Incorporation of alien atoms into TiO2 is an effective means to extend its light absorption edge for utilizing solar energy sufficiently. Herein, taking rutile and anatase as precursors, respectively, Rh element was attempted to dope into TiO2 by an immersion-calcination process. The results showed that Rh species were readily immerged in the crystal structure of rutile at a temperature above 973 K, while they were constantly positioned on the surface of anatase in a separate form of Rh2O3 nanoparticle even at 1173 K. Density functional theory simulations revealed that the Rh-rutile sample owned a higher negative formation energy than Rh-anatase. Under visible light irradiation and in the presence of ascorbic acid as a sacrificial reagent, photocatalytic hydrogen evolution activity over Rh-doped rutile was about 50 times of that over Rh-doped anatase powders. The present work demonstrates the roles of the crystal phase in atom doping that eventually dominates photocatalytic activities.
References
1.
A. J.
Bard
and M. A.
Fox
, “Artificial photosynthesis: Solar splitting of water to hydrogen and oxygen
,” Acc. Chem. Res.
28
, 141
–145
(1995
).2.
A.
Kudo
and Y.
Miseki
, “Heterogeneous photocatalyst materials for water splitting
,” Chem. Soc. Rev.
38
, 253
–278
(2009
).3.
X.
Wang
, F.
Wang
, Y.
Sang
, and H.
Liu
, “Full-spectrum solar-light-activated photocatalysts for light–chemical energy conversion
,” Adv. Energy Mater.
7
, 1700473
(2017
).4.
Y. K.
Kho
, A.
Iwase
, W. Y.
Teoh
, L.
Madler
, A.
Kudo
, and R.
Amal
, “Photocatalytic H2 evolution over TiO2 nanoparticles. the synergistic effect of anatase and rutile
,” J. Phys. Chem. C
114
, 2821
–2829
(2010
).5.
J.
Liqiang
, S.
Xiaojun
, X.
Baifu
, W.
Baiqi
, C.
Weimin
, and F.
Honggang
, “The preparation and characterization of La doped TiO2 nanoparticles and their photocatalytic activity
,” J. Solid State Chem.
177
, 3375
–3382
(2004
).6.
J.
Zhang
, X.
Chen
, Y.
Bai
, C.
Li
, Y.
Gao
, R.
Li
, and C.
Li
, “Boosting photocatalytic water splitting by tuning built-in electric field at phase junction
,” J. Mater. Chem. A
7
, 10264
–10272
(2019
).7.
Y.
Zhang
, J.
Zhang
, Q.
Xu
, S.
Yan
, S.
Zhao
, G.
Luo
, and C.
Li
, “Surface phase of TiO2 modified with La2O3 and its effect on the photocatalytic H2 evolution
,” Mater. Res. Bull.
53
, 107
–115
(2014
).8.
C.-H.
Liao
, C.-W.
Huang
, and J.
Wu
, “Hydrogen production from semiconductor-based photocatalysis via water splitting
,” Catalysts
2
, 490
–516
(2012
).9.
X.-Y.
Sun
, C.
Liu
, Z.
Chen
, and Y.-Q.
Ma
, “The photocatalytic performance of Ta and Rh co-doped TiO2 tuned by the average dopant valence
,” Mater. Res. Bull.
100
, 153
–160
(2018
).10.
F.
Oropeza
and R.
Egdell
, “Control of valence states in Rh-doped TiO2 by Sb co-doping: A study by high resolution x-ray photoemission spectroscopy
,” Chem. Phys. Lett.
515
, 249
–253
(2011
).11.
R.
Niishiro
, R.
Konta
, H.
Kato
, W.-J.
Chun
, K.
Asakura
, and A.
Kudo
, “Photocatalytic O2 evolution of rhodium and antimony-codoped rutile-type TiO2 under visible light irradiation
,” J. Phys. Chem. C
111
, 17420
–17426
(2007
).12.
E.
Glover
, S.
Ellington
, G.
Sankar
, and R.
Palgrave
, “The nature and effects of rhodium and antimony dopants on the electronic structure of TiO2: Towards design of Z-scheme photocatalysts
,” J. Mater. Chem. A
4
, 6946
–6954
(2016
).13.
A.
Kudo
, S.
Yoshino
, T.
Tsuchiya
, Y.
Udagawa
, Y.
Takahashi
, M.
Yamaguchi
, I.
Ogasawara
, H.
Matsumoto
, and A.
Iwase
, “Z-scheme photocatalyst systems employing Rh- and Ir-doped metal oxide materials for water splitting under visible light irradiation
,” Faraday Discuss.
215
, 313
–328
(2019
).14.
S.
Ida
, K.
Sato
, T.
Nagata
, H.
Hagiwara
, M.
Watanabe
, N.
Kim
, Y.
Shiota
, M.
Koinuma
, S.
Takenaka
, T.
Sakai
et al, “A cocatalyst that stabilizes a hydride intermediate during photocatalytic hydrogen evolution over a rhodium-doped TiO2 nanosheet
,” Angew. Chem., Int. Ed.
130
, 9211
–9215
(2018
).15.
K.
Fujihara
, T.
Ohno
, and M.
Matsumura
, “Splitting of water by electrochemical combination of two photocatalytic reactions on TiO2 particles
,” J. Chem. Soc., Faraday Trans.
94
, 3705
–3709
(1998
).16.
M.
Andersson
, L.
Österlund
, S.
Ljungstroem
, and A.
Palmqvist
, “Preparation of nanosize anatase and rutile TiO2 by hydrothermal treatment of microemulsions and their activity for photocatalytic wet oxidation of phenol
,” J. Phys. Chem. B
106
, 10674
–10679
(2002
).17.
J.
Zhang
, Q.
Xu
, Z.
Feng
, M.
Li
, and C.
Li
, “Importance of the relationship between surface phases and photocatalytic activity of TiO2
,” Angew., Chem. Int. Ed.
120
, 1790
–1793
(2008
).18.
J.
Zhang
, M.
Li
, Z.
Feng
, J.
Chen
, and C.
Li
, “UV Raman spectroscopic study on TiO2. I. Phase transformation at the surface and in the bulk
,” J. Phys. Chem. B
110
, 927
–935
(2006
).19.
P.
Kubelka
, “New contributions to the optics of intensely light-scattering materials. Part I
,” J. Opt. Soc. Am.
38
, 448
–457
(1948
).20.
R. D.
Shannon
, “Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
,” Acta Crystallogr., Sect. A
32
, 751
–767
(1976
).21.
X. Y.
Li
, Y. L.
Wang
, W. F.
Liu
, G. H.
Jiang
, and C. F.
Zhu
, “Study of oxygen vacancies' influence on the lattice parameter in ZnO thin film
,” Mater. Lett.
85
, 25
–28
(2012
).22.
X.
Li
, W.
Li
, S.
Gu
, X.
Liu
, H.
Li
, C.
Ren
, X.
Ma
, and H.
Zhou
, “Efficient ytterbium-doped Bi2WO6 photocatalysts: Synthesis, the formation of oxygen vacancies and boosted superoxide yield for enhanced visible-light photocatalytic activity
,” J. Alloys Compd.
851
, 156935
(2021
).23.
T.
Ohsaka
, F.
Izumi
, and Y.
Fujiki
, “Raman spectrum of anatase, TiO2
,” J. Raman Spectrosc.
7
, 321
–324
(1978
).24.
V.
Swamy
, B. C.
Muddle
, and Q.
Dai
, “Size-dependent modifications of the Raman spectrum of rutile TiO2
,” Appl. Phys. Lett.
89
, 163118
(2006
).25.
O.
Frank
, M.
Zukalova
, B.
Laskova
, J.
Kürti
, J.
Koltai
, and L.
Kavan
, “Raman spectra of titanium dioxide (anatase, rutile) with identified oxygen isotopes (16, 17, 18)
,” Phys. Chem. Chem. Phys.
14
, 14567
–14572
(2012
).26.
P. J.
Huang
, H.
Chang
, C. T.
Yeh
, and C. W.
Tsai
, “Phase transformation of TiO2 monitored by Thermo-Raman spectroscopy with TGA/DTA
,” Thermochim. Acta
297
, 85
–92
(1997
).27.
Y.
Masuda
and K.
Kato
, “Synthesis and phase transformation of TiO2 nanocrystals in aqueous solutions
,” J. Ceram. Soc. Jpn.
117
, 373
–376
(2009
).28.
N.
Wetchakun
, B.
Incessungvorn
, K.
Wetchakun
, and S.
Phanichphant
, “Influence of calcination temperature on anatase to rutile phase transformation in TiO2 nanoparticles synthesized by the modified sol–gel method
,” Mater. Lett.
82
, 195
–198
(2012
).29.
G. E.
Lloyd
, “Atomic number and crystallographic contrast images with the SEM: A review of backscattered electron techniques
,” Mineral. Mag.
51
, 3
–19
(1987
).30.
P.
Hohenberg
and W.
Kohn
, “Density functional theory (DFT)
,” Phys. Rev.
136
, B864
(1964
).31.
G.
Kresse
and J.
Furthmüller
, “Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
,” Computational Materials Science
6
, 15
–50
(1996
).32.
Z.
Yang
, G.
Luo
, Z.
Lu
, and K.
Hermansson
, “Oxygen vacancy formation energy in Pd-doped ceria: A DFT + U study
,” J. Chem. Phys.
127
, 074704
(2007
).33.
L.
Minervini
, M. O.
Zacate
, and R. W.
Grimes
, “Defect cluster formation in M2O3-doped CeO2
,” Solid State Ionics
116
, 339
–349
(1999
).34.
R.
Wu
, G.
Peng
, L.
Liu
, Y.
Feng
, Z.
Huang
, and Q.
Wu
, “Ferromagnetism in Mg-doped AIN from ab initio study
,” Appl. Phys. Lett.
89
, 142501
(2006
).35.
K. K.
Ghuman
and C. V.
Singh
, “A DFT + U study of (Rh, Nb)-codoped rutile TiO2
,” J. Phys. Condens. Matter
25
, 085501
(2013
).36.
V.
Popescu
and A.
Zunger
, “Effective band structure of random alloys
,” Phys. Rev. Lett.
104
, 236403
(2010
).37.
V.
Popescu
and A.
Zunger
, “Extracting E versus K effective band structure from supercell calculations on alloys and impurities
,” Phys. Rev. B
85
, 085201
(2012
).© 2021 Author(s). Published under an exclusive license by AIP Publishing.
2021
Author(s)
You do not currently have access to this content.