Co particles separated by immiscible Ag on yttria-stabilized zirconia as durable methane dry reforming catalyst under pressurized conditions

doi:10.1016/S1872-2067(25)64677-8

Abstract

Abstract:

It is economical to perform methane and carbon dioxide reforming (DRM) under industrially relevant high-pressure conditions, but the harsh operation condition poses a grand challenge for coke-resistant catalyst design. Here, we propose to boost the coke- tolerance of Co catalyst by applying a contact potential introduced by immiscible Ag clusters. We demonstrate that Co clusters separated by neighboring Ag on Yttria-stabilized zirconia (YSZ) support can serve as a coke- and sintering-resistant DRM catalyst under diluent gas-free, stoichiometric CH₄ and CO₂ feeding, 1123 K and 20 bar. Since immiscible metals are ubiquitous and metal contact influences surface work function in general, this new design concept may have general implications for tailoring catalytic properties of metals.

Key words: Methane dry reforming, Carbon dioxide, Heterogeneous catalysis, Co, Ag

Shi-Ning Li, Juntao Yao, Shuxin Pang, Jing-Peng Zhang, Shiying Li, Zhicheng Liu, Lu Han, Weibin Fan, Kake Zhu, Yi-An Zhu. Co particles separated by immiscible Ag on yttria-stabilized zirconia as durable methane dry reforming catalyst under pressurized conditions[J]. Chinese Journal of Catalysis, 2025, 74: 82-96.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64677-8

https://www.cjcatal.com/EN/Y2025/V74/I7/82

Figures/Tables 13

Scheme 1. Simplified DRM mechanism and formation mechanism of various carbon species on catalyst surfaces.

Fig. 1. XRD patterns for fresh Co/YSZ, Ag0.03-Co1/YSZ, Ag1-Co1/YSZ catalysts and Ag/YSZ (a) and TEM image (b) and elemental mappings (c-f) for Ag1-Co1/YSZ. A structure model of Ag1-Co1/YSZ is presented in (g).

Table 1 Physicochemical properties of Ag-Co/YSZ catalysts.

Catalyst	Metal Loading				S_BET m² g^-1	H₂-chemisorption (q) Mmol g^-1	Work function eV
Catalyst	Ag wt%	Co wt%	Ag mol%	Co mol%	S_BET m² g^-1	H₂-chemisorption (q) Mmol g^-1	Work function eV
YSZ					41
Ag₉-Co₁/YSZ	18.1	1.2	16.7	2.0	27	3.01
Ag₃-Co₁/YSZ	14.4	2.8	13.0	4.8	28	6.30
Ag_1.5-Co₁/YSZ	12.2	4.5	11.1	7.6	22	8.38
Ag₁-Co₁/YSZ	10.0	6.2	9.2	10.5	23	9.26	4.38^a (4.90^b)
Ag_0.25-Co₁/YSZ	3.1	7.5	4.2	18.7	26
Ag_0.03-Co₁/YSZ	0.4	9.3	0.6	23.1	27		4.13
Co/YSZ	0	14	0	23.7	20	5.36	3.63 (4.62)

Fig. 2. Semi in situ XPS spectra of Co 2p (a), Ag 3d (b), O 1s (c), and C 1s (d) for representative Co/YSZ and Ag1-Co1/YSZ after exposing to H2 at 1073 K for 3 min and mixture gas feed of CH4, CO2 at 1073 K for 10 min. (e) A structure cartoon for the surface structure is diagrammatically illustrated in (d).

Table 2 Surface composition(mol%) of fresh Ag-Co/YSZ catalysts determined by semi in situ XPS at H2 atmosphere.

Catalyst	Ag⁰	Co⁰	Co²⁺	C
Catalyst	Ag⁰	Co⁰	Co²⁺	C-C	C-O	C=O
Co/YSZ	—	0.070	0.068	0.039	0.050	0.013
Ag_0.03-Co₁/YSZ	0.05	0.06	0.077	0.038	0.041	0.014
Ag₁-Co₁/YSZ	0.071	0.090	0.072	0.034	0.032	0.018

Fig. 3. Catalytic stability for Ag1-Co1/YSZ, Ag0.03-Co1/YSZ and Co/YSZ catalysts, displayed for CH4 conversion (a), CO2 conversion (b) and the corresponding H2/CO ratio variations (c) as a function of TOS at 1123 K and pressures from 1.0 to 20.0 bar with a space velocity of 3636 mL h-1 g-cat-1. The dashed line in (a) indicates the equilibrium conversion of CH4.

Fig. 4. (a) XRD patterns of spent Ag-Co/YSZ. TEM micrographs (b-f) and nanoparticle dispersion (g) of Co for spent Ag1-Co1/YSZ.

Fig. 5. CO2-TGA (a), air-TGA (b), quantity of coke detected on typical samples (c) and Raman pattern (d) for typical spent Co/YSZ, Ag0.03-Co1/YSZ and Ag1-Co1/YSZ catalysts.

Fig. 6. TPSR plots of Co/YSZ, Ag0.03-Co1/YSZ and Ag1-Co1/YSZ, conducted under ambient pressure, CH4= CO2 = 15 mL min-1, T = 323-1173 K.

Fig. 7. (a) Activation energy and TOF value of Co/YSZ, Ag0.03-Co1/YSZ and Ag1-Co1/YSZ. (b-e) relationship among CH4 turnover rate and gas partial pressure (CH4, CO2, H2, CO). (f) TOF value and Ea for Co/YSZ, Ag0.03-Co1/YSZ and Ag1-Co1/YSZ

Fig. 8. Potential energy profiles along the reaction coordinate for DRM on representative fcc- Co(111) and Ag-Co(111) surfaces.

Fig. 9. (a) Gibbs free energy diagrams for DRM over Co (111) through CH+O path, Ag-Co(111) through C+O path at 1123 K. Flux analysis of DRM under experimental reactor inlet conditions (1123 K, 20 bar of total pressure, with a gas composition of 50% CH4, 50% CO2, 0% CO, 0% H2, and 0% H2O) over Ag-Co(111) (b), Co(111) (c). The arrows, which are labeled with the percentage of the total reaction flux, show the direction the reversible elementary steps actually proceed. The percentage of the reaction flux was calculated as the absolute value of the net rate for that elementary step divided by the rate for methane consumption.

Fig. 10. (a) The model of graphene island is semi-hexagonal and attached to a step edge. The total energy (E) of a graphene island, the edge and bulk energies on Co (b), and Ag-Co (c) as a function of number of C atoms Ntot. The dotted lines are bulk energy, the dashed lines are the edge energy, and the full lines are the total energy of the island. The red line indicates the critical island size.

References

[1]	L. A. Schulz, L. C. S. Kahle, K. H. Delgado, S. A. Schunk, A. Jentys, O. Deutschmann, J. A. Lercher, Appl. Catal. A, 2015, 504, 599-607.
[2]	A. Ramirez, K. Lee, A. Harale, L. Gevers, S. Telalovic, B. Al Solami, J. Gascon, ChemCatChem, 2020, 12, 5919-5925.
[3]	L. C. S. Kahle, T. Roussiere, L. Maier, K. H. Delgado, G. Wasserschaff, S. A. Schunk, O. Deutschmann, Ind. Eng. Chem. Res., 2013, 52, 14727-14727.
[4]	S. Helveg, C. López-Cartes, J. Sehested, P. L. Hansen, B. S. Clausen, J. R. Rostrup-Nielsen, F. Abild-Pedersen, J. K. Nørskov, Nature, 2004, 427, 426-429.
[5]	G. Zhang, J. Liu, Y. Xu, Y. Sun, Int. J. Hydrogen Energy, 2018, 43, 15030-15054.
[6]	F. Abild-Pedersen, J. K. Nørskov, J. R. Rostrup-Nielsen, J. Sehested, S. Helveg, Phys. Rev. B, 2006, 73, 115419.
[7]	S. L. Leung, J. Wei, W. L. Holstein, M. Avalos-Borja, E. Iglesia, J. Phys. Chem. C, 2020, 124, 20143-20160.
[8]	J. R. Rostrup-Nielsen, J. Catal., 1984, 85, 31-43.
[9]	F. Besenbacher, I. Chorkendorff, B. S. Clausen, B. Hammer, A. M. Molenbroek, J. K. Nørskov, I. Stensgaard, Science, 1998, 279, 1913-1915.
[10]	E. Nikolla, J. Schwank, S. Linic, J. Catal., 2009, 263, 220-227.
[11]	Q. Liu, Y. Liu, N. Zhou, P. Zhang, Z. Liu, E. I. Vovk, Y.-A. Zhu, Y. Yang, K. Zhu, Appl. Catal. B, 2023, 339, 123102.
[12]	Z. Liu, F. Gao, Y.-A. Zhu, Z. Liu, K. Zhu, X. Zhou, Chem. Commun., 2020, 56, 13536-13539.
[13]	B. Pant, S. M. Stagg-Williams, Catal. Commun., 2004, 5, 305-309.
[14]	S. Joo, K. Kim, O. Kwon, J. Oh, H. J. Kim, L. Zhang, J. Zhou, J.-Q. Wang, H. Y. Jeong, J. W. Han, G. Kim, Angew. Chem. Int. Ed, 2021, 60, 15912-15919.
[15]	T. Zhang, Y. Wu, J. Zhang, Q. Zhang, G. Yang, N. Tsubaki, Y. Tan, Appl. Surf. Sci., 2019, 479, 55-63.
[16]	Z. Alipour, M. Rezaei, F. Meshkani, J. Ind. Eng. Chem., 2014, 20, 2858-2863.
[17]	A. Di Giuliano, K. Gallucci, P. U. Foscolo, C. Courson, Int. J. Hydrogen Energy, 2019, 44, 6461-6480.
[18]	Y. Zhao, X. Min, Z. Ding, S. Chen, C. Ai, Z. Liu, T. Yang, X. Wu, Y.g. Liu, S. Lin, Z. Huang, P. Gao, H. Wu, M. Fang, Adv. Sci., 2020, 7, 1902051.
[19]	E. Solano, J. Dendooven, M. M. Minjauw, R. K. Ramachandran, K. Van de Kerckhove, T. Dobbelaere, D. Hermida-Merino, C. Detavernier, Nanoscale, 2017, 9, 18109-18109.
[20]	J. K. Nørskov, T. Bligaard, J. Rossmeisl, C. H. Christensen, Nat. Chem., 2009 , 1, 37-46.
[21]	B. Hammer, J. K. Nørskov, Adv. Catal., 2000, 45, 71-129.
[22]	N. Acerbi, S. C. E. Tsang, G. Jones, S. Golunski, P. Collier, Angew. Chem. Int. Ed., 2013, 52, 7737-7741.
[23]	M. T. Gorzkowski, A. Lewera, J. Phys. Chem. C, 2015, 119, 18389-18395.
[24]	X. Wu, Z. Shao, Q. Zhu, X. Hou, C. Wang, J. Zeng, K. Huang, S. Feng, ACS Catal., 2024, 14, 5888-5897.
[25]	Z. W. Chen, J. Li, P. Ou, J. E. Huang, Z. Wen, L. Chen, X. Yao, G. Cai, C. C. Yang, C. V. Singh, Q. Jiang, Nat. Commun., 2024, 15, 359-370.
[26]	G. Feng, F. Ning, Y. Pan, T. Chen, J. Song, Y. Wang, R. Zou, D. Su, D. Xia, J. Am. Chem. Soc., 2023, 145, 11140-11150.
[27]	N. A. K. Aramouni, J. G. Touma, B. Abu Tarboush, J. Zeaiter, M. N. Ahmad, Renewable Sustainable Energy Rev., 2018, 82, 2570-2585.
[28]	J. Li, C. Chen, L. Xu, Y. Zhang, W. Wei, E. Zhao, Y. Wu, C. Chen,, JACS Au, 2023, 3, 736-755.
[29]	J. Oh, S. Joo, C. Lim, H. J. Kim, F. Ciucci, J.-Q. Wang, J. W. Han, G. Kim, Angew. Chem. Int. Ed., 2022, 61, e202204990.
[30]	Z. Xia, S. Guo, Chem. Soc. Rev., 2019, 48, 3265-3278.
[31]	Q. Wang, H. Tang, M. Wang, L. Guo, S. Chen, Z. Wei, Chem. Commun., 2021, 57, 4047-4050.
[32]	J. Li, J. Luo, H. Chen, B. Qin, C. Yuan, N. Wu, G. Liu, X. Liu, Chem. Commun., 2022, 58, 9918-9921.
[33]	G. A. Somorjai, A. S. Mujumdar, Drying Technol., 1994, 13, 507-508.
[34]	A. Kanwal, A. Jalil, R. A. Raza, S. Ahmed, T. Zhao, A. Hassan, S. Z. Ilyas, J. Phys. Chem. Solids, 2024, 185, 111776.
[35]	P. Zhang, J. Yao, Y.-A. Zhu, Z. Liu, K. Zhu, ChemNanoMat, 2025, 11, e202400460.
[36]	W. Tu, M. Ghoussoub, C. V. Singh, Y.-H. C. Chin, J. Am. Chem. Soc, 2017, 139, 6928-6945.
[37]	J. G. Zhang, H. Wang, A. K. Dalai, J. Catal., 2007, 249, 300-310.
[38]	Z. X. Wu, B. Yang, S. Miao, W. Liu, J. L. Xie, S. Lee, M. J. Pellin, D. Q. Xiao, D. S. Su, D. Ma, ACS Catal., 2019, 9, 2693-2700.
[39]	C. Y. Jiang, E. Loisel, D. A. Cullen, J. A. Dorman, K. M. Dooley, J. Catal., 2021, 393, 215-229.
[40]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[41]	J. Wellendorff, K. T. Lundgaard, A. Møgelhøj, V. Petzold, D. D. Landis, J. K. Nørskov, T. Bligaard, K. W. Jacobsen, Phys. Rev. B, 2012, 85, 235149.
[42]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[43]	H. J. Monkhorst, J. D. Pack, Phys. Rev. B, 1976, 13, 5188-5192.
[44]	M. Methfessel, A. T. Paxton, Phys. Rev. B, 1989, 40, 3616-3621.
[45]	D. Sheppard, R. Terrell, G. Henkelman, J. Chem. Phys., 2008, 128, 134106.
[46]	A. J. Medford, C. Shi, M. J. Hoffmann, A. C. Lausche, S. R. Fitzgibbon, T. Bligaard, J. K. Nørskov, Catal. Lett., 2015, 145, 794-807.
[47]	Y. Huang, G. Cheng, M. Lei, M. Yang, D. Chen, X. Zhou, Y.-A. Zhu, ACS Catal., 2024, 14, 7978-7995.
[48]	P. J. Linstrom, W. G. Mallard, J. Chem. Eng. Data, 2001, 46, 1059-1063.
[49]	S. R. Bahn, K. W. Jacobsen, Comput. Sci. Eng., 2002, 4(3), 56-66.
[50]	L. Xiao, F. Ma, Y.-A. Zhu, Z. Sui, J. Zhou, X. Zhou, D. Chen, W. Yuan, Chem. Eng. J., 2019, 377, 120049.
[51]	W. Kiatkittipong, T. Tagawa, S. Goto, S. Assabumrungrat, K. Silpasup, P. Praserthdam, Chem. Eng. J., 2005, 115, 63-71.
[52]	D. L. King, J. J. Strohm, X. Wang, H.-S. Roh, C. Wang, Y.-H. Chin, Y. Wang, Y. Lin, R. Rozmiarek, P. Singh, J. Catal., 2008, 258, 356-365.
[53]	W. Jamsak, S. Assabumrungrat, P. L. Douglas, N. Laosiripojana, R. Suwanwarangkul, S. Charojrochkul, E. Croiset, Chem. Eng. J., 2007, 133, 187-194.
[54]	C. Deng, H. Jiang, J. Zhao, L. Zhang, J. He, J. Mater. Sci., 2021, 56, 3455-3471.
[55]	Z. Zhao, A. Fisher, D. Cheng, Nanotechnology, 2016, 27, 115702.
[56]	F. Zhang, Z. Liu, S. Zhang, N. Akter, R. M. Palomino, D. Vovchok, I. Orozco, D. Salazar, J. A. Rodriguez, J. Llorca, J. Lee, D. Kim, W. Xu, A. I. Frenkel, Y. Li, T. Kim, S. D. Senanayake, ACS Catal. 2018, 8, 3550-3560.
[57]	J. Greeley, J. K. Nørskov, Surf. Sci., 2005, 592, 104-111.
[58]	I. Karakaya, W. T. Thompson, Bull. Alloy Phase Diagr, 1986, 7, 259-263.
[59]	A. Holewinski, J.-C. Idrobo, S. Linic, Nat. Chem., 2014, 6, 828-834.
[60]	A. V. Ruban, H. L. Skriver, J. K. Nørskov, Phys. Rev. B, 1999, 59, 15990-16000.
[61]	M. Karatok, M. G. Sensoy, E. I. Vovk, H. Ustunel, D. Toffoli, E. Ozensoy, ACS Catal., 2021, 11, 6200-6209.
[62]	A. Nagy, G. Mestl, Appl. Catal. A, 1999, 188, 337-353.
[63]	V. K. Kaushik, J. Electron. Spectrosc. Relat. Phenom., 1991, 56, 273-277.
[64]	G. Corro, E. Vidal, S. Cebada, U. Pal, F. Bañuelos, D. Vargas, E. Guilleminot, Appl. Catal. B, 2017, 216, 1-10.
[65]	G. Schön, Acta Chem. Scand., 1973, 27, 2623-2633.
[66]	A. M. Ferraria, A. P. Carapeto, A. M. Botelho do Rego, Vacuum, 2012, 86, 1988-1991.
[67]	G. Ortega, E. German, M. J. Lopez, J. A. Alonso, Int. J. Hydrogen Energy, 2022, 47, 19038-19050.
[68]	A. J. Medford, A. Vojvodic, J. S. Hummelshøj, J. Voss, F. Abild-Pedersen, F. Studt, T. Bligaard, A. Nilsson, J. K. Nørskov, J. Catal., 2015, 328, 36-42.
[69]	R. Yao, J. Pinals, R. Dorakhan, J. E. Herrera, M. Zhang, P. Deshlahra, Y.-H. C. Chin, ACS Catal., 2022, 12, 12227-12245.
[70]	A. H. Dam, H. M. Wang, R. Dehghan-Niri, X. F. Yu, J. C. Walmsley, A. Holmen, J. Yang, D. Chen, ChemCatChem, 2019, 11, 3401-3412.
[71]	M. Yu, Y.-A. Zhu, Y. Lu, G. Tong, K. Zhu, X. Zhou, Appl. Catal. B, 2015, 165, 43-56.
[72]	N. V. Parizotto, K. O. Rocha, S. Damyanova, F. B. Passos, D. Zanchet, C. M. P. Marques, J. M. C. Bueno, Appl. Catal. A, 2007, 330, 12-22.
[73]	I. Parsina, F. Baletto, J. Phys. Chem. C, 2010, 114, 1504-1511.
[74]	C. Weidenthaler, Nanoscale, 2011, 3, 792-810.
[75]	M. S. Dresselhaus, G. Dresselhaus, R. Saito, A. Jorio, Phys. Rep., 2005, 409, 47-99.
[76]	L. M. Malard, M. A. Pimenta, G. Dresselhaus, M. S. Dresselhaus, Phys. Rep., 2009, 473, 51-87.
[77]	T. Zhang, Z. Liu, Y.-A. Zhu, Z. Liu, Z. Sui, K. Zhu, X. Zhou, Appl. Catal. B, 2020, 264, 118497.
[78]	J. Wei, E. Iglesia, J. Catal., 2004, 224, 370-383.
[79]	B. V. Ayodele, S. S. Hossain, S. S. Lam, O. U. Osazuwa, M. R. Khan, C. K. Cheng, J. Nat. Gas Sci. Eng., 2016, 34, 873-885
[80]	H. S. Bengaard, J. K. Nørskov, J. Sehested, B. S. Clausen, L. P. Nielsen, A. M. Molenbroek, J. R. Rostrup-Nielsen, J. Catal., 2002, 209, 365-384.
[81]	J. R. Rostrup-Nielsen, Catal. Today, 2000, 63, 159-164.