Suppressing Charge Recombination by Engineering Homojunctions in Brookite TiO2 Nanorods for Enhanced Photocatalytic Hydrogen Evolution

S1
Suppo ing in o ma ion
Supp essing cha ge ecombina ion by enginee ing
homojunc ions in b ooki e TiO2 nano ods o enhanced
pho oca aly ic hyd ogen e olu ion
S. M. Hossein Hejazi,*†‡ Mahdi Shah ezaei,†§ Se gii Kaly chuk,† Jose Kalk,† Voj ch Kupka,†
Alessia Zollo,∥ Ma io Chiesa,∥ S e ano Li aghi,∥ Radek Zboil,†‡ Ma co Al oma e,⊥ Š pán
Kmen ,*†‡ Albe o Naldoni,*∥
†Czech Ad anced Technology and Resea ch Ins i u e, Regional Cen e o Ad anced
Technologies and Ma e ials, Palack Uni e si y Olomouc, Kko skho 511/8, 77900
Olomouc, Czech Republic
‡Nano echnology Cen e, Cen e o Ene gy and En i onmen al Technologies, VSB−Technical
Uni e si y o Os a a, 17. Lis opadu 2172/15, 708 00 Os a a Po uba, Czech Republic
§Depa men o Physical Chemis y, Facul y o Science, Palacky Uni e si y, 17. lis opadu
1192/12, 779 00 Olomouc, Czech Republic
∥Depa men o Chemis y and NIS Cen e, Uni e si y o Tu in, 10125 Tu in, I aly
⊥Depa men o Chemical Enginee ing, MESA+ Ins i u e o Nano echnology, Uni e si y o
Twen e, D iene lolaan 5, 7522 NB Enschede, The Ne he lands
*Email: Seyy[email p o ec ed].
*Email: [email p o ec ed].
*Email: [email p o ec ed].
S2
Table S1. Powe o he ligh sou ce used o measu ing AQY.
Wa eleng h (nm)
Powe (mW cm-2)
316
1.6
334
1.2
360
2.8
369
8.7
386
5.0
402
17.7
Figu e S1. N2 adso p ion/deso p ion ype IV iso he ms (mesopo ous solids) a 77 K o B-US0
(bo om), B-US4 (middle) and B-CU2-US4-HNO3 ( op) sample.
S3
Figu e S2. (A) Ul a iole - isible di use e lec ance spec a (UV-Vis DRS) o B-US2, B-US4
and B-US8 sono educed b ooki e. (B) Co esponding Tauc plo s o calcula ion o band gap
acco ding o he base-line me hod.
S4
Figu e S3. HR-XPS spec a o Ti 2p egion o (A) B-US0, (B) B-US1 and (C) B-US4, and (D)
B-US8. (E) The a omic pe cen age o Ti3+ a he su ace o he samples ea ed wi h di e en ime
o sonica ion.
S5
Figu e S4. HRTEM image o b ooki e nano ods a e coppe pa icle pho odeposi ion and 4 h
sonica ion (B-CU2-US4) in low (A) and high (B) magni ica ion, and a e acid ea men (B-CU2-
US4-HNO3) in low (C) and high (D) magni ica ion.

S6
Figu e S5. E ec o he amoun o Cu ions employed in he masking p ocess on he pho oca aly ic
H2 e olu ion a e om me hanol pho o e o ming ( he numbe be o e CU is he amoun o coppe
in w . % o TiO2 p esen in he solu ion employed o pho odeposi ion). All o he samples a e
ea ed wi h HNO3 o emo e he Cu pa icles and o simplici y, he p e ix "HNO3" in he sample
name has been omi ed.
S7
Figu e S6. HR-XPS spec a o Ti 2p egion o (A) B-0.1CU1-US4-HNO3, (B) B-0.1CU2-US4-
HNO3 and (C) B-0.1CU3-US4-HNO3 samples. (D) The a omic pe cen age o Ti3+ a he su ace
o he samples wi h di e en du a ion o pho o educ ion eac ion.
S8
Figu e S7. TEM images o TiO2 b ooki e nano ods loaded wi h Cu pho odeposi ed pa icles om
a solu ion con aining 0.1 w . % o coppe p ecu so illumina ed o (A) 1h, (B) 2h and (C) 3h, and
1 w . % o coppe p ecu so illumina ed o (D) 1h, (E) 2h and (F) 3h.
S9
Figu e S8. The size dis ibu ion o coppe pa icle based on di e en loading ime and coppe sal
concen a ion o pho odecomposi ion. The size dis ibu ion o coppe nanopa icles is based on
TEM image measu emen s o 100 pa icles.
Figu e S9. The pho oca aly ic ac i i y o he mos ac i e sample (B-CU2-US4-HNO3)
unc ionalized wi h 1w . % P in (A) seawa e and (B) pu e wa e .