AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Mechanocatalysis of CO to CO2 on TiO2 surface controlled at atomic scale

Yuuki Adachi1, Robert Turanský2, Ján Brndiar3, Kamil Tokár3, Qiang Zhu1, Huan Fei Wen5, Yasuhiro Sugawara1, Ivan Štich3,4, Yan Jun Li1( )
Department of Applied Physics, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
Institute of Physics, Slovak Academy of Sciences, Bratislava 84511, Slovakia
Institute of Informatics, Slovak Academy of Sciences, Bratislava 84507, Slovakia
Faculty of Natural Sciences, University of Ss. Cyril and Methodius, Trnava 91701, Slovakia
Key Laboratory of Instrumentation Science and Dynamic Measurement, School of Instrument and Electronics, North University of China, Taiyuan 030051, China
Show Author Information

Graphical Abstract

The scanning probe microscopy resolved the atomic mechanocatalytic reaction.

Abstract

The common ways to activate a chemical reaction are by heat, electric current, or light. However, mechanochemistry, where the chemical reaction is activated by applied mechanical force, is less common and only poorly understood at the atomic scale. Here we report a tip-induced activation of chemical reaction of carbon monoxide to dioxide on oxidized rutile TiO2 (110) surface. The activation is studied by atomic force microscopy, Kelvin probe force microscopy under ultrahigh-vacuum and liquid nitrogen temperature conditions, and density functional theory (DFT) modeling. The reaction is inferred from hysteretic behavior of frequency shift signal further supported by vector force mapping of vertical and lateral forces needed to trigger the chemical reaction with torque motion of carbon monoxide towards an oxygen adatom. The reaction is found to proceed stochastically at very small tip-sample distances. Furthermore, the local contact potential difference reveals the atomic-scale charge redistribution in the reactants required to unlock the reaction. Our results open up new insights into the mechanochemistry on metal oxide surfaces at the atomic scale.

Keywords

atomic resolutionmechanochemistryatomic force microscopyKelvin probe force microscopydensity functional theory (DFT) simulationCO oxidationcatalysisrutile TiO2 surface

Electronic Supplementary Material

Download File(s)
6539_ESM.pdf (2.7 MB)

References

[1]

Garcia-Manyes, S.; Beedle, A. E. M. Steering chemical reactions with force. Nat. Rev. Chem. 2017, 1, 0083.
Crossref Google Scholar
[2]

Liang, J.; Fernández, J. M. Mechanochemistry: One bond at a time. ACS Nano 2009, 3, 1628–1645.
Crossref Google Scholar
[3]

Davis, D. A.; Hamilton, A.; Yang, J. L.; Cremar, L. D.; Van Gough, D.; Potisek, S. L.; Ong, M. T.; Braun, P. V.; Martínez, T. J.; White, S. R. et al. Force-induced activation of covalent bonds in mechanoresponsive polymeric materials. Nature 2009, 459, 68–72.
Crossref Google Scholar
[4]

Hickenboth, C. R.; Moore, J. S.; White, S. R.; Sottos, N. R.; Baudry, J.; Wilson, S. R. Biasing reaction pathways with mechanical force. Nature 2007, 446, 423–427.
Crossref Google Scholar
[5]

Wiita, A. P.; Perez-Jimenez, R.; Walther, K. A.; Gräter, F.; Berne, B. J.; Holmgren, A.; Sanchez-Ruiz, J. M.; Fernandez, J. M. Probing the chemistry of thioredoxin catalysis with force. Nature 2007, 450, 124–127.
Crossref Google Scholar
[6]

Wiita, A. P.; Ainavarapu, S. R. K.; Huang, H. H.; Fernandez, J. M. Force-dependent chemical kinetics of disulfide bond reduction observed with single-molecule techniques. Proc. Natl. Acad. Sci. USA 2006, 103, 7222–7227.
Crossref Google Scholar
[7]

Ikeda, S.; Takata, T.; Kondo, T.; Hitoki, G.; Hara, M.; Kondo, J. N.; Domen, K.; Hosono, H.; Kawazoe, H.; Tanaka, A. Mechano-catalytic overall water splitting. Chem. Commun. 1998, 2185–2186
Crossref Google Scholar
[8]

den Boer, D.; Shklyarevskii, O. I.; Coenen, M. J. J.; van der Maas, M.; Peters, T. P. J.; Elemans, J. A. A. W.; Speller, S. Mechano-catalysis: Cyclohexane oxidation in a silver nanowire break junction. J. Phys. Chem. C 2011, 115, 8295–8299.
Crossref Google Scholar
[9]

Nguyen, T. Q.; Kausch, H. H. Effects of solvent viscosity on polystyrene degradation in transient elongational flow. Macromolecules 1990, 23, 5137–5145.
Crossref Google Scholar
[10]

Sohma, J. Mechanochemistry of polymers. Prog. Polym. Sci. 1989, 14, 451–596.
Crossref Google Scholar
[11]

Procyk, A. D.; Bocia, D. F. Vibrational characteristics of tetrapyrrolic macrocycles. Annu. Rev. Phys. Chem. 1992, 43, 465–496.
Crossref Google Scholar
[12]

Nguyen, K. L.; Friščič, T.; Day, G. M.; Gladden, L. F.; Jones, W. Terahertz time-domain spectroscopy and the quantitative monitoring of mechanochemical cocrystal formation. Nat. Mater. 2007, 6, 206–209.
Crossref Google Scholar
[13]

Peller, D.; Kastner, L. Z.; Buchner, T.; Roelcke, C.; Albrecht, F.; Moll, N.; Huber, R.; Repp, J. Sub-cycle atomic-scale forces coherently control a single-molecule switch. Nature 2020, 585, 58–62.
Crossref Google Scholar
[14]

Ladenthin, J. N.; Frederiksen, T.; Persson, M.; Sharp, J. C.; Gawinkowski, S.; Waluk, J.; Kumagai, T. Force-induced tautomerization in a single molecule. Nat. Chem. 2016, 8, 935–940.
Crossref Google Scholar
[15]

Qi, J.; Gao, Y. X.; Jia, H. H.; Richter, M.; Huang, L.; Cao, Y.; Yang, H.; Zheng, Q.; Berger, R.; Liu, J. Z. et al. Force-activated isomerization of a single molecule. J. Am. Chem. Soc. 2020, 142, 10673–10680.
Crossref Google Scholar
[16]

Shiotari, A.; Nakae, T.; Iwata, K.; Mori, S.; Okujima, T.; Uno, H.; Sakaguchi, H.; Sugimoto, Y. Strain-induced skeletal rearrangement of a polycyclic aromatic hydrocarbon on a copper surface. Nat. Commun. 2017, 8, 16089.
Crossref Google Scholar
[17]

Ishii, A.; Shiotari, A.; Sugimoto, Y. Mechanically induced single-molecule helicity switching of graphene-nanoribbon-fused helicene on Au (111). Chem. Sci. 2021, 12, 13301–13306.
Crossref Google Scholar
[18]

Emmrich, M.; Huber, F.; Pielmeier, F.; Welker, J.; Hofmann, T.; Schneiderbauer, M.; Meuer, D.; Polesya, S.; Mankovsky, S.; Ködderitzsch, D. et al. Subatomic resolution force microscopy reveals internal structure and adsorption sites of small iron clusters. Science 2015, 348, 308–311.
Crossref Google Scholar
[19]

Sugimoto, Y.; Pou, P.; Abe, M.; Jelinek, P.; Pérez, R.; Morita, S.; Custance, Ó. Chemical identification of individual surface atoms by atomic force microscopy. Nature 2007, 446, 64–67.
Crossref Google Scholar
[20]

Ternes, M.; Lutz, C. P.; Hirjibehedin, C. F.; Giessibl, F. J.; Heinrich, A. J. The force needed to move an atom on a surface. Science 2008, 319, 1066–1069.
Crossref Google Scholar
[21]

Esat, T.; Friedrich, N.; Tautz, F. S.; Temirov, R. A standing molecule as a single-electron field emitter. Nature 2018, 558, 573–576.
Crossref Google Scholar
[22]

Stroscio, J. A.; Celotta, R. J. Controlling the dynamics of a single atom in lateral atom manipulation. Science 2004, 306, 242–247.
Crossref Google Scholar
[23]

Langewisch, G.; Falter, J.; Fuchs, H.; Schirmeisen, A. Forces during the controlled displacement of organic molecules. Phys. Rev. Lett. 2013, 110, 036101.
Crossref Google Scholar
[24]

Emmrich, M.; Schneiderbauer, M.; Huber, F.; Weymouth, A. J.; Okabayashi, N.; Giessibl, F. J. Force field analysis suggests a lowering of diffusion barriers in atomic manipulation due to presence of STM tip. Phys. Rev. Lett. 2015, 114, 146101.
Crossref Google Scholar
[25]

Shiotari, A.; Odani, T.; Sugimoto, Y. Torque-induced change in configuration of a single NO molecule on Cu (110). Phys. Rev. Lett. 2018, 121, 116101.
Crossref Google Scholar
[26]

Adachi, Y.; Sugawara, Y.; Li, Y. J. Probing CO on a rutile TiO2 (110) surface using atomic force microscopy and Kelvin probe force microscopy. Nano Res. 2022, 15, 1909–1915.
Crossref Google Scholar
[27]

Grill, L.; Rieder, K. H.; Moresco, F.; Stojkovic, S.; Gourdon, A.; Joachim, C. Exploring the interatomic forces between tip and single molecules during STM manipulation. Nano Lett. 2006, 6, 2685–2689.
Crossref Google Scholar
[28]

Hla, S. W.; Braun, K. F.; Rieder, K. H. Single-atom manipulation mechanisms during a quantum corral construction. Phys. Rev. B 2003, 67, 201402.
Crossref Google Scholar
[29]

Diebold, U. The surface science of titanium dioxide. Surf. Sci. Rep. 2003, 48, 53–229.
Crossref Google Scholar
[30]

Reticcioli, M.; Sokolović, I.; Schmid, M.; Diebold, U.; Setvin, M.; Franchini, C. Interplay between adsorbates and polarons: CO on rutile TiO2 (110). Phys. Rev. Lett. 2019, 122, 016805.
Crossref Google Scholar
[31]

Zhao, Y.; Wang, Z.; Cui, X. F.; Huang, T.; Wang, B.; Luo, Y.; Yang, J. L.; Hou, J. G. What are the adsorption sites for CO on the reduced TiO2 (110)-1 × 1 surface. J. Am. Chem. Soc. 2009, 131, 7958–7959.
Crossref Google Scholar
[32]

Wang, Z.; Zhao, Y.; Cui, X. F.; Tan, S. J.; Zhao, A. D.; Wang, B.; Yang, J. L.; Hou, J. G. Adsorption of CO on rutile TiO2 (110)-1 × 1 surface with preadsorbed O adatoms. J. Phys. Chem. C 2010, 114, 18222–18227.
Crossref Google Scholar
[33]

Lee, J.; Zhang, Z.; Deng, X. Y.; Sorescu, D. C.; Matranga, C.; Yates, J. T. Jr. Interaction of CO with oxygen adatoms on TiO2 (110) . J. Phys. Chem. C 2011, 115, 4163–4167.
Crossref Google Scholar
[34]

Ramalho, J. P. P.; Illas, F.; Gomes, J. R. B. Adsorption of CO on the rutile TiO2 (110) surface: A dispersion-corrected density functional theory study. Phys. Chem. Chem. Phys. 2017, 19, 2487–2494.
Crossref Google Scholar
[35]

Hu, S. L.; Wang, Z.; Mattsson, A.; Österlund, L.; Hermansson, K. Simulation of IRRAS spectra for molecules on oxide surfaces: CO on TiO2 (110). J. Phys. Chem. C 2015, 119, 5403–5411.
Crossref Google Scholar
[36]

Petrik, N. G.; Mu, R. T.; Dahal, A.; Wang, Z. T.; Lyubinetsky, I.; Kimmel, G. A. Diffusion and photon-stimulated desorption of CO on TiO2 (110). J. Phys. Chem. C 2018, 122, 15382–15389.
Crossref Google Scholar
[37]

Petrik, N. G.; Kimmel, G. A. Adsorption geometry of CO versus coverage on TiO2 (110) from S- and P-polarized infrared spectroscopy. J. Phys. Chem. Lett. 2012, 3, 3425–3430.
Crossref Google Scholar
[38]

Lee, J.; Sorescu, D. C.; Deng, X. Y. Electron-induced dissociation of CO2 on TiO2 (110). J. Am. Chem. Soc. 2011, 133, 10066–10069.
Crossref Google Scholar
[39]

Lee, J.; Sorescu, D. C.; Deng, X. Y.; Jordan, K. D. Diffusion of CO2 on the rutile TiO2 (110) surface. J. Phys. Chem. Lett. 2011, 2, 3114–3117.
Crossref Google Scholar
[40]

Tan, S. J.; Zhao, Y.; Zhao, J.; Wang, Z.; Ma, C. X.; Zhao, A. D.; Wang, B.; Luo, Y.; Yang, J. L.; Hou, J. G. CO2 dissociation activated through electron attachment on the reduced rutile TiO2 (110)-1 × 1 surface. Phys. Rev. B 2011, 84, 155418.
Crossref Google Scholar
[41]

Lin, X.; Wang, Z. T.; Lyubinetsky, I.; Kay, B. D.; Dohnálek, Z. Interaction of CO2 with oxygen adatoms on rutile TiO2 (110). Phys. Chem. Chem. Phys. 2013, 15, 6190–6195.
Crossref Google Scholar
[42]

Lin, X.; Yoon, Y.; Petrik, N. G.; Li, Z. J.; Wang, Z. T.; Glezakou, V. A.; Kay, B. D.; Lyubinetsky, I.; Kimmel, G. A.; Rousseau, R. et al. Structure and dynamics of CO2 on rutile TiO2 (110)-1 × 1. J. Phys. Chem. C 2012, 116, 26322–26334.
Crossref Google Scholar
[43]

Petrik, N. G.; Kimmel, G. A. Off-normal CO2 desorption from the photooxidation of CO on reduced TiO2 (110). J. Phys. Chem. Lett. 2010, 1, 2508–2513.
Crossref Google Scholar
[44]

Adachi, Y.; Sugawara, Y.; Li, Y. J. Atomic scale three-dimensional Au nanocluster on a rutile TiO2 (110) surface resolved by atomic force microscopy. J. Phys. Chem. Lett. 2020, 11, 7153–7158.
Crossref Google Scholar
[45]

Wen, H. F.; Miyazaki, M.; Zhang, Q. Z.; Adachi, Y.; Li, Y. J.; Sugawara, Y. Direct observation of atomic step edges on the rutile TiO2 (110)-(1 × 1) surface using atomic force microscopy. Phys. Chem. Chem. Phys. 2018, 20, 28331–28337.
Crossref Google Scholar
[46]

Sun, Z. X.; Boneschanscher, M. P.; Swart, I.; Vanmaekelbergh, D.; Liljeroth, P. Quantitative atomic force microscopy with carbon monoxide terminated tips. Phys. Rev. Lett. 2011, 106, 046104.
Crossref Google Scholar
[47]

Adachi, Y.; Wen, H. F.; Zhang, Q. Z.; Miyazaki, M.; Sugawara, Y.; Sang, H. Q.; Brndiar, J.; Kantorovich, L.; Štich, I.; Li, Y. J. Tip-induced control of charge and molecular bonding of oxygen atoms on the rutile TiO2 (110) surface with atomic force microscopy. ACS Nano 2019, 13, 6917–6924.
Crossref Google Scholar
[48]

Zhang, Q. Z.; Li, Y. J.; Wen, H. F.; Adachi, Y.; Miyazaki, M.; Sugawara, Y.; Xu, R.; Cheng, Z. H.; Brndiar, J.; Kantorovich, L. et al. Measurement and manipulation of the charge state of an adsorbed oxygen adatom on the rutile TiO2 (110)-1 × 1 surface by nc-AFM and KPFM. J. Am. Chem. Soc. 2018, 140, 15668–15674.
Crossref Google Scholar
[49]

Guggisberg, M.; Bammerlin, M.; Loppacher, C.; Pfeiffer, O.; Abdurixit, A.; Barwich, V.; Bennewitz, R.; Baratoff, A.; Meyer, E.; Güntherodt, H. J. Separation of interactions by noncontact force microscopy. Phys. Rev. B 2000, 61, 11151.
Crossref Google Scholar
[50]

Hamaker, H. C. The London–van der Waals attraction between spherical particles. Physica 1937, 4, 1058–1072.
Crossref Google Scholar
[51]

Kumagai, T.; Hanke, F.; Gawinkowski, S.; Sharp, J.; Kotsis, K.; Waluk, J.; Persson, M.; Grill, L. Controlling intramolecular hydrogen transfer in a porphycene molecule with single atoms or molecules located nearby. Nat. Chem. 2014, 6, 41–46.
Crossref Google Scholar
[52]

Dieška, P.; Štich, I.; Pérez, R. Nanomanipulation using only mechanical energy. Phys. Rev. Lett. 2005, 95, 126103.
Crossref Google Scholar
[53]

Naitoh, Y.; Turansky, R.; Brndiar, J.; Li, Y. J.; Štich, I.; Sugawara, Y. Subatomic-scale force vector mapping above a Ge (001) dimer using bimodal atomic force microscopy. Nat. Phys. 2017, 13, 663–667.
Crossref Google Scholar
[54]

Sugimoto, Y.; Namikawa, T.; Miki, K.; Abe, M.; Morita, S. Vertical and lateral force mapping on the Si (111)-(7 × 7) surface by dynamic force microscopy. Phys. Rev. B 2008, 77, 195424.
Crossref Google Scholar
[55]

Albers, B. J.; Schwendemann, T. C.; Baykara, M. Z.; Pilet, N.; Liebmann, M.; Altman, E. I.; Schwarz, U. D. Three-dimensional imaging of short-range chemical forces with picometre resolution. Nat. Nanotechnol. 2009, 4, 307–310.
Crossref Google Scholar
[56]

Ruschmeier, K.; Schirmeisen, A.; Hoffmann, R. Atomic-scale force-vector fields. Phys. Rev. Lett. 2008, 101, 156102.
Crossref Google Scholar
[57]

Pawlak, R.; Fremy, S.; Kawai, S.; Glatzel, T.; Fang, H. J.; Fendt, L. A.; Diederich, F.; Meyer, E. Directed rotations of single porphyrin molecules controlled by localized force spectroscopy. ACS Nano 2012, 6, 6318–6324.
Crossref Google Scholar
[58]

Gross, L.; Mohn, F.; Liljeroth, P.; Repp, J.; Giessibl, F. J.; Meyer, G. Measuring the charge state of an adatom with noncontact atomic force microscopy. Science 2009, 324, 1428–1431.
Crossref Google Scholar
[59]

Steurer, W.; Fatayer, S.; Gross, L.; Meyer, G. Probe-based measurement of lateral single-electron transfer between individual molecules. Nat. Commun. 2015, 6, 8353.
Crossref Google Scholar
[60]

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
Crossref Google Scholar
[61]

Adamo, C.; Barone, V. Toward reliable density functional methods without adjustable parameters: The PBE0 model. J. Chem. Phys. 1999, 110, 6158–6170.
Crossref Google Scholar
Nano Research
Volume 17 Issue 7,
July 2024
Pages 5826-5834
DOI: 10.1007/s12274-024-6539-z
Cite this article:
Adachi Y, Turanský R, Brndiar J, et al. Mechanocatalysis of CO to CO2 on TiO2 surface controlled at atomic scale. Nano Research, 2024, 17(7): 5826-5834. https://doi.org/10.1007/s12274-024-6539-z
Topics:
Catalytic oxidation

1135

Views

0

Crossref

0

Web of Science

0

Scopus

0

CSCD

Altmetrics
Received: 01 November 2023
Revised: 16 January 2024
Accepted: 02 February 2024
Published: 03 April 2024
© Tsinghua University Press 2024
Return