132st KCS General Meeting of the Korean Chemical Society

Photoelectrocatalysis Effects Of IrO2

Cocatalysts On SrTiO3 Nanocubes
Hyun Ju Yang, Jinju Kim, and Je Hyun Bae*
([email protected])

Graduate School of Analytical Science and Technology (GRAST),

Chungnam National University, Daejeon 34134, Republic of Korea

Presentation date : 2023.10.27

 Background
• Heterojunction structure (co-catalyst)
: Lead to the highest efficiency of the photocatalyst

• CoOOH, RuO2 and IrO2 (Co-catalysts, Typical OER electrocatalysts)

-> remarkably improve the OER.

2
Synthesis Of Strontium titanate(SrTiO3) & Iridium Oxide(IrO2)

Sr

Synthesis SrTiO3 Ti
1) NaOH + deionized water (50 mL 10 mol/L NaOH solution)

2) Sr(OH)2∙8H2O (1.6 g) and TiO2 (0.48 g) mix. Stirring & slowly adding NaOH O
3) Autoclave and heated to 220 ℃ for 20 h, Wash (DI water) - remove NaOH.

4) Centrifugation 5 times at 3500 rpm for 10 min ( pH to 7, HCl added) Ir

5) Dried in furnace, 24 h at 60 ℃.
O
Synthesis IrO2/SrTiO3

1) SrTiO3 (0.3 g) + (NH4)2IrCl6

2) The solution (porcelain crucible) heated in a furnace at 80 ℃ for 24 h,(remove the solvent)

3) Calcined in furnace at 400 ℃ for 2 h, naturally cooled 12h .

3
Microstructural Properties Of SrTiO3 And Structural Analysis
Of 0.44 wt%-IrO2/SrTiO3
(110) SrTiO3

Intensity (a.u.)
(200)
(211)
(111)
(212)
(310)
(100)
(210) (300)

20 30 40 50 60 70 80
2 (degree)
SrTiO3 pattern: ICDD card number 00-035-0734

0.225 nm

4
 XPS Analysis Sr 3d, Ti 2p, Ir 4f, O 1s of IrO2/SrTiO3

Sr 3d 132.9 eV Ti 2p 458.1 eV
3d5/2 2p3/2
Intensity (a.u.)

Intensity (a.u.)
134.6 eV
3d3/2

464 eV Material Peak BE/eV

2p1/2
Sr 3d3/2 134.7 eV
Sr 3d5/2 132.9 eV
Ti 2p1/2 464.2 eV
140 138 136 134 132 130 128 468 466 464 462 460 458 456 454
Binding Energy (eV) Binding Energy (eV) Ti 2p3/2 458.5 eV
O Lattice oxygen 529.8 eV
Ir 4f 62.1 eV O 1s
4f7/2 529.3 eV O 1s 531.6 eV
65.1 eV
4f5/2
IrO2 4f7/2 62.5 eV
Intensity (a.u.)

Intensity (a.u.)

IrO2 4f5/2 65.5 eV

532 eV National Institute for Science and Technology

XPS database for Sr, Ti, O and Ir50.

68 67 66 65 64 63 62 61 60 534 533 532 531 530 529 528 527 526

Binding Energy (eV) Binding Energy (eV)

5
 Linear Sweep Voltametry (LSV) & Tafel Plot
9 24
2.5
IrO2/SrTiO3 in light
IrO2/SrTiO3 in dark IrO2/SrTiO3 in light
IrO2/SrTiO3 in dark
SrTiO3 in dark SrTiO3 in light
SrTiO3 in light 270 mV dec-1
18
6

E-IR (V vs RHE)
SrTiO3 in dark

jgeo (mAcm )
jgeo (mAcm )

-2
-2

2.0
12
240 mV dec-1
3

6
1.5 140 mV dec-1
0
0 110 mV dec-1
1.2 1.5 1.8 2.1 2.4 1.2 1.5 1.8 2.1 2.4 -4.8 -3.2
-2
E-IR (V vs RHE) E-IR (V vs RHE) log (j (mAcm ))

Fabrication of catalyst ink Cyclic Voltammetry (CV)

1) SrTiO3 (0.5mg) or 0.44 wt IrO2/SrTiO3 (0.5mg), 10 μl of Nafion, 95μl 1) glassy carbon electrode (RDE, GCE Glassy carbon disk electrode,

of DI water, and 95 μl of IPA : Total volume of 200 μl. disk diameter 3mm, BAS) and the Platinum wire , Hg/HgO (1M

2) Drop-casted 4 μl of the freshly prepared ink NaOH, RE-61AP, BAS)

(Total catalysts loading on the GC electrode : 140 μgcm-2 ) 2) 10mV/s in the potential region between 0.5 and 1.6V vs. Hg/HgO,

3) Dry electrode 1 hr, rotate 1600rpm in 0.1M NaOH electrolyte.

6
 EIS Fitting Result
IrO2/SrTiO3 in dark IrO2/SrTiO3 in light
45
SrTiO3 in dark 30 SrTiO3 in light

Electrochemical Impedance Spectroscopy (EIS)

30
-Z" (cm )

-Z" (cm )
20
2

2
1) potentiostat (GAMRY Reference 600+), and

Rotating Disk Electrode (RDE, RRDE-3A, BAS)

10 Hz
15 10
2) DC voltage of 1.4V vs. Hg/HgO and an AC
5 Hz
8 Hz voltage of 10mV rms
0
12.4 Hz 0
0 15 30 45 0 10 20 30
2
Z' (cm ) 2
Z' (cm )

EIS fitting result

parameters Ru Q α Wd Rct Ceff
[ohm] [sα/ohm] 1/2
[s /ohm] [ohm] [μF]
IrO2/SrTiO3 in light 107 6.97E-06 8.62E-01 7.91E-03 173.6 2.03E-06

IrO2/SrTiO3 in dark 112.3 3.04E-06 9.42E-01 7.33E-03 250.7 1.81E-06

SrTiO3 in light 97.49 2.92E-06 9.42E-01 2.48E-03 388.1 1.75E-06

SrTiO3 in dark 90.38 3.01E-06 9.31E-01 5.79E-04 536.9 1.63E-06

7
 Conclusions

1. Nanoparticles show different catalytic activity depending on their surface energy.

2. A cubic structure can cover a larger area than other shapes, resulting in an increase
in surface energy. When the surface energy is increased, the photocatalytic activity
can be increased by making the movement of electrons slightly smoother.

3. IrO2 is loaded as a co-catalyst on the surface of SrTiO3, it inhibits electron-hole

recombination and lowers the overpotential, increasing the oxygen evolution rate.
Acknowledgement

Funding