Correlated electron–nuclear dynamics of photoinduced water dissociation on rutile TiO2
Source abstract
Abstract
Elucidating the mechanism of photoinduced water splitting on TiO2 is important for advancing the understanding of photocatalysis and the ability to control photocatalytic surface reactions. However, incomplete experimental information and complex coupled electron-nuclear motion make the microscopic understanding challenging. Here we analyse the atomic-scale pathways of photogenerated charge carrier transport and photoinduced water dissociation at the prototypical water-rutile TiO2(110) interface using first-principles dynamics simulations. Two distinct mechanisms are observed. Field-initiated electron migration leads to adsorbed water dissociation via proton transfer to a surface bridging oxygen. In the other pathway, adsorbed water dissociation occurs via proton donation to a second-layer water molecule coupled to photoexcited-hole transfer promoted by in-plane surface lattice distortions. Two stages of non-adiabatic in-plane lattice motion-expansion and recovery-are observed, which are closely associated with population changes in Ti3d orbitals. Controlling such highly correlated electron-nuclear dynamics may provide opportunities for boosting the performance of photocatalytic materials.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: TiO2 Photocatalysis and Solar Cells · Advanced Photocatalysis Techniques · Electronic and Structural Properties of Oxides
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (49)
Show source-provided references
1. Fujishima, A. & Honda, K. Electrochemical photolysis of water at a semiconductor electrode. Nature 238, 37–38 (1972).10.1038/238037a0 ↗
2. Khan, S. U. M., Al-Shahry, M. & Ingler, W. B. Efficient photochemical water splitting by a chemically modified n-TiO2. Science 297, 2243–2245 (2002).10.1126/science.1075035 ↗
3. Hashimoto, K., Irie, H. & Fujishima, A. TiO2 photocatalysis: a historical overview and future prospects. Jpn. J. Appl. Phys. 44, 8269–8285 (2005).10.1143/JJAP.44.8269 ↗
4. Schneider, J. et al. Understanding TiO2 photocatalysis: mechanisms and materials. Chem. Rev. 114, 9919–9986 (2014).10.1021/cr5001892 ↗
5. Guo Q., Zhou C., Ma Z. & Yang X. Fundamentals of TiO2 photocatalysis: concepts, mechanisms, and challenges. Adv. Mater. 31, 1901997 (2019).10.1002/adma.201901997 ↗
6. Anpo, M. & Takeuchi, M. The design and development of highly reactive titanium oxide photocatalysts operating under visible light irradiation. J. Catal. 216, 505–516 (2003).10.1016/S0021-9517(02)00104-5 ↗
7. Yin, W.-J., Wen, B., Zhou, C., Selloni, A. & Liu, L.-M. Excess electrons in reduced rutile and anatase TiO2. Surf. Sci. Rep. 73, 58–82 (2018).10.1016/j.surfrep.2018.02.003 ↗
8. Ma, Y. et al. Titanium dioxide-based nanomaterials for photocatalytic fuel generations. Chem. Rev. 114, 9987–10043 (2014).10.1021/cr500008u ↗
9. Bourikas, K., Kordulis, C. & Lycourghiotis, A. Titanium dioxide (anatase and rutile): surface chemistry, liquid-solid interface chemistry, and scientific synthesis of supported catalysts. Chem. Rev. 114, 9754–9823 (2014).10.1021/cr300230q ↗
10. Kowalski, P. M., Camellone, M. F., Nair, N. N., Meyer, B. & Marx, D. Charge localization dynamics induced by oxygen vacancies on the TiO2(110) surface. Phys. Rev. Lett. 105, 146405 (2010).10.1103/PhysRevLett.105.146405 ↗
11. Bikondoa, O. et al. Direct visualization of defect-mediated dissociation of water on TiO2(110). Nat. Mater. 5, 189–192 (2006).10.1038/nmat1592 ↗
12. Wendt, S. et al. Formation and splitting of paired hydroxyl groups on reduced TiO2(110). Phys. Rev. Lett. 96, 066107 (2006).10.1103/PhysRevLett.96.066107 ↗
13. Tan, S. et al. Observation of photocatalytic dissociation of water on terminal Ti sites of TiO2(110)-1 × 1 surface. J. Am. Chem. Soc. 134, 9978–9985 (2012).10.1021/ja211919k ↗
14. Yang, W. et al. Effect of the hydrogen bond in photoinduced water dissociation: a double-edged sword. J. Phys. Chem. Lett. 7, 603–608 (2016).10.1021/acs.jpclett.6b00015 ↗
15. Tan, S. et al. Interfacial hydrogen-bonding dynamics in surface-facilitated dehydrogenation of water on TiO2(110). J. Am. Chem. Soc. 142, 826–834 (2020).10.1021/jacs.9b09132 ↗
16. Nakamura, R. & Nakato, Y. Primary intermediates of oxygen photoevolution reaction on TiO2 (rutile) particles, revealed by in situ FTIR absorption and photoluminescence measurements. J. Am. Chem. Soc. 126, 1290–1298 (2004).10.1021/ja0388764 ↗
17. Wang, D., Sheng, T., Chen, J., Wang, H.-F. & Hu, P. Identifying the key obstacle in photocatalytic oxygen evolution on rutile TiO2. Nat. Catal. 1, 291–299 (2018).10.1038/s41929-018-0055-z ↗
18. Migani, A. & Blancafort, L. What controls photocatalytic water oxidation on rutile TiO2(110) under ultra-high-vacuum conditions? J. Am. Chem. Soc. 139, 11845–11856 (2017).10.1021/jacs.7b05121 ↗
19. Franchini, C., Reticcioli, M., Setvin, M. & Diebold, U. Polarons in materials. Nat. Rev. Mater. 6, 560–586 (2021).10.1038/s41578-021-00289-w ↗
20. Rousseau, R., Glezakou, V.-A. & Selloni, A. Theoretical insights into the surface physics and chemistry of redox-active oxides. Nat. Rev. Mater. 5, 460–475 (2020).10.1038/s41578-020-0198-9 ↗
21. Di Valentin, C. & Selloni, A. Bulk and surface polarons in photoexcited anatase TiO2. J. Phys. Chem. Lett. 2, 2223–2228 (2011).10.1021/jz2009874 ↗
22. Cheng, J., VandeVondele, J. & Sprik, M. Identifying trapped electronic holes at the aqueous TiO2 interface. J. Phys. Chem. C 118, 5437–5444 (2014).10.1021/jp500769q ↗
23. Selcuk, S. & Selloni, A. Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces. Nat. Mater. 15, 1107–1112 (2016).10.1038/nmat4672 ↗
24. Cheng, J. & Sprik, M. Acidity of the aqueous rutile TiO2(110) surface from density functional theory based molecular dynamics. J. Chem. Theory Comput. 6, 880–889 (2010).10.1021/ct100013q ↗
25. Liu, L.-M., Zhang, C., Thornton, G. & Michaelides, A. Structure and dynamics of liquid water on rutile TiO2(110). Phys. Rev. B 82, 161415 (2010).10.1103/PhysRevB.82.161415 ↗
26. Long, R., Fang, W.-H. & Prezhdo, O. V. Strong interaction at the perovskite/TiO2 interface facilitates ultrafast photoinduced charge separation: a nonadiabatic molecular dynamics study. J. Phys. Chem. C 121, 3797–3806 (2017).10.1021/acs.jpcc.6b12921 ↗
27. Cheng, C., Fang, W. H., Long, R. & Prezhdo, O. V. Water splitting with a single-atom Cu/TiO2 photocatalyst: atomistic origin of high efficiency and proposed enhancement by spin selection. JACS Au 1, 550–559 (2021).10.1021/jacsau.1c00004 ↗
28. Pisana, S. et al. Breakdown of the adiabatic Born-Oppenheimer approximation in graphene. Nat. Mater. 6, 198–201 (2007).10.1038/nmat1846 ↗
29. Che, L. et al. Breakdown of the Born-Oppenheimer approximation in the F + o-D2→DF + D reaction. Science 317, 1061–1064 (2007).
30. Lian, C., Guan, M., Hu, S., Zhang, J. & Meng, S. Photoexcitation in solids: first-principles quantum simulations by real-time TDDFT. Adv. Theory Simul. 1, 1800055 (2018).10.1002/adts.201800055 ↗
31. You P., Chen D., Lian C., Zhang C. & Meng S. First-principles dynamics of photoexcited molecules and materials towards a quantum description. WIREs Comput. Mol. Sci. 11, e1492 (2020).10.1002/wcms.1492 ↗
32. Carneiro, L. M. et al. Excitation-wavelength-dependent small polaron trapping of photoexcited carriers in α-Fe2O3. Nat. Mater. 16, 819–825 (2017).10.1038/nmat4936 ↗
33. Diebold, U. Perspective: a controversial benchmark system for water-oxide interfaces: H2O/TiO2(110). J. Chem. Phys. 147, 040901 (2017).10.1063/1.4996116 ↗
34. Wen, B., Calegari Andrade, M. F., Liu, L. M. & Selloni, A. Water dissociation at the water-rutile TiO2(110) interface from ab initio-based deep neural network simulations. Proc. Natl Acad. Sci. USA 120, e2212250120 (2023).10.1073/pnas.2212250120 ↗
35. Wang, Z. T. et al. Probing equilibrium of molecular and deprotonated water on TiO2(110). Proc. Natl Acad. Sci. USA 114, 1801–1805 (2017).10.1073/pnas.1613756114 ↗
36. Li, Y.-F. & Selloni, A. Pathway of photocatalytic oxygen evolution on aqueous TiO2 anatase and insights into the different activities of anatase and rutile. ACS Catal. 6, 4769–4774 (2016).10.1021/acscatal.6b01138 ↗
37. Burns, P. C. & Hawthorne, F. C. Static and dynamic Jahn-Teller effects in Cu2+ oxysalt minerals. Can. Mineral. 34, 1089–1105 (1996).
38. Fu, K. M. et al. Observation of the dynamic Jahn-Teller effect in the excited states of nitrogen-vacancy centers in diamond. Phys. Rev. Lett. 103, 256404 (2009).10.1103/PhysRevLett.103.256404 ↗
39. Di Valentin, C., Pacchioni, G. & Selloni, A. Electronic structure of defect states in hydroxylated and reduced rutile TiO2(110) surfaces. Phys. Rev. Lett. 97, 166803 (2006).10.1103/PhysRevLett.97.166803 ↗
40. Wang, Z. et al. Localized excitation of Ti3+ ions in the photoabsorption and photocatalytic activity of reduced rutile TiO2. J. Am. Chem. Soc. 137, 9146–9152 (2015).10.1021/jacs.5b04483 ↗
41. Sidiropoulos, T. P. H. et al. Probing the energy conversion pathways between light, carriers, and lattice in real time with attosecond core-level spectroscopy. Phys. Rev. X 11, 041060 (2021).
42. Wagstaffe, M. et al. Photoinduced dynamics at the water/TiO2(101) interface. Phys. Rev. Lett. 130, 108001 (2023).10.1103/PhysRevLett.130.108001 ↗
43. Chen, X. et al. The formation time of Ti–O• and Ti–O•–Ti radicals at the n-SrTiO3/aqueous interface during photocatalytic water oxidation. J. Am. Chem. Soc. 139, 1830–1841 (2017).10.1021/jacs.6b09550 ↗
44. Kim, H. Y. et al. Attosecond field emission. Nature 613, 662–666 (2023).10.1038/s41586-022-05577-1 ↗
45. Garcia, A. et al. SIESTA: recent developments and applications. J. Chem. Phys. 152, 204108 (2020).10.1063/5.0005077 ↗
46. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
47. Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA+U study. Phys. Rev. B 57, 1505–1509 (1998).10.1103/PhysRevB.57.1505 ↗
48. Sheppard, D., Xiao, P., Chemelewski, W., Johnson, D. D. & Henkelman, G. A generalized solid-state nudged elastic band method. J. Chem. Phys. 136, 074103 (2012).10.1063/1.3684549 ↗
49. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).10.1016/0927-0256(96)00008-0 ↗