Spectroscopically probing the cobalt state in TiO2-supported CO2 hydrogenation catalysts derived from tailored materials via atomic layer deposition and surface organometallic chemistry

doi:10.1016/S1872-2067(26)65131-5

Abstract

Abstract:

TiO₂ is ubiquitous as a support in catalytic applications. However, its highly absorptive nature hampers the use of transmission-based spectroscopic techniques such as X-ray absorption spectroscopy (XAS), limiting in-situ/operando structure-activity studies. Here, we developed a combined atomic layer deposition (ALD) and surface organometallic chemistry (SOMC) approach to synthesize cobalt nanoparticles (NPs) supported on a TiO₂ thin film dispersed on SiO₂, yielding a spectroscopically accessible Co/TiO₂-SiO₂ model catalyst. The Co/TiO₂-SiO₂ exhibits CO₂ methanation activity similarly to Co/TiO₂ but in contrast to Co/SiO₂, which preferentially catalyzes the reverse water gas shift reaction. In-situ Co K-edge XAS during CO₂ hydrogenation conditions demonstrates that cobalt remains metallic, consistent with the observed methanation activity. This study highlights that combining ALD and SOMC provides a versatile platform for constructing TiO₂-supported model catalysts and enables their characterization via in situ spectroscopy.

Key words: CO₂ hydrogenation, TiO₂-supported cobalt, Atomic layer deposition, Surface organometallic chemistry, X-ray absorption spectroscopy

Xiaoyu Zhou, Wei Zhou, James Paterson, Jamie Southouse, Alexey Fedorov, Christoph R. Müller, Christophe Copéret. Spectroscopically probing the cobalt state in TiO₂-supported CO₂ hydrogenation catalysts derived from tailored materials via atomic layer deposition and surface organometallic chemistry[J]. Chinese Journal of Catalysis, 2026, 89: 402-409.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65131-5

https://www.cjcatal.com/EN/Y2026/V89/I10/402

Figures/Tables 5

Scheme 1. Schematic representation of a protocol for the SOMC-based synthesis of cobalt NPs supported on an ALD-derived TiO2 thin film with SiO2 as a bulk phase: ALD deposition of TiO2 via pulsed cycles of TDMAT/H2O (a), grafting of Co(CH2tBu)2tmeda (b), and H2 treatment for the Co NPs formation (c).

Fig. 1. Optimization of the TDMAT deposition on SiO2-500 followed by FTIR spectroscopy (a), calcination of TDMAT6-SiO2-500 at different temperatures (b), STEM-EDX of TiO2-SiO2-350 showing Si and Ti mappings in red and green, respectively (c).

Fig. 2. (a) FTIR spectra of the SOMC-based preparation of Co/TiO2-SiO2. Particle size distribution obtained by HAADF-STEM (b), and HAADF-STEM micrographs (c) of Co/TiO2-SiO2 and EDX mappings (d-f) of Co (blue), Ti (red), and Si (green) in pristine Co/TiO2-SiO2.

Fig. 3. CO2 hydrogenation on Co/TiO2-SiO2 with a contact time-dependent conversion (a) and product selectivity (b). (c) Selectivity comparison of the SOMC-deposited Co-based catalysts Co/SiO2 (“SiO2”), Co/TiO2-SiO2 (“ALD”), and Co/TiO2 (“TiO2”) compared at 3% CO2 conversion. Reaction conditions: 230 °C, 25 bar(g), CO2:H2:Ar = 1:3:1, 6-50 mL min-1.

Fig. 4. (a) Normalized Co K-edge XANES spectra for pristine and post-reaction Co/TiO2-SiO2 and reference data of metallic Co (Co foil) and Co(II) (Co(Np)tmeda@SiO2) and their respective 1st derivatives shown in (b) as green, blue, dark gray, and light gray, respectively. (c) In-situ XANES traces of Co/TiO2-SiO2 under CO2 hydrogenation conditions (230 °C, 25 bar) from light blue to dark blue traces over time on stream, along with the difference spectrum between the initial and final XANES spectra measured for a total of 2 h.

References

[1]	A. J. Haider, Z. N. Jameel, I. H. M. Al-Hussaini, Energy Procedia, 2019, 157, 17-29.
[2]	A. D. Racovita, Int. J. Environ. Res. Public Health, 2022, 19, 5681.
[3]	T. Xu, X. Wu, Y. Gao, Q. Lin, J. Hu, D. Weng, Catal. Commun., 2017, 93, 33-36.
[4]	M. Aguilar-Romero, R. Camposeco, S. Castillo, J. Marín, V. Rodríguez-González, L. A. García-Serrano, I. Mejía-Centeno, Fuel, 2017, 198, 123-133.
[5]	K. Zhao, W. Han, Z. Tang, G. Zhang, J. Lu, G. Lu, X. Zhen, Colloids Surf. A Physicochem. Eng. Asp., 2016, 503, 53-60.
[6]	M. H. Kim, S. W. Park, Catal. Commun., 2016, 86, 82-85.
[7]	Y. He, M. E. Ford, M. Zhu, Q. Liu, U. Tumuluri, Z. Wu, I. E. Wachs, Appl. Catal. B: Environ., 2016, 193, 141-150.
[8]	G. Jacobs, T. K. Das, Y. Zhang, J. Li, G. Racoillet, B. H. Davis, Appl. Catal. A: Gen., 2002, 233, 263-281.
[9]	E. Iglesia, Appl. Catal. A: Gen., 1997, 161, 59-78.
[10]	T. Komaya, A. T. Bell, Z. Wengsieh, R. Gronsky, F. Engelke, T. S. King, M. Pruski, J. Catal., 1994, 150, 400-406.
[11]	M. Lindley, P. Stishenko, J. W. M. Crawley, F. Tinkamanyire, M. Smith, J. Paterson, M. Peacock, Z. Xu, C. Hardacre, A. S. Walton, A. J. Logsdail, S. J. Haigh, ACS Catal., 2024, 14, 10648-10657.
[12]	J. Paterson, M. Peacock, R. Purves, R. Partington, K. Sullivan, G. Sunley, J. Wilson, ChemCatChem, 2018, 10, 5154-5163.
[13]	I. C. ten Have, B. M. Weckhuysen, Chem Catal., 2021, 1, 339-363.
[14]	S. W. Chun, J. Y. Jang, D. W. Park, H. C. Woo, J. S. Chung, Appl. Catal. B: Environ, 1998, 16, 235-243.
[15]	P. D. Clark, N. I. Dowling, M. Huang, Appl. Catal. B: Environ., 2001, 31, 107-112.
[16]	P. D. Clark, N. I. Dowling, M. Huang, Appl. Catal. A: Gen., 2015, 489, 111-116.
[17]	H. S. Russell, L. B. Frederickson, O. Hertel, T. Ellermann, S. S. Jensen, Catalysts, 2021, 11, 675.
[18]	S. Scirè, R. Fiorenza, M. Bellardita, L. Palmisano, in: Titanium Dioxide (TiO₂) and Its Applications, F. Parrino, L. Palmisano Eds., Amsterdam: Elsevier, 2021, 637-679.
[19]	S. Bagheri, N. Muhd Julkapli, S. Bee Abd Hamid, Sci. World J., 2014, 2014, 727496.
[20]	X. Jiang, M. Manawan, T. Feng, R. Qian, T. Zhao, G. Zhou, F. Kong, Q. Wang, S. Dai, J. H. Pan, Catal. Today, 2018, 300, 12-17.
[21]	B. A. T. Mehrabadi, S. Eskandari, U. Khan, R. D. White, J. R. Regalbuto, Adv. Catal., 2017, 61, 1-35.
[22]	F. Morales, F. M. F. de Groot, P. Glatzel, E. Kleimenov, H. Bluhm, M. Hävecker, A. Knop-Gericke, B. M. Weckhuysen, J. Phys. Chem. B, 2004, 108, 16201-16207.
[23]	C. Qiu, Y. Odarchenko, Q. Meng, P. Cong, M. A. W. Schoen, A. Kleibert, T. Forrest, A. M. Beale, Chem. Sci., 2020, 11, 13060-13070.
[24]	S. M. George, Chem. Rev., 2010, 110, 111-131.
[25]	F. Zaera, Chem. Rev., 2022, 122, 8594-8757.
[26]	S. T. Barry, A. V. Teplyakov, F. Zaera, Acc. Chem. Res., 2018, 51, 800-809.
[27]	X. Meng, X. Wang, D. Geng, C. Ozgit-Akgun, N. Schneider, J. W. Elam, Mater. Horiz., 2017, 4, 133-154.
[28]	Z. Chen, S. R. Docherty, P. Florian, A. Kierzkowska, I. B. Moroz, P. M. Abdala, C. Copéret, C. R. Müller, A. Fedorov, Catal. Sci. Technol., 2022, 12, 5861-5868.
[29]	H. Zhou, S. R. Docherty, N. Phongprueksathat, Z. Chen, A. V. Bukhtiyarov, I. P. Prosvirin, O. V. Safonova, A. Urakawa, C. Copéret, C. R. Müller, A. Fedorov, JACS Au, 2023, 3, 2536-2549.
[30]	C. Copéret, A. Comas-Vives, M. P. Conley, D. P. Estes, A. Fedorov, V. Mougel, H. Nagae, F. Núñez-Zarur, P. A. Zhizhko, Chem. Rev., 2016, 116, 323-421.
[31]	C. Copéret, Acc. Chem. Res., 2019, 52, 1697-1708.
[32]	S. R. Docherty, C. Copéret, J. Am. Chem. Soc., 2021, 143, 6767-6780.
[33]	Q. Xie, Y.-L. Jiang, C. Detavernier, D. Deduytsche, R. L. Van Meirhaeghe, G.-P. Ru, B.-Z. Li, X.-P. Qu, J. Appl. Phys., 2007, 102, 083521.
[34]	B. Abendroth, T. Moebus, S. Rentrop, R. Strohmeyer, M. Vinnichenko, T. Weling, H. Stöcker, D. C. Meyer, Thin Solid Films, 2013, 545, 176-182.
[35]	B. A. Sperling, J. Hoang, W. A. Kimes, J. E. Maslar, K. L. Steffens, N. V. Nguyen, J. Vac. Sci. Technol. A, 2014, 32, 031513.
[36]	Z. Chen, N. K. Zimmerli, M. Zubair, A. V. Yakimov, S. Björgvinsdóttir, N. Alaniva, E. Willinger, A. B. Barnes, N. M. Bedford, C. Copéret, P. Florian, P. M. Abdala, A. Fedorov, C. R. Müller, Chem. Mater., 2023, 35, 7475-7490.
[37]	M. Kaushik, C. Leroy, Z. Chen, D. Gajan, E. Willinger, C. R. Müller, F. Fayon, D. Massiot, A. Fedorov, C. Copéret, A. Lesage, P. Florian, Chem. Mater., 2021, 33, 3335-3348.
[38]	M. Nadjafi, A. M. Kierzkowska, A. Armutlulu, R. Verel, A. Fedorov, P. M. Abdala, C. R. Müller, J. Phys. Chem. C, 2021, 125, 14065-14074.
[39]	Y. Hu, Y. Pan, Z. Wang, T. Lin, Y. Gao, B. Luo, H. Hu, F. Fan, G. Liu, L. Wang, Nat. Commun., 2020, 11, 2129.
[40]	X. Zhou, G. A. Price, G. J. Sunley, C. Copéret, Angew. Chem. Int. Ed., 2023, 62, e202314274.
[41]	D. H. Pearson, C. C. Ahn, B. Fultz, Phys. Rev. B, 1993, 47, 8471-8478.
[42]	N. Ichikuni, Y. Iwasawa, Catal. Lett., 1993, 20, 87-95.
[43]	J. A. van Bokhoven, J. T. Miller, J. Phys. Chem. C, 2007, 111, 9245-9249.
[44]	R. E. Colborn, M. F. Garbauskas, C. I. Hejna, Inorg. Chem., 1988, 27, 3661-3663.
[45]	V. Riollet, E. A. Quadrelli, C. Copéret, J.-M. Basset, R. A. Andersen, K. Köhler, R.-M. Böttcher, E. Herdtweck, Chem. Eur. J., 2005, 11, 7358-7365.
[46]	A. Enachi, D. Baabe, M.-K. Zaretzke, P. Schweyen, M. Freytag, J. Raeder, M. D. Walter, Chem. Commun., 2018, 54, 13798-13801.
[47]	B. Ravel, M. Newville, J. Synchrotron Radiat., 2005, 12, 537-541.

Spectroscopically probing the cobalt state in TiO₂-supported CO₂ hydrogenation catalysts derived from tailored materials via atomic layer deposition and surface organometallic chemistry

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