1. Institute of Sciences and Technologies for Sustainable Energy and Mobility-CNR, Naples 80125, Italy 2. Department of Chemical, Materials and Production Engineering, University of Naples Federico II, Naples 80125, Italy
Within the “hydrogen chain”, the high-temperature water gas shift reaction represents a key step to improve the H2 yield and adjust the H2/COx ratio to fit the constraints of downstream processes. Despite the commercial application of the high-temperature water gas shift, novel catalysts characterized by higher intrinsic activity (especially at low temperatures), good thermal stability, and no chromium content are needed. In this work, we propose bimetallic iron-copper catalysts supported on ceria, characterized by low active phase content (iron oxide + copper oxide < 5 wt %). Fresh and used samples were characterized by inductively coupled plasma mass spectrometry, X-ray diffraction, nitrogen physisorption, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, and temperature programmed reduction in hydrogen to relate physicochemical features and catalytic activity. The sample with iron/copper ≈ 1 and 4 wt % active phase content showed the best catalytic properties in terms of turnover frequency, no methane formation, and stability. Its unique properties were due to both strong iron-copper interaction and strong metal-support interaction, leading to outstanding redox behavior.
J E Lee, I Shafiq, M Hussain, S S Lam, G H Rhee, Y K Park. A review on integrated thermochemical hydrogen production from water. International Journal of Hydrogen Energy, 2022, 47(7): 4346–4356 https://doi.org/10.1016/j.ijhydene.2021.11.065
2
Q Hassan, A M Abdulateef, S A Hafedh, A Al-samari, J Abdulateef, A Z Sameen, H M Salman, A K Al-Jiboory, S Wieteska, M Jaszczur. Renewable energy-to-green hydrogen: a review of main resources routes, processes and evaluation. International Journal of Hydrogen Energy, 2023, 48(46): 17383–17408 https://doi.org/10.1016/j.ijhydene.2023.01.175
3
Y L Lee, K J Kim, G R Hong, H S Roh. Target-oriented water-gas shift reactions with customized reaction conditions and catalysts. Chemical Engineering Journal, 2023, 458: 141422 https://doi.org/10.1016/j.cej.2023.141422
Oliveira C S de, Neto É Teixeira, I O Mazali. Stabilization and Au sintering prevention promoted by ZnO in CeOx-ZnO porous nanorods decorated with Au nanoparticles in the catalysis of the water-gas shift (WGS) reaction. Journal of Alloys and Compounds, 2022, 892: 162179 https://doi.org/10.1016/j.jallcom.2021.162179
7
Y Li, M Kottwitz, J L Vincent, M J Enright, Z Liu, L Zhang, J Huang, S D Senanayake, W C D Yang, P A Crozier, R G Nuzzo, A I Frenkel. Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction. Nature Communications, 2021, 12(1): 914 https://doi.org/10.1038/s41467-021-21132-4
8
Y Zhang, A Jia, Z Li, Z Yuan, W Huang. Titania-morphology-dependent Pt-TiO2 interfacial catalysis in water-gas shift reaction. ACS Catalysis, 2023, 13(1): 392–399 https://doi.org/10.1021/acscatal.2c04046
9
M Zhu, I E Wachs. Iron-based catalysts for the high-temperature water-gas shift (HT-WGS) reaction: a review. ACS Catalysis, 2016, 6(2): 722–732 https://doi.org/10.1021/acscatal.5b02594
10
C Rhodes, B P Williams, F King, G J Hutchings. Promotion of Fe3O4/Cr2O3 high temperature water gas shift catalyst. Catalysis Communications, 2002, 3(8): 381–384 https://doi.org/10.1016/S1566-7367(02)00156-5
11
C R F Lund, J A Dumesic. Strong oxide-oxide interactions in silica-supported magnetite catalysts: IV. Catalytic consequences of the interaction in water-gas shift. Journal of Catalysis, 1982, 76(1): 93–100 https://doi.org/10.1016/0021-9517(82)90240-8
12
F Miccio, A Picarelli, G Ruoppolo. Increasing tar and hydrocarbons conversion by catalysis in bubbling fluidized bed gasifiers. Fuel Processing Technology, 2016, 141: 31–37 https://doi.org/10.1016/j.fuproc.2015.06.007
13
M Bahmani, M Nazari, M Mehreshtiagh. A study on the mechanical strength of Fe2O3/Cr2O3/CuO catalyst for high temperature water gas shift reaction. Journal of Porous Materials, 2021, 28(3): 683–693 https://doi.org/10.1007/s10934-020-01014-8
14
L Zhang, X Wang, J M M Millet, P H Matter, U S Ozkan. Investigation of highly active Fe-Al-Cu catalysts for water-gas shift reaction. Applied Catalysis A, General, 2008, 351(1): 1–8 https://doi.org/10.1016/j.apcata.2008.08.019
15
L Pastor-Pérez, F Baibars, Sache E Le, H Arellano-García, S Gu, T R Reina. CO2 valorisation via reverse water-gas shift reaction using advanced Cs doped Fe-Cu/Al2O3 catalysts. Journal of CO2 Utilization, 2017, 21: 423–428
16
L Zhang, J M M Millet, U S Ozkan. Effect of Cu loading on the catalytic performance of Fe-Al-Cu for water-gas shift reaction. Applied Catalysis A, General, 2009, 357(1): 66–72 https://doi.org/10.1016/j.apcata.2009.01.011
17
T Popa, G Xu, T F Barton, M D Argyle. High temperature water gas shift catalysts with alumina. Applied Catalysis A, General, 2010, 379(1–2): 15–23 https://doi.org/10.1016/j.apcata.2010.02.021
18
M Zhu, Ö Yalçın, I E Wachs. Revealing structure-activity relationships in chromium free high temperature shift catalysts promoted by earth abundant elements. Applied Catalysis B: Environmental, 2018, 232: 205–212 https://doi.org/10.1016/j.apcatb.2018.03.051
19
G K Reddy, P G Smirniotis. Effect of copper as a dopant on the water gas shift activity of Fe/Ce and Fe/Cr modified ferrites. Catalysis Letters, 2011, 141(1): 27–32 https://doi.org/10.1007/s10562-010-0465-2
20
D Damma, T Boningari, P G Smirniotis. High-temperature water-gas shift over Fe/Ce/Co spinel catalysts: study of the promotional effect of Ce and Co. Molecular Catalysis, 2018, 451: 20–32 https://doi.org/10.1016/j.mcat.2017.10.013
21
A Trovarelli, J Llorca. Ceria catalysts at nanoscale: How do crystal shapes shape catalysis?. ACS Catalysis, 2017, 7(7): 4716–4735 https://doi.org/10.1021/acscatal.7b01246
22
E Aneggi, M Boaro, S Colussi, C de Leitenburg, A Trovarelli. Ceria-based materials in catalysis: historical perspective and future trends. Handbook on the Physics and Chemistry of Rare Earths, 2016, 50: 209–242 https://doi.org/10.1016/bs.hpcre.2016.05.002
23
J Zhang, D Zhu, J Yan, C A Wang. Strong metal-support interactions induced by an ultrafast laser. Nature Communications, 2021, 12(1): 6665 https://doi.org/10.1038/s41467-021-27000-5
24
J Chen, Y Zhang, Z Zhang, D Hou, F Bai, Y Han, C Zhang, Y Zhang, J Hu. Metal-support interactions for heterogeneous catalysis: mechanisms, characterization techniques and applications. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2023, 11(16): 8540–8572 https://doi.org/10.1039/D2TA10036C
25
J Lu, J Wang, Q Zou, D He, L Zhang, Z Xu, S He, Y Luo. Unravelling the nature of the active species as well as the doping effect over Cu/Ce-based catalyst for carbon monoxide preferential oxidation. ACS Catalysis, 2019, 9(3): 2177–2195 https://doi.org/10.1021/acscatal.8b04035
26
J Xu, L Li, J Pan, W Cui, X Liang, Y Yu, B Liu, X Wang, S Song, H Zhang. Boosting the catalytic performance of CuOx in CO2 hydrogenation by incorporating CeO2 promoters. Advanced Sustainable Systems, 2022, 6(8): 2200287 https://doi.org/10.1002/adsu.202200287
27
H Wang, M S Bootharaju, J H Kim, Y Wang, K Wang, M Zhao, R Zhang, J Xu, T Hyeon, X Wang, S Song, H Zhang. Synergistic interactions of neighboring platinum and iron atoms enhance reverse water-gas shift reaction performance. Journal of the American Chemical Society, 2023, 145(4): 2264–2270 https://doi.org/10.1021/jacs.2c10435
28
L Chen, D Wu, C Wang, M Ji, Z Wu. Study on Cu-Fe/CeO2 bimetallic catalyst for reverse water gas shift reaction. Journal of Environmental Chemical Engineering, 2021, 9(3): 105183 https://doi.org/10.1016/j.jece.2021.105183
29
G Luciani, G Landi, A Aronne, A Di Benedetto. Partial substitution of B cation in La0.6Sr0.4MnO3 perovskites: a promising strategy to improve the redox properties useful for solar thermochemical water and carbon dioxide splitting. Solar Energy, 2018, 171: 1–7 https://doi.org/10.1016/j.solener.2018.06.058
30
E Aneggi, C de Leitenburg, G Dolcetti, A Trovarelli. Promotional effect of rare earths and transition metals in the combustion of diesel soot over CeO2 and CeO2-ZrO2. Catalysis Today, 2006, 114(1): 40–47 https://doi.org/10.1016/j.cattod.2006.02.008
31
P S Barbato, S Colussi, A Di Benedetto, G Landi, L Lisi, J Llorca, A Trovarelli. CO preferential oxidation under H2-rich streams on copper oxide supported on Fe promoted CeO2. Applied Catalysis A, General, 2015, 506: 268–277 https://doi.org/10.1016/j.apcata.2015.09.018
32
S Scirè, C Crisafulli, P M Riccobene, G Patanè, A Pistone. Selective oxidation of CO in H2-rich stream over Au/CeO2 and Cu/CeO2 catalysts: an insight on the effect of preparation method and catalyst pretreatment. Applied Catalysis A, General, 2012, 417–418: 66–75 https://doi.org/10.1016/j.apcata.2011.12.025
33
A Di Benedetto, G Landi, L Lisi. Improved CO-PROX performance of CuO/CeO catalysts by using nanometric ceria as support. Catalysts, 2018, 8(5): 209 https://doi.org/10.3390/catal8050209
34
A Di Benedetto, G Landi, L Lisi. Nanostructured Catalysts for Environmental Applications. Cham: Springer, 2021, 79–112:
35
M Ronda-Lloret, S Rico-Francés, A Sepúlveda-Escribano, E V Ramos-Fernandez. CuOx/CeO2 catalyst derived from metal organic framework for reverse water-gas shift reaction. Applied Catalysis A, General, 2018, 562: 28–36 https://doi.org/10.1016/j.apcata.2018.05.024
36
A V Fedorov, R G Kukushkin, P M Yeletsky, O A Bulavchenko, Y A Chesalov, V A Yakovlev. Temperature-programmed reduction of model CuO, NiO and mixed CuO-NiO catalysts with hydrogen. Journal of Alloys and Compounds, 2020, 844: 156135 https://doi.org/10.1016/j.jallcom.2020.156135
37
L Yang, L Pastor-Pérez, J J Villora-Pico, A Sepúlveda-Escribano, F Tian, M Zhu, Y F Han, T R Reina. Highly active and selective multicomponent Fe-Cu/CeO2-Al2O3 catalysts for CO2 upgrading via RWGS: impact of Fe/Cu ratio. ACS Sustainable Chemistry & Engineering, 2021, 9(36): 12155–12166 https://doi.org/10.1021/acssuschemeng.1c03551
38
T R Reina, S Ivanova, M I Domínguez, M A Centeno, J A Odriozola. Sub-ambient CO oxidation over Au/MOx/CeO2-Al2O3 (M = Zn or Fe). Applied Catalysis A, General, 2012, 419–420: 58–66 https://doi.org/10.1016/j.apcata.2012.01.012
39
P S Barbato, S Colussi, A Di Benedetto, G Landi, L Lisi, J Llorca, A Trovarelli. Origin of high activity and selectivity of CuO/CeO2 catalysts prepared by solution combustion synthesis in CO-PROX reaction. Journal of Physical Chemistry C, 2016, 120(24): 13039–13048 https://doi.org/10.1021/acs.jpcc.6b02433
40
K Han, S Wang, N Hu, W Shi, F Wang. Alloying Ni-Cu nanoparticles encapsulated in SiO2 nanospheres for synergistic catalysts in CO2 reforming with methane reaction. ACS Applied Materials & Interfaces, 2022, 14(20): 23487–23495 https://doi.org/10.1021/acsami.2c03757
41
Y H Lee, H M Kim, C H Jeong, D W Jeong. Effects of precipitants on the catalytic performance of Cu/CeO2 catalysts for the water-gas shift reaction. Catalysis Science & Technology, 2021, 11(19): 6380–6389 https://doi.org/10.1039/D1CY00964H
42
Y M Park, J M Cho, G Y Han, J W Bae. Roles of highly ordered mesoporous structures of Fe-Ni bimetal oxides for an enhanced high-temperature water-gas shift reaction activity. Catalysis Science & Technology, 2021, 11(9): 3251–3260 https://doi.org/10.1039/D1CY00164G
