Insights into the Reactivity of Brookite TiO2 Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations

Agosta, Lorenzo; Zollo, Giuseppe; Selloni, Annabella

doi:10.1021/acscatal.5c09228

Title: Insights into the Reactivity of Brookite TiO₂ Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations

Journal Article · Mon Feb 09 00:00:00 UTC 2026 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.5c09228 · OSTI ID:3366380

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Uppsala Univ. (Sweden); Princeton Univ., NJ (United States)
Univ. of Rome (Italy)
Princeton Univ., NJ (United States)

Brookite TiO₂, a rare natural polymorph of TiO₂, has been reported to be an excellent photocatalyst for the production of hydrogen from water and aqueous alcohol solutions, especially when it is reduced and synthesized in the form of nanorods. Here, we investigate the reactivity of stoichiometric and reduced brookite nanorods in liquid water using ab initio molecular dynamics and hybrid density functional theory calculations. Our simulations show a much higher water dissociation fraction on reduced nanorods than on stoichiometric ones, with an accumulation of the resulting bridging hydroxyls (O_brH) and terminal hydroxyls (Ti –OH) on different facets of the nanorod. ObrH groups accumulate preferentially on low-energy (210) facets, where they are stabilized by adjacent reduced Ti (Ti³⁺) sites, while Ti –OH groups prefer to form at the four-fold coordinated Ti atoms on high-energy (010) facets. This hydroxylation pattern also favors the spatial localization of excited holes on the (010) facets. This coupling between water-induced surface chemistry and charge separation underpins the enhanced photocatalytic activity of brookite nanorods, providing useful information for the design of more efficient TiO2-based nanostructures for solar-driven hydrogen evolution.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0007347

OSTI ID:: 3366380

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 8 Vol. 16; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (46)

cp2k: atomistic simulations of condensed matter systems Hutter, Jürg; Iannuzzi, Marcella; Schiffmann, Florian Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1159	journal	June 2013
The surface science of titanium dioxide Diebold, Ulrike Surface Science Reports, Vol. 48, Issue 5-8 https://doi.org/10.1016/S0167-5729(02)00100-0	journal	January 2003
Surface structures and thermodynamics of low-index of rutile, brookite and anatase – A comparative DFT study Esch, Tobit R.; Gadaczek, Immanuel; Bredow, Thomas Applied Surface Science, Vol. 288 https://doi.org/10.1016/j.apsusc.2013.10.021	journal	January 2014
Defect engineering over anisotropic brookite toward substrate-specific photo-oxidation of alcohols Hejazi, S. M. Hossein; Shahrezaei, Mahdi; Błoński, Piotr Chem Catalysis, Vol. 2, Issue 5 https://doi.org/10.1016/j.checat.2022.03.015	journal	May 2022
Dependence of photocatalytic activity on aspect ratio of a brookite TiO2 nanorod and drastic improvement in visible light responsibility of a brookite TiO2 nanorod by site-selective modification of Fe3+ on exposed faces Ohno, Teruhisa; Higo, Takayoshi; Saito, Hirofumi Journal of Molecular Catalysis A: Chemical, Vol. 396 https://doi.org/10.1016/j.molcata.2014.09.036	journal	January 2015
TiO2 photocatalysis and related surface phenomena Fujishima, A.; Zhang, X.; Tryk, D. Surface Science Reports, Vol. 63, Issue 12 https://doi.org/10.1016/j.surfrep.2008.10.001	journal	December 2008
A surface science perspective on TiO2 photocatalysis Henderson, Michael A. Surface Science Reports, Vol. 66, Issue 6-7 https://doi.org/10.1016/j.surfrep.2011.01.001	journal	June 2011
Particulate Photocatalysts for Light-Driven Water Splitting: Mechanisms, Challenges, and Design Strategies Wang, Qian; Domen, Kazunari Chemical Reviews, Vol. 120, Issue 2 https://doi.org/10.1021/acs.chemrev.9b00201	journal	August 2019
Bridging Hydroxyls on Anatase TiO ₂ (101) by Water Dissociation in Oxygen Vacancies Nadeem, Immad M.; Harrison, George T.; Wilson, Axel The Journal of Physical Chemistry B, Vol. 122, Issue 2 https://doi.org/10.1021/acs.jpcb.7b06955	journal	October 2017
Morphology of TiO₂ Nanoparticles as a Fingerprint for the Transient Absorption Spectra: Implications for Photocatalysis Morales-García, Ángel; Valero, Rosendo; Illas, Francesc The Journal of Physical Chemistry C, Vol. 124, Issue 22 https://doi.org/10.1021/acs.jpcc.0c02946	journal	May 2020
Defect States and Polarons in Photocatalytic Semiconductors Revealed via Time-Resolved Spectroscopy Xu, Yanjun; Wang, Zhuan; Weng, Yuxiang The Journal of Physical Chemistry C, Vol. 128, Issue 39 https://doi.org/10.1021/acs.jpcc.4c03688	journal	July 2024
Hydration Accelerates Radiative and Nonradiative Recombination in Small TiO₂ Nanoclusters Recio-Poo, Miguel; Shakiba, Mohammad; Illas, Francesc The Journal of Physical Chemistry C, Vol. 129, Issue 3 https://doi.org/10.1021/acs.jpcc.4c07180	journal	January 2025
Hydration Structure of Brookite TiO ₂ (210) Holmström, Eero; Ghan, Simiam; Asakawa, Hitoshi The Journal of Physical Chemistry C, Vol. 121, Issue 38 https://doi.org/10.1021/acs.jpcc.7b05524	journal	September 2017
Subtle Structure Matters: The Vicinity of Surface Ti_5c Cations Alters the Photooxidation Behaviors of Anatase and Rutile TiO₂ under Aqueous Environments Li, Fei; Chen, Jian-Fu; Gong, Xue-Qing ACS Catalysis, Vol. 12, Issue 14 https://doi.org/10.1021/acscatal.2c01339	journal	June 2022
Influence of Hole Transport and Thermal Reactions in Photo-Driven Water Oxidation Kinetics on Crystalline TiO₂ Wang, Pan; Benitez, Gabriel; Houle, Frances A. ACS Catalysis, Vol. 15, Issue 9 https://doi.org/10.1021/acscatal.5c00945	journal	April 2025
Pathways of Photocatalytic Oxidation of Formic Acid on Dry and Hydrated Anatase TiO₂ Surfaces Daldossi, Chiara; Di Valentin, Cristiana; Selloni, Annabella ACS Catalysis, Vol. 15, Issue 13 https://doi.org/10.1021/acscatal.5c01848	journal	June 2025
Photocatalysis with Reduced TiO ₂ : From Black TiO ₂ to Cocatalyst-Free Hydrogen Production Naldoni, Alberto; Altomare, Marco; Zoppellaro, Giorgio ACS Catalysis, Vol. 9, Issue 1 https://doi.org/10.1021/acscatal.8b04068	journal	November 2018
Tailored Titanium Dioxide Nanomaterials: Anatase Nanoparticles and Brookite Nanorods as Highly Active Photocatalysts Kandiel, Tarek A.; Feldhoff, Armin; Robben, Lars Chemistry of Materials, Vol. 22, Issue 6 https://doi.org/10.1021/cm903472p	journal	March 2010
Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications Chen, Xiaobo; Mao, Samuel S. Chemical Reviews, Vol. 107, Issue 7 https://doi.org/10.1021/cr0500535	journal	July 2007
Titanium Dioxide (Anatase and Rutile): Surface Chemistry, Liquid–Solid Interface Chemistry, and Scientific Synthesis of Supported Catalysts Bourikas, Kyriakos; Kordulis, Christos; Lycourghiotis, Alexis Chemical Reviews, Vol. 114, Issue 19 https://doi.org/10.1021/cr300230q	journal	May 2014
Titanium Dioxide Crystals with Tailored Facets Liu, Gang; Yang, Hua Gui; Pan, Jian Chemical Reviews, Vol. 114, Issue 19 https://doi.org/10.1021/cr400621z	journal	May 2014
Understanding TiO ₂ Photocatalysis: Mechanisms and Materials Schneider, Jenny; Matsuoka, Masaya; Takeuchi, Masato Chemical Reviews, Vol. 114, Issue 19 https://doi.org/10.1021/cr5001892	journal	May 2014
Brookite vs Anatase TiO ₂ in the Photocatalytic Activity for Organic Degradation in Water Li, Zhen; Cong, Shan; Xu, Yiming ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500785z	journal	August 2014
Evidence for Crystal-Face-Dependent TiO ₂ Photocatalysis from Single-Molecule Imaging and Kinetic Analysis Tachikawa, Takashi; Yamashita, Soichiro; Majima, Tetsuro Journal of the American Chemical Society, Vol. 133, Issue 18 https://doi.org/10.1021/ja201415j	journal	May 2011
Synthesis of High-Quality Brookite TiO ₂ Single-Crystalline Nanosheets with Specific Facets Exposed: Tuning Catalysts from Inert to Highly Reactive Lin, Haifeng; Li, Liping; Zhao, Minglei Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja3014049	journal	May 2012
Excitonic Interfacial Proton-Coupled Electron Transfer Mechanism in the Photocatalytic Oxidation of Methanol to Formaldehyde on TiO₂(110) Migani, Annapaola; Blancafort, Lluís Journal of the American Chemical Society, Vol. 138, Issue 49 https://doi.org/10.1021/jacs.6b11067	journal	December 2016
What Controls Photocatalytic Water Oxidation on Rutile TiO₂(110) under Ultra-High-Vacuum Conditions? Migani, Annapaola; Blancafort, Lluís Journal of the American Chemical Society, Vol. 139, Issue 34 https://doi.org/10.1021/jacs.7b05121	journal	August 2017
Bulk and Surface Polarons in Photoexcited Anatase TiO ₂ Di Valentin, Cristiana; Selloni, Annabella The Journal of Physical Chemistry Letters, Vol. 2, Issue 17 https://doi.org/10.1021/jz2009874	journal	August 2011
Black TiO ₂ Nanotubes: Cocatalyst-Free Open-Circuit Hydrogen Generation Liu, Ning; Schneider, Christopher; Freitag, Detlef Nano Letters, Vol. 14, Issue 6 https://doi.org/10.1021/nl500710j	journal	May 2014
Synergy of Low-Energy {101} and High-Energy {001} TiO ₂ Crystal Facets for Enhanced Photocatalysis Roy, Nitish; Sohn, Youngku; Pradhan, Debabrata ACS Nano, Vol. 7, Issue 3 https://doi.org/10.1021/nn305877v	journal	March 2013
Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces Selcuk, Sencer; Selloni, Annabella Nature Materials, Vol. 15, Issue 10 https://doi.org/10.1038/nmat4672	journal	June 2016
Multihole water oxidation catalysis on haematite photoanodes revealed by operando spectroelectrochemistry and DFT Mesa, Camilo A.; Francàs, Laia; Yang, Ke R. Nature Chemistry, Vol. 12, Issue 1 https://doi.org/10.1038/s41557-019-0347-1	journal	October 2019
Theoretical insights into the surface physics and chemistry of redox-active oxides Rousseau, Roger; Glezakou, Vassiliki-Alexandra; Selloni, Annabella Nature Reviews Materials, Vol. 5, Issue 6 https://doi.org/10.1038/s41578-020-0198-9	journal	May 2020
The kinetics of metal oxide photoanodes from charge generation to catalysis Corby, Sacha; Rao, Reshma R.; Steier, Ludmilla Nature Reviews Materials, Vol. 6, Issue 12 https://doi.org/10.1038/s41578-021-00343-7	journal	August 2021
Identifying the key obstacle in photocatalytic oxygen evolution on rutile TiO2 Wang, Dong; Sheng, Tian; Chen, Jianfu Nature Catalysis, Vol. 1, Issue 4 https://doi.org/10.1038/s41929-018-0055-z	journal	April 2018
Reactive wetting properties of TiO₂ nanoparticles predicted by ab initio molecular dynamics simulations Brandt, Erik G.; Agosta, Lorenzo; Lyubartsev, Alexander P. Nanoscale, Vol. 8, Issue 27 https://doi.org/10.1039/C6NR02791A	journal	January 2016
Reduced grey brookite for noble metal free photocatalytic H₂evolution Wierzbicka, Ewa; Altomare, Marco; Wu, Mingjian Journal of Materials Chemistry A, Vol. 9, Issue 2 https://doi.org/10.1039/D0TA09066B	journal	January 2021
Untangling product selectivity on clean low index rutile TiO₂ surfaces using first-principles calculations Malik, Anum Shahid; Fredin, Lisa A. Physical Chemistry Chemical Physics, Vol. 25, Issue 3 https://doi.org/10.1039/D2CP04939B	journal	January 2023
Crystal faces of rutile and anatase TiO2 particles and their roles in photocatalytic reactions Ohno, Teruhisa; Sarukawa, Koji; Matsumura, Michio New Journal of Chemistry, Vol. 26, Issue 9 https://doi.org/10.1039/b202140d	journal	July 2002
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Diffusion and reaction pathways of water near fully hydrated TiO ₂ surfaces from ab initio molecular dynamics Agosta, Lorenzo; Brandt, Erik G.; Lyubartsev, Alexander P. The Journal of Chemical Physics, Vol. 147, Issue 2 https://doi.org/10.1063/1.4991381	journal	July 2017
Engineering titania nanostructure to tune and improve its photocatalytic activity Cargnello, Matteo; Montini, Tiziano; Smolin, Sergey Y. Proceedings of the National Academy of Sciences, Vol. 113, Issue 15 https://doi.org/10.1073/pnas.1524806113	journal	March 2016
First-principles study of the structures and energetics of stoichiometric brookiteTiO2surfaces Gong, Xue-Qing; Selloni, Annabella Physical Review B, Vol. 76, Issue 23 https://doi.org/10.1103/PhysRevB.76.235307	journal	December 2007
Interplay between Adsorbates and Polarons: CO on Rutile TiO 2 ( 110 ) Reticcioli, Michele; Sokolović, Igor; Schmid, Michael Physical Review Letters, Vol. 122, Issue 1 https://doi.org/10.1103/PhysRevLett.122.016805	journal	January 2019
The role of medium size facilities in the HPC ecosystem: the case of the new CRESCO4 cluster integrated in the ENEAGRID infrastructure Ponti, G.; Palombi, F.; Abate, D. 2014 International Conference on High Performance Computing & Simulation (HPCS) https://doi.org/10.1109/HPCSim.2014.6903807	conference	July 2014
Brookite: Nothing New under the Sun? Monai, Matteo; Montini, Tiziano; Fornasiero, Paolo Catalysts, Vol. 7, Issue 10 https://doi.org/10.3390/catal7100304	journal	October 2017

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Title: Insights into the Reactivity of Brookite TiO2 Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations

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Title: Insights into the Reactivity of Brookite TiO₂ Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations