 800 °C for 3 h in Ar an alumina crucible, and the crucible was covered by another alumina
atmosphere. crucible. Meanwhile, for the experiments with respect to the amount of
Synthesis of SiO2@mSiO2−C and SiO2 Encapsulated in reactants mixture, 10, 25, or 50 mg of mixture composed of SiO2@
Hollow Carbon Shell (SiO2@void@C). Synthesis of SiO2@void@ void@C and Mg where the molar ratio between SiO2 and Mg was
C was performed by a previously reported procedure.20 Briefly, 200 fixed as 2.1:1 was used. Also, for the experiments regarding the limit
nm SiO2 nanoparticles were synthesized by the Stöber process. Then, specific contact area for formation of Si crystal, 13 piles of mixture
SiO2 nanoparticles were encapsulated by mesoporous shells. Three composed of SiO2/C composite (SBA15-C or SiO2@3DOmC) and
grams of core SiO2 nanoparticle, 108 g of ethanol, 225 g of DI water, Mg where the molar ratio between SiO2 and Mg was fixed as 2.1:1 was
1.11 g of CTAB, 3 g of aqueous ammonia solution, and 2 g of TEOS placed in the crucible. The each pile of mixture was 3 mg and
were used for the encapsulation reaction. The products were purified separated from each other with distance at least 2 cm. Then, it was
by centrifugation and calcined at 600 °C for 3 h. Then, the pores of annealed in a horizontal tube furnace at a programmed temperature
the mesoporous SiO2 were filled with phenol-formaldehyde resin by a (600, 650, or 750 °C) for 5 h under Ar flow. The heating rate was 10
gas phase polymerization using a procedure similar to that of mSiO2− °C/min unless otherwise specified.
C (SiO2@mSiO2−C indicates the material at this point). In order to Rietveld Quantification. The Rietveld refinement calculation was
alleviate sintering of materials during carbonization step, a thin SiO2 performed by the well-known Rietveld program named as “Fullprof”
layer (3−5 nm thick) was coated on SiO2@mSiO2 containing carbon with an interface provided by the software “Match!”.45 The XRD
source.6 Then, it was carbonized at 800 °C for 3 h in Ar atmosphere. patterns obtained from the HCl treated samples of reduced SiO2@
Finally, SiO2 was partially etched in NaOH solution. The products void@C at various reduction conditions were used for the refinement.
were reannealed at 800 °C for 1 h in Ar atmosphere to remove Referred crystalline phase information on Si (Crystallography Open
dangling bonds formed on the carbon shell and SiO2 surface. Database (COD) number: 2102763) and SiC (COD number:
Preparation of SiO2−C Mix. SiO2 nanoparticles and carbon 1010995) were provided as initial models. Refined scale factors of
chunks were separately prepared and mixed to obtain SiO2−C each crystalline phase were used for obtaining weight ratio between Si
composites. Then, 200 nm SiO2 nanoparticles were synthesized by and SiC.
Stöber process. The colloidal products were purified and calcined at Preparation of Hollow Mesoporous Shell SiC Nanoparticle
600 °C for 3 h. The carbon chunks were prepared by the following (HMS-SiC). Two hundred milligrams of SiO2@mSiO-C (synthetic
procedure. Two grams of resorcinol and 2 mL of 37% formaldehyde method of SiO2@mSiO2−C is described above) was mixed with 134
were mixed., and 0.3 mL of aqueous ammonia solution was injected to mg of magnesium. The mixture was annealed at 650 °C for 5 h in Ar
the mixture. The resulting solid products were purified by repeated atmosphere with heating rate of 10 °C/min. The result mixture was
filtration and then carbonized at 800 °C for 3 h. treated with 1 M HCl for 5 h, and then it was washed by repeated
Preparation of SBA15-C. Initially, SBA15 was prepared using a centrifugation. Additionally, the washed product was immersed in 2 M
block copolymer templating method. Four grams of pluronic P123, 30 NaOH at 75 °C for 16 h, followed by washing through repeated
g of DI water, and 120 g of 2 M aqueous HCl were mixed. After centrifugation. Finally, residual carbon was removed by calcination at
complete dissolution of P123 polymer, 8.4 g of TEOS was injected to 600 °C for 3 h in muffle furnace.
the reaction mixture. After stirring at 35 °C for 24 h, the mixture was Characterizations. Transmission Electron Microscope (TEM)
heated at 100 °C for another 24 h without stirring. As-prepared solid images were acquired by a Hitachi-7600 system (Hitachi, Japan).
product was washed with ethanol three times by centrifugation and Scanning Electron Microscope (SEM) images were recorded using a
then calcined at 700 °C for 3 h in a muffle furnace. One gram of Hitachi S-4300 instrument (Hitachi, Japan). High-Resolution TEM
prepared SBA15 was mixed with AlCl3·6H2O in a cosolvent of 20 mL (HR-TEM) images were obtained with a JEM-2100F (JEOL). The
of ethanol and 20 mL of DI water by sonication for 1 h. Solid products thermogravimetric analysis (TGA) was performed using an SDT Q600
were collected by centrifugation and dried at 80 °C under reduced device (TA Instruments Inc.), XRD measurement was performed by
pressure, and the product was calcined at 700 °C for 3 h in a muffle D8 Advance (Bruker), with Cu radiation (λ = 1.5406 Å) at 40 kV and
furnace. Then, 200 mg of calcined product, 95 mg of phenol, and 100 40 mA. Nitrogen sorption isotherms were measured at 77 K using
mg of paraformaldehyde were sealed in glass container, and the liquid nitrogen on a Belsorp Mini-II device. All samples were degassed
container was heated at 100 °C for 12 h in an oven to allow gas-phase at 160 °C in static vacuum (p < 10−5 bar) for 12 h. The Brunauer−
polymerization. Finally, it was carbonized at 800 °C for 3 h in Ar Emmett−Teller (BET) method was applied to estimate the specific
atmosphere. surface areas, and the total pore volumes were obtained at P/P0 = 0.99.
Preparation of SiO2@3DOmC Composites. SiO2 nanoparticles The pore size distributions were obtained by the Barrett−Joyner−
of size 33 nm were prepared using a modified Stöber method using a Halenda (BJH) method applied to the adsorption branches of all
basic amino acid (L-lysine) as catalyst, following previous reports.37,38 samples.
Briefly, around 15 nm sized SiO2 nanoparticle seeds were first
synthesized. Eighty milligrams of L-lysine was dissolved in 70 g of DI
water. Then, 5.3 g of TEOS was added to the solution with vigorous
■ RESULTS AND DISCUSSION
Understanding of Reaction System from Literature.
stirring under 90 °C for 2 days. In order to obtain 33 nm sized SiO2
Prior to discussing about the synthesis parameters that affect
nanoparticles, seeded growth using the 15 nm SiO2 nanoparticles was
employed. Then, 21.2 g of TEOS was added to the 15 nm seed the final crystalline phases, we present the thermodynamics of
solution, and the synthesis was allowed to continue at 90 °C for 2 the magnesiothermic reduction of SiO2/C composite in order
days. After filtration, the solution mixture was dried at 80 °C overnight to understand the fundamentals of the reaction.46 When the
in a vibration free environment to obtain closely packed SiO2 formation reactions of Si and SiC are assumed to occur as in
nanoparticles, which was then calcined at 500 °C for 6 h to remove reaction (1) and (2), the Gibbs free energy changes as a
1528 DOI: 10.1021/acs.chemmater.5b05037
Chem. Mater. 2016, 28, 1526−1536
Chemistry of Materials Article

function of the temperature could be calculated (Figure S1, see

Supporting Information for details).
SiO2 (s) + 2Mg(g) + C(s) → Si(s) + C(s) + 2MgO(s)
(1)

SiO2 (s) + 2Mg(g) + C(s) → SiC(s) + 2MgO(s) (2)

As depicted in Figure S1, the free energy change for the

formation of SiC is lower than that of Si in the entire
temperature range. In other words, SiC formation is
thermodynamically preferred, implying that kinetic consider-
ations should account for the formation of Si in this system.
In order to find the kinetic aspect influential to the formation
of Si or SiC, the proposed formation mechanisms of SiC during
the magnesiothermic reduction of SiO2/C composite were
surveyed in the literature. It was noted that direct reaction Figure 1. Schematic representation of Si and SiC formation
between produced Si and carbon is hardly considered as the mechanism by magnesiothermic reduction of SiO2/C composite.
formation reaction of SiC, because it is known that the direct
reaction requires much higher reaction temperature (at least
1100 °C) to be initiated than ordinary temperatures used by
magnesiothermic reduction.47 Therefore, it is widely accepted
that intermediate chemical species should participate in the
formation of SiC. One of suggested intermediates is magnesium
silicide (Mg2Si). Nguyen et al. reported that crystalline phases
of Mg 2 Si, tetragonal MgC 2 /SiC, and cubic SiC were
sequentially observed during magnesiothermic reduction of
chiral nematic SiO2/C composite.42 It implies that SiO2 is
initially reduced by magnesium to form Mg2Si then reacts with
carbon. In addition, the direction of mass transfer is from SiO2
to carbon because the morphology of SiC product resembles
the parent carbon structure.26,29 As a consequence, based on
the SiC formation mechanism, it can be supposed that the
silicon intermediates (mainly in situ-formed Mg2Si) should
encounter carbon by a solid state diffusion process to form SiC.
The diffusion process that takes place in the solid state is
commonly thought to be a kinetically limiting process, so SiC
formation could strongly depend on the diffusion of silicon Figure 2. (a) TEM image of carbon nanosphere; (b,c) TEM image
intermediates. (0.25 nm refers to the interlayer spacing of SiC (111) plane); and (d)
At the same time, according to numerous reports, Mg2Si has XRD pattern of HCl and NaOH treated sample from the reaction
been considered as intermediates of Si during magnesiothermic between Mg2Si and carbon nanoparticle at 750 °C.
reduction of SiO2.40,41 On the basis of these facts, one can
imagine that the kinetic product of Si could be formed if generate SiC when encounting carbon. On the other hand, it is
conversion from SiO2 to Si is completed before the silicon noted that the peak located around 43° could be assigned to
intermediates reach carbon. In other words, Si could be MgC2 which was also reported by Nguyen et al.42
synthesized if insufficient diffusion of Si intermediates to carbon Variation in Crystalline Phases: Effect of Contact Area
is prompted. Schematic representation of the suggested between SiO2 and Carbon. In the previous section, we
mechanism of Si and SiC formation by magnesiothermic proposed that encounter between silicon intermediates and
reduction of SiO2/C composite is depicted in Figure 1. carbon results in the formation of SiC, otherwise Si can be
In order to prove the aforementioned discussion, reaction formed. It implies that formation of Si and SiC in
between silicon intermediate (Mg2Si) and carbon nanosphere magnesiothermic reduction of SiO2/C composite could be
were carried out to find the evidence of SiC formation. controlled if the encounter between silicon intermediates and
Pelletized mixture of prestine Mg2Si and carbon nanospheres carbon is manipulated. In order to confirm this presumption
(328 ± 27 nm, Figure 2a, see more information at experimental experimentally, we first manipulated the actual contact area of
section) was annealed at 750 °C for 5 h in Ar flowing tube SiO2 and carbon. If the contact area is large enough for all
furnace. Then, the product was treated by HCl and NaOH to carbon surfaces to face the intermediates effectively, SiC
remove remaining Mg2Si and the side product of Si. Monitored formation occurs vigorously. However, if the actual contact is
by TEM analysis, it was clearly observed that crystalline fringes quite small, encounter of the intermediates and carbon could be
of (111) planes of SiC was identified on the surface of carbon significantly restricted because most of the silicon intermediates
nanospheres after the reaction (Figure 2b and 2c). Also, the could be located much farther from the carbon surface than the
formation of SiC crystal was observed in the XRD pattern length of diffusion at a given condition. Therefore, low SiO2/C
(Figure 2d) and the size of the crystal with around 7.3 nm contact materials could increase the chances of Si formation.
determined by the Scherrer equation is well matched with TEM As model parent SiO2/C composites, three types of SiO2/C
investigation, strongly evidencing the role of Mg2Si that can composites with different SiO2/C contact areas (mSiO2−C,
1529 DOI: 10.1021/acs.chemmater.5b05037
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SiO2@void@C, and SiO2−C mix) were prepared (Figure 3). The SiO2/C models were then used as reactants for
For mSiO2−C, carbon was confined inside mesoporous SiO2 magnesiothermic reduction. In a typical reaction, SiO2/C was
mixed with magnesium, and annealed at 650 °C for 5 h in Ar
flow with a heating rate of 10 °C/min. The magnesium to SiO2
molar ratio was kept as 2.1:1, nearly stoichiometric. XRD was
employed to analyze the products (Figure 4). The XRD

Figure 4. XRD patterns of samples reduced at 650 °C from SiO2/C

composites with different contact areas (heating rate: 10 °C/min,
reactant weight: 81 mg).

patterns clearly show that the resultant crystalline structures are

Figure 3. Graphic representations and TEM images of (a) mSiO2−C, different for the products obtained from different contact areas
(b) SiO2@void@C, and (c) SiO2−C mix (inset: magnified image of of the parent SiO2/C composites. Solely Si and SiC products
the marginal region). were obtained from SiO2−C mix and mSiO2−C, respectively,
but a mixture of Si and SiC was prepared from SiO2@void@C.
nanoparticles. The pore size of the mesoporous SiO 2 These observations strongly support the assumption that the
nanoparticle (mSiO2) was mostly 2 nm as determined by the crystalline phase of the products in magnesiothermic reduction
BJH method using nitrogen sorption isotherm (Figure S2). of SiO2/C composite is strongly related to the solid state
Energy-dispersive X-ray (EDX) mapping of mSiO2−C revealed diffusion of the silicon intermediates to encounter carbon. In
that the carbon is well-dispersed in the entire mSiO2−C particle the case of mSiO2−C with the highest contact surface area,
(Figure S3). SiO2@void@C has a yolk−shell structure where silicon intermediates could meet most of carbon atoms at a very
hollow carbon shell encapsulates the SiO2 nanoparticle. SiO2− short diffusion length, resulting in thermodynamically preferred
C mix is a simple mixture of SiO2 nanoparticles and carbon SiC formation. On the other hand, for SiO2@void@C and
chunks with sizes over tens of micrometers (Figure S4). SiO2−C mix, there was a part of the silicon intermediates could
mSiO2−C should have the largest contact between SiO2 and not encounter carbon due to the diffusion limits at the given
carbon, and SiO2−C mix should have the smallest. SiO2@ conditions. Thereby, the part of silicon intermediates that are
void@C was thought to have the midrange contact compared away from the carbon surface could be converted to Si. To
to the other models. avoid confusion, it should be emphasized that the low contact
We have adopted a criterion that numerically expresses the material, i.e., SiO2−C mix, does not totally prevent the
contact area between SiO2 and carbon, which is in the formation of SiC, thereby forming both Si and SiC. Indeed,
dimension of contact surface area per SiO2 mass. The contact SiC was observed in the reduced product of the SiO2−C mix
areas of our models were estimated by performing simple (Figure 5a). The reason why the SiC feature was not observed
calculations with assumptions or by nitrogen sorption experi- in the XRD pattern should be attributed to the relative amounts
ment (see Supporting Information for details). The contact of the two crystalline phases.
areas of mSiO2−C, SiO2@void@C, and SiO2−C mix were In addition, the evidence supporting the silicon intermediates
estimated to be 1.6 × 103, 1.5 × 101, 8.9 × 10−2 m2/g, are the main subjects of diffusion were observed. According to
respectively. It is noteworthy that the surface areas of the the TEM images of HCl-treated products obtained from
composites differed by at least 2 orders of magnitude; therefore, reduced SiO2@void@C (Figure S6), the shape of carbon shell
the model SiO2/C composites were appropriately designed and remains intact, while the SiO2 particle inside the shell is totally
prepared. Meanwhile, atomic ratios between SiO2 and carbon deformed. Furthermore, SiC in the carbon shell part and Si in
in the three models were similarly controlled in order to the core part are observed under TEM measurements (Figure
exclude the stoichiometric issues. The atomic ratios of SiO2:C 5b). Therefore, it is likely that the silicon intermediates are
were determined to be around 1:1.8 using TGA as depicted in diffused into the carbon shell to form SiC. Gao et al. has already
Figure S5. reported a similar observation.26,29
1530 DOI: 10.1021/acs.chemmater.5b05037
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Chemistry of Materials Article

Thermodynamic preference of the crystalline phase of the

product in this system cannot be changed by temperature, as
seen in the calculation in Figure S1. However, the diffusion
could be affected by the reaction temperature. The dependence
of solid-state diffusion on temperature could be expressed with
the following equations. The diffusion coefficient (D) of solid
state follows the Arrhenius equation.48
D = D0 ·e−Ea / kT
where D0, Ea, k, T are the maximum diffusion coefficient,
activation energy, Boltzmann constant, absolute temperature,
respectively. Mean diffusion length (L) of the diffusion species
in the solid state is given as follows.48
L = (D·t )0.5
In the equation above, t is the lifetime of diffusing chemical
species. These equations imply that the temperature change
affects the diffusion coefficient, thereby changing the diffusion
length of the silicon intermediates. Therefore, control of the
temperature would help in controlling the resultant crystalline
phases.
The SiO2/C models were annealed at two different
temperatures of 600 and 750 °C, while the other parameters
were not manipulated compared to the experiments performed
at 650 °C. The result product was analyzed by XRD (Figure 6).
In the case of mSiO2−C and SiO2@void@C reduction at 600
°C, the peak identification of the product was not clear, so the
XRD patterns of the corresponding 1 M HCl-treated samples
Figure 5. HR-TEM images of HCl treated samples of reduced (a) are presented in Figure S7. Some important points could be
SiO2−C mix, (b) SiO2@void@C, and (c) mSiO2−C mix at 650 °C noted from the XRD patterns in Figure 6. SiO2@void@C
(heating rate: 10 °C/min, reactant weight: 81 mg, 0.25 and 0.31 nm exhibits a temperature-dependent phase generation behavior.
refer to the interlayer spacing of SiC (111) plane and Si (111) plane, At 750 °C, the relative peak intensity of SiC to Si is increased
respectively). compared to the case at 650 °C. On the other hand, at 600 °C,
only a peak corresponding to Si was observed.
Variation in Crystalline Phases: Effect of Reaction In order to quantify the amounts of Si and SiC obtained at
Temperature. In the previous section, we observed that final different reaction temperatures from SiO2@void@C, the
crystalline phases could be varied if the chance of encounter Rietveld refinement and TGA were employed (Table 1 and
between silicon intermediates and carbon is manipulated by Figure S8). The Rietveld refinement was performed on the
controlling the SiO2/C contact. In this section, we found that XRD patterns of HCl-treated samples (the acid treatment was
reaction temperature also can be influential to the final used for MgO removal). In addition, TGA data were collected
crystalline phases. for the samples treated with HCl and NaOH in order to

Figure 6. XRD patterns of as-reduced products from (a) mSiO2−C, (b) SiO2@void@C, and (c) SiO2−C mix reduced at various reaction
temperatures with a heating rate of 10 °C/min and reactant weight of 81 mg.

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Chem. Mater. 2016, 28, 1526−1536
Chemistry of Materials Article

Table 1. Quantitative Analysis Results for the Reduced However, there was an unsolved question that the dominant
SiO2@void@C at Various Reaction Conditions formation of Si from the SiO2/C composites with two digits of
contact areas from the literature was performed with the
quantification results (atomic
reduction parameters %) temperature over 650 °C, at which considerable amount of SiC
was also obtained with major product of Si in this study as seen
Rietveld TGA
temp ramp rate weight of in Figure 6b. Therefore, other parameters could be involved in
(°C) (°C/min) reactant (mg) Si SiC Si SiC determining the crystalline phases during magnesiothermic
750 10 81 43.5 56.5 39.0 61.0 reduction.
650 60.9 39.1 67.4 32.6 Variation in Crystalline Phases: Effect of Heating Rate.
600 94.6 5.4 91.3 8.7 We investigated the influences of the heating rate on our
650 20 81 17.8 82.2 9.9 90.1 reaction system. SiO2@void@C was chosen as a model system
10 60.9 39.1 67.4 32.6 due to its variation in crystalline phases of the products on
1 94.3 5.7 90.4 9.6 changing the reduction temperatures. The heating rates of 1
650 20 50 3.5 96.5 8.6 91.4 °C/min and 20 °C/min were employed to compare with the
25 26.6 73.4 28.0 72.0 result of 10 °C/min heating rate, which was already verified.
10 83.4 16.6 81.8 18.2 According to XRD (Figure 7a), the formation of Si and SiC is

remove MgO and Si, respectively. TGA provided the ratio

between carbon and SiC, which could be eventually converted
to the ratio of Si and SiC by a simple calculation (see
Supporting Information for more details). As seen in the Table
1, SiC was mostly produced at higher reaction temperatures,
whereas the amount of Si was increased at lower reaction
temperatures. Both the analyses by the Rietveld method and
TGA are found to be in good agreement. These observations
are as expected from the equations; higher temperature
enhances the diffusion length of the silicon intermediates,
resulting in the formation of SiC as the major product. In other
words, part of SiO2, which could not participate in the
formation of SiC at lower temperatures, could take part in the
SiC formation at higher temperatures. On the other hand,
diffusion at lower temperature was restricted, and this
suppressed the formation of SiC, while reduction of SiO2 to
Si by magnesium was still possible. Therefore, only Si could be Figure 7. XRD patterns of reduced SiO2@void@C at 650 °C with a
observed when the experiment was performed at 600 °C. heating rate of 1 °C/min, 10 °C/min, and 20 °C/min (81 mg of
Additionally, it can be noticed that the observable results mixture).
were not affected by temperature if the contact area between
SiO2 and carbon was either very small (<8.9 × 10−2 m2/g, in
the case of SiO2−C mix) or large (>1.6 × 103 m2/g, in the case affected by the heating rate. Higher heating rate induces an
of mSiO2−C) at all reaction temperatures (Figure 6a,c). increased SiC formation, whereas, under the lower heating rate
mSiO2−C was a limiting case for large contact areas because conditions, less SiC is formed. Interestingly, the peak of SiC
the thickness of SiO2 layer between carbon mesopores was obtained at a heating rate of 20 °C/min exhibits higher
supposed to be around several nanometers, so that the diffusion intensities than those of the samples obtained at 750 °C with
length at lower temperature was still enough to make all of heating rate of 10 °C/min (Figure 6b). This implies that the
intermediates to react with carbon. Meanwhile, SiO2−C mix effects of heating rate could be more crucial than the reaction
seemed to be an oppositely limiting case of small contact; temperature.
therefore, the amount of the produced ratio of SiC is always Quantification of Si and SiC using the Rietveld refinement
much smaller than Si in spite of an increased SiC formation at and TGA was carried out (Table 1 and Figure S9). Atomic
higher temperatures. Consequently, SiC was not observed percentages of SiC were 82.2% and 90.1% from the Rietveld
under XRD investigations. refinement and TGA, respectively, for a sample prepared at a
The validity of our assumption was examined with the results heating rate of 20 °C/min, whereas the sample prepared with 1
reported in the literature.18,19,21−24,26−29,42 Estimations of the °C/min heating rate showed atomic percentages of SiC as 5.7%
contact areas between SiO2 and carbon and the resulting (the Rietveld refinement) and 9.6% (TGA), which strongly
crystalline phases of the products obtained from various studies supported the findings from XRD measurements.
are listed in Table S1. According to the data in Table S1, the Influence of heating rate on the results of magnesiothermic
contact area and the resultant crystalline phase are related. For reduction has been already presented by the Cui group.49 They
example, parent SiO2/C composites which were dominantly reported that the nanostructure of silicon reduced from rice
reduced to SiC usually have contact areas over 102 m2/g, husk can be modified by heating rate. It was suggested that
whereas Si was mainly produced when the contact areas were heating rate can change the local accumulation of heat released
around 10° ∼ 101 m2/g except in one case (entry 8 in Table by magnesiothermic reduction (ΔH = −593 kJ/molSi for
S1). This clearly shows that the crystalline phase of the product reaction (1)), thereby higher heating rate resulted in more
is definitely dependent on the contact areas. coarsoned silicon products. Likewise, the effect of heating rate
1532 DOI: 10.1021/acs.chemmater.5b05037
Chem. Mater. 2016, 28, 1526−1536
Chemistry of Materials Article

on our system can be also rationalized by adopting the heat explore the limit in terms of the contact area between SiO2 and
accumulation effect modified by heating rate. The heat arising carbon, in which formation of crystalline Si is allowed.
from the reaction cannot be efficiently dissipated under a high Hence, a model system that has different contact areas of
heating rate because sufficient time is not allowed, resulting in a SiO2/C composites including mSiO2−C, SBA15-C, and SiO2@
higher local temperature and the formation of thermodynami- 3DOmC (Figure 9) is proposed to find the limit of contact
cally favored product (SiC). On the other hand, low heating
rate allows enough heat-dissipation time and the local
temperature is not largely elevated. Therefore, the actual
reaction temperature can vary according to the heating rate,
resulting in different crystalline products.
Variation in Crystalline Phases: Effect of the Weight
of Reactants. We also found that the crystalline phase of the
products of magnesiothermic reduction could be affected by the
amount of the reactants used. When analyzing the products
obtained with different amounts of reactant mixtures (i.e., 10,
25, and 50 mg) under the same heating rate condition of 20
°C/min by XRD, different crystalline phases were identified
(Figure 8). Large amounts of the reactant mixture resulted in

Figure 9. Graphic representations and TEM images of (a) SBA15-C

(inset: HR-TEM image) and (b) SiO2@3DOmC.

area, which can provide Si from magnesiothermic reduction

under specific conditions. First, SBA15-C was synthesized with
carbon confined in the 2D hexagonally arrayed SiO2 mesopores
of around 6 nm (Figure 9a). The contact area was measured as
5.0 × 102 m2/g from nitrogen sorption experiment (Figure
S11). The molar ratio between SiO2 and carbon was 1:1.8 from
TGA plot (Figure S11e). In addition, SiO2@3DOmC is a
composite of closely packed SiO2 nanoparticles with the
interparticle spaces filled with carbon (Figure 9b). The contact
Figure 8. XRD patterns of reduced SiO2@void@C at 650 °C for 5 h area of these materials, measured by nitrogen sorption, are 1.7
with a reactant weight of 10, 25, and 50 mg experiments and (heating
× 102 m2/g for SiO2@3DOmC. Carbon content of SiO2@
rate: 20 °C/min).
3DOmC was slightly lower than other models (Figure S11e),
but carbon is still excess to the SiO2 (SiO2:C = 1:1.2).
On the basis of the findings that restrict the formation of SiC,
the dominant formation of SiC, but the lower amounts of the magnesiothermic reductions of the model composites were
mixture resulted in formation of less SiC in the product. In performed at 600 °C using a heating rate of 1 °C/min and 3 mg
addition, quantification by the Rietveld refinement and TGA of reactant mixture. According to the XRD patterns of the as-
was performed (Figure S10, Table 1). As observed in the XRD, reduced product and HCl treated sample of mSiO2−C (Figure
mostly SiC (96.5% from the Rietveld refinement and 91.4% by 10), SiC is hardly observed. However, Raman signal
the TGA) was identified when 50 mg of the reactants were corresponding to Si−C bonding at around 800 cm−1 was
used; on the other hand, mostly Si (83.4% from the Rietveld observed (Figure S12), suggesting that SiO2 and carbon reacted
refinement and 81.8% by the TGA) was formed 10 mg of with each other at the interface to form SiC, even though no
weight of the reactants. It could be suggested that the larger detectable peak was observed in XRD. The reason why XRD
heat release from the larger amount of reactant resulted in peaks of SiC was not detected seemed that the reaction
higher elevation of local temperature, thereby more formation conditions do not allow SiC crystallite to have enough
of SiC could occur. crystallinity to be detected in XRD. Meanwhile, XRD peaks
Limit of Contact Area of SiO2/C Composite for corresponding to crystalline Si were also not observed, implying
Formation of Si Crystal. Up to now, we have examined the that the encounter between the silicon intermediates and
parameters that affect the crystalline phases of the products carbon readily occurs due to the large contact area (1.6 × 103
from magnesiothermic reduction using various kinds of SiO2/C m2/g) between SiO2 and carbon for the mSiO2−C sample. In
composites. It has been revealed that the parameters such as the addition, crystalline Si peak was also not observed in the XRD
low contact area, low temperature, low heating rate, and low patterns of the product of SBA15-C and Raman signal of SiC
reactant weight, all of which were associated with the chance of was detected as similar to mSiO2−C (Figure 10 andFigure
encounter between silicon intermediates and carbon, restricted S12). Whereas, crystalline Si peaks were observed for the
the formation of SiC, resulting in an increase of the relative product from SiO2@3DOmC sample (Figure 11). Therefore,
amounts of Si. On the basis of these findings, we tried to in conclusion SiO2/C composites with contact areas lower than
1533 DOI: 10.1021/acs.chemmater.5b05037
Chem. Mater. 2016, 28, 1526−1536
Chemistry of Materials Article

Figure 11. (a) Graphic representation of SiO2@mSiO2−C, (b) XRD

patterns of reduced SiO2@mSiO2−C at each preparation step, (c)
Figure 10. XRD patterns of (a) as-prepared products reduced at 600
TEM image (inset: magnified image), (d) HR-TEM image (0.25 nm
°C for 5 h with heating rate of 1 °C/min and 3 mg reactant weight for
refers to the interlayer spacing of SiC (111) plane, inset: SAED
mSiO2−C, SBA15-C, and SiO2@3DOmC, (b) HCl-treated materials.
pattern), (e) TGA plot, and (f) BJH pore distribution of HMS-SiC.

1.7 × 102 m2/g could provide Si crystal at the given reaction

conditions. In addition, it should be mentioned that 29.7% of The morphology of HMS-SiC after calcination was
SiC compared to Si (70.3%) was detected for reduced SiO2@ confirmed by TEM analysis (Figure 11c,d). HMS-SiC showed
3DOmC by TGA quantification method (Figure S13). a hollow shell structure with a void core as expected.
Preparation of Hollow Mesoporous Shell SiC Nano- Crystallites with d-spacing corresponding to SiC (111) were
particle (HMS-SiC). In this section, we demonstrate how these observed in the shell part, confirming the successful
understandings on magnesiothermic reduction of SiO2/C pseudomorphic transformation of SiO2/C composite shell
composites could be utilized to prepare functional materials. into the SiC shell (Figure 11d). The selected area diffraction
As an example, hollow mesoporous shell SiC nanoparticle pattern (SAED) clearly shows the ring patterns of SiC,
(HMS-SiC) was prepared by using SiO2@mSiO2−C as a parent implying the polycrystalline feature of HMS-SiC. In addition,
SiO2/C composite (Figure 11a). SiO2@mSiO2−C is formed in nitrogen sorption experiment revealed that HMS-SiC showed a
the synthetic process of SiO2@void@C before the partial BET surface area of 223 m2/g, and most of pore sizes were in
etching of SiO2. The core of SiO2@mSiO2−C constitutes the range of ∼3−4 nm in the BJH pore size distribution,
nonporous SiO2, but the part of shell is composed of strongly indicating a successful transformation of mesoporosity
mesoporous SiO2 with carbonaceous materials present inside from the parent SiO2/C composite (Figure 11f).
the mesopores (Figure 11a and Figure S14). Because it has In addition, it is worthwhile to mention that the thickness of
been determined that SiC is formed only in the confined the carbon shell and diameter of the hollow core can be
regions of SiO 2 /C mesopores, we expect SiC to be manipulated by adjusting the corresponding dimensions of the
pseudomorphically formed in the mesoporous SiO 2/C parent material with already established methods.20 Therefore,
composite shell while the inside part could be converted to this procedure could be utilized to synthesize HMS-SiC with
controlled thickness of shell and hollow core diameter.

■
Si, which can be selectively removed.
First, SiO2@mSiO2−C was reduced at 650 °C with a heating
rate of 10 °C/min, and subsequent HCl and NaOH treatments CONCLUSIONS
were performed in order to remove MgO, Si, and the remaining It is suggested that silicon intermediates (mainly in situ-formed
SiO2. The final product formed was SiC, as identified from the Mg2Si) show a pivotal role for determining resultantant
XRD patterns (Figure 11b). Calcination at 600 °C for 3 h was crystalline phases during magnesiothermic reduction of SiO2/
performed to remove carbon residues (ca. 3.8 wt % of free C composites. When in situ-formed Mg2Si readily faces carbon,
carbon was detected by TGA, Figure S15). No significant SiC is preferentially formed at the interface between silica and
weight loss was observed in TGA after calcination (Figure 11e), the carbon surface. This hypothesis is supported by a designed
indicating the thermal stability of the HMS-SiC sample. reaction of Mg2Si and carbon nanosphere that resulted in SiC
1534 DOI: 10.1021/acs.chemmater.5b05037
Chem. Mater. 2016, 28, 1526−1536
Chemistry of Materials Article

formation on the carbon surface. In contrast, Si is considered as

a kinetic product which can be usually formed away from the
■ ACKNOWLEDGMENTS
This work was supported by the Basic Science Research
carbon surface because the encounter between silicon Program through the National Research Foundation of Korea
intermediates and carbon surface is more restricted when the (2014R1A1A2057204).

■
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1536 DOI: 10.1021/acs.chemmater.5b05037

Chem. Mater. 2016, 28, 1526−1536