Effect of In2O3 particle size on CO2 hydrogenation to lower olefins over bifunctional catalysts

doi:10.1016/S1872-2067(21)63851-2

Abstract

Abstract:

A reaction-coupling strategy is often employed for CO₂ hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts. Because the oxide components are responsible for CO₂ activation, understanding the structural effects of these oxides is crucial, however, these effects still remain unclear. In this study, we combined In₂O₃, with varying particle sizes, and SAPO-34 as bifunctional catalysts for CO₂ hydrogenation. The CO₂ conversion and selectivity of the lower olefins increased as the average In₂O₃ crystallite size decreased from 29 to 19 nm; this trend mainly due to the increasing number of oxygen vacancies responsible for CO₂ and H₂ activation. However, In₂O₃ particles smaller than 19 nm are more prone to sintering than those with other sizes. The results suggest that 19 nm is the optimal size of In₂O₃ for CO₂ hydrogenation to lower olefins and that the oxide particle size is crucial for designing catalysts with high activity, high selectivity, and high stability.

Key words: Carbon dioxide hydrogenation, Bifunctional catalysis, Particle size effect, Indium oxide, Lower olefins

Siyu Lu, Haiyan Yang, Zixuan Zhou, Liangshu Zhong, Shenggang Li, Peng Gao, Yuhan Sun. Effect of In₂O₃ particle size on CO₂ hydrogenation to lower olefins over bifunctional catalysts[J]. Chinese Journal of Catalysis, 2021, 42(11): 2038-2048.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63851-2

https://www.cjcatal.com/EN/Y2021/V42/I11/2038

Figures/Tables 11

Table 1 Texture properties of the In2O3-x samples prepared at different calcination temperatures.

Sample	Calcination temperature (°C)	Crystal size (nm)					Surface area^f (m² g^-1)
Sample	Calcination temperature (°C)	Fresh		Used ^a			Surface area^f (m² g^-1)
In₂O₃-300	300	7 ^a	5 ^b	15 ^c	17 ^d	16 ^e	127
In₂O₃-400	400	10 ^a	9 ^b	17 ^c	18 ^d	18 ^e	93
In₂O₃-500	500	15 ^a	15 ^b	19 ^c	21 ^d	20 ^e	47
In₂O₃-600	600	19 ^a	18 ^b	22 ^c	22 ^d	21 ^e	28
In₂O₃-650	650	23 ^a	23 ^b	24 ^c	25 ^d	25 ^e	17
In₂O₃-700	700	28 ^a	27 ^b	29 ^c	29 ^d	29 ^e	16

Fig. 1. TEM images and size distributions (insert) of the various In2O3-x samples. (a) In2O3-300; (b) In2O3-400; (c) In2O3-500; (d) In2O3-600; (e) In2O3-650; (f) In2O3-700.

Fig. 2. (a) N2 adsorption-desorption curves and BJH pore size distributions (insert) of the pure In2O3 samples. (b) Correlation between the particle size of In2O3 and the calcination temperature. The blue and red lines represent sizes of the fresh In2O3 obtained from TEM and XRD, respectively. The olive and magenta lines represent those of the In2O3-x samples after 24 and 50 h of reaction, respectively. (c) The BET specific surface areas of fresh In2O3-x (red) and spent In2O3-x after reaction for 24 h (olive).

Fig. 3. XPS O 1s spectra of pretreated In2O3-x samples in Ar and the corresponding fractions of surface oxygen atoms next to a defect calculated from the deconvoluted O 1s peaks.

Fig. 4. (a) EPR spectra of In2O3-x samples; (b) Correlation between the oxygen vacancy density and the particle size of fresh In2O3.

Fig. 5. Surface properties of various In2O3-x samples. (a) CO2-TPD spectra; (b) H2-TPD spectra; (c) NH3-TPD profiles; (d) H2-TPR profiles.

Table 2 Catalytic performance for CO2 hydrogenation over bifunctional catalysts containing In2O3 oxides with different crystal sizes and SAPO-34 zeolites.

Sample	Particle size (nm) ^a	CO₂ conv. (%)	CO sel. (%)	Hydrocarbon distribution (C%)				C₂-C₄ O/P
Sample	Particle size (nm) ^a	CO₂ conv. (%)	CO sel. (%)	CH₄			C₅₊	C₂-C₄ O/P
In₂O₃-300	15	13.3	63.2	1.5	22.2	71.3	5.0	3.2
In₂O₃-400	17	13.8	65.9	1.8	19.1	74.4	4.7	3.9
In₂O₃-500	19	14.1	60.9	1.8	16.1	76.9	5.2	4.8
In₂O₃-600	22	12.0	62.4	2.1	20.9	71.8	5.2	3.4
In₂O₃-650	24	11.9	61.8	1.4	21.5	71.2	5.9	3.3
In₂O₃-700	29	11.6	57.2	1.6	27.4	65.1	5.9	2.4

Fig. 6. Correlation between hydrocarbon selectivity under the standard reaction conditions and the particle size of In2O3 corresponding to the data given in Table 2. (a) Selectivities of C2=-C4= and C2o-C4o among all hydrocarbons; (b) Ratio of lower olefins to lower paraffins; (c) Selectivities of C2=, C3=, and C4=; (d) STY of lower olefins and paraffins.

Fig. 8. Catalytic stability of the In2O3-x/SAPO-34 catalyst under the reaction conditions shown in Table 2. (a) In2O3-300/SAPO-34; (b) In2O3-500/SAPO-34; (c) In2O3-700/SAPO-34.

Fig. 7. CO2 conversion (a) and CO selectivity (b) over In2O3-x/SAPO-34 bifunctional catalysts as a function of In2O3 particle size; (c) CO2 conversion and CH3OH selectivity over pure In2O3-x catalysts as a function of In2O3 particle size; (d) Arrhenius plots for CO2 hydrogenation to methanol over In2O3-x. Reaction conditions: In2O3 (0.4 g) + SAPO-34 (0.8 g), F = 180 mL min-1, 3.0 MPa, 350 °C, H2/CO2 = 3.

Fig. 9. Size dependence of the TOF of hydrocarbons: (a) TOFCH4; (b) TOFlower olefins and TOFlower paraffins. Reaction conditions: In2O3 (0.3 g) + SAPO-34 (0.6 g), 3.0 MPa, 350 °C, H2/CO2 = 3, WHSV = 12000 or 15000 mL gcat-1 h-1.

References

[1]	A. Goeppert, M. Czaun, J. P. Jones, G. K. Surya Prakash, G. A. Olah, Chem. Soc. Rev., 2014, 43, 7995-8048.
[2]	A. Alvarez, A. Bansode, A. Urakawa, A. V. Bavykina, T. A. Wezendonk, M. Makkee, J. Gascon, F. Kapteijn, Chem. Rev., 2017, 117,9804-9838.
[3]	X. Jiang, X. Nie, X. Guo, C. Song, J. G. Chen, Chem. Rev., 2020, 120, 7984-8034.
[4]	K. Sordakis, C. H. Tang, L. K. Vogt, H. Junge, P. J. Dyson, M. Beller, G. Laurenczy, Chem. Rev., 2018, 118, 372-433.
[5]	B. Yang, W. Deng, L. M. Guo, T. Ishihara, Chin. J. Catal., 2020, 41, 1348-1359.
[6]	X. L. Liu, J. L. Li, N. Li, B. Y. Li, X. H. Bu, Chin. J. Chem., 2020, 39, 440-462.
[7]	A. Dokania, A. Ramirez, A. Bavykina, J. Gascon, ACS Energy Lett., 2018, 4, 167-176.
[8]	J. C. Li, L. G. Wang, Y. Gao, C. J. Zhang, P. He, H. Q. Li, Chin. J. Chem. Eng, 2018, 24, 2266-2279.
[9]	Z. Y. You, W. P. Deng, Q. H. Zhang, Y. Wang, Chin. J. Catal., 2013, 34, 956-963.
[10]	D. X. Yang, Q. G. Zhu, B. X. Han, The Innovation, 2020, 1, 100016.
[11]	L. Zhu, Y. Y. Lin, K. Liu, E. Cortés, H. M. Li, J.H. Hu, Y. Akira, X. L. Liu, M. Masahiro, J. Fu, M. Liu, Chin. J. Catal., 2021, 42, 1500-1508
[12]	Z. Ma, M. D. Porosoff, ACS Catal., 2019, 9, 2639-2656.
[13]	Z. L. Li, J. J. Wang, Y. Z. Qu, H. L. Liu, C. Z. Tang, S. Miao, Z. C. Feng, H. Y. An, C. Li, ACS Catal., 2017, 7, 8544-8548.
[14]	P. Gao, L. N. Zhang, S. G. Li, Z. X. Zhou, Y. H. Sun, ACS Cent. Sci., 2020, 6, 1657-1670.
[15]	E. C. Ra, K. Y. Kim, E. H. Kim, H. Lee, K. An, J. S. Lee, ACS Catal., 2020, 10, 11318-11345.
[16]	G. Song, M. Li, P. Yan, M. A. Nawaz, D. Liu, ACS Catal., 2020, 10, 11268-11279.
[17]	C. Zhou, J. Shi, W. Zhou, K. Cheng, Q. Zhang, J. Kang, Y. Wang, ACS Catal., 2019, 10, 302-310.
[18]	W. Zhou, K. Cheng, J. C. Kang, C. Zhou, V. Subramanian, Q. H. Zhang, Y. Wang, Chem. Soc. Rev, 2019, 48, 3193-3228.
[19]	Z. Li, Y. Qu, J. Wang, H. Liu, M. Li, S. Miao, C. Li, Joule, 2019, 3, 570-583.
[20]	X. Liu, M. Wang, H. Yin, J. Hu, K. Cheng, J. Kang, Q. Zhang, Y. Wang, ACS Catal. 2020, 15, 8303-8314.
[21]	P. Gao, S. G. Li, X. N. Bu, S. S. Dang, Z. Y. Liu, H. Wang, L. S. Zhong, M. H. Qiu, C. G. Yang, J. Cai, W. Wei, Y. H. Sun, Nat. Chem., 2017, 9, 1019-1024.
[22]	P. Gao, S. S. Dang, S. G. Li, X. N. Bu, Z. Y. Liu, M. H. Qiu, C. G. Yang, H. Wang, L. S. Zhong, Y. Han, Q. Liu, W. Wei, Y. H. Sun, ACS Catal., 2017, 8, 571-578.
[23]	X. L. Liu, M. H. Wang, C. Zhou, W. Zhou, K. Cheng, J. C. Kang, Q. H. Zhang, W. P. Deng, Y. Wang, ChemComm., 2018, 5, 140-143.
[24]	X. B. Zhang, A. F. Zhang, X. Jiang, J. Zhu, J. H. Liu, J. J. Li, G. H. Zhang, C. S. Song, X. W. Guo, J. CO₂ Util., 2019, 29, 140-145.
[25]	J. Ye, C. Liu, D. Mei, Q. F, Ge, ACS Catal., 2013, 3, 1296-1306.
[26]	S. S. Dang, B. Qin, Y. Yang, H. Wang, J. Cai, Y. Han, S. G. Li, P. Gao, Y. H. Sun, Sci. Adv., 2020, 6, eaaz2060.
[27]	S. Wang, P. Wang, Z. Qin, W. Yan, M. Dong, J. Li, J. Wang, W. Fan, J. Catal., 2020, 391, 459-470.
[28]	K. H. Sun, Z. G. Fan, J. Y. Ye, J. M. Yan, Q. F. Ge, Y. N. Li, W. J. He, W. M. Yang, C. J. Liu, J. CO₂ Util., 2015, 12, 1-6.
[29]	J. Zhong, X. Yang, Z. Wu, B. Liang, Y. Huang, T. Zhang, Chem. Soc. Rev., 2020, 49, 1385-1413.
[30]	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.
[31]	T. Numpilai, C. Wattanakit, M. Chareonpanich, J. Limtrakul, T. Witoon, Energy Convers. Manage., 2019, 118, 511-523.
[32]	N. Rui, Z. Wang, K. Sun, J. Ye, Q. Ge, C. J. Liu, Appl. Catal. B, 2017, 218, 488-497.
[33]	S. Yang, C. L. Pei, R. Luo, S. H. Liu, Y. N. Wang, Z. Y. Wang, Z. J. Zhao, J. L. Gong, J. Am. Chem. Soc., 2020, 142, 19523-19531.
[34]	M. S. Frei, C. Mondelli, A. Cesarini, F. Krumeich, R. Hauert, J. A. Stewart, D. Curulla Frerre, J. Perez-Ramirez, ACS Catal., 2019, 10, 1133-1145.
[35]	G. Centi, E. A. Quadrelli, S. Perathoner, Energy Environ. Sci., 2013, 6, 1711-1731.
[36]	A. Garcia-Trenco, A. Regoutz, E. R. White, D. J. Payne, M. S. P. Shaffer, C. K. Williams, Appl. Catal. B, 2017, 220, 9-18.
[37]	N. Rui, F. Zhang, K. H. Sun, Z. Y. Liu, W. Q. Xu, E. Stavitski, S. D. Senanayake, J. A. Rodriguez, C. J. Liu, ACS Catal., 2020, 10, 11307-11317.
[38]	T. Y. Chen, C. X. Cao, T. B. Chen, X. X. Ding, H. Huang, S. Liang, X. Y. Gao, M. H. Zhu, X. Jing, J. Gao, Y. F. Han, ACS Catal., 2019, 9, 8785-8797.
[39]	M. S. Frei, C. Mondelli, R. Garcia-Muelas, K. S. Kley, B. Puertolas, N. Lopez, O. V. Safonova, J. A. Stewart, D. Curulla Ferre, J. Perez-Ramirez, Nat. Commun., 2019, 10, 3377.
[40]	Y. Jia, E. Z. Tveten, C. De, A. Holmen, Langmuir, 2010, 26, 16558-16567.
[41]	N. Li, F. Jiao, X. Pan, Y. Ding, J. Feng, X. Bao, ACS Catal., 2018, 9, 960-966.
[42]	H. M. Torres Galvis, J. H. Bitter, T. Davidian, M. Ruitenbeek, A.I. Dugulan, K. P. de Jong, J. Am. Chem. Soc., 2012, 134, 16207-16215.
[43]	J. Liu, Y. He, L. Yan, K. Li, C. Zhang, H. Xiang, X. Wen, Y. Li, Catal. Sci. Technol., 2019, 9, 2982-2992.
[44]	S. S. Dang, P. Gao, Z. Y. Liu, X. Q. Chen, C. G. Yang, H. Wang, L. S. Zhong, S. G. Li, Y. H. Sun, J. Catal., 2018, 364, 382-393.
[45]	M. Kaur, N. Jain, K. Sharma, S. Bhattacharya, M. Roy, A. K. Tyagi, S.K. Gupta, J. V. Yakhmi, Sensor. Actuat. B, 2008, 133, 456-461.
[46]	X. Jia, K. Sun, J. Wang, C. Shen, C. J. Liu, J. Energy Chem., 2020, 50, 409-415.
[47]	F. Xue, C. Miao, Y. Yue, W. Hua, Z. Gao, Green Chem., 2017, 19, 5582-5590.
[48]	S. Tan, L. B. Gil, N. Subramanian, D. S. Sholl, S. Nair, C. W. Jones, J. S. Moore, Y. Liu, R. S. Dixit, J. G. Pendergast, Appl. Catal. A, 2015, 498, 167-175.
[49]	M. Wang, Y. D. Wang, Z. K. Xie, Chin. J. Catal., 2018, 39, 1272-1279.
[50]	A. Gao, Z. B. Wang, H. Li, J. K. Nørskov, ACS Catal., 2021, 11, 1780-1786.
[51]	Meng, W. Zhan, Y. Guo, Y. Guo, L. Wang, G. Lu, ACS Catal., 2015, 5, 5973-5983.

Effect of In₂O₃ particle size on CO₂ hydrogenation to lower olefins over bifunctional catalysts

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 11

References

Related Articles 11

Recommended Articles

Metrics

[1]	Zixuan Zhou, Peng Gao. Direct carbon dioxide hydrogenation to produce bulk chemicals and liquid fuels via heterogeneous catalysis [J]. Chinese Journal of Catalysis, 2022, 43(8): 2045-2056.
[2]	Longtai Li, Bin Yang, Biao Gao, Yifu Wang, Lingxia Zhang, Tatsumi Ishihara, Wei Qi, Limin Guo. CO₂ hydrogenation selectivity shift over In-Co binary oxides catalysts: Catalytic mechanism and structure-property relationship [J]. Chinese Journal of Catalysis, 2022, 43(3): 862-876.
[3]	Shihui Zou, Zhinian Li, Qiuyue Zhou, Yang Pan, Wentao Yuan, Lei He, Shenliang Wang, Wu Wen, Juanjuan Liu, Yong Wang, Yonghua Du, Jiuzhong Yang, Liping Xiao, Hisayoshi Kobayashi, Jie Fan. Surface coupling of methyl radicals for efficient low-temperature oxidative coupling of methane [J]. Chinese Journal of Catalysis, 2021, 42(7): 1117-1125.
[4]	Lei Ma, Li Yan, An-Hui Lu, Yunjie Ding. Effects of Ni particle size on amination of monoethanolamine over Ni-Re/SiO₂ catalysts [J]. Chinese Journal of Catalysis, 2019, 40(4): 567-579.
[5]	Zhibiao Shi, Haiyan Yang, Peng Gao, Xinqing Chen, Hongjiang Liu, Liangshu Zhong, Hui Wang, Wei Wei, Yuhan Sun. Effect of alkali metals on the performance of CoCu/TiO₂ catalysts for CO₂ hydrogenation to long-chain hydrocarbons [J]. Chinese Journal of Catalysis, 2018, 39(8): 1294-1302.
[6]	Xiaosu Dong, Feng Li, Ning Zhao, Yisheng Tan, Junwei Wang, Fukui Xiao. CO₂ hydrogenation to methanol over Cu/Zn/Al/Zr catalysts prepared by liquid reduction [J]. Chinese Journal of Catalysis, 2017, 38(4): 717-725.
[7]	Liang Li, Jianghong Ding, Jin-Gang Jiang, Zhiguo Zhu, Peng Wu. One-pot synthesis of 5-hydroxymethylfurfural from glucose using bifunctional [Sn,Al]-Beta catalysts [J]. Chinese Journal of Catalysis, 2015, 36(6): 820-828.
[8]	Ting Xu, Hang Song, Weiping Deng, Qinghong Zhang, Ye Wang. Catalytic conversion of methyl chloride to lower olefins over modified H-ZSM-34 [J]. Chinese Journal of Catalysis, 2013, 34(11): 2047-2056.
[9]	Sen Lin, Xinxin Ye. First-principle insights into the catalytic role of indium oxide in methanol steam reforming [J]. Chinese Journal of Catalysis, 2013, 34(10): 1855-1860.
[10]	XIAO Kang, BAO Zheng-Hong, QI Xing-Zhen, WANG Xin-Xing, ZHONG Liang-Shu, FANG Ke-Gong, LIN Ming-Gui, SUN Yu-Han. Advances in bifunctional catalysis for higher alcohol synthesis from syngas [J]. Chinese Journal of Catalysis, 2013, 34(1): 116-129.
[11]	Giuseppe BELLUSSI, Andreas HAAS, Sandra RABL, Dominic SANTI, Marco FERRARI, Vincenzo CALEMMA, Jens WEITKAMP. Catalytic Ring Opening of Perhydroindan - Hydrogenolytic and Cationic Reaction Paths [J]. Chinese Journal of Catalysis, 2012, 33(1): 70-84.