Understanding the correlation between zinc speciation and coupling conversion of CO2 and n-butane on zinc/ZSM-5 catalysts

doi:10.1016/S1872-2067(24)60036-7

Abstract

Abstract:

The coupling reaction of alkanes and CO₂ into high value-added bulk chemical products is a promising way for CO₂ utilization. The Zn-introduced ZSM-5 catalyst plays an essential role in this process; however, the correlation between the catalytic performance and Zn species of the catalyst has yet to be established. Herein, the structural properties, the acid sites, and the existence status of the Zn species in the Zn-introduced catalysts were systematically characterized by several techniques. And the influence of the state of Zn species in the coupling reaction was discussed. The results indicate that the Zn species exist in the form of ZnO cluster, Zn-OH⁺, and (Zn-O-Zn)²⁺ species, thereinto (Zn-O-Zn)²⁺ species are produced by the Zn-OH⁺ group with the increasing Zn loading. The decrease of Brønsted acid sites, the formation of newly active sites caused by Zn species, and the accumulation of coarse ZnO species, are responsible for the change of n-butane conversion. The Zn-OH⁺ group serves as the primary catalytic center for the conversion of CO₂. Both the Zn-OH⁺ group and the (Zn-O-Zn)²⁺ species enhance the dehydrogenation performance of the Zn-introduced catalysts, thereby promoting the generation of aromatics. The Zn5%-ZSM-5 sample showed the most excellent catalytic performance; the n-butane conversion was 94.71%, the CO₂conversion was 30.43%, and the aromatics selectivity was 53.71%. Simultaneously, we propose a more specific mechanism for the coupling reaction.

Key words: Coupling reaction, CO₂ utilization, Zn-introduced, Zn-OH⁺, (Zn-O-Zn)²⁺, ZSM-5

Xuke Sun, Rongsheng Liu, Gaili Fan, Yuhan Liu, Fangxiu Ye, Zhengxi Yu, Zhongmin Liu. Understanding the correlation between zinc speciation and coupling conversion of CO₂ and n-butane on zinc/ZSM-5 catalysts[J]. Chinese Journal of Catalysis, 2024, 61: 154-163.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60036-7

https://www.cjcatal.com/EN/Y2024/V61/I6/154

Figures/Tables 7

Fig. 1. Characterization results of all samples. (a) N2 sorption isotherms; (b) XRD patterns; (c) 27Al MAS NMR spectra; (d) 29Si MAS NMR spectra.

Fig. 2. (a) UV-vis spectra of all samples. (b) XPS spectra of Zn 2p3/2 for the Zn-introduced samples. (c) The distributions and content of Zn species in the Zn-introduced samples with increasing Zn loading and provided data are determined from the combination of XPS and XRF. (d) 1H MAS NMR spectra with corresponding deconvolution results of all samples. FTIR (e) and Py-FTIR (f) spectra of all samples.

Table 1 Zn species distribution of the Zn-introduced samples.

Sample	Zn by type
Sample	Total ^a (wt%)	Zn_fr ^b (wt%)	ZnO ^b (wt%)	Zn_fr/ZnO ^b
Zn3%-ZSM-5	3.12	1.93	1.19	1.62
Zn5%-ZSM-5	5.10	2.75	2.35	1.17
Zn7%-ZSM-5	6.92	2.91	4.01	0.73

Table 2 OH species concentration of all samples.

Sample	OH concentration/mmol g^‒1
Sample	Si-OH-Al_(H-bond)	Si-OH-Al	Al-OH	Si-OH	Zn-OH
H-ZSM-5	1.21	0.71	0.62	0.41	0
Zn3%-ZSM-5	0.52	0.52	0.15	0.29	0.17
Zn5%-ZSM-5	0.25	0.36	0.14	0.25	0.19
Zn7%-ZSM-5	0.16	0.14	0.09	0.17	0.07

Table 3 Acidic properties of all samples.

Sample	Acidity by strength ^a (mmol g^‒1)			Acidity by type ^b (mmol g^‒1)
Sample	Strong	Weak	Total	Brønsted	Lewis	B/L
H-ZSM-5	0.509	0.763	1.272	0.775	0.497	1.56
Zn3%-ZSM-5	0.404	0.863	1.267	0.140	1.127	0.12
Zn5%-ZSM-5	0.349	0.906	1.255	0.113	1.142	0.10
Zn7%-ZSM-5	0.331	0.917	1.248	0.067	1.181	0.06

Fig. 3. Catalytic performances of coupling reaction on all samples with the time on stream (TOS). (a) H-ZSM-5; (b) Zn3%-ZSM-5; (c) Zn5%-ZSM-5; (d) Zn7%-ZSM-5. Reaction conditions: 1 g sample, P = 1 bar, T = 550 °C, total WHSV = 5 h?1 (WHSVn-butane = 4.20 h?1, WHSVCO2 = 0.80 h?1), CO2/n-butane = 0.25 (molar ratio), TOS = 145 min. Notes: The product distribution of aromatics and others were shown in Figs. S5 and S6, respectively. The detailed product distribution, reactant conversion, and important product selectivity were shown in Tables S2 and S3.

Fig. 4. Proposed mechanism for the coupling reaction on the Zn-introduced catalysts.

References

[1]	M. B. Ansari, S.-E. Park, Energy Environ. Sci., 2012, 5, 9419-9437.
[2]	R. Snoeckx, A. Bogaerts, Chem. Soc. Rev., 2017, 46, 5805-5863.
[3]	Z.-Z. Yang, L.-N. He, J. Gao, A.-H. Liu, B. Yu, Energy Environ. Sci., 2012, 5, 6602-6639.
[4]	W. Leitner, Angew. Chem. Int. Ed., 1995, 34, 2207-2221.
[5]	R. A. F. Tomás, J. C. M. Bordado, J. F. P. Gomes, Chem. Rev., 2013, 113, 7421-7469.
[6]	D. Miao, Y. Ding, T. Yu, J. Li, X. Pan, X. Bao, ACS Catal., 2020, 10, 7389-7397.
[7]	E. Gomez, X. Nie, J. H. Lee, Z. Xie, J. G. Chen, J. Am. Chem. Soc., 2019, 141, 17771-17782.
[8]	P. He, J. S. Jarvis, S. Meng, Q. Li, G. M. Bernard, L. Liu, X. Mao, Z. Jiang, H. Zeng, V. K. Michaelis, H. Song, Appl. Catal. B, 2019, 250, 99-111.
[9]	J. A. Biscardi, E. Iglesia, Catal. Today, 1996, 31, 207-231.
[10]	K. Yang, J. Li, C. Wei, Z. Zhao, Z. Liu, ACS Catal., 2023, 13, 10405-10417.
[11]	C. Wei, W. Zhang, K. Yang, X. Bai, S. Xu, J. Li, Z. Liu, Chin. J. Catal., 2023, 47, 138-149.
[12]	M. Aresta, A. Dibenedetto, E. Quaranta, J. Catal., 2016, 343, 2-45.
[13]	A. A. Gabrienko, S. S. Arzumanov, Z. N. Lashchinskaya, A. V. Toktarev, D. Freude, J. Haase, A. G. Stepanov, J. Catal., 2020, 391, 69-79.
[14]	S. S. Arzumanov, A. A. Gabrienko, A. V. Toktarev, Z. N. Lashchinskaya, D. Freude, J. Haase, A. G. Stepanov, J. Phys. Chem. C, 2019, 123, 30473-30485.
[15]	A. A. Gabrienko, S. S. Arzumanov, A. V. Toktarev, I. G. Danilova, I. P. Prosvirin, V. V. Kriventsov, V. I. Zaikovskii, D. Freude, A. G. Stepanov, ACS Catal., 2017, 7, 1818-1830.
[16]	A. A. Gabrienko, S. S. Arzumanov, A. V. Toktarev, D. Freude, J. Haase, A. G. Stepanov, J. Phys. Chem. C, 2019, 123, 27573-27583.
[17]	Z. Chen, Y. Ni, Y. Zhi, F. Wen, Z. Zhou, Y. Wei, W. Zhu, Z. Liu, Angew. Chem. Int. Ed., 2018, 57, 12549-12553.
[18]	C. Wei, J. Li, K. Yang, Q. Yu, S. Zeng, Z. Liu, Chem Catal., 2021, 1, 1273-1290.
[19]	X. Niu, J. Gao, K. Wang, Q. Miao, M. Dong, G. Wang, W. Fan, Z. Qin, J. Wang, Fuel Process. Technol., 2017, 157, 99-107.
[20]	Y. Ni, W. Peng, A. Sun, W. Mo, J. Hu, T. Li, G. Li, J. Ind. Eng. Chem., 2010, 16, 503-505.
[21]	H. A. Zaidi, K. K. Pant, Catal. Today, 2004, 96, 155-160.
[22]	B. Yu, C. Ding, J. Wang, Y. Zhang, Y. Meng, J. Dong, H. Ge, X. Li, J. Phys. Chem. C, 2019, 123, 18993-19004.
[23]	X. Chen, M. Dong, X. Niu, K. Wang, G. Chen, W. Fan, J. Wang, Z. Qin, Chin. J. Catal., 2015, 36, 880-888.
[24]	X. Niu, J. Gao, Q. Miao, M. Dong, G. Wang, W. Fan, Z. Qin, J. Wang, Microporous Mesoporous Mater., 2014, 197, 252-261.
[25]	R. Liu, B. Fan, Y. Zhi, C. Liu, S. Xu, Z. Yu, Z. Liu, Angew. Chem. Int. Ed., 2022, 61, e202210658.
[26]	M. Ravi, V. L. Sushkevich, J. A. van Bokhoven, Chem. Sci., 2021, 12, 4094-4103.
[27]	K. Iyoki, K. Kikumasa, T. Onishi, Y. Yonezawa, A. Chokkalingam, Y. Yanaba, T. Matsumoto, R. Osuga, S. P. Elangovan, J. N. Kondo, A. Endo, T. Okubo, Toru Wakihara, J. Am. Chem. Soc., 2020, 142, 3931-3938.
[28]	R. Liu, S. Zeng, T. Sun, S. Xu, Z. Yu, Y. Wei, Z. Liu, ACS Catal., 2022, 12, 4491-4500.
[29]	M. Ravi, V. L. Sushkevich, J. A. van Bokhoven, Nat. Mater., 2020, 19, 1047-1056.
[30]	A. Sultana, T. Nanba, M. Haneda, M. Sasaki, H. Hamada, Appl. Catal. B, 2010, 101, 61-67.
[31]	V. Petranovskii, E. Stoyanov, V. Gurin, N. Katada, M. A. Hernandez, M. Avalos, A. Pestryakov, F. C. Rivas, R. Z. Ulloa, R. Portillo, Rev. Mex. Fis., 2013, 59, 170-185.
[32]	J. T. Kloprogge, J. Porous Mater., 1998, 5, 5-41.
[33]	F. Basile, G. Fornasari, M. Gazzano, A. Vaccari, Appl. Clay Sci., 2000, 16, 185-200.
[34]	S. Bordiga, C. Lamberti, G. Ricchiardi, L. Regli, F. Bonino, A. Damin, K.-P. Lillerud, M. Bjorgen, A. Zecchina, Chem. Commun., 2004, 2300-2301.
[35]	M. Haase, H. Weller, A. Henglein, J. Phys. Chem., 1988, 92, 482-487.
[36]	J. Liu, A. S. N. L. Hong, N. He, G. Liu, C. Liang, X. Zhang, H. Guo, Chem. Eng. J., 2013, 218, 1-8.
[37]	L. Wang, S. Sang, S. Meng, Y. Zhang, Y. Qi, Z. Liu, Mater. Lett., 2007, 61, 1675-1678.
[38]	J. Chen, Z. C. Feng, P. L. Ying, C. Li, J. Phys. Chem. B, 2004, 108, 12669-12676.
[39]	E. A. Pidko, R. A. van Santen, J. Phys. Chem. C, 2007, 111, 2643-2655.
[40]	Y. Han, J. Yu, T. Chen, X. Liu, L. Sun, J. Energy Inst., 2021, 94, 210-221.
[41]	X. Shang, G. Liu, X. Su, Y. Huang, T. Zhang, ACS Catal., 2022, 12, 13741-13754.
[42]	R. Geng, Y. Liu, Y. Guo, P. Wang, M. Dong, S. Wang, J. Wang, Z. Qin, W. Fan, ACS Catal., 2022, 12, 14735-14747.
[43]	M. Avramovska, D. Freude, J. Haase, A. V. Toktarev, S. S. Arzumanov, A. A. Gabrienko, A. G. Stepanov, Phys. Chem. Chem. Phys., 2023, 25, 28043-28051.
[44]	G. Qi, Q. Wang, J. Xu, J. Trébosc, O. Lafon, C. Wang, J.-P. Amoureux, F. Deng, Angew. Chem. Int. Ed., 2016, 55, 15826-15830.
[45]	A.Stepanov, in: Zeolites and zeolite-like materials, B. F. Sels, L. M. Kustov eds., Elsevier, 2016, 137-188.
[46]	M. Hunger, Catal. Rev. Sci. Eng., 1997, 39, 345-393.
[47]	A. Mehdad, R. F. Lobo, Catal. Sci. Technol., 2017, 7, 3562-3572.
[48]	Y. Yuan, R. F. Lobo, ACS Catal., 2023, 13, 4971-4984.
[49]	N. M. Phadke, M. J. Van der, E. Mansoor, A. B. Getsoian, M. Head-Gordon, A. T. Bell, ACS Catal., 2018, 8, 6106-6126.
[50]	Y. G. Kolyagin, V. V. Ordomsky, Y. Z. Khimyak, A. I. Rebrov, F. Fajula, I. I. Ivanova, J. Catal., 2006, 238, 122-133.
[51]	E. M. El-Malki, R. A. van Santen, W. M. H. Sachtler, J. Phys. Chem. B, 1999, 103, 4611-4622.
[52]	L. C. Lerici, M. S. Renzini, U. Sedran, L. B. Pierella, Energy Fuels, 2013, 27, 2202-2208.
[53]	R. Buzzoni, S. Bordiga, G. Ricchiardi, C. Lamberti, A. Zecchina, G. Bellussi, Langmuir, 1996, 12, 930-940.
[54]	D. Liu, L. Cao, G. Zhang, L. Zhao, J. Gao, C. Xu, Fuel Process. Technol., 2021, 216, 106770.
[55]	G. Xiaohong, C. Q. Yang, Text. Res. J., 2000, 70, 64-70.
[56]	T. Forester, R. F. Howe, J. Am. Chem. Soc., 1987, 109, 5076-5082.
[57]	J.-Y. Zhou, G.-D. Lu, S.-H. Wu, Synth. Commun., 1992, 22, 481-487.
[58]	C. Lievens, D. Mourant, M. He, R. Gunawan, X. Li, C.-Z. Li, Fuel, 2011, 90, 3417-3423.

Understanding the correlation between zinc speciation and coupling conversion of CO₂ and n-butane on zinc/ZSM-5 catalysts

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