Supporting Information-revised [#L14-01977R1]
Observations on size confinement effect in B-C-N nanoparticles
embedded in mesoporous silica channels
Neeti Tripathi,1 Masaru Yamashita,1 Takeyuki Uchida2 and Tomoko
Akai1,a)
1Advanced
Glass Group, Research Institute for Ubiquitous Energy Devices, National Institute of
Advanced Industrial Science and Technology (AIST),1-8-31, Midorigaoka, Ikeda, Osaka 563-8577,
Japan.
2Materials
Science Research Group, Research Institute for Ubiquitous Energy Devices. National Institute
of Advanced Industrial Science and Technology (AIST)1-8-31, Midorigaoka, Ikeda, Osaka 563-8577,
Japan.
a)Electronic
mail: t-akai@aist.go.jp
1. Characterization techniques details:
Pore size and surface area of B-C-N/silica samples were measured using NOVA 3200e surface
area and pore size analyzer. Formation of B-C-N was confirmed by x-ray diffraction (XRD)
[RIGAKU, Ultima IV] using Cu-Ka radiation. Transmission electron microscopy (TEM) and
energy electron loss spectroscopy (EELS) were performed using Techni G2 at 200 keV.
Information about the bonding states were extracted from Fourier transform infrared
spectroscopy [FTIR-8700, SHIMADZU] and x-ray photoemission spectroscopy (XPS) [PerkinElmer  04-500 dual anode x-ray source instrument]. Before recording the XPS data, sample
surface was etched by using low energy argon ion gun to remove the surface contaminations.
Photoluminescence (PL) and UV-visible spectra were recorded using Hitachi F-4500
fluorescence spectrometer and U-4100 spectrophotometer, respectively. All the measurements
were performed at room temperature.
2. Low angle X-ray measurement
These results demonstrate that the low angle XRD pattern of pure and B-C-N/silica (~12 nm
pore size) samples. Presence of (100) diffraction peak in B-C-N/silica sample indicates the
persistence of long-range ordering after incorporation of B-C-N nanoparticles. The results also
showed that after loading B-C-N nanoparticles, the intensity of the diffraction peak decreased,
which indicated the distortion of the mesoporous framework due to presence of B-C-N
nanoparticles.
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Figure S1: Low angle X-ray diffraction pattern for pure and B-C-N loaded mesoporous silica
particle.
2. TEM image of pure silica sample:
The porous structure of pure mesoporous silica particle is shown in Fig. S2. The void spaces
are filled by the B-C-N nanoparticles and forming the compact structure of B-C-N/silica
composite as shown in 2 (b) of the main article.
Figure S2: STEM images of pure mesoporous silica particle.
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3. X-ray photoemission spectroscopy (XPS)
Figure S3 demonstrates the XPS core level spectra of B, C, N and Si elements, for the sample
BCN@silica-13 nm pore size. Figure S3 (a) show the B1s spectrum, which could be
deconvoluted in to two Gaussians curves with low energy component positioned at 191.4 eV
and a high energy component at 193.2 eV respectively. These positions in B1s spectra attribute
to the B-N and B-O bonds respectively. [1-5] Figure S3 (b) exhibits three components at positions
281.6, 284.3 and 285.5 eV, respectively for C1s spectrum. Mannan et al. [6] assigned the lower
binding energy component at 282.5 eV to the C-B bond. Considering the change in the chemical
environment, peak (I) can be refer to the C-B bonding.[6] Furthermore, peak (II) positioned at
284.4 eV was the same as reported for graphite structure, shows a C atom bonding with 3 C
atoms. The FWHM for peak (II) (2.2 eV) is higher than that for graphite (0.25 eV), which
indicates the contribution of B-C and C-N bonding other than the C atom bonding with three C
atoms. Similar results obtained in case of other B-C-N compounds such as BC2N. [3] The higher
energy component (III) at 285.5 eV revealed that a significant number of carbon atoms are
bonded to the nitrogen.[7] The deconvolution of N 1s revealed the presence of at least two
contributions at energy 397.4 eV and 398.5 eV, as shown in the Figure S3(c). Peak (I) at lower
energy side is assigned to N-B bonding, whereas, peak (II) at higher energy side designated to
the C-N bonding. [8] In Figure S3 (d), peak (I) at 100.8 eV is assigned to SiC, whereas peak (II)
at 102.5 eV referred to SiO2.[7] XPS results support the fact that B-C-N nanoparticles formed
within mesoporous silica matrix.
Figure S3. XPS spectrum (a) B1s (b) C1s (c) N1s (d) Si-2p for B-C-N/silica (pore size 13 nm).
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