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## Creator

Rafat Tahawy, Mohamed Esmat, [Hamza El-Hosainy](https://orcid.org/0000-0001-8244-4382), Fatma E Farghaly, El-Sayed A Abdel-Aal, Fouad I El-Hosiny, [Yusuke Ide](https://orcid.org/0000-0002-6901-6954)

## Rights

This is a pre-copyedited, author-produced version of an article accepted for publication in Bulletin of the Chemical Society of Japan following peer review. The version of record Rafat Tahawy, Mohamed Esmat, Hamza El-Hosainy, Fatma E Farghaly, El-Sayed A Abdel-Aal, Fouad I El-Hosiny, Yusuke Ide, A layered titanate nanowire helps Pt/TiO2 photocatalyst for solar hydrogen evolution from water with high quantum efficiency, Bulletin of the Chemical Society of Japan, Volume 97, Issue 8, August 2024, uoae079 is available online at: https://doi.org/10.1093/bulcsj/uoae079.[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

## Other metadata

[A layered titanate nanowire helps Pt/TiO2 photocatalyst for solar hydrogen evolution from water with high quantum efficiency](https://mdr.nims.go.jp/datasets/4a44aa8f-a895-406d-b06f-c3ef8b2e5438)

## Fulltext

A Layered Titanate Nanowire Helps Pt/TiO2 Photocatalyst for Solar Hydrogen Evolution from Water with High Quantum EfficiencyRafat Tahawy,1,2 Mohamed Esmat,1,3 Hamza El-Hosainy,1,4 Fatma E. Farghaly,2 El-Sayed A. Abdel-Aal,2  F. I. El-Hosiny,5 Yusuke Ide1,6*1Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan2Central Metallurgical Research and Development Institute (CMRDI), P.O. Box 87 Helwan, 11421 Cairo, Egypt3Materials Science and Nanotechnology Department, Faculty of Postgraduate Studies for Advanced Sciences (PSAS), Beni-Suef University (BSU), Beni-Suef 62511, Egypt4Institute of Nanoscience & Nanotechnology, Kafrelsheikh University, Kafrelsheikh 33511, Egypt5Department of Chemistry, Faculty of Science, Ain shams University, 11566 Abassia, Cairo, Egypt6Graduate School of Engineering Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan*Corresponding author: CSJ Editorial Office, 1-1, Namiki, Ibaraki, Tsukuba 305-0044. Email: ide.yusuke@nims.go.jpAbstractResearch into TiO2 photocatalysts for solar H2 evolution from water is still growing for environmentally benign and economically valid H2 production. Herein, in contrast to many researches on the modification of TiO2 toward higher photocatalytic activities, we develop a photocatalytically inactive TiO2-based nanostructure and use it, like graphene, as a booster of a benchmark TiO2. A layered potassium titanate with two-dimensional plate-like particle morphology was converted to the corresponding one-dimensional nanowire form via a hydrothermal reaction, after which the layered potassium titanate nanowire was acid-treated to obtain a layered titanate nanowire. This nanowire was completely inactive toward H2 evolution from water containing methanol under solar simulator irradiation. However, when Pt nanoparticle-loaded P25 TiO2 (Pt/P25) was mixed with a considerably smaller amount of the layered titanate nanowire in water, a durable composite was obtained and the composite showed a good photocatalytic activity three times higher than Pt/P25. The apparent quantum efficiency of the reaction at wavelength of 350 nm was 56%, which was higher than or comparable to those of the state-of-the-art TiO2-based photocatalysts. The possible reason for the enhanced photocatalytic activity of the Pt/P25 and layered titanate nanowire composite involved the transfer of photogenerated holes from Pt/P25 to the nanowire to suppress charge recombination and/or disaggregation (improved dispersion) of Pt/P25 particles on the nanowire.Keywords: Layered titanate, nanowire, P25, hydrogenGraphical abstractYusuke IdeHe received his Ph.D. from Waseda University in 2007. After working as a research associate there, in 2010, he moved to Hiroshima University to work as an assistant professor. In 2012, he became a senior researcher at NIMS and promoted to a principal researcher in 2020. Since 2023, he has been a group leader in NIMS as well as a professor in Yokohama National University. His current interests include the development of high-performance, cost-effective and environmentally friendly materials alternative to existing commodities and industrial products. He also tries to synthesize key materials for realizing hydrogen society.Chemistry Letters Vol. 35,  No. 1  (2006)123Copyright ©2006 The Chemical Society of JapanChemistry Letters Vol. 35,  No. 1  (2006)5Chemistry Letters Vol. 35,  No. 1  (2006)4Chemistry Letters Vol. 35,  No. 1  (2006)3Published on the web (Advance View) April 1, 2006;     DOI  10.1246/cl.2006.***1. IntroductionSolar-driven water splitting, such as overall water splitting (stoichiometric H2 and O2 evolution) and H2 evolution from water (containing sacrificial agents), using solid photocatalysts is a potentially feasible means of realizing a hydrogen society. To attain high solar energy conversion efficiency, in addition to design narrow-bandgap photocatalysts to effectively utilize visible-to-near infrared light of the incident solar light, the quantum efficiency of photocatalytic reactions must be increased over a wide wavelength range. The development of solid photocatalyst for water splitting showing high quantum efficiency even at UV region, occupying 3-5 % of the incident solar spectrum, is still challenging;1,2 almost 100% of quantum efficiency has been just recently attained in overall water splitting using a cocatalyst-modified aluminum-doped strontium titanate at wavelength of < 365 nm.3Titanium dioxide (TiO2), a prototype solid photocatalyst for water splitting (especially for H2 evolution from water),4 has long been attracting research interest owing to its cost-effectiveness, high chemical stability and excellent UV-induced activity.5,6 However, it has a certain drawback, the fast recombination of photogenerated electron-hole pairs. Therefore, significant efforts have been still devoted to the development of modified TiO2 with enhanced charge separation efficiency.7 A recent good example is reduced (colored) TiO2, originally developed as black TiO2.8-13 Although the photocatalytic mechanism remains unresolved (they often show UV-enhanced activity despite the narrowed band gap compared to TiO2), reduced TiO2 showed the quantum efficiency in H2 evolution from water reaching 44% at 365 nm even without any cocatalyst metals.9 The modification of TiO2 with single-atom catalysts (e.g., Pt, Cu) has also been recognized as a powerful tool to enhance the charge separation and H2 evolution efficiences.14-17 A state-of-the-art single-atom Cu-supported TiO2 showed the quantum efficiency of up to 56% at 365 nm.16,17 So far, several one-dimensional (1D) TiO2-based photocatalysts, including TiO2 nanowires, have shown higher charge separation and photocatalytic efficiencies than those in other TiO2 nanomaterials.5,18-22 Herein, in contrast to these high performance 1D TiO2-based photocatalysts, we report that a newly developed photocatalytically inactive layered titanate nanowire boosts the solar H2 evolution on a benchmark TiO2 photocatalyst. P25 is one of the most active TiO2 for many photocatalytic reactions among commercial TiO223 and Pt nanoparticle cocatalyst-loaded P25 (Pt/P25) has been used as a de facto benchmark photocatalyst for solar H2 evolution from water.9,13 We demonstrate that the layered titanate nanowire is simply mixed with Pt/P25 to form a particulate composite and the composite shows an impressive apparent quantum efficiency higher than or comparable to the state-of-the-art TiO2-based photocatalysts. We expect that the layered titanate nanowire would facilitate many TiO2 photocatalytic reactions like graphene.242. ExperimentalPreparation of a layered titanate nanowireKTLO and its nanowire (named KTLO NW) was prepared according to the method in our preliminary report.25 Briefly, K2CO3 (Nacalai Tesque, 99.5%), Li2CO3 (Tokyo Chemical Industry, >98%), and TiO2 (P25) (Nippon Aerosil), in the molar ratio of 2.4:0.8:10.4, were ground together in an agate mortar for 2 h, then the mixture was calcined in air at 600 °C for 20 h. After cooling to 21-22 °C, the powder was ground again and then calcined in air at 600 ˚C for 20 h, to obtain KTLO. Following this, 0.2 g of KTLO was mixed with 0.014 g of NH4F (Sigma-Aldrich, >99.9%) in 0.78 g of a tetrapropylammonium hydroxide solution (Tokyo Chemical Industry, 40 wt% aqueous solution) and the mixture was hydrothermally treated at 170 °C for 1 week. After the hydrothermal reaction, the precipitate was separated by centrifugation, washed with ethanol (four times), and dried at 60 °C overnight. The obtained KTLO NW (100 mg) was mixed in 0.01M HCl and the mixture was stirred at 21-22 °C for 24 h. The precipitate was then separated by centrifugation. This acid treatment was repeated thrice, using fresh 0.01M HCl solution each time. Finally, the obtained precipitate was washed thoroughly with water and dried at room temperature in a vacuum oven for 24 h. The product was named HTO NW.Synthesis of HTO NW-Pt/P25 compositePt/P25 with 0.5wt% of Pt-cocatalyst was prepared according to a previously reported method.26 HTO NW and Pt/P25 were mixed in different ratios (15 mg in total) in water (5 mL) and the mixture was sonicated for 1 min, after which the pH of the mixture was adjusted to approximately 4.0 using 0.01M HCl. The obtained mixture was vigorously stirred using a homogenizer (MICROTEC Co. Ltd., mixing rate of 20000 rpm) for 10 min, after which the aqueous solution was evaporated in a vacuum oven at room temperature for 3 days. The product was named HTO NW-Pt/P25(X:Y), where X and Y denote the amount (mg) of each powder added.CharacterizationsPowder X-ray diffraction (XRD) patterns were obtained using a powder X-ray diffractometer (RIGAKU smart-lab) with Cu Kα radiation at 40 kV and 40 mA. Micro-Raman scattering measurements (Photon Design Company) were obtained at room temperature using a 100× objective and a 532 nm excitation light source. X-ray photoelectron spectroscopy (XPS) was performed using a PHI Quantera SXM instrument, operated with Al Kα radiation at 5 mA and 20 kV. The energies were calibrated as C 1s peak as 285.0 eV.  The morphology of the powder samples was examined using a HITACHI SU-8000 scanning electron microscope (SEM). High-resolution transmission electron microscope (HRTEM) and high-angle annular dark-field scanning TEM (HAADF-STEM) images were taken using a JEOL JEM-2100F microscope (operated at 300 kV). UV-Vis diffused reflectance spectra were recorded on a JASCO V-570 spectrophotometer integrated with the sphere (722 attachment).  Dynamic light scattering (DLS) was performed on an Otsuka Electronics zeta-potential/particle-size analyzer.Photocatalytic tests for H2 evolution15 mg of powder was added to an aqueous methanol/water solution (50 vol%, 5 mL) in a Pyrex glass tube (34 ml). After sonication for 1 min and subsequent Ar-bubbling for 30 min, the tube was sealed with a rubber septum and, under stirring, was subsequently irradiated with a solar simulator (San-Ei Electric, λ > 300 nm, 150 Wm−2). The headspace gas during the reaction was withdrawn with a gas-tight syringe and analyzed using a Shimadzu GC-2010 Plus gas chromatograph equipped with a barrier ionization discharge detector. For AQE measurements, the Pyrex glass tube was irradiated with monochromated light using an Ushion 500 W Xe lamp with a Bunkoukeiki SM-25 monochromator. The number of incident photons was determined using a Bunchoukeiki S1337-1010BQ silicon photodiode. An apparent quantum efficiency (AQE, %) was defined as: [number of H2 evolved] × 2/ [number of incident photons] × 100. Photocatalytic tests for formic acid oxidation15 mg of powder was added to an aqueous solution of formic acid (5 vol%, 5 mL) in a Pyrex glass tube (34 mL) and purged with pure oxygen gas (> 99%) for 30 min. Then, the tube was sealed with a rubber septum and irradiated, under stirring, with a solar simulator. The headspace gas from the reaction was analyzed with a Shimadzu GC-2010.3. Results and discussionSynthesis of layered titanate nanowire and its compositeIn our preliminary study, the mixture of the protonated type of a typical layered alkali titanate (K0.8Ti1.73Li0.27O4, KTLO), named HTO, and Pt/P25 exhibited no significant enhancement (only 1.2 times) in the solar photocatalytic activity, compared with that in Pt/P25, for H2 evolution from water containing methanol.27 However, we have recently reported a unique 2D-to-1D conversion of KTLO and the enhanced solar photocatalytic activity of the resultant KTLO NW toward the reduction of Cd cations in water.25 These results motivated the creation of mixture/composite of HTO NW and Pt/P25 for a significant enhancement in the photocatalytic activity for H2 evolution.Fig. 1. (a) XRD patterns and (b) Raman spectra of KTLO, KTLO NW, and HTO NW. (c) Ti 2p- and (d) O 1s-region XPS spectra of P25 and HTO NW.In contrast to HTO, which can be prepared from KTLO via treatment with 0.1M HCl,27,28 KTLO NW was observed to dissolve when treated under the same conditions. Thus, a careful investigation of the protonation conditions for KTLO NW, for obtaining HTO NW without losing the original lepidocrocite structure, was performed. Fig. 1a shows the XRD pattern of the product prepared via the treatment of KTLO NW with 0.01M HCl. Almost all obtained diffraction peaks were in agreement with those reported for HTO (H1.07Ti1.73☐0.27O4, d020 value of 0.92 nm).28 Additionally, in the Raman spectrum of the product, the observed peaks (270, 383, 449, 656, and 703 cm−1) were in good agreement with those reported for HTO (Fig. 2b).25,29 Considering that K was scarcely detected in the XPS survey spectrum of the product (data not shown), these results confirm the successful protonation of KTLO NW to form HTO NW.To investigate the formation of any defects due to the HCl treatment of KTLO NW, XPS measurements were performed on the product (Fig. 1c, d). The peak positions observed for Ti 2p- and O 1s- region spectra of the product were almost identical to those observed for P25, one of the most crystalline (least defective) TiO2.23 These results confirm that HTO NW has no significant defects (such as Vo and Ti3+),30 which may result from the protonation of KTLO NW, likely due to the mild conditions of the treatment.Fig. 2. SEM images of (a) KTLO NW, and (b, c) HTO NW. (d) HAADF-STEM and (e) HRTEM images of HTO NW-Pt/P25(2:13).As expected, HTO NW is composed of nanowires with a length of several hundred nanometers and a diameter of approximately 10 nm, identical to nanowires comprising KTLO NW, as shown in the SEM images (Fig. 2a-c). Following this, we mixed the HTO NW particles and Pt/P25 particles in aqueous solutions to create their composites. The HAADF-STEM and HRTEM images of HTO NW-Pt/P25(2:13), a typical example of the mixed product, reveal that an HTO NW particle contacts several Pt/P25 particles to form particle interfaces (Fig. 2d, e). Considering the isoelectronic points of HTO (~2)31,32 and P25 (6.4),33 the mixing of HTO NW and Pt/P25 in an aqueous solution (pH 4.0) with a homogenizer, and the subsequent removal of the solvent produced the required heterojunction-like composite via electrostatic interactions between each component.27Solar H2 evolution activity of the compositeHTO NW significantly enhanced the photocatalytic activity of Pt/P25 toward H2 evolution from water containing methanol under solar simulator irradiation (Fig. 3a). HTO NW by itself was inactive for the reaction (while showing a moderate activity after Pt loading as shown in later). It was inactive even after treating with dilute HCl under the same condition used for the synthesis of HTO NW-Pt/P25 composite (the product was named Acid HTO NW). In contrast, HTO NW-Pt/P25 samples showed increased activity with an increase in the relative amounts of Pt/P25. HTO NW-Pt/P25(2:13) showed the highest activity, which was three times higher than that of Pt/P25. Further, an apparent quantum efficiency (AQE) of 56 and 94% was achieved at 350 and 320 nm, respectively (Fig. 3b). These values are comparable to or higher than those of the state-of-the-art TiO2-based photocatalysts including single-atom-anchored TiO2 (Table S1).7-17Fig. 3. (a) Time-course evolution of H2 from water containing methanol on different materials under solar simulator irradiation. (b) Action spectrum for H2 evolution from the aqueous methanol solution on HTO NW-Pt/P25(2:13). (c) Cycling performance of HTO NW-Pt/P25(2:13).Further, the durability of HTO NW-Pt/P25(2:13) was also tested. No significant loss in its photocatalytic activity was observed after four successive runs (90 min for each) with the evacuation of the headspace gas in each run (Fig. 3c). This high durability of HTO NW-Pt/P25(2:13) can be a result of electrostatic interactions between HTO NW and Pt/P25.Photocatalytic mechanism of the compositeAs shown in Fig. 3b, the AQE of the HTO NW-Pt/P25(2:13) composite for H2 evolution from the aqueous methanol is well-correlated with the photoabsorption of HTO NW-Pt/P25(2:13). This indicates the synergy effects of the co-presence of HTO NW and Pt/P25 on the photocatalytic mechanism of the composite. To understand the photocatalytic mechanism, we first examined the electronic structures of the components. Fig. 4a shows the diffuse-reflectance UV-vis spectra of HTO NW and P25. HTO NW and P25 had absorption onsets of ~370 and ~410 nm, respectively. The Tauc plots, prepared from the UV-vis spectra, showed band gaps of 3.35 and 3.13 eV, respectively (Fig. 4b). Valence band (VB) XPS measurements revealed that the VB-top was ~3.0 eV for both HTO NW and P25 (Fig. 4c). Therefore, by combining the UV-vis and VB-XPS data, we obtained the energy diagrams of the two components in the HTO NW-Pt/P25 composite as presented in Fig. 4d.Fig. 4. (a) UV-vis spectra, (b) Tauc plots, and (c) VB-XPS spectra of HTO NW and P25. (d) Band gap diagram determined by combining (b) and (c), and the scheme for electrons/holes transfer between HTO NW and P25.According to the energy diagram above, a transfer of photogenerated holes from Pt/P25 to HTO NW is possible (Fig. 4d, red lines), which can retard the recombination of photogenerated electrons and holes, and hence enhance the charge separation and photocatalytic activity in HTO NW-Pt/P25 (transfer of photogenerated electrons from Pt/P25 to HTO NW is thermodynamically unfavorable). To confirm this, a photocatalytic reaction was conducted under simulated solar light with a wavelength longer than 350 nm, at which HTO NW is not noticeably excited but Pt/P25 is (Fig. 4a). Even under these irradiation conditions, HTO NW-Pt/P25 (2:13) showed an approximately 3-fold enhancement in photocatalytic activity compared to that of Pt/P25 (Fig. 5a). Considering that HTO NW shows good photocatalytic activity toward the oxidation of an organic compound (formic acid) in water, comparable to P25, which is the most active for the reaction among the commercially available TiO2 (Fig. 5b),23,24 this result strongly suggests that under full-spectrum solar light, hole transfer from Pt/P25 to HTO NW occurs to enhance both the reduction of water on Pt-cocatalyst (Pt/P25) and the oxidation of sacrificial methanol in water on HTO NW.Fig. 5. Control photocatalytic tests to understand the photocatalytic mechanism of HTO NW-Pt/P25 for solar H2 evolution from an aqueous methanol solution. (a) Time-course evolution of H2 from aqueous methanol solution on Pt/P25 and HTO NW-Pt/P25(2:13) under λ > 350 nm solar simulator irradiation. (b) Time-course evolution of CO2 from water containing formic acid on Pt/P25 and HTO NW under solar simulator irradiation. (c) Time-course evolution of H2 from aqueous methanol solution on Pt/P25, Pt/HTO NW, and Pt/HTO NW-P25(2:13) under solar simulator irradiation.Although a transfer of photogenerated electrons and/or holes from HTO NW to Pt/P25 is also possible according to the energy diagram above (Fig. 4d, blue dot lines), it likely to have little or minor contribution to the enhancement of the photocatalytic activity of HTO NW-Pt/P25 as follows. Fig. 5c compares the photocatalytic activity of Pt/P25, Pt-cocatalyst-loaded HTO NW (Pt/HTO NW), and a composite of Pt/HTO NW and P25 (Pt/HTO NW-P25). The activity of Pt/HTO NW is considerably lower than that of Pt/P25. This result, considering the role of Pt nanoparticles as the electron pool, means the poor charge separation ability of HTO NW considerably lower than that of P25. Thus, the enhancement in activity of the HTO NW component in the HTO NW-Pt/P25(2:13) composite via electron transfer from HTO NW to Pt/P25 is negligible. Moreover, Pt/HTO NW showed an activity almost identical to that of the Pt/HTO NW-P25 composite, implying a negligible transfer of photogenerated holes from Pt/HTO NW to P25.Fig. 6. Particle size distribution determined by DLS of Pt/P25 and HTO NW-Pt/P25(2:13) in aqueous methanol.On the other hand, we propose another reason for the enhanced photocatalytic activity of HTO NW-Pt/P25 composite, the improved dispersion of Pt/P25 particles on HTO NW. In order to evaluate the effect of HTO NW on the aggregated state of Pt/P25 in an aqueous methanol (solvent used for photocatalytic H2 evolution tests), we performed DLS analyses of Pt/P25 and HTO NW-Pt/P25(2:13) in the solvent (Fig. 6). Pt/P25 showed a main peak with a size of ~400 nm. This peak is assigned to aggregated Pt/P25 particles because the primary particle size of P25 was 20-50 nm.34 In contrast, HTO NW-Pt/P25(2:13) showed peaks with a size of ~400 nm and ~6000 nm, which are assigned to aggregated Pt/P25 particles and HTO NW (aggregates), respectively. Importantly, HTO NW-Pt/P25(2:13) had the number of aggregated Pt/P25 particles considerably smaller than Pt/P25. We can thus consider that Pt/P25 can disaggregate on HTO NW to take a highly dispersed state for less light scattering (higher photocatalytic activity).4. ConclusionWe have reported that a composite of Pt-cocatalyst-loaded TiO2 (P25), a de facto benchmark TiO2, and a smaller amount (ca. 10 wt%) of a photocatalytically inactive layered titanate nanowire shows the state-of-the-art apparent quantum efficiency for H2 evolution from water containing sacrificial methanol. The remarkable photocatalytic activity was thought to result from the transfer of photogenerated holes from the TiO2 component to the layered titanate nanowire component, suppressing the charge recombination in the composite. As another reason, the enhanced dispersion of Pt-loaded P25 particles by loading on the nanowire was proposed. This simple method using the layered titanate nanowire can be applied to many state-of-the-art TiO2-based photocatalysts, making them more practical for solar energy conversion.AcknowledgementWe would like to gratefully acknowledge the financial support provided by the joint supervision scholarship from the Cultural Affairs and Missions Sector, Egyptian Ministry of Higher Education (MOHE). Supplementary dataSupplementary material is available at Bulletin of the Chemical Society of Japan.FundingThis work was supported by the Cultural Affairs and Missions Sector, Egyptian Ministry of Higher Education (MOHE).  Conflict of interest statement. 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