Photoelectrocatalytic Effects of IrO2 Co-catalysts

on SrTiO3 Nanocubes
Hyun Ju Yang, Jinju Kim, and Je Hyun Bae*
Graduate School of Analytical Science and Technology (GRAST), Chungnam National University, Daejeon 34134, Republic of Korea
Entering the 21st century, environmental pollution problems such as global warming are increasing due to the limited use of fossil fuels. Therefore, in order
to meet the global energy demand without emitting environmental pollutants, it is necessary to develop inexpensive and efficient renewable energy. Forming
a heterojunction structure by loading a co-catalyst on the photocatalyst is one of the methods that can lead to the highest efficiency of the photocatalyst.
IrO2/SrTiO3 heterojunction structures were prepared by loading IrO2 on the surface of SrTiO3 by controlling the amount of Ir precursor through the
impregnation method. the XPS (X-ray Photoelectron Spectroscopy) analysis result showed that IrO2 clearly exists, as a peak value consistent with IrO2 was
observed at a specific binding energy. The (photo)electrocatalytic activity of the synthesized nanocatalysts for photoelectrochemical water oxidation was
investigated using linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). It was confirmed that IrO2 nanoparticles plays a
good role as co-catalysts on the nanocubic SrTiO3 surface for OER (Oxygen Evolution Reaction).
Background

Hydrogen Global energy demand

: abundant clean energy on without emitting
Earth, automobiles, ships and environmental pollutants is
electricity generation. necessary to develop
inexpensive and efficient
renewable energy.

Preparation of SrTiO3 and IrO2/SrTiO3 XRD Patterns of SrTiO3 and IrO2/SrTiO3

SrTiO3 pattern: ICDD card number 00-035-0734
(110) SrTiO3
A B
Fig. 5. (A) XRD patterns of
Intensity (a.u.)

pure cubic shape SrTiO3

(200) and (B) XRD patterns of
(211) pure cubic shape IrO2/
(111)
(212)
(310) SrTiO3
(100)
(210) (300)

Fig. 1. SrTiO3 (0.3 g) and the appropriate amount of an aqueous solution of (NH4)2IrCl6 were 20 30 40 50 60 70 80

thoroughly mixed well in vial. After mixing, the resulting solution was transferred to a porcelain 2 (degree)

crucible. The solution in the porcelain crucible was heated in a furnace at 80 ℃ for 24 h to remove
the solvent. The resulting powder was calcined in furnace at 400 ℃ for 2 h. After the calcination Photoelectrocatalytic Activity of SrTiO3 and IrO2/SrTiO3
process, the final powder was naturally cooled for 12 h by opening the furnace.
Linear Sweep Voltammetry (LSV) & Tafel Plot
Structure of SrTiO3 and IrO2/SrTiO3 9
24 IrO2/SrTiO3 in light
IrO2/SrTiO3 in dark
SrTiO3 in dark
A IrO2/SrTiO3 in light
SrTiO3 in light
B 2.5
IrO2/SrTiO3 in dark C
18 SrTiO3 in light
A B 6
jgeo (mAcm )

E-IR (V vs RHE)
jgeo (mAcm )

-2
-2

SrTiO3 in dark
2.0
12
272 mV dec-1
3 243 mV dec-1
6
1.5
87 mV dec-1 70 mV dec-1
0
0
1.2 1.5 1.8 2.1 2.4 1.2 1.5 1.8 2.1 2.4 -3 -2 -1 0
-2
E-IR (V vs RHE) E-IR (V vs RHE) log (j (mAcm ))
Fig. 2. The structure of the IrO2 (A) and SrTiO3 (B) using VESTA. SrTiO3 (STO) is a semiconductor
Fig. 6. iR-corrected LSV of SrTiO3 and IrO2/SrTiO3 (A) without light and (B) under illumination in
catalyst with a band gap and nanoparticles show different catalytic activity depending on their
the air-saturated 0.1M NaOH electrolyte at a scan rate of 10 mV s-1 on the RDE rotating at 1600
surface energy.
rpm. (C) Tafel plots drawn from the LSV curve of (A,B).

TEM Images of SrTiO3 and IrO2/SrTiO3 Electrochemical Impedance Spectroscopy (EIS)

45
IrO2/SrTiO3 in dark A IrO2/SrTiO3 in light B C
A B C SrTiO3 in dark
30
SrTiO3 in light

30 20
-Z" (cm )

-Z" (cm )
2

10 Hz
15 10 5 Hz
2 0 n m

12.4 Hz 8 Hz
Fig. 3. Synthesize SrTiO3 with Hydrothermal method and The size distribution of SrTiO3 in the TEM 0 0
0 15 30 45 0 10 20 30
image was found to be 40-80 nm. It was confirmed that the peak narrows the crystallinity very well 2 2
Z' (cm ) Z' (cm )
and is consistent with the SrTiO3 ICDD card number in pure phase. (A) TEM image of as-prepared Fig. 7. Nyquist plots of the impedance data of SrTiO3 and IrO2/SrTiO3 (A) without light and (B)
SrTiO3 through hydrothermal method. (B) TEM image of IrO2/SrTiO3 through impregnation method. under illumination in the air-saturated 0.1M NaOH electrolyte. The data (symbols) were fitted
(C) High-resolution TEM image of IrO2/SrTiO3. using the (C) general equivalent circuit with a constant phase element.
XPS Analysis EIS fitting result
458.1 eV 62.1 eV 529.3 eV parameters Ru Q α Wd Rct Ceff
Sr 3d 3d5/2 132.9 eV Ti 2p Ir 4f 65.1 eV 4f7/2 O 1s
2p3/2 [ohm] [sα/Mohm] [s1/2/kohm] [ohm] [μF] Table. 2. Values obtained
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)

134.6 eV
3d3/2 4f5/2
IrO2/SrTiO3 in light 107 6.97 0.86 7.91 174 2.03 from the fitting process
532 eV shown in Fig. 7 are
2p1/2
464 eV
IrO2/SrTiO3 in dark 112 30.4 0.94 7.33 251 1.81
SrTiO3 in light
summarized.
97 2.92 0.94 2.48 388 1.75
140 138 136 134 132 130 128 468 466 464 462 460 458 456 454 68 67 66 65 64 63 62 61 60 534 533 532 531 530 529 528 527 526 SrTiO3 in dark 90 3.01 0.93 5.79 537 1.63
Binding Energy (eV) Binding Energy (eV) Binding Energy (eV) Binding Energy (eV)

Material Peak BE/eV Fig. 4. As a result of XPS analysis, B.E. of Sr, Ti, and Expected Contribution
Sr 3d3/2 134.7 eV O and NIST XPS database were almost identical The system developed here can be efficiently utilized to investigate the role of co-catalysts on
Sr 3d5/2 132.9 eV (XPS error range: ~0.7 eV) semiconductor nanophotocatalysts.
Ti 2p1/2 464.2 eV
Acknowledgements
This work was supported by the National Research Foundation of Korea (NRF) grant funded
Ti 2p3/2 458.5 eV by the Korea government (MSIT) (no.RS-2023-00248645), the Commercialization Promotion
O (SrTiO3) Lattice oxygen 529.8 eV Agency for R&D Outcomes(COMPA) funded by the Ministry of Science and ICT(MSIT) (2023-
O (IrO2) 1s 531.6 eV 23020001-11, R&D Equipment Engineer Education Program), and BK21 FOUR Program by
Table. 1. National Institute for Science and Technology
IrO2 4f7/2 62.5 eV Chungnam National University Research Grant, 2023. H.J.Y. was supported by the National
XPS database for Sr, Ti, O and Ir50
IrO2 4f5/2 65.5 eV Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT)
2022R1A6A3A13070966.