An experimental and computational investigation on structural evolution of the In2O3 catalyst during the induction period of CO2 hydrogenation

doi:10.1016/S1872-2067(25)64657-2

Abstract

Abstract:

As one of the most important industrially viable methods for carbon dioxide (CO₂) utilization, methanol synthesis serves as a platform for production of green fuels and commodity chemicals. For sustainable methanol synthesis, In₂O₃ is an ideal catalyst and has garnered significant attention. Herein, cubic In₂O₃ nanoparticles were prepared via the precipitation method and evaluated for CO₂ hydrogenation to produce methanol. During the initial 10 h of reaction, CO₂ conversion gradually increased, accompanied by a slow decrease of methanol selectivity, and the reaction reached equilibrium after 10-20 h on stream. This activation and induction stage may be attributed to the sintering of In₂O₃ nanoparticles and the creation of more oxygen vacancies on In₂O₃ surfaces. Further experimental studies demonstrate that hydrogen induction created additional oxygen vacancies during the catalyst activation stage, enhancing the performance of In₂O₃catalyst for CO₂ hydrogenation. Density functional theory calculations and microkinetic simulations further demonstrated that surfaces with higher oxygen vacancy coverages or hydroxylated surfaces formed during this induction period can enhance the reaction rate and increase the CO₂ conversion. However, they predominantly promote the formation of CO instead of methanol, leading to reduced methanol selectivity. These predictions align well with the above-mentioned experimental observations. Our work thus provides an in-depth analysis of the induction stage of the CO₂ hydrogenation process on In₂O₃ nano-catalyst, and offers valuable insights for significantly improving the CO₂ reactivity of In₂O₃-based catalysts while maintaining long-term stability.

Key words: In₂O₃, CO₂ hydrogenation, Methanol production, Induction and activation, Structural evolution

Zhangqian Wei, Mingxiu Wang, Xinnan Lu, Zixuan Zhou, Ziqi Tang, Chunran Chang, Yong Yang, Shenggang Li, Peng Gao. An experimental and computational investigation on structural evolution of the In₂O₃ catalyst during the induction period of CO₂ hydrogenation[J]. Chinese Journal of Catalysis, 2025, 72: 301-313.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64657-2

https://www.cjcatal.com/EN/Y2025/V72/I5/301

Figures/Tables 8

Fig. 1. Comparison of CO2 conversion (XCO2), methanol selectivity (SCH3OH) and methanol STY over In2O3 catalysts as a function of pressure (a), temperature (b), and time on stream (c). Reaction conditions: H2/CO2 = 3, GHSV = 7200 mL h?1 gcat?1, and (a) 300°C, 1-5 MPa, (b) 220-300 °C, 5 MPa, (c) 300 °C, 5 MPa.

Fig. 2. XRD patterns of In2O3 under different situations.

Fig. 3. TEM images of In2O3 under various conditions: fresh (a), 1 h (b), 5 h (c), 10 h (d), 20 h (e), and 40 h (f), where insets are the corresponding In2O3 particle size distributions.

Table 1 Texture properties of the In2O3 samples under various conditions.

Sample	Spent time (h)	S_BET ^a (m² g^-1)	Pore volume ^b (cm³ g^-1)	Pore width ^c (nm)
Fresh	0	129	0.25	7.8
1 h	1	28	0.22	31.2
5 h	5	35	0.23	31.0
10 h	10	37	0.22	31.1
20 h	20	30	0.19	31.3
40 h	40	28	0.23	30.9

Fig. 4. BET adsorption-desorption isotherms (a) and pore size distributions (b) of In2O3 under different situations. (c) CO2-TPD profiles for In2O3 under various conditions (CO2 was adsorbed without any pretreatment of the In2O3 samples). (d) H2-TPR profiles for In2O3 under various conditions.

Fig. 5. (a) Visible Raman spectra of the In2O3 catalysts under various conditions, where inset is the comparison of the relative amount of oxygen vacancies according to the I2/I1 ratio. (b) XPS spectra of O 1s for In2O3 under various situations with the percentages of the lattice and defect oxygen sites shown.

Fig. 6. (a) Top views of In2O3 (111)-one-VO, (111)-all-VO and (111)-33%-H model surfaces with the blue circle representing VO. (b,c) Pathways of methanol and CO formations with the energy barriers of the elementary steps (_D represents the defective surface with VO, _P represents the surface where the VO is filled by O, and * stands for the adsorption site).

Fig. 7. (a) Reaction rates predicted from microkinetic simulations. (b) Product selectivity predicted for the (111)-one-VO surface. (c) Product selectivities predicted for the (111)-all-VO, (111)-33%-H and (110)-33%-H surfaces, which are all similar. (d,e,f) DRC values from the microkinetic simulations for the (111)-one-VO, (111)-all-VO, and (111)-33%-H surfaces. Elementary reactions involved in the microkinetic simulations are shown in Table S5, and the energetics and harmonic frequencies for the studied surfaces are given in Tables S6-S9.

References

[1]	J. P. Holdren, Innov. Technol. Gov. Glob., 2006, 1(2), 3-23.
[2]	N. Armaroli, V. Balzani, Angew. Chem. Int. Ed., 2007, 46, 52-66.
[3]	A. Tsoukalou, P. M. Abdala, D. Stoian, X. Huang, M.-G. Willinger, A. Fedorov, C. R. Mueller, J. Am. Chem. Soc., 2019, 141, 13497-13505.
[4]	X. Yang, X. Su, D. Chen, T. Zhang, Y. Huang, Chin. J. Catal., 2020, 41, 561-573.
[5]	J. L. Holechek, H. M. E. Geli, M. N. Sawalhah, R. Valdez, Sustainability, 2022, 14, 4792.
[6]	F. Sha, S. Tang, C. Tang, Z. Feng, J. Wang, C. Li, Chin. J. Catal., 2023, 45, 162-173.
[7]	J. Wang, J. Meeprasert, Z. Han, H. Wang, Z. Feng, C. Tang, F. Sha, S. Tang, G. Li, E. A. Pidko, C. Li, Chin. J. Catal., 2022, 43, 761-770.
[8]	B. Yang, W. Deng, L. Guo, T. Ishihara, Chin. J. Catal., 2020, 41, 1348-1359.
[9]	C.-M. Wang, Y.-D. Wang, Z.-K. Xie, Chin. J. Catal., 2018, 39, 1272-1279.
[10]	E. Lam, K. Larmier, S. Tada, P. Wolf, O. V. Safonova, C. Coperet, Chin. J. Catal., 2019, 40, 1741-1748.
[11]	J. Ma, N. Sun, X. Zhang, N. Zhao, F. Mao, W. Wei, Y. Sun, Catal. Today, 2009, 148, 221-231.
[12]	M. Aresta, A. Dibenedetto, E. Quaranta, J. Catal., 2016, 343, 2-45.
[13]	Z. Zhou, P. Gao, Chin. J. Catal., 2022, 43, 2045-2056.
[14]	Z. You, W. Deng, Q. Zhang, Y. Wang, Chin. J. Catal., 2013, 34, 956-963.
[15]	G. A. Olah, A. Goeppert, G. K. S. Prakash, J. Org. Chem., 2009, 74, 487-498.
[16]	T. Zhang, Chin. J. Catal., 2017, 38, 1781-1783.
[17]	G. Varvoutis, A. Lampropoulos, E. Mandela, M. Konsolakis, G. E. Marnellos, Energies, 2022, 15, 4790.
[18]	S. S. Tabibian, M. Sharifzadeh, Renewable Sustainable Energy Rev., 2023, 179, 113281.
[19]	K. Sun, Z. Fan, J. Ye, J. Yan, Q. Ge, Y. Li, W. He, W. Yang, C. J. Liu, J. CO₂ Util., 2015, 12, 1-6.
[20]	S. Lu, H. Yang, Z. Zhou, L. Zhong, S. Li, P. Gao, Y. Sun, Chin. J. Catal., 2021, 42, 2038-2048.
[21]	J. Wang, G. Zhang, J. Zhu, X. Zhang, F. Ding, A. Zhang, X. Guo, C, ACS Catal., 2021, 11, 1406-1423.
[22]	Y. Shi, W. Su, L. Kong, J. Wang, P. Lv, J. Hao, X. Gao, G. Yu, J. Colloid Interface Sci., 2022, 623, 1048-1062.
[23]	J. Wang, C. Y. Liu, T. P. Senftle, J. Zhu, G. Zhang, X. Guo, C. Song, ACS Catal., 2019, 10, 3264-3273.
[24]	S. Dang, B. Qin, Y. Yang, H. Wang, J. Cai, Y. Han, S. Li, P. Gao, Y. Sun, Sci. Adv., 2020, 6, eaaz2060.
[25]	M. Ziemba, M. Radtke, L. Schumacher, C. Hess, Angew. Chem. Int. Ed., 2022, 61, e202209388.
[26]	A. Ayeshamariam, M. Bououdina, C. Sanjeeviraja, Mater. Sci. Semicond. Process., 2013, 16, 686-695.
[27]	O. Martin, A. J. Martin, C. Mondelli, S. Mitchell, T. F. Segawa, R. Hauert, C. Drouilly, D. Curulla-Ferre, J. Perez-Ramirez, Angew. Chem. Int. Ed., 2016, 55, 6261-6265.
[28]	B. Qin, Z. Zhou, S. Li, P. Gao, J. CO₂ Util., 2021, 49, 101543.
[29]	J. Ye, C. Liu, Q. Ge, J. Phys. Chem. C, 2012, 116, 7817-7825.
[30]	K. H. Ernst, C. T. Campbell, G. Moretti, J. Catal., 1992, 134, 66-74.
[31]	J. Yoshihara, C. T. Campbell, J. Catal., 1996, 161, 776-782.
[32]	J. Ye, C. Liu, D. Mei, Q. Ge, ACS Catal., 2013, 3, 1296-1306.
[33]	M. S. Frei, M. Capdevila-Cortada, R. Garcia-Muelas, C. Mondelli, N. Lopez, J. A. Stewart, D. C. Ferre, J. Perez-Ramirez, J. Catal., 2018, 361, 313-321.
[34]	T. Bielz, H. Lorenz, W. Jochum, R. Kaindl, F. Klauser, B. Kloetzer, S. Penner, J. Phys. Chem. C, 2010, 114, 9022-9029.
[35]	A. Posada-Borbon, H. Gronbeck, ACS Catal., 2021, 11, 9996-10006.
[36]	A. Posada-Borbon, H. Gronbeck, Phys. Chem. Chem. Phys., 2020, 22,16193-16202.
[37]	L. Wu, R. Zou, C. Shen, C. J. Liu, Energy Fuels, 2023, 37, 18120-18127.
[38]	J. Wang, R. Li, G. Zhang, C. Dong, Y. Fan, S. Yang, M. Chen, X. Guo, R. Mu, Y. Ning, M. Li, Q. Fu, X. Bao, J. Am. Chem. Soc., 2024, 146, 5523-5531.
[39]	P. Gao, S. Li, X. Bu, S. Dang, Z. Liu, H. Wang, L. Zhong, M. Qiu, C. Yang, J. Cai, W. Wei, Y. Sun, Nat. Chem., 2017, 9, 1019-1024.
[40]	M. S. Frei, C. Mondelli, R. Garcia-Muelas, K. S. Kley, B. Puertolas, N. Lopez, O. V. Safonova, J. A. Stewart, D. C. Ferre, J. Perez-Ramirez, Nat. Commun., 2019, 10, 3377.
[41]	K. Sun, N. Rui, Z. Zhang, Z. Su, Q. Ge, C. J. Liu, Green Chem., 2020, 22, 5059-5066.
[42]	C. Yang, C. Pei, R. Luo, S. Liu, Y. Wang, Z. Wang, Z.-J. Zhao, J. Gong, J. Am. Chem. Soc., 2020, 142, 19523-19531.
[43]	C. Meng, G. Zhao, X.-R. Shi, P. Chen, Y. Liu, Y. Lu, Sci. Adv., 2021, 7, eabi6012.
[44]	Z. Zhou, Z. Wei, J. Zhang, H. Yang, S. Li, P. Gao, Ind. Eng. Chem. Res., 2024, 63, 9026-9037.
[45]	Z. Zhou, Y. Wang, Y. Bao, H. Yang, J. Li, C. Chang, S. Li, P. Gao, Sci. China Chem., 2024, 67, 1715-1728.
[46]	Y. Wang, Z. Zhou, B. Qin, Q.-Y. Chang, S. Dang, Y. Hu, K. Li, Y. Bao, J. Mao, H. Yang, Y. Liu, J. Li, S. Li, D. A. Dixon, Y. Sun, P. Gao, EES Catal., 2025, 3, 106-118.
[47]	Y. Wang, G. Wang, L. I. van der Wal, K. Cheng, Q. Zhang, K. P. de Jong, Y. Wang,, Angew. Chem. Int. Ed., 2021, 60, 17735-17743.
[48]	Z. Dong, M. Huo, J. Li, J. Li, P. Li, H. Sun, L. Gu, Y. Lu, M. Wang, Y. Wang, Z. Chen, Nature, 2024, 630, 847-852.
[49]	G. Kresse, J. Furthmuller, Comput. Mater. Sci., 1996, 6, 15-50.
[50]	G. Kresse, J. Furthmuller, Phys. Rev. B, 1996, 54, 11169-11186.
[51]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[52]	G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[53]	G. Henkelman, B. P. Uberuaga, H. Jónsson, J. Chem. Phys., 2000, 113, 9901-9904.
[54]	S. Smidstrup, A. Pedersen, K. Stokbro, H. Jónsson, J. Chem. Phys., 2014, 140, 214106.
[55]	A. H. MacDonald, Phys. Rev. B, 1978, 18, 5897-5899.
[56]	A. J. Medford, C. Shi, M. J. Hoffmann, A. C. Lausche, S. R. Fitzgibbon, T. Bligaard, J. K. Norskov, Catal. Lett., 2015, 145, 794-807.
[57]	S. Kozuch, S. Shaik, J. Am. Chem. Soc., 2006, 128, 3355-3365.
[58]	S. Kozuch, S. Shaik, J. Phys. Chem. A, 2008, 112, 6032-6041.
[59]	C. Stegelmann, A. Andreasen, C. T. Campbell, J. Am. Chem. Soc., 2009, 131, 8077-8082.
[60]	C. T. Campbell, ACS Catal., 2017, 7, 2770-2779.
[61]	I. G. Nielsen, S. Sommer, B. B. Iversen, Nanoscale, 2021, 13, 4038-4050.
[62]	M. A. Al-Ghouti, D. A. Da'ana, J. Hazard. Mater., 2020, 393, 122383.
[63]	J. Wang, K. Sun, X. Jia, C. J. Liu, Catal. Today, 2021, 365, 341-347.
[64]	C. Shi, J. Liu, W. Li, X. Jiang, H. Yang, Q. Liu, Ceram. Int., 2018, 44, 22235-22240.
[65]	N. Rui, Z. Wang, K. Sun, J. Ye, Q. Ge, C. J. Liu, Appl. Catal. B, 2017, 218, 488-497.
[66]	J. Gan, X. Lu, J. Wu, S. Xie, T. Zhai, M. Yu, Z. Zhang, Y. Mao, S.C.I. Wang, Y. Shen, Y. Tong, Sci. Rep., 2013, 3, 1021.
[67]	S. Elouali, L. G. Bloor, R. Binions, I. P. Parkin, C. J. Carmalt, J. A. Darr, Langmuir, 2012, 28, 1879-1885.
[68]	M. Ziemba, L. Schumacher, C. Hess, J. Phys. Chem. Lett., 2021, 12, 3749-3754.
[69]	C. Shen, K. Sun, Z. Zhang, N. Rui, X. Jia, D. Mei, C. J. Liu, ACS Catal., 2021, 11, 4036-4046.
[70]	W. Wang, Z. Qu, L. Song, Q. Fu, J. Energy Chem., 2020, 47, 18-28.
[71]	Y. Yang, C. Shen, K. Sun, D. Mei, C. J. Liu, ACS Catal., 2023, 13, 6154-6168.
[72]	Y. Wang, L. Zhu, Y. Liu, E. I. Vovk, J. Lang, Z. Zhou, P. Gao, S. Li, Y. Yang, Appl. Surf. Sci., 2023, 631, 157534.
[73]	Z. Liu, X. Lv, J. Zhang, A. Guan, C. Yang, S. Yan, Y. Chen, K. Liu, G. Zheng, Adv. Mater. Interfaces, 2022, 9, 2101956.
[74]	M. Dou, M. Zhang, Y. Chen, Y. Yu, New J. Chem. 2018, 42, 3293-3300.
[75]	D. Albani, M. Capdevila-Cortada, G. Vilé, S. Mitchell, O. Martin, N. López, J. Pérez-Ramírez, Angew. Chem. Int. Ed., 2017, 56, 10755-10760.
[76]	B. Qin, S. Li, Phys. Chem. Chem. Phys., 2020, 22, 3390-3399.
[77]	K. Li, Z. Wei, Q. Chang, S. Li, Comput. Theor. Chem., 2023, 1225, 114174.

An experimental and computational investigation on structural evolution of the In₂O₃ catalyst during the induction period of CO₂ hydrogenation

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