In situ FTIR and ex situ XPS/HS-LEIS study of supported Cu/Al2O3 and Cu/ZnO catalysts for CO2 hydrogenation

doi:10.1016/S1872-2067(20)63672-5

Abstract

Abstract:

Cu-based catalysts are commonly used in industry for methanol synthesis. In this study,supported catalysts of 5 wt% Cu/Al2O3 and 5 wt% Cu/ZnO were prepared,and their surface characteristics during H2 reduction and CO2 hydrogenation were investigated using in situ Fourier transform infrared spectroscopy (FTIR),ex situ X-ray photoelectron spectroscopy,and high sensitivity low energy ion scattering spectroscopy. During the H2 reduction and CO2 hydrogenation processes,it was found that Al2O3 can stabilize Cu+. In situ FTIR spectra indicated that the 5 wt% Cu/Al2O3 can adsorb large amounts of bicarbonate and carbonate species,which then convert into formate during CO2 hydrogenation. For the 5 wt% Cu/ZnO,it was found that Cu nanoparticles were gradually covered by a highly defective ZnOx overlayer during H2 reduction,which can effectively dissociate H2. During CO2 hydrogenation,the adsorbed bicarbonate or carbonate species can convert into formate and then into a methoxy species. Using these surface sensitive methods,a more in-depth understanding of the synergistic effect among the Cu,Al2O3,and ZnO components of Cu-based catalysts was achieved.

Key words: Cu-based catalyst, in situ FTIR, ex situ XPS/HS-LEIS, CO2 hydrogenation, ZnOx overlayer

Jun Hu, Yangyang Li, Yanping Zhen, Mingshu Chen, Huilin Wan. In situ FTIR and ex situ XPS/HS-LEIS study of supported Cu/Al₂O₃ and Cu/ZnO catalysts for CO₂ hydrogenation[J]. Chinese Journal of Catalysis, 2021, 42(3): 367-375.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63672-5

https://www.cjcatal.com/EN/Y2021/V42/I3/367

Figures/Tables 9

Fig. 1. Powder X-ray diffraction XRD patterns after calcination of Al2O3 and 5 wt% Cu/Al2O3 (a) and ZnO and 5 wt% Cu/ZnO (b). The rhombus marks represent the diffraction peaks of CuO.

Fig. 2. N2 adsorption-desorption isotherms and the corresponding pore size distribution curves (inset) for Al2O3,5 wt% Cu/Al2O3,ZnO,and 5 wt% Cu/ZnO.

Fig. 3. CO adsorption bands of (a) the 5 wt% Cu/Al2O3 and (b) the 5 wt% Cu/ZnO after different treatments ([O],[V],and [H] are representative of the O2 oxidization,evacuation,and H2 reduction processes,respectively; PO2 = 100 Torr and PH2 = 100 Torr).

Fig. 4. XPS spectra of Cu 2p (a),Cu L3M4.5M4.5 (b); (c) XPS intensity ratio of Cu0,Cu+,and Cu2+ after the O2 oxidization and H2 reduction processes ([O] and [H] are representative of O2 oxidization and H2 reduction processes,respectively; PO2 = 1 atm and PH2 = 1 atm).

Fig. 5. XPS spectra of Cu 2p (a) and Cu L3M4.5M4.5 (b) after O2 oxidization and H2 reduction processes ([O] and [H] are representative of O2 oxidization and H2 reduction processes,respectively; PO2 = 1 atm and PH2 = 1 atm).

Fig. 6. In situ FTIR spectra of the 5 wt% Cu/Al2O3 (a,b) and the 5 wt%Cu/ZnO (c,d) during CO2 hydrogenation reactions (PCO2 = 33 Torr and PH2 = 100 Torr) at different temperatures after pre‐reduction by H2 at 523 K (PH2 = 100 Torr).

Table 1 IR band assignments for the adsorption species on Al2O3,ZnO,and Cu.

Adsorbed species	Band (cm^-1)	Assignment	Ref.
Bicarbonate on Al₂O₃	1658 1424-1439 1227	ν_as(OCO) ν_s(OCO) δ(OH)	[51-53]
Monodentate carbonate on Al₂O₃	1480 1390 1077	ν_as(OCO) ν_s(OCO) ν(CO)	[54,55]
Polydentate carbonate on Al₂O₃	1525 1330	ν_as(OCO) ν_s(OCO)	[56]
Bidentate formate on Al₂O₃	1592 1377 1393 2769 2904 2999	ν_as(OCO) ν_s(OCO) δ(C-H) δ(C-H) + ν_s(OCO) ν(C-H) δ(C-H) + ν_as(OCO)	[51,57,58]
Bicarbonate on ZnO	1634 1418 1225	ν_as(OCO) ν_s(OCO) δ(OH)	[59,60]
Bidentate carbonate on ZnO	1606 1343	ν_as(OCO) ν_s(OCO)	[56,59]
Polydentate carbonate on ZnO	1513 1326	ν_as(OCO) ν_s(OCO)	[56,61]
Uncoordinated carbonate on ZnO	1445	ν_as(OCO)	[62]
Bidentate formate on ZnO	1576 1382 1365 2876 2970	ν_as(OCO) δ(C-H) ν_s(OCO) ν(C-H) δ(C-H)+ ν_as(OCO)	[61-63]
Methoxy on ZnO	2930 2815 1050	ν_as(CH₃) ν_s(CH₃) ν(C-O)	[31,62,63]
Bidentate formate on Cu	1636 1328 1354 2745 2855 2929	ν_as(OCO) ν_s(OCO) δ(C-H) δ(C-H) + ν_s(OCO) ν(C-H) δ(C-H)+ ν_as(OCO)	[51,63]

Fig. 7. XPS spectra of Cu 2p (a),Cu L3M4.5M4.5 (b); (c) the XPS intensity ratios of Cu0,Cu+,Cu2+; (d) the corresponding HS-LEIS spectra; (e) the top surface content of Cu after H2 pre-reduction and CO2 hydrogenation reactions for the 5 wt% Cu/Al2O3 (PH2 = 1 atm during 523 K H2 pre-reduction,PCO2 = 0.33 atm,and PH2 = 0.67 atm during CO2 hydrogenation reactions).

Fig. 8. In situ FTIR spectra of the 5 wt% Cu/ZnO-Al2O3 (Zn/Al molar ratio of 3) during CO2 hydrogenation reactions (PCO2 = 33 Torr and PH2 = 100 Torr) after pre-reduction by 100 Torr H2 at 523 K.

References

[1]	T.R. Knutson, R.E. Tuleya, J. Climate, 2004,17, 3477-3495.
[2]	J. Hansen, M. Sato, R. Ruedy, K. Lo, D. W. Lea, M. Medina-Elizade, Proc. Natl. Acad. Sci. USA, 2006,103, 14288-14293.
[3]	G. A. Olah, G. K. S. Prakash, J. Am. Chem. Soc., 2011,133, 12881-12898.
[4]	M. D. Porosoff, B. Yan, J. G. Chen, Energy Environ. Sci., 2016,9, 62-73.
[5]	X. Xiaoding, J. A. Moulijn, Energy Fuels, 1996,10, 305-325.
[6]	T. Zhang, Chin. J. Catal., 2017,38, 1781-1783.
[7]	M. Saito, T. Fujitani, M. Takeuchi, T. Watanabe, Appl. Catal. A, 1996,138, 311-318.
[8]	X. S. Dong, F. Li, N. Zhao, Y. S. Tan, J. W. Wang, F. K. Xiao, Chin. J. Catal., 2017,38, 717-725.
[9]	M. S. Spencer, Top. Catal., 1999,8, 259-266.
[10]	S. Wang, H. C. Liu, Chin. J. Catal., 2014,35, 631-643.
[11]	Y. Liu, Y. Pan, H. Y. Wang, Y. Q. Liu, C. G. Liu, Chin. J. Catal., 2018,39, 1543-1551.
[12]	P. L. Hansen, J. B. Wagner, S. Helveg, J. R. Rostrup-Nielsen, B. S. Clausen, H. Topsøe, Science, 2002,295, 2053-2055.
[13]	M. Behrens, F. Studt, I. Kasatkin, S. Kühl, M. Hävecker, F. Abild-Pedersen, S. Zander, F. Girgsdies, B.-L. Kniep, M. Tovar, R. W. Fischer, J. K. Nørskov, R. Schlögl, Science, 2012,336, 893-897.
[14]	S. Kuld, C. Conradsen, P. G. Moses, I. Chorkendorff, J. Sehested, Angew. Chem. In. Ed., 2014,53, 5941-5945.
[15]	S. Kuld, M. Thorhauge, H. Falsig, C. F. Elkjær, S. Helveg, I. Chorkendorff, J. Sehested, Science, 2016,352, 969-974.
[16]	S. Kattel, P. J. Ramírez, J. G. Chen, J. A. Rodriguez, P. Liu, Science, 2017,355, 1296-1299.
[17]	P. C. K Vesborg, I. Chorkendorff I. Knudsen, O. Balmes, J. Nerlov, A. M. Molenbroek, B. S. Clausen, S. Helveg, J. Catal., 2009,262, 65-72.
[18]	I. Kasatkin, P. Kurr, B. Kniep, A. Trunschke, R. Schlögl, Angew. Chem. In. Ed., 2007,119, 7465-7468.
[19]	J. D. Grunwaldt, A. M. Molenbroek, N. Y. Topsøe, H. Topsøe, B. S. Clausen, J. Catal., 2000,194, 452-460.
[20]	E. D. Batyrev, N. R. Shiju, G. Rothenberg, J. Phys. Chem. C, 2012,116, 19335-19341.
[21]	M. M. Viitanen, W. P. A Jansen, R. G. van Welzenis, H. H. Brongersma, D. S. Brands, E. K. Poels, A. Bliek, J. Phys. Chem. B, 1999,103, 6025-6029.
[22]	W. P. A Jansen, J. Beckers, J. C. van der Heuvel, A. W. Denier van der Gon, A. Bliek, H. H. Brongersma, J. Catal., 2002,210, 229-236.
[23]	V. Schott, H. Oberhofer, A. Birkner, M. Xu, Y. Wang, M. Muhler, K. Reuter, C. Wöll, Angew. Chem. In. Ed., 2013,52, 11925-11929.
[24]	T. Lunkenbein, J. Schumann, M. Behrens, R. Schlögl, M. G. Willinger, Angew. Chem. In. Ed., 2015,127, 4627-4631.
[25]	M. V. Twigg, M. S. Spencer, Top. Catal., 2003,22, 191-203.
[26]	M. Behrens, S. Zander, P. Kurr, N. Jacobsen, J. Senker, G. Koch, T. Ressler, R. W. Fischer, R. Schlögl. J. Am. Chem. Soc., 2013,135, 6061-6068.
[27]	J. Schumann, M. Eichelbaum, T. Lunkenbein, N. Thomas, M. C Álvarez Galván, R. Schlögl, M. Behrens,. ACS Catal., 2015,5, 3260-3270.
[28]	J. Hu, Y. Y. Song, J. J. Huang, Y. Y. Li, M. S. Chen, H. L. Wan, Chem. Eur.J., 2017,23, 10632-10637.
[29]	A. Dandekar, M. A. Vannice, J. Catal., 1998,178, 621-639.
[30]	N.-Y. Topsøe, H. Topsøe, J. Mol. Catal. A, 1999,141, 95-105.
[31]	R. Q. Yang, Y. L. Fu, Y. Zhang, N. Tsubaki, J. Catal., 2004,228, 23-35.
[32]	Y. Y. Li, J. Hu, J. Xu, Y. P. Zheng, M. S. Chen, H. Wan, Q. Fu, F. Yang, X. H. Bao, Appl. Surf. Sci., 2019,494, 353-360.
[33]	X. F. Weng, H. J. Ren, M. S. Chen, H. L. Wan, ACS Catal., 2014,4, 2598-2604.
[34]	H. B. Li, Y. Y. Cui, Y. X. Liu, W. L. Dai, Acta Chim. Sin., 2019,77, 371-378.
[35]	Y. Y. Li, J. Hu, D. D. Ma, Y. P. Zheng, M. S. Chen, H. L. Wan, ACS Catal., 2018,8, 1790-1795.
[36]	J. J. Huang, Y. Y. Song, D. D. Ma, Y. P. Zheng, M. S. Chen, H. L. Wan, Chin. J. Catal, 2017,38, 1229-1236.
[37]	L. Zhou, L. R. Enakonda, Y. Saih, S. Loptain, D. Gary, P. Del-Gallo, J.-M. Basset, ChemSusChem, 2016,9, 1243-1248.
[38]	P. Khemthong, P. Photai, N. Grisdanurak, Int. J. Hydrogen Energy, 2013,38, 15992-16001.
[39]	A. Catana, J.-P. Locquet, S. M. Paik, I. K. Schuller, Phys. Rev. B, 1992,46, 15477-15483.
[40]	J. Ma, S. J. Peng, G. J. Li, Q. Wang, Ceram. Int., 2016,42, 19141-19146.
[41]	Y. Y. Zhao, H. X. Shi, M. D. Chen, F. Teng, CrystEngComm, 2014,16, 2417-2423.
[42]	S. S. Yi, X. Z. Yue, D. D. Xu, Z. P. Liu, F. Zhao, D. J. Wang, Y. H. Lin, New J. Chem., 2015,39, 2917-2924.
[43]	B. H. Sakakini, J. Tabatabaei, M. J. Watson, K. C. Waugh, J. Mol. Catal. J. Mol. Catal. A 2000,162, 297-306.
[44]	S. J. Tauster, S. C. Fung, R. L. Garten. J. Am. Chem. Soc. 1978,100, 170-175.
[45]	S. J. Tauster, S. C. Fung, R. T. K, R. T. K. Baker, J. A. Horsley. Science, 1981,211, 1121-1125.
[46]	Q. Fu, T. Wagner, Surf. Sci. Rep., 2007,62, 431-498.
[47]	H. Li, X. F. Weng, Z. Y. Tang, H. Zhang, D. Ding, M. S. Chen, H. L. Wan, ACS Catal., 2018,8, 10156-10163.
[48]	Y. P. Zheng, L. H. Zhang, S. L. Wang, Z. Y. Tang, D. Ding, M. S. Chen, H. L. Wan, Langmuir, 2013,29, 9090-9097.
[49]	C. D. Wagner, L. H. Gale, R. H. Raymond, Anal. Chem., 1979,51, 466-482.
[50]	W.-L. Dai, Q. Sun, J.-F. Deng, D. Wu, Y.-H. Sun, Appl. Surf. Sci., 2001,177, 172-179.
[51]	K. K. Bando, K. Sayama, H. Kusama, K. Okabe, H. Arakawa, Appl. Catal. A, 1997,165, 391-409.
[52]	J. L. Robbins, E. Marucchi-Soos, J. Phys. Chem., 1989,93, 2885-2888.
[53]	J. Baltrusaitis, J. H. Jensen, V. H. Grassian, J. Phys. Chem, B., 2006,110, 12005-12016.
[54]	A. Iordan, M. I. Zaki, C. Kappenstein, J. Chem. Soc., Faraday Trans., 1993,89, 2527-2536.
[55]	A. Bensalem, B. M. Weckhuysen, R. A. Schoonheydt, J. Chem. Soc., Faraday Trans., 1997,93, 4065-4069.
[56]	J. Saussey, J.-C. Lavalley, C. Bovet, J. Chem. Soc., Faraday Trans. 1, 1982,78, 1457-1463.
[57]	D. K. Captain, M. D. Amiridis, J. Catal., 1999,184, 377-389.
[58]	S. Guerrero, J. T. Miller, A. J. Kropf, E. E. Wolf, J. Catal., 2009,262, 102-110.
[59]	S. Bailey, G. F. Froment, J. W. Snoeck, K. C. Waugh, Catal. Lett., 1994,30, 99-111.
[60]	F. Boccuzzi, A. Chiorino, J. Phys. Chem., 1996,100, 3617-3624.
[61]	S. Fujita, M. Usui, H. Ito, N. Takezawa, J. Catal., 1995,157, 403-413.
[62]	J. F. Edwards, G. L. Schrader, J. Phys. Chem., 1985,89, 782-788.
[63]	S.-I. Fujita, M. Usui, E. Phys. Ohara, N. Takezawa, Catal. Lett., 1992,13, 349-358.
[64]	J. Schumann, J. Kröhnert, E. Frei, R. Schlögl, A. Trunschke, Top. Catal., 2017,60, 1735-1743.

In situ FTIR and ex situ XPS/HS-LEIS study of supported Cu/Al₂O₃ and Cu/ZnO catalysts for CO₂ hydrogenation

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 9

References

Related Articles 7

Recommended Articles

Metrics

[1]	Huanhuan Yang, Shiying Li, Qun Xu. Efficient strategies for promoting the electrochemical reduction of CO₂ to C₂₊ products over Cu-based catalysts [J]. Chinese Journal of Catalysis, 2023, 48(5): 32-65.
[2]	Feng Sha, Shan Tang, Chizhou Tang, Zhendong Feng, Jijie Wang, Can Li. The role of surface hydroxyls on ZnZrO_x solid solution catalyst in CO₂ hydrogenation to methanol [J]. Chinese Journal of Catalysis, 2023, 45(2): 162-173.
[3]	Dongni Yu, Weili Dai, Guangjun Wu, Naijia Guan, Landong Li. Stabilizing copper species using zeolite for ethanol catalytic dehydrogenation to acetaldehyde [J]. Chinese Journal of Catalysis, 2019, 40(9): 1375-1384.
[4]	Shuai Shen, Xiuli Wang, Qian Ding, Shaoqing Jin, Zhaochi Feng, Can Li. Effect of Pt cocatalyst in Pt/TiO₂ studied by in situ FTIR of CO adsorption [J]. Chinese Journal of Catalysis, 2014, 35(11): 1990-1906.
[5]	YU Qiang, GAO Fei, DONG Lin. Recent Progress of Cu-Based Catalysts for Catalytic Elimination of CO [J]. Chinese Journal of Catalysis, 2012, 33(8): 1245-1256.
[6]	WANG Dongsheng;TAN Yisheng*;HAN Yizhuo;Noritatsu TSUBAKI. Effect of CO2 on Stability of Cu-Based Catalyst for Dimethyl Ether Synthesis in Slurry Phase [J]. Chinese Journal of Catalysis, 2008, 29(1): 63-68.
[7]	ZHAI Xufang1,2, Jun SHAMOTO3, XIE Hongjuan1, TAN Yisheng1, HAN Yizhuo1*, Noritatsu TSUBAKI3. Deactivation Mechanism of Cu-Based Catalyst for Methanol Synthesis in Slurry Phase [J]. Chinese Journal of Catalysis, 2007, 28(1): 51-56.