Initial Research on the 1%CuO – 6CeO2 – 4ZrO2 Catalysts by TPR-H2 for the Carbon Monoxide Preferential Oxidation (CO-PROX Reaction)
Main Article Content
Abstract
The 1wt%CuO – 6CeO2 – 4ZrO2 catalysts were synthesized by sol-gel method with two different procedures: (i) impregnating CuO on CeO2-ZrO2 support (CuO/CeO2-ZrO2), (ii) sol-gel of the Cu, Ce and Zr precursor together (CuO-CeO2-ZrO2). These catalysts were applied for the preferential oxidation of carbon monoxide (CO-PROX) to remove a small quantity of CO in an H2-rich stream (the new research direction in Viet Nam), fueling the proton exchange membrane fuel cell (PEMFC) energy system. The findings of the TPR-H2 experiment indicated that the catalyst produced through the first method exhibited an α reduction peak at 174 °C, which shows the effective dispersion of copper species. In combination with EPR results, the author anticipates a significant dispersion arising from isolated copper, which is recognized as a pivotal site in the CO-PROX reaction per numerous reputable studies. The catalyst synthesized by the second method did not provide a clear indication of the oxidation behavior of Cu-species. Therefore, it can be inferred that this catalyst is inappropriate for the low-temperature CO-PROX reaction.
Keywords
CuO-CeO2-ZrO2, TPR-H2, CO-PROX reaction, PEMFC
Article Details
References
[1] P. Sharma and O. P. Pandey, Chapter 1 - Proton exchange membrane fuel cells: fundamentals, advanced technologies, and practical applications, PEM Fuel Cells: Fundamentals, Advanced technologies, and Practical Application, G. Kaur, Ed.
Elsevier, 2022, pp. 1–24. https://doi.org/10.1016/B978-0-12-823708-3.00006-7
[2] G. Xiang et al., Atomically dispersed Au catalysts for preferential oxidation of CO in H2-rich stream, Appl. Catal. B Environ., vol. 296, p. 120385, 2021. https://doi.org/10.1016/j.apcatb.2021.120385
[3] Z. Boukha, J. R. González-Velasco, and M. A. Gutiérrez-Ortiz, Exceptional performance of gold supported on fluoridated hydroxyapatite catalysts in CO-cleanup of H2-rich stream: High activity and resistance under PEMFC operation conditions, Appl.
Catal. B Environ., vol. 292, p. 120142, 2021. https://doi.org/10.1016/j.apcatb.2021.120142
[4] V. Palma, C. Ruocco, M. Martino, E. Meloni, and A.Ricca, Catalysts for conversion of synthesis gas, in Bioenergy Systems for the Future, Elsevier, 2017, pp. 217–277. https://doi.org/10.1016/B978-0-08-101031-0.00007-7
[5] E. Poggio-Fraccari, A. Abele, N. Zitta, J. Francesconi, and F. Mariño, CO removal for hydrogen purification via Water Gas Shift and CO-PROX reactions with monolithic catalysts, Fuel, vol. 310, p. 122419, 2022. https://doi.org/10.1016/j.fuel.2021.122419
[6] Y. Chen, J. Lin, L. Li, X. Pan, X. Wang, and T. Zhang, Local structure of Pt species dictates remarkable performance on Pt/A2O3 for preferential oxidation of CO in H2, Appl. Catal. B Environ., vol. 282, p. 119588, 2021 https://doi.org/10.1016/j.apcatb.2020.119588.
[7] L.-H. Chang, Y.-L. Yeh, and Y.-W. Chen, Preferential oxidation of CO in hydrogen stream over nano-gold catalysts prepared by photodeposition method, Int. J. Hydrogen Energy, vol. 33, no. 7, pp. 1965–1974, 2008. https://doi.org/10.1016/j.ijhydene.2008.01.014
[8] Q. Zou et al., Ceria-nano supported copper oxide catalysts for CO preferential oxidation: Importance of oxygen species and metal-support interaction, Appl. Surf. Sci., vol. 494, pp. 1166–1176, 2019. https://doi.org/10.1016/j.apsusc.2019.07.210
[9] A. Di Benedetto, G. Landi, and L. Lisi, Improved CO- PROX performance of CuO/CeO2 catalysts by using nanometric ceria as support, Catalysts, vol. 8, no. 5, p. 209, 2018. https://doi.org/10.3390/catal8050209
[10] J. Kašpar, P. Fornasiero, and N. Hickey, Automotive catalytic converters: current status and some perspectives, Catal. today, vol. 77, no. 4, pp. 419–449, 2003. https://doi.org/10.1016/S0920-5861(02)00384-X
[11] H. Vidal et al., Redox behavior of CeO2–ZrO2 mixed oxides: I. Influence of redox treatments on high surface area catalysts, Appl. Catal. B Environ., vol. 27, no. 1, pp. 49–63, 2000. https://doi.org/10.1016/S0926-3373(00)00138-7
[12] P. Ratnasamy et al., Influence of the support on the preferential oxidation of CO in hydrogen-rich steam reformates over the CuO–CeO2–ZrO2 system, J. Catal., vol. 221, no. 2, pp. 455–465, 2004. https://doi.org/10.1016/j.jcat.2003.09.006
[13] Martínez-Munuera, J. C., Giménez-Mañogil, J., Yeste, M. P., Hungría, A. B., Cauqui, M. A., García-García, A., & Calvino, J. J. (2022). New findings regarding the role of copper entity particle size on the performance of Cu/ceria-based catalysts in the CO-PROX reaction. Applied Surface Science, 575, 151717. https://doi.org/10.1016/j.apsusc.2021.151717
[14] K. A. Cychosz, R. Guillet-Nicolas, J. García-Martínez, and M. Thommes, Recent advances in the textural characterization of hierarchically structured nanoporous materials, Chem. Soc. Rev., vol. 46, no. 2, pp. 389–414, 2017. https://doi.org/10.1039/C6CS00391E
[15] J. Mosrati et al., Tiny Species with Big Impact: High Activity of Cu Single Atoms on CeO2-TiO2 Deciphered by Operando Spectroscopy, ACS Catal., vol. 11, no. 17, pp. 10933–10949, 2021 https://doi.org/10.1021/acscatal.1c02349.
[16] J. Chen, Y. Zhan, J. Zhu, C. Chen, X. Lin, and Q. Zheng, The synergetic mechanism between copper species and ceria in NO abatement over Cu/CeO2 catalysts, Appl. Catal. A Gen., vol. 377, no. 1–2, pp. 121–127, 2010.
https://doi.org/10.1016/j.apcata.2010.01.027
[17] A. Pintar, J. Batista, and S. Hočevar, TPR, TPO, and TPD examinations of Cu0.15Ce0.85O2 mixed oxides prepared by co-precipitation, by the sol-gel peroxide route, and by citric acid-assisted synthesis, J. Colloid Interface Sci., vol. 285, no. 1, pp. 218–231, 2005, https://doi.org/10.1016/j.jcis.2004.11.049.
[18] G. Avgouropoulos, T. Ioannides, and H. Matralis, Influence of the preparation method on the performance of CuO–CeO2 catalysts for the selective oxidation of CO, Appl. Catal. B Environ., vol. 56, no. 1–2, pp. 87–93, 2005. https://doi.org/10.1016/j.apcatb.2004.07.017
[19] A. Martínez-Arias et al., Characterization of active sites/entities and redox/catalytic correlations in copper-ceria-based catalysts for preferential oxidation of CO in H2-rich streams, Catalysts, vol. 3, no. 2, pp. 378–400, 2013, https://doi.org/10.3390/catal3020378.
[20] Wang, Feng, et al., In situ EPR study of the redox properties of CuO–CeO2 catalysts for preferential CO oxidation (PROX), ACS catalysis 6.6 (2016): 3520- 3530. https://doi.org/10.1021/acscatal.6b00589
[21] G. Avgouropoulos and T. Ioannides, Effect of synthesis parameters on catalytic properties of CuO- CeO2, Appl. Catal. B Environ., vol. 67, no. 1, pp. 1– 11, 2006. https://doi.org/10.1016/j.apcatb.2006.04.005
[22] F. Wang et al., A Photoactivated Cu–CeO2 Catalyst with Cu‐[O]‐Ce Active Species Designed through MOF Crystal Engineering, Angew. Chemie, vol. 132, no. 21, pp. 8280–8286, 2020. https://doi.org/10.1002/ange.201916049
[23] X. Gong et al., Boosting Cu-Ce interaction in CuxO/CeO2 nanocube catalysts for enhanced catalytic performance of preferential oxidation of CO in H2-rich gases, Mol. Catal., vol. 436, pp. 90–99, 2017. https://doi.org/10.1016/j.mcat.2017.04.013
[24] X. Guo and R. Zhou, Identification of the nano/microstructure of CeO2 (rod) and the essential role of interfacial copper-ceria interaction in CuCe (rod) for selective oxidation of CO in H2-rich streams, J. Power Sources, vol. 361, pp. 39–53, 2017. https://doi.org/10.1016/j.jpowsour.2017.06.064
[25] M.-F. Luo, Y.-J. Zhong, X. Yuan, and X.-M. Zheng, TPR and TPD studies of CuO-CeO2 catalysts for low temperature CO oxidation, Appl. Catal. A Gen., vol. 162, no. 1–2, pp. 121–131, 1997. https://doi.org/10.1016/S0926-860X(97)00089-6
[26] A. Arango-Díaz et al., Comparative study of CuO supported on CeO2, Ce0.8Zr0.2O2 and Ce0.8Al0.2O2 based catalysts in the CO-PROX reaction, Int. J. Hydrogen Energy, vol. 39, no. 8, pp. 4102–4108, 2014. https://doi.org/10.1016/j.ijhydene.2013.04.062
Elsevier, 2022, pp. 1–24. https://doi.org/10.1016/B978-0-12-823708-3.00006-7
[2] G. Xiang et al., Atomically dispersed Au catalysts for preferential oxidation of CO in H2-rich stream, Appl. Catal. B Environ., vol. 296, p. 120385, 2021. https://doi.org/10.1016/j.apcatb.2021.120385
[3] Z. Boukha, J. R. González-Velasco, and M. A. Gutiérrez-Ortiz, Exceptional performance of gold supported on fluoridated hydroxyapatite catalysts in CO-cleanup of H2-rich stream: High activity and resistance under PEMFC operation conditions, Appl.
Catal. B Environ., vol. 292, p. 120142, 2021. https://doi.org/10.1016/j.apcatb.2021.120142
[4] V. Palma, C. Ruocco, M. Martino, E. Meloni, and A.Ricca, Catalysts for conversion of synthesis gas, in Bioenergy Systems for the Future, Elsevier, 2017, pp. 217–277. https://doi.org/10.1016/B978-0-08-101031-0.00007-7
[5] E. Poggio-Fraccari, A. Abele, N. Zitta, J. Francesconi, and F. Mariño, CO removal for hydrogen purification via Water Gas Shift and CO-PROX reactions with monolithic catalysts, Fuel, vol. 310, p. 122419, 2022. https://doi.org/10.1016/j.fuel.2021.122419
[6] Y. Chen, J. Lin, L. Li, X. Pan, X. Wang, and T. Zhang, Local structure of Pt species dictates remarkable performance on Pt/A2O3 for preferential oxidation of CO in H2, Appl. Catal. B Environ., vol. 282, p. 119588, 2021 https://doi.org/10.1016/j.apcatb.2020.119588.
[7] L.-H. Chang, Y.-L. Yeh, and Y.-W. Chen, Preferential oxidation of CO in hydrogen stream over nano-gold catalysts prepared by photodeposition method, Int. J. Hydrogen Energy, vol. 33, no. 7, pp. 1965–1974, 2008. https://doi.org/10.1016/j.ijhydene.2008.01.014
[8] Q. Zou et al., Ceria-nano supported copper oxide catalysts for CO preferential oxidation: Importance of oxygen species and metal-support interaction, Appl. Surf. Sci., vol. 494, pp. 1166–1176, 2019. https://doi.org/10.1016/j.apsusc.2019.07.210
[9] A. Di Benedetto, G. Landi, and L. Lisi, Improved CO- PROX performance of CuO/CeO2 catalysts by using nanometric ceria as support, Catalysts, vol. 8, no. 5, p. 209, 2018. https://doi.org/10.3390/catal8050209
[10] J. Kašpar, P. Fornasiero, and N. Hickey, Automotive catalytic converters: current status and some perspectives, Catal. today, vol. 77, no. 4, pp. 419–449, 2003. https://doi.org/10.1016/S0920-5861(02)00384-X
[11] H. Vidal et al., Redox behavior of CeO2–ZrO2 mixed oxides: I. Influence of redox treatments on high surface area catalysts, Appl. Catal. B Environ., vol. 27, no. 1, pp. 49–63, 2000. https://doi.org/10.1016/S0926-3373(00)00138-7
[12] P. Ratnasamy et al., Influence of the support on the preferential oxidation of CO in hydrogen-rich steam reformates over the CuO–CeO2–ZrO2 system, J. Catal., vol. 221, no. 2, pp. 455–465, 2004. https://doi.org/10.1016/j.jcat.2003.09.006
[13] Martínez-Munuera, J. C., Giménez-Mañogil, J., Yeste, M. P., Hungría, A. B., Cauqui, M. A., García-García, A., & Calvino, J. J. (2022). New findings regarding the role of copper entity particle size on the performance of Cu/ceria-based catalysts in the CO-PROX reaction. Applied Surface Science, 575, 151717. https://doi.org/10.1016/j.apsusc.2021.151717
[14] K. A. Cychosz, R. Guillet-Nicolas, J. García-Martínez, and M. Thommes, Recent advances in the textural characterization of hierarchically structured nanoporous materials, Chem. Soc. Rev., vol. 46, no. 2, pp. 389–414, 2017. https://doi.org/10.1039/C6CS00391E
[15] J. Mosrati et al., Tiny Species with Big Impact: High Activity of Cu Single Atoms on CeO2-TiO2 Deciphered by Operando Spectroscopy, ACS Catal., vol. 11, no. 17, pp. 10933–10949, 2021 https://doi.org/10.1021/acscatal.1c02349.
[16] J. Chen, Y. Zhan, J. Zhu, C. Chen, X. Lin, and Q. Zheng, The synergetic mechanism between copper species and ceria in NO abatement over Cu/CeO2 catalysts, Appl. Catal. A Gen., vol. 377, no. 1–2, pp. 121–127, 2010.
https://doi.org/10.1016/j.apcata.2010.01.027
[17] A. Pintar, J. Batista, and S. Hočevar, TPR, TPO, and TPD examinations of Cu0.15Ce0.85O2 mixed oxides prepared by co-precipitation, by the sol-gel peroxide route, and by citric acid-assisted synthesis, J. Colloid Interface Sci., vol. 285, no. 1, pp. 218–231, 2005, https://doi.org/10.1016/j.jcis.2004.11.049.
[18] G. Avgouropoulos, T. Ioannides, and H. Matralis, Influence of the preparation method on the performance of CuO–CeO2 catalysts for the selective oxidation of CO, Appl. Catal. B Environ., vol. 56, no. 1–2, pp. 87–93, 2005. https://doi.org/10.1016/j.apcatb.2004.07.017
[19] A. Martínez-Arias et al., Characterization of active sites/entities and redox/catalytic correlations in copper-ceria-based catalysts for preferential oxidation of CO in H2-rich streams, Catalysts, vol. 3, no. 2, pp. 378–400, 2013, https://doi.org/10.3390/catal3020378.
[20] Wang, Feng, et al., In situ EPR study of the redox properties of CuO–CeO2 catalysts for preferential CO oxidation (PROX), ACS catalysis 6.6 (2016): 3520- 3530. https://doi.org/10.1021/acscatal.6b00589
[21] G. Avgouropoulos and T. Ioannides, Effect of synthesis parameters on catalytic properties of CuO- CeO2, Appl. Catal. B Environ., vol. 67, no. 1, pp. 1– 11, 2006. https://doi.org/10.1016/j.apcatb.2006.04.005
[22] F. Wang et al., A Photoactivated Cu–CeO2 Catalyst with Cu‐[O]‐Ce Active Species Designed through MOF Crystal Engineering, Angew. Chemie, vol. 132, no. 21, pp. 8280–8286, 2020. https://doi.org/10.1002/ange.201916049
[23] X. Gong et al., Boosting Cu-Ce interaction in CuxO/CeO2 nanocube catalysts for enhanced catalytic performance of preferential oxidation of CO in H2-rich gases, Mol. Catal., vol. 436, pp. 90–99, 2017. https://doi.org/10.1016/j.mcat.2017.04.013
[24] X. Guo and R. Zhou, Identification of the nano/microstructure of CeO2 (rod) and the essential role of interfacial copper-ceria interaction in CuCe (rod) for selective oxidation of CO in H2-rich streams, J. Power Sources, vol. 361, pp. 39–53, 2017. https://doi.org/10.1016/j.jpowsour.2017.06.064
[25] M.-F. Luo, Y.-J. Zhong, X. Yuan, and X.-M. Zheng, TPR and TPD studies of CuO-CeO2 catalysts for low temperature CO oxidation, Appl. Catal. A Gen., vol. 162, no. 1–2, pp. 121–131, 1997. https://doi.org/10.1016/S0926-860X(97)00089-6
[26] A. Arango-Díaz et al., Comparative study of CuO supported on CeO2, Ce0.8Zr0.2O2 and Ce0.8Al0.2O2 based catalysts in the CO-PROX reaction, Int. J. Hydrogen Energy, vol. 39, no. 8, pp. 4102–4108, 2014. https://doi.org/10.1016/j.ijhydene.2013.04.062