Suppressing Charge Recombination by Engineering Homojunctions in Brookite TiO2 Nanorods for Enhanced Photocatalytic Hydrogen Evolution
Abstract
This is the open access version of the article published in: ACS Applied Energy Materials, 2024, 7, 20, 9422–9432, https://doi.org/10.1021/acsaem.4c01950. Deposited according to the requirements of project TECHSCALE (No. CZ.02.01.01/00/22_008/0004587), financed by the MEYS OP JAC Excellent research programme, supported by ERDF/ESF MEYS OP JAC Excellent research programme, supported by ERDF/ESF.
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S1 Supporting information Suppressing charge recombination by engineering homojunctions in brookite TiO2 nanorods for enhanced photocatalytic hydrogen evolution S. M. Hossein Hejazi,*†‡ Mahdi Shahrezaei,†§ Sergii Kalytchuk,† Josef Kalk,† Vojtch Kupka,† Alessia Zollo,∥ Mario Chiesa,∥ Stefano Livraghi,∥ Radek Zboil,†‡ Marco Altomare,⊥ Štpán Kment,*†‡ Alberto Naldoni,*∥ †Czech Advanced Technology and Research Institute, Regional Centre of Advanced Technologies and Materials, Palack University Olomouc, Kkovskho 511/8, 77900 Olomouc, Czech Republic ‡Nanotechnology Centre, Centre for Energy and Environmental Technologies, VSB−Technical University of Ostrava, 17. Listopadu 2172/15, 708 00 Ostrava Poruba, Czech Republic §Department of Physical Chemistry, Faculty of Science, Palacky University, 17. listopadu 1192/12, 779 00 Olomouc, Czech Republic ∥Department of Chemistry and NIS Centre, University of Turin, 10125 Turin, Italy ⊥Department of Chemical Engineering, MESA+ Institute for Nanotechnology, University of Twente, Drienerlolaan 5, 7522 NB Enschede, The Netherlands *Email: Seyy[email protected]. *Email: [email protected]. *Email: [email protected].
S2 Table S1. Power of the light source used for measuring AQY. Wavelength (nm) Power (mW cm-2) 316 1.6 334 1.2 360 2.8 369 8.7 386 5.0 402 17.7 Figure S1. N2 adsorption/desorption type IV isotherms (mesoporous solids) at 77 K for B-US0 (bottom), B-US4 (middle) and B-CU2-US4-HNO3 (top) sample.
S3 Figure S2. (A) Ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS) of B-US2, B-US4 and B-US8 sonoreduced brookite. (B) Corresponding Tauc plots for calculation of band gap according to the base-line method.
S4 Figure S3. HR-XPS spectra of Ti 2p region for (A) B-US0, (B) B-US1 and (C) B-US4, and (D) B-US8. (E) The atomic percentage of Ti3+ at the surface of the samples treated with different time of sonication.
S5 Figure S4. HRTEM image of brookite nanorods after copper particle photodeposition and 4 h sonication (B-CU2-US4) in low (A) and high (B) magnification, and after acid treatment (B-CU2US4-HNO3) in low (C) and high (D) magnification.
S6 Figure S5. Effect of the amount of Cu ions employed in the masking process on the photocatalytic H2 evolution rate from methanol photoreforming (the number before CU is the amount of copper in wt. % of TiO2 present in the solution employed for photodeposition). All of the samples are treated with HNO3 to remove the Cu particles and for simplicity, the prefix "HNO3" in the sample name has been omitted.
S7 Figure S6. HR-XPS spectra of Ti 2p region for (A) B-0.1CU1-US4-HNO3, (B) B-0.1CU2-US4HNO3 and (C) B-0.1CU3-US4-HNO3 samples. (D) The atomic percentage of Ti3+ at the surface of the samples with different duration of photoreduction reaction.
S8 Figure S7. TEM images of TiO2 brookite nanorods loaded with Cu photodeposited particles from a solution containing 0.1 wt. % of copper precursor illuminated for (A) 1h, (B) 2h and (C) 3h, and 1 wt. % of copper precursor illuminated for (D) 1h, (E) 2h and (F) 3h.
S9 Figure S8. The size distribution of copper particle based on different loading time and copper salt concentration for photodecomposition. The size distribution of copper nanoparticles is based on TEM image measurements for 100 particles. Figure S9. The photocatalytic activity of the most active sample (B-CU2-US4-HNO3) functionalized with 1wt. % Pt in (A) seawater and (B) pure water.