The authors thank Dr. Yi Hao Chew (Kobe University) for his
comments on the manuscript. This study was supported by JSPS
KAKENHI (Grants 18KK0161, 19H00915, and 22H00344).
(1) Iwata, K.; Takaya, T.; Hamaguchi, H.; Yamakata, A.; Ishibashi, T.;
Onishi, H.; Kuroda, H. Carrier Dynamics in TiO2 and Pt/TiO2
Powders Observed by Femtosecond Time-Resolved Near-Infrared
326
https://doi.org/10.1021/acs.jpcb.2c07433
J. Phys. Chem. B 2023, 127, 321−327
The Journal of Physical Chemistry B
pubs.acs.org/JPCB
Spectroscopy at a Spectral Region of 0.9−1.5 μm with the Direct
Absorption Method. J. Phys. Chem. B 2004, 108, 20233−20239.
(2) Paz, Y. Transient IR spectroscopy as a tool for studying
photocatalytic materials. J. Phys.: Condens. Matter 2019, 31, 503004.
(3) Kranz, C.; Wächtler, M. Characterizing photocatalysts for water
splitting: from atoms to bulk and from slow to ultrafast processes. Chem.
Soc. Rev. 2021, 50, 1407−1437.
(4) Takanabe, K. Addressing fundamental experimental aspects of
photocatalysis studies. J. Catal. 2019, 370, 480−484.
(5) Kosaka, T.; Teduka, Y.; Ogura, T.; Zhou, Y.; Hisatomi, T.;
Nishiyama, H.; Domen, K.; Takahashi, Y.; Onishi, H. Transient
Kinetics of O2 Evolution in Photocatalytic Water-Splitting Reaction.
ACS Catal. 2020, 10, 13159−13164.
(6) Cronemeyer, D. C. Electrical and Optical Properties of Rutile
Single Crystals. Phys. Rev. 1952, 87, 876−886.
(7) Bogomolov, V. N.; Mirlin, D. N. Optical Absorption by Polarons
in Rutile (TiO2) Single Crystals. Phys. Status Solidi 1968, 27, 443−453.
(8) Yamakata, A.; Ishibashi, T.; Onishi, H. Time-Resolved Infrared
Absorption Spectroscopy of Photo-Generated Electrons in Platinized
TiO2 Particles. Chem. Phys. Lett. 2001, 333, 271−277.
(9) Panayotov, D. A.; Yates, J. T., Jr. n-type doping of TiO2 with
atomic hydrogen-observation of the production of conduction band
electrons by infrared spectroscopy. Chem. Phys. Lett. 2007, 436, 204−
208.
(10) Panayotov, D. A.; Burrows, S. P.; Morris, J. R. Infrared
spectroscopic studies of conduction band and trapped electrons in
UV-photoexcited, H-atom n-doped, and thermally reduced TiO2. J.
Phys. Chem. C 2012, 116, 4535−4544.
(11) Yamakata, A.; Vequizo, J. J. M.; Matsunaga, H. Distinctive
Behavior of Photogenerated Electrons and Holes in Anatase and Rutile
TiO2 Powders. J. Phys. Chem. C 2015, 119, 24538−24545.
(12) Shinoda, T.; Murakami, N. Photoacoustic Fourier Transform
Near- and Mid-Infrared Spectroscopy for Measurement of Energy
Levels of Electron Trapping Sites in Titanium(IV) Oxide Photocatalyst
Powders. J. Phys. Chem. C 2019, 123, 12169−12175.
(13) Fu, Z.; Hirai, T.; Onishi, H. Long-Life Electrons in Metal-Doped
Alkali-Metal Tantalate Photocatalysts Excited under Water. J. Phys.
Chem. C 2021, 125, 26398−26405.
(14) The refractive index at 1 μm wavelength of diamond and water
was quoted from the CRC Handbook of Chemistry andPhysics, 92nd ed.;
Haynes, W. M., Lide, D. R., Eds.; CRC Press: Boca Raton, FL, 2011;
Chapters 10 and 12.
(15) Yamakata, A.; Ishibashi, T.; Onishi, H. Time-Resolved Infrared
Absorption Study of Nine TiO2 Photocatalysts. Chem. Phys. 2007, 339,
133−137.
(16) Ohno, T.; Haga, D.; Fujihara, K.; Kaizaki, K.; Matsumura, M.
Unique Effects of Iron(III) Ions on Photocatalytic and Photoelectrochemical Properties of Titanum Dioxide. J. Phys. Chem. B
1997, 101, 6415−6419.
(17) Sayama, K.; Mukasa, K.; Abe, R.; Abe, Y.; Arakawa, H.
Stoichiometric water splitting into H2 and O2 using a mixture of two
different photocatalysts and an IO3−/I− shuttle redox mediator under
visible light irradiation. Chem. Commun. 2001, 2416−2417.
(18) Savory, D. M.; McQuillan, A. J. IR spectroscopic behavior of
polaronic trapped electrons in TiO2 under aqueous photocatalytic
conditions. J. Phys. Chem. C 2014, 118, 13680−13692.
(19) An, L.; Onishi, H. Electron-Hole Recombination Controlled by
Doping Sites in Perovskite-Structured Photocatalysts: Sr-Doped
NaTaO3. ACS Catal. 2015, 5, 3196−3206.
(20) Warren, D. S.; McQuillan, A. J. Influence of Adsorbed Water on
Phonon and UV-Induced IR Absorptions of TiO2 Photocatalytic
Particle Films. J. Phys. Chem. B 2004, 108, 19373−19379.
(21) Ohtani, B.; Prieto-Mahaney, O. O.; Li, D.; Abe, R. What is
Degussa (Evonik) P25? Crystalline composition analysis, reconstruction from isolated pure particles and photocatalytic activity test. J.
Photochem. Photobio. A 2010, 216, 179−182.
(22) Lewis, N. S.; Rosenbluth, M. L.Theory of Semiconductor
Materials. In Photocatalysis, Fundamentals and Applications; Serpone,
Article
N., Pelizzeti, E., Eds.; John Wiley and Sons: New York, 1989; pp 60−62
and Figure 3.8.
(23) Kopp, G.; Lean, J. L. A new, lower value of total solar irradiance:
Evidence and climate significance,. Geophys. Res. Lett. 2011, 38,
L01706.
(24) Franchini, C.; Reticcioli, M.; Setvin, M.; Diebold, U. Polarons in
materials. Nat. Rev. Mater. 2021, 6, 560−586. and references therein.
(25) Emin, D. Optical properties of large and small polarons and
bipolarons. Phys. Rev. B 1993, 48, 13691−13702.
(26) Onishi, H.; Aruga, T.; Egawa, C.; Iwasawa, Y. Modification of
Surface Electronic Structure on TiO2(110) and TiO2(441) by Na
Deposition. Surf. Sci. 1988, 199, 54−66.
(27) Moser, S.; Moreschini, L.; Jácimovíc, J.; Barišíc, O. S.; Berger, H.;
Magrez, A.; Chang, Y. J.; Kim, K. S.; Bostwick, A.; Rotenberg, E.; Forró,
L.; Grioni, M. Tunable Polaronic Conduction in Anatase TiO2. Phys.
Rev. Lett. 2013, 110, 196403.
(28) Iwase, A.; Kato, H.; Kudo, A. The Effect of Alkaline Earth Metal
Ion Dopants on Photocatalytic Water Splitting by NaTaO3 Powder.
ChemSusChem 2009, 2, 873−877.
(29) Onishi, H. Sodium Tantalate Photocatalysts Doped with Metal
Cations: Why Are They Active for Water Splitting? ChemSusChem
2019, 12, 1825−1834.
(30) Deskins, N. A.; Dupuis, M. Electron transport via polaron
hopping in bulk TiO2: a density functional theory characterization.
Phys. Rev. B 2007, 75, 195212.
(31) Di Valentin, C.; Selloni, A. Bulk and Surface Polarons in
Photoexcited Anatase TiO2. J. Phys. Chem. Lett. 2011, 2, 2223−2228.
(32) Davies, D. W.; Savory, C. N.; Frost, J. M.; Scanlon, D. O.;
Morgan, B. J.; Walsh, A. Descriptors for electron and hole charge
carriers in metal oxides. J. Phys. Chem. Lett. 2020, 11, 438−444.
(33) Uratani, H.; Nakai, H. Simulating the Coupled StructuralElectronic Dynamics of Photoexcited Lead Iodide Perovskites. J. Phys.
Chem. Lett. 2020, 11, 4448−4455.
(34) Sezen, H.; Shang, H.; Bebensee, F.; Yang, C.; Buchholz, M.;
Nefedov, A.; Heissler, S.; Carbogno, C.; Scheffler, M.; Rinke, P.; et al.
Evidence for photogenerated intermediate hole polarons in ZnO. Nat.
Commun. 2015, 6, 6901.
(35) Bandaranayake, S.; Hruska, E.; Londo, S.; Biswas, S.; Baker, L. R.
Small polarons and surface defects in metal oxide photocatalysts studied
using XUV reflection-absorption spectroscopy. J. Phys. Chem. C 2020,
124, 22853−22870.
(36) Shelton, J. L.; Knowles, K. E. Thermally Activated Optical
Absorption into Polaronic States in Hematite. J. Phys. Chem. Lett. 2021,
12, 3343−3351.
(37) Tanner, A. J.; Thornton, G. TiO2 Polarons in the Time Domain:
Implications for Photocatalysis. J. Phys. Chem. Lett. 2022, 13, 559−566.
(38) Ji, Y.; Wang, B.; Luo, Y. Location of trapped hole on rutileTiO2(110) surface and its role in water oxidation. J. Phys. Chem. C 2012,
116, 7863−7866.
(39) Di Valentin, C. A mechanism for the hole-mediated water
photooxidation on TiO2(101) surfaces. J. Phys.: Condens. Matter 2016,
28, 074002.
(40) Gono, P.; Wiktor, J.; Ambrosio, F.; Pasquarello, A. Surface
Polarons Reducing Overpotentials in the Oxygen Evolution Reaction.
ACS Catal. 2018, 8, 5847−5851.
(41) Rajan, A. G.; Martirez, J. M. P.; Carter, E. A. Why do we use the
materials and operating conditions we use for heterogeneous
(photo)electrochemical water splitting. ACS Catal. 2020, 10, 11177−
11234.
327
https://doi.org/10.1021/acs.jpcb.2c07433
J. Phys. Chem. B 2023, 127, 321−327
...
論文の公開元へ
