AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
PDF (30.6 MB)
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript AI Chat Paper
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article | Open Access

Breakthrough scalable synthesis of anti-coking Cs-Ni/CeOx-Al2O3 nanocatalysts for optimal dry reforming performance

Kyung Hee Oh1,2, Shin Wook Kang1, Jin Gyu Lee1, Jung-Il Yang1, Byung-Hyun Kim3, Chang Seop Hong2( ), Ji Chan Park1,4( )
Clean Fuel Research Laboratory, Korea Institute of Energy Research, Daejeon 34129, Republic of Korea
Department of Chemistry, Korea University, Seoul 02841, Republic of Korea
Department of Chemical and Molecular Engineering, Hanyang University ERICA, Ansan 15588, Republic of Korea
Energy Engineering, University of Science and Technology, Daejeon 34113, Republic of Korea
Show Author Information

Graphical Abstract

The Cs-Ni/CeOx-Al2O3 nanocatalysts synthesized via an automated system containing ~ 5 nm Ni nanoparticles showed excellent coke resistance and high conversion rates under various dry reforming conditions, confirming their potential for cost-effective, stable syngas production and greenhouse gas reduction.

Abstract

The dry reforming (DR) reaction is an eco-friendly process for producing synthesis gas (CO, H2) from greenhouse gases (CH4, CO2). Despite advancements in various nickel (Ni)-supported catalysts for this reaction, achieving high catalyst stability against carbon deposition and improving conversion rates remain significant challenges. In this paper, we introduce a novel approach for synthesizing uniform Ni nanocatalysts with cesium (Cs) and cerium oxide (CeOx). This synthesis is achieved using an automated device based on a co-melt infiltration technique. Our method addresses the limitations of conventional catalyst synthesis, such as complex procedures, low reproducibility, and difficulties in scaling up. The resulting catalysts contain uniformly small Ni particles, approximately 5 nm in size, with Cs and CeOx evenly distributed throughout the alumina (Al2O3) support. The developed Ni/CeOx-Al2O3 and Cs-Ni/CeOx-Al2O3 nanocatalysts demonstrate improved conversion performance and stability under various DR conditions. This improvement is attributed to the synergistic effect of Cs and CeOx, which creates a pathway to inhibit and remove carbon deposition. Additionally, these nanocatalysts exhibited superior resistance to carbon deposition compared to conventional Ni/Al2O3 and commercial Ni catalysts under identical reaction conditions.

Keywords

co-melt infiltrationnanocatalystpromoterdry reforming reactioncoke resistance

Electronic Supplementary Material

Video
7116_Movie S1.mp4
Download File(s)
7116_ESM.pdf (1.6 MB)

References

[1]

Abdulrasheed, A.; Jalil, A. A.; Gambo, Y.; Ibrahim, M.; Hambali, H. U.; Hamid, M. Y. S. A review on catalyst development for dry reforming of methane to syngas: Recent advances. Renew. Sustain. Energy Rev. 2019, 108, 175–193.
Crossref Google Scholar
[2]

He, M. Y.; Sun, Y. H.; Han, B. X. Green carbon science: Efficient carbon resource processing, utilization, and recycling towards carbon neutrality. Angew. Chem., Int. Ed. 2022, 134, e202112835.
Crossref Google Scholar
[3]

Pakhare, D.; Spivey, J. A review of dry (CO2) reforming of methane over noble metal catalysts. Chem. Soc. Rev. 2014, 43, 7813–7837.
Crossref Google Scholar
[4]

Bhattar, S.; Abedin, M. A.; Kanitkar, S.; Spivey, J. J. A review on dry reforming of methane over perovskite derived catalysts. Catal. Today 2021, 365, 2–23.
Crossref Google Scholar
[5]

Song, Y.; Ozdemir, E.; Ramesh, S.; Adishev, A.; Subramanian, S.; Harale, A.; Albuali, M.; Fadhel, B. A.; Jamal, A.; Moon, D. et al. Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO. Science 2020, 367, 777–781.
Crossref Google Scholar
[6]

Akri, M.; Zhao, S.; Li, X. Y.; Zang, K. T.; Lee, A. F.; Isaacs, M. A.; Xi, W.; Gangarajula, Y.; Luo, J.; Ren, Y. J. et al. Atomically dispersed nickel as coke-resistant active sites for methane dry reforming. Nat. Commun. 2019, 10, 5181.
Crossref Google Scholar
[7]

Pawar, V.; Ray, D.; Subrahmanyam, C.; Janardhanan, V. M. Study of short-term catalyst deactivation due to carbon deposition during biogas dry reforming on supported Ni catalyst. Energy Fuels 2015, 29, 8047–8052.
Crossref Google Scholar
[8]

Niu, J. T.; Wang, Y. L.; Liland, S. E.; Regli, S. K.; Yang, J.; Rout, K. R.; Luo, J.; Rønning, M.; Ran, J. Y.; Chen, D. Unraveling enhanced activity, selectivity, and coke resistance of Pt–Ni bimetallic clusters in dry reforming. ACS Catal. 2021, 11, 2398–2411.
Crossref Google Scholar
[9]

Fan, M. S.; Abdullah, A. Z.; Bhatia, S. Catalytic technology for carbon dioxide reforming of methane to synthesis gas. ChemCatChem 2009, 1, 192–208.
Crossref Google Scholar
[10]

Jang, W. J.; Shim, J. O.; Kim, H. M.; Yoo, S. Y.; Roh, H. S. A review on dry reforming of methane in aspect of catalytic properties. Catal. Today 2019, 324, 15–26.
Crossref Google Scholar
[11]

Cai, L. H.; Han, S. L.; Xu, W. L.; Chen, S.; Shi, X. X.; Lu, J. L. Formation of a porous crystalline Mg1− x Al2O y overlayer on metal catalysts via controlled solid-state reactions for high-temperature stable catalysis. Angew. Chem., Int. Ed. 2024, 63, e202404398.
Crossref Google Scholar
[12]

Li, X. Y.; Li, D.; Tian, H.; Zeng, L.; Zhao, Z. J.; Gong, J. L. Dry reforming of methane over Ni/La2O3 nanorod catalysts with stabilized Ni nanoparticles. Appl. Catal. B: Environ. 2017, 202, 683–694.
Crossref Google Scholar
[13]

Ferrandon, M. S.; Byron, C.; Celik, G.; Zhang, Y. Y.; Ni, C. Y.; Sloppy, J.; McCormick, R. A.; Booksh, K.; Teplyakov, A. V.; Delferro, M. Grafted nickel-promoter catalysts for dry reforming of methane identified through high-throughput experimentation. Appl. Catal. A 2022, 629, 118379.
Crossref Google Scholar
[14]

Liu, Y.; Chen, Y.; Gao, Z. R.; Zhang, X.; Zhang, L. J.; Wang, M.; Chen, B. B.; Diao, Y. N.; Li, Y. L.; Xiao, D. Q. et al. Embedding high loading and uniform Ni nanoparticles into silicalite-1 zeolite for dry reforming of methane. Appl. Catal. B: Environ. 2022, 307, 121202.
Crossref Google Scholar
[15]

Huang, J. J.; Yan, Y.; Saqline, S.; Liu, W.; Liu, B. High performance Ni catalysts prepared by freeze drying for efficient dry reforming of methane. Appl. Catal. B: Environ. 2020, 275, 119109.
Crossref Google Scholar
[16]

Min, H. K.; Kweon, S.; Kim, Y. W.; An, H.; Jo, D.; Park, E. D.; Shin, C. H.; Park, M. B. Atomically dispersed nickel species in a two-dimensional molecular sieve: Origin of high activity and stability in dry reforming of methane. Appl. Catal. B: Environ. 2021, 298, 120627.
Crossref Google Scholar
[17]

Le Saché, E.; Reina, T. R. Analysis of Dry Reforming as direct route for gas phase CO2 conversion. The past, the present and future of catalytic DRM technologies. Prog. Energy Combust. Sci. 2022, 89, 100970.
Crossref Google Scholar
[18]

Seo, J. C.; Kim, H.; Lee, Y. L.; Nam, S.; Roh, H. S.; Lee, K.; Park, S. B. One-pot synthesis of full-featured mesoporous Ni/Al2O3 catalysts via a spray pyrolysis-assisted evaporation-induced self-assembly method for dry reforming of methane. ACS Sustainable Chem. Eng. 2021, 9, 894–904.
Crossref Google Scholar
[19]

Aramouni, N. A. K.; Zeaiter, J.; Kwapinski, W.; Ahmad, M. N. Thermodynamic analysis of methane dry reforming: Effect of the catalyst particle size on carbon formation. Energy Convers. Manage. 2017, 150, 614–622.
Crossref Google Scholar
[20]

Wang, F. G.; Han, B. L.; Zhang, L. J.; Xu, L. L.; Yu, H.; Shi, W. D. CO2 reforming with methane over small-sized Ni@SiO2 catalysts with unique features of sintering-free and low carbon. Appl. Catal. B: Environ. 2018, 235, 26–35.
Crossref Google Scholar
[21]

Zhu, L. Y.; Lv, Z. Z.; Huang, X.; Ran, J. Y.; Chen, J.; Qin, C. L. Understanding the role of support structure in methane dry reforming for syngas production. Fuel 2022, 327, 125163.
Crossref Google Scholar
[22]

Xu, L. L.; Wang, F. G.; Chen, M. D.; Fan, X. L.; Yang, H. M.; Nie, D. Y.; Qi, L. Alkaline-promoted Co–Ni bimetal ordered mesoporous catalysts with enhanced coke-resistant performance toward CO2 reforming of CH4. J. CO2 Util. 2017, 18, 1–14.
Crossref Google Scholar
[23]

Palmer, C.; Upham, D. C.; Smart, S.; Gordon, M. J.; Metiu, H.; McFarland, E. W. Dry reforming of methane catalysed by molten metal alloys. Nat. Catal. 2020, 3, 83–89.
Crossref Google Scholar
[24]

Bian, Z. F.; Zhong, W. Q.; Yu, Y.; Wang, Z. G.; Jiang, B.; Kawi, S. Dry reforming of methane on Ni/mesoporous-Al2O3 catalysts: Effect of calcination temperature. Int. J. Hydrogen Energy 2021, 46, 31041–31053.
Crossref Google Scholar
[25]

Tsiotsias, A. I.; Charisiou, N. D.; Yentekakis, I. V.; Goula, M. A. The role of alkali and alkaline earth metals in the CO2 methanation reaction and the combined capture and methanation of CO2. Catalysts 2020, 10, 812.
Crossref Google Scholar
[26]

Aziz, M. A. A.; Jalil, A. A.; Wongsakulphasatch, S.; Vo, D. V. N. Understanding the role of surface basic sites of catalysts in CO2 activation in dry reforming of methane: A short review. Catal. Sci. Technol. 2020, 10, 35–45.
Crossref Google Scholar
[27]

Zeng, F.; Zhang, J.; Xu, R.; Zhang, R. J.; Ge, J. P. Highly dispersed Ni/MgO–mSiO2 catalysts with excellent activity and stability for dry reforming of methane. Nano Res. 2022, 15, 5004–5013.
Crossref Google Scholar
[28]

Seo, J. C.; Cho, E.; Kim, J.; Kim, S. B.; Youn, J. R.; Kim, D. H.; Ramasamy, P. K.; Lee, K.; Ko, C. H. Bifunctional metal doping engineering of Ni-supported alumina catalyst for dry methane reforming. J. Environ. Chem. Eng., 2022, 10, 108058.
Crossref Google Scholar
[29]

Franz, R.; Kühlewind, T.; Shterk, G.; Abou-Hamad, E.; Parastaev, A.; Uslamin, E.; Hensen, E. J. M.; Kapteijn, F.; Gascon, J.; Pidko, E. A. Impact of small promoter amounts on coke structure in dry reforming of methane over Ni/ZrO2. Catal. Sci. Technol. 2020, 10, 3965–3974.
Crossref Google Scholar
[30]

Song, P.; Su, T. M.; Luo, Y. H.; Luo, X.; Ji, H. B.; Qin, Z. Z. Ni−Mg−Al catalysts for dry reforming of methane: Effect of surface properties on coke formation and CO2 activation. Ind. Eng. Chem. Res. 2024, 63, 16077–16090.
Crossref Google Scholar
[31]

Zhan, H. J.; Shi, X. Y.; Ma, B. J.; Liu, W. Y.; Jiao, X.; Huang, X. Facile one-step preparation of ordered mesoporous Ni–M–Al (M = K, Mg, Y, and Ce) oxide catalysts for methane dry reforming. New J. Chem. 2019, 43, 12292–12298.
Crossref Google Scholar
[32]

Oh, K. H.; Lee, J. H.; Kim, K.; Lee, H. K.; Kang, S. W.; Yang, J. I.; Park, J. H.; Hong, C. S.; Kim, B. H.; Park, J. C. A new automated synthesis of a coke-resistant Cs-promoted Ni-supported nanocatalyst for sustainable dry reforming of methane. J. Mater. Chem. A 2023, 11, 1666–1675.
Crossref Google Scholar
[33]

Lorber, K.; Zavašnik, J.; Arčon, I.; Huš, M.; Teržan, J.; Likozar, B.; Djinović, P. CO2 activation over nanoshaped CeO2 decorated with nickel for low-temperature methane dry reforming. ACS Appl. Mater. Interfaces 2022, 14, 31862–31878.
Crossref Google Scholar
[34]

Vasiliades, M. A.; Damaskinos, C. M.; Lykaki, M.; Stefa, S.; Binas, V. D.; Kentri, T.; Boghosian, S.; Konsolakis, M.; Efstathiou, A. M. Deciphering the role of nano-CeO2 morphology on the dry reforming of methane over Ni/CeO2 using transient and isotopic techniques. Appl. Catal. B: Environ. 2024, 350, 123906.
Crossref Google Scholar
[35]

Kim, B. J.; Seo, J. C.; Kim, D. H.; Lee, Y. L.; Lee, K.; Roh, H. S. Oxygen defective bimodal porous Ni–CeO2– x– MgO–Al2O3 catalyst with multi-void spherical structure for CO2 reforming of CH4. J. CO2 Util. 2022, 58, 101917.
Crossref Google Scholar
[36]

Kawi, S.; Kathiraser, Y.; Ni, J.; Oemar, U.; Li, Z. W.; Saw, E. T. Progress in synthesis of highly active and stable nickel-based catalysts for carbon dioxide reforming of methane. ChemSusChem 2015, 8, 3556–3575.
Crossref Google Scholar
[37]

Arora, S.; Prasad, R. An overview on dry reforming of methane: Strategies to reduce carbonaceous deactivation of catalysts. RSC Adv. 2016, 6, 108668–108688.
Crossref Google Scholar
[38]

Park, J. C.; Chun, D. H.; Yang, J. I.; Lee, H. T.; Hong, S.; Rhim, G. B.; Jang, S.; Jung, H. Cs promoted Fe5C2/charcoal nanocatalysts for sustainable liquid fuel production. RSC Adv. 2015, 5, 44211–44217.
Crossref Google Scholar
[39]

Oh, K. H.; Lee, H. K.; Kang, S. W.; Yang, J. I.; Nam, G.; Lim, T.; Lee, S. H.; Hong, C. S.; Park, J. C. Automated synthesis and data accumulation for fast production of high-performance Ni nanocatalsts. J. Ind. Eng. Chem. 2022, 106, 449–459.
Crossref Google Scholar
[40]

Cho, E. H.; Kim, M. J.; Yoon, B. S.; Kim, Y. J.; Song, D.; Koo, K. Y.; Jung, U.; Jeon, S. G.; Park, Y. K.; Ko, C. H. Enhancement in nickel-silica interface generation by surfactant-assisted melt-infiltration: Surfactant selection and application in CO2 hydrogenation. Chem. Eng. J. 2022, 437, 135166.
Crossref Google Scholar
[41]

Lee, H. K.; Kang, S. W.; Yang, J. I.; Chun, D. H.; Lee, J. H.; Oh, D.; Ban, J. M.; Jung, T.; Jung, H.; Park, J. C. A new systematic synthesis of ultimate nickel nanocatalysts for compact hydrogen generation. React. Chem. Eng. 2020, 5, 1218–1223.
Crossref Google Scholar
[42]

Oh, J.; Joo, S.; Lim, C.; Kim, H. J.; Ciucci, F.; Wang, J. Q.; Han, J. W.; Kim, G. Precise modulation of triple-phase boundaries towards a highly functional exsolved catalyst for dry reforming of methane under a dilution-free system. Angew. Chem., Int. Ed. 2022, 61, e202204990.
Crossref Google Scholar
[43]

Djinović, P.; Črnivec, I.G.O.; Pintar, A. Biogas to syngas conversion without carbonaceous deposits via the dry reforming reaction using transition metal catalysts. Catal. Today 2015, 253, 155–162.
Crossref Google Scholar
[44]

Zhu, H. B.; Chen, H. C.; Zhang, M. H.; Liang, C.; Duan, L. H. Recent advances in promoting dry reforming of methane using nickel-based catalysts. Catal. Sci. Technol. 2024, 14, 1712–1729.
Crossref Google Scholar
[45]

Zhao, X. H.; Joseph, B.; Kuhn, J.; Ozcan, S. Biogas reforming to syngas: A review. iScience 2020, 23, 101082.
Crossref Google Scholar
[46]

Dou, J.; Bao, Z. H.; Yu, F. Mesoporous Ni(OH)2/CeNi x O y composites derived Ni/CeNi x O y catalysts for dry reforming of methane. ChemCatChem 2018, 10, 250–258.
Crossref Google Scholar
[47]

Baron, M.; Bondarchuk, O.; Stacchiola, D.; Shaikhutdinov, S.; Freund, H. J. Interaction of gold with cerium oxide supports: CeO2(111) thin films vs CeO x nanoparticles. J. Phys. Chem. C 2009, 113, 6042–6049.
Crossref Google Scholar
[48]

Fang, Y.; Zhao, C. B.; Gong, Z. M.; Wang, S. P.; Ye, X. Q.; Pan, Q. F.; Li, G.; Cui, Y.; Yao, Y. X.; Luo, W. H. In situ NAP-XPS study of CO2 and H2O adsorption on cerium oxide thin films. Chem. Phys. Lett. 2022, 794, 139496.
Crossref Google Scholar
[49]

Liang, T. Y.; Lin, C. Y.; Chou, F. C.; Wang, M. Q.; Tsai, D. H. Gas-phase synthesis of Ni–CeO x hybrid nanoparticles and their synergistic catalysis for simultaneous reforming of methane and carbon dioxide to syngas. J. Phys. Chem. C 2018, 122, 11789–11798.
Crossref Google Scholar
[50]

Wittich, K.; Krämer, M.; Bottke, N.; Schunk, S. A. Catalytic dry reforming of methane: Insights from model systems. ChemCatChem 2020, 12, 2130–2147.
Crossref Google Scholar
[51]

Kahle, L. C. S.; Roussière, T.; Maier, L.; Herrera Delgado, K.; Wasserschaff, G.; Schunk, S. A.; Deutschmann, O. Methane dry reforming at high temperature and elevated pressure: Impact of gas-phase reactions. Ind. Eng. Chem. Res. 2013, 52, 11920–11930.
Crossref Google Scholar
[52]

Apuzzo, J.; Cimino, S.; Lisi, L. Ni or Ru supported on MgO/γ–Al2O3 pellets for the catalytic conversion of ethanol into butanol. RSC Adv. 2018, 8, 25846–25855.
Crossref Google Scholar
Nano Research
Volume 18 Issue 2,
February 2025
Article number: 94907116
DOI: 10.26599/NR.2025.94907116
Cite this article:
Oh KH, Kang SW, Lee JG, et al. Breakthrough scalable synthesis of anti-coking Cs-Ni/CeOx-Al2O3 nanocatalysts for optimal dry reforming performance. Nano Research, 2025, 18(2): 94907116. https://doi.org/10.26599/NR.2025.94907116
Topics:
Synthesis

319

Views

68

Downloads

0

Crossref

0

Web of Science

0

Scopus

0

CSCD

Altmetrics
Received: 19 August 2024
Revised: 25 October 2024
Accepted: 05 November 2024
Published: 06 January 2025
© The Author(s) 2025. Published by Tsinghua University Press.

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, https://creativecommons.org/licenses/by/4.0/).
Return