Supporting Information

Mild Synthesis of Size-Tunable CeO2 Octahedra for Band Gap Variation

Yi-Chun Huang, Shi-Hong Wu, Chien-Hsuan Hsiao, An-Ting Lee, and Michael H.
Huang*
Department of Chemistry and Frontier Research Center on Fundamental and Applied
Sciences of Matters, National Tsing Hua University, Hsinchu 30013, Taiwan

Ce(NO3)3 ethanol

DI water stir 10 min stir 10 min

150 ºC, 60 min
Figure S1. Schematic illustration of the synthesis procedure for CeO2 octahedra.

Figure S2. Size distribution histograms and standard deviations of CeO2 octahedra
with tunable sizes. (a) 52 nm, (b) 67 nm, (c) 75nm, (d) 85 nm, (e) 100 nm, and (f) 110
nm.

Figure S3. Photograph showing solutions of CeO2 octahedra with tunable sizes.

S1
 a

Ce 3d5 Ce 3d
O KLL
Ce 3d3
300000

250000

intensity
200000

Ce MNN
150000

O 1S
100000

Ce 4d
C 1S
50000

O 2S
0
1000 800 600 400 200 0
binding energy (eV)
Ce 3d3/2 Ce 3d5/2
b
40000 c
916.0 897.6
900.2 528.5
881.8
O 1S
907.0 20000
531.2
intensity

30000

intensity
888.1

10000

20000

920 910 900 890 880 536 534 532 530 528 526

binding energy (eV) binding energy (eV)

Figure S4. (a) Full XPS spectrum of 110 nm CeO2 octahedra. (b, c) Expanded spectra
showing the cerium and oxygen peaks.

Figure S5. Tauc plots of size-tunable CeO2 octahedra and the determined band gaps.

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Table S1. Octahedron heights and side lengths for particle volumes and volume
deviations.
Height
Edge length Edge length Volume Volume deviation
Height (nm) deviation
(nm) deviation (nm) (104 nm 3) (104 nm 3)
(nm)
52 8 36.8 5.7 2.3 0.5
67 10 47.4 7.1 5.0 1.1
75 14 53.0 9.9 7.0 1.9
85 14 60.1 9.9 10.2 2.4
100 12 70.7 8.5 16.7 2.8
110 14 77.8 9.9 22.2 4.0

Here height (h) refers to opposite corner distance of an octahedron. Edge length (a) is
ℎ/ 2. Edge length deviation, a, is equal to h/ 2, where h is standard deviation of
particle height, obtained from particle size distribution histograms in Figure S2.
Volume of an octahedron = ( 2/3)a3
For volume deviation, the formula for cubes is (v/V)2 = 32(a/a)2
For octahedra, v,oct = v,cube × 2/3
Thus, for 52 nm octahedra, v,oct = 2.3 × 104 nm3 × 3 × (5.7 nm/36.8 nm) × 2/3 =
0.5 × 104 nm3

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 a 307
307
307
nm
nm
nm
1.8 b 313
316
318
nm
nm
nm
0.8 1.6
306 nm 314 nm
306 nm 1.4 316 nm
307 nm 314 nm
Absorbance

Absorbance
0.6 1.2

1.0
0.4
0.8

0.6
0.2
0.4

0.2
0.0
0.0

200 300 400 500 600 700 800 200 300 400 500 600 700 800

Wavelength (nm) Wavelength (nm)

0.9 c 326
323
328
nm
nm
nm
2.0 d 335
333
nm
nm
0.8 333 nm
325 nm 1.8
332 nm
0.7 323 nm
1.6 336 nm
326 nm

Absorbance
Absorbance

0.6 1.4

0.5 1.2

0.4 1.0

0.8
0.3
0.6
0.2
0.4
0.1
0.2
0.0
0.0
200 300 400 500 600 700 800
200 300 400 500 600 700 800
Wavelength (nm) Wavelength (nm)
e 343
344
nm
nm 0.8
f 347
348
nm
nm
0.7 344 nm 349 nm
345 nm 0.7 349 nm
0.6
0.6
0.5
0.5
Absorbance

Absorbance

0.4
0.4

0.3
0.3

0.2 0.2

0.1 0.1

0.0 0.0

200 300 400 500 600 700 800 200 300 400 500 600 700 800

Wavelength (nm) Wavelength (nm)

25
g h
Volume (104 nm3)

20

15

10

0
300 310 320 330 340 350

Wavelength (nm)

Figure S6. UV–vis spectra recorded for multiple samples of CeO2 octahedra with
sizes of (a) 52, (b) 67, (c) 75, (d) 85, (e) 100, and (f) 110 nm. The labeled numbers are
the absorption band positions. (g) The error bars give the range of the absorption band
positions. (h) Table showing the average band positions and their standard deviations.

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Table S2. Detailed calculations of EC (vs. Ag/AgCl) of CeO2 octahedra from
Mott‒Schottky plots.

= EC = Efb +

slope EC (vs.
Efb (V) (cm-3) (cm-3)
(F–2 cm4 V–1) Ag/AgCl) (V)

52 nm –0.45 10.03 5.74 –11.60 –0.298 –0.75

85 nm –0.52 8.92 6.45 6.27 –11.48 –0.295 –0.82

110 nm –0.59 7.48 7.70 –11.31 –0.290 –0.88

Table S3. Calculated conduction band (EC) and valence band (EV) positions of CeO2
crystals with tunable sizes in RHE scale.
E (V vs. RHE) = E (V vs. Ag/AgCl) + 0.21 + 0.0591*(6.16)
EC (vs. Ag/AgCl) (V) EC (vs. RHE) (V) Band gap (eV) EV (vs. RHE) (V)

52 nm –0.75 –0.18 3.42 3.24

85 nm –0.82 –0.25 3.11 2.86

110 nm –0.88 –0.31 2.94 2.63

Figure S7. Band diagram of CeO2 octahedra showing the electrochemical water
splitting reactions with respect to the band energies.

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