An active and durable anode catalytic layer with in-situ exsolved Pd-Ni nanoparticles for protonic ceramic fuel cells on hydrocarbon fuels

doi:10.1016/S1872-2067(25)64913-8

Abstract

Abstract:

Operating hydrocarbons on protonic ceramic fuel cells (PCFCs) is promising and attractive, on account of their high energy conversion efficiency and potential for low carbon emissions compared to traditional thermal power generation. However, poor coking tolerance and insufficient catalytic activity at intermediate temperatures greatly hinder the development of PCFCs on hydrocarbons. Exploring a catalytic layer with high activity and durability is an effective way to achieve high-performance PCFCs on hydrocarbon fuels. Herein, we report an anode catalytic layer (ACL) with an optimized formula of Pd_0.01Ni_0.09Ce_1.9O_2-_δ (P1NC). Pd-Ni alloy nanoparticles are exsolved from the ACL under a hydrogen atmosphere. The high oxygen vacancy concentration in P1NC has shown a positive effect on the oxygen storage capacity, which may facilitate carbon gasification, thereby reducing performance degradation during PCFC operation, as supported by the Raman and scanning electron microscopy observations. PCFCs with this ACL achieved a decent peak power density (P_max) of 1.20 W cm^-2 and stably operated at 0.2 A cm^-2 at 650 °C on CH₄. In addition, the cells with P1NC ACL exhibited encouraging P_max of 1.00 and 0.87 W cm^-2 at 650 °C on liquid fuels such as methanol and ethanol, respectively, exhibiting good fuel flexibility.

Key words: Protonic ceramic fuel cells, Steam methane reforming, Anode catalytic layer, Pd-Ni nanoparticles, Fuel flexibility

Wenjie Gong, Yangsen Xu, Hao Liu, Wanbin Lin, Zhiwei Du, Yixuan Huang, Jiang Liu, Yu Chen. An active and durable anode catalytic layer with in-situ exsolved Pd-Ni nanoparticles for protonic ceramic fuel cells on hydrocarbon fuels[J]. Chinese Journal of Catalysis, 2026, 82: 125-134.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64913-8

https://www.cjcatal.com/EN/Y2026/V82/I3/125

Figures/Tables 4

Fig. 1. Micro-structure and characterizations of reduced P1NC catalyst. (a) XRD patterns of P2NC, P1NC, NC, and CeO2 powder after reduction. (b) Corresponding enlarged scanning range of 2θ from 40° to 55°. (c) AC-TEM image of the reduced P1NC. (d) HAADF and EDS elemental mappings of reduced P1NC. (e) The fitted XPS spectra of Pd 3d for reduced P1NC. (f) The fitted Ni 2p spectra for reduced P1NC. (g) The fitted Ce 3d spectra for reduced P1NC and CeO2. (h) The O 1s spectra for reduced P1NC and CeO2.

Fig. 2. P1NC catalyst enhances catalytic activity for SMR. (a) Equilibrium composition analysis for steam methane reforming (CH4:H2O = 1:2). (b) Gibbs free energy as a function of temperature of relevant reactions during SMR. (c) Schematic of symmetrical anode cell, tested with humidified CH4 (66.7% H2O). (d) EIS curves of the bare anode and anode with P1NC ACL tested in humidified H2 (3% H2O) or humidified CH4 (66.7% H2O). (e) DRT plots of EIS of the bare anode or the anode with P1NC ACL in humidified CH4 (66.7% H2O) at 650 °C. (f) Arrhenius plot of Rp values of bare anode and anode with catalytic layers of P1NC, P2NC, and NC.

Fig. 3. Electrochemical performance of single cells (P1NC | Ni-BZCYYb4411 | BZCYYb4411 | PBSCF). (a) Schematic illustration of the PCFCs with the P1NC ACL. (b) I-V-P curves of a single cell with the P1NC ACL, employing humidified CH4 (66.7% H2O) as fuel. (c) Comparison of ohmic resistance (Rohm) and Rp of single cells with and without the P1NC ACL. (d) I-V-P curves of a single cell with the P1NC ACL, employing an evaporated mixture of molar ratio H2O:CH3OH:N2 of 1:1:1 as fuel. (e) I-V-P curves of a single cell with the P1NC ACL, employing an evaporated mixture of molar ratio H2O:C2H5OH:N2 of 3:1:3 as fuel. (f) Comparison of Pmax of state-of-the-art hydrocarbon-SOFCs at 600 °C.

Fig. 4. Analyses of electrochemical performance and coking tolerance of PCFC with P1NC ACL. (a) Short term durability of PCFC with P1NC ACL fueled by methane, methanol, and ethanol. (b) Schematic illustration of characterizations on PCFCs with the bare anode using Raman spectroscopy. Raman mapping of D-band (c) and G-band (d) for PCFC with bare anode after durability evaluation on humidified methane (66.7% H2O) at 650 °C. (e) Schematic illustration of characterization on PCFCs with the P1NC ACL. Raman mapping of D-band (f) and G-band (g) for P1NC ACL after short term test on CH4 at 650 °C.

References

[1]	F. Liu, D. Diercks, P. Kumar, A. Seong, M. H. A. Jabbar, C. Gumeci, Y. Furuya, N. Dale, T. Oku, M. Usuda, P. Kazempoor, I. Ghamarian, L. Liu, L. Fang, D. Chen, Z. Wang, S. Skinner, C. Duan, Sci. Adv., 2025, 11, eadq2507.
[2]	H. Tian, Z. Luo, Y. Song, Y. Zhou, M. Gong, W. Li, Z. Shao, M. Liu, X. Liu, Int. Mater. Rev., 2023, 68, 272-300.
[3]	C. Duan, J. Tong, M. Shang, S. Nikodemski, M. Sanders, S. Ricote, A. Almansoori, R. O’Hayre, Science, 2015, 349, 1321-1326.
[4]	Y. Chen, S. Yoo, W. Zhang, J. H. Kim, Y. Zhou, K. Pei, N. Kane, B. Zhao, R. Murphy, Y. Choi, M. Liu, ACS Catal., 2019, 9, 7137-7142.
[5]	Y. Chen, S. Yoo, Y. Choi, J. H. Kim, Y. Ding, K. Pei, R. Murphy, Y. Zhang, B. Zhao, W. Zhang, H. Chen, Y. Chen, W. Yuan, C. Yang, M. Liu, Energy Environ. Sci., 2018, 11, 2458-2466.
[6]	W. Bian, W. Wu, B. Wang, W. Tang, M. Zhou, C. Jin, H. Ding, W. Fan, Y. Dong, J. Li, D. Ding, Nature, 2022, 604, 479-485.
[7]	F. Liu, H. Deng, D. Diercks, P. Kumar, M. H. A. Jabbar, C. Gumeci, Y. Furuya, N. Dale, T. Oku, M. Usuda, P. Kazempoor, L. Fang, D. Chen, B. Liu, C. Duan, Nat. Energy, 2023, 8, 1145-1157.
[8]	H. Zhang, Y. Zhou, K. Pei, Y. Pan, K. Xu, Y. Ding, B. Zhao, K. Sasaki, Y. Choi, Y. Chen, M. Liu, Energy Environ. Sci., 2022, 15, 287-295.
[9]	H. Zhang, K. Xu, Y. Xu, F. He, F. Zhu, K. Sasaki, Y. Choi, Y. Chen, Energy Environ. Sci., 2024, 17, 3433-3442.
[10]	Y. Choi, E. C. Brown, S. M. Haile, W. Jung, Nano Energy, 2016, 23, 161-171.
[11]	C. Duan, R. J. Kee, H. Zhu, C. Karakaya, Y. Chen, S. Ricote, A. Jarry, E. J. Crumlin, D. Hook, R. Braun, N. P. Sullivan, R. O’Hayre, Nature, 2018, 557, 217-222.
[12]	S. H. Hwang, S. K. Kim, J.-T. Nam, J.-S. Park, Int. J. Hydrogen Energy, 2021, 46, 33551-33560.
[13]	Y. Chen, B. de Glee, Y. Tang, Z. Wang, B. Zhao, Y. Wei, L. Zhang, S. Yoo, K. Pei, J. H. Kim, Y. Ding, P. Hu, F. F. Tao, M. Liu, Nat. Energy, 2018, 3, 1042-1050.
[14]	D. Konwar, H. H. Yoon, J. Mater. Chem. A, 2016, 4, 5102-5106.
[15]	F. Liu, H. Deng, H. Ding, P. Kazempoor, B. Liu, C. Duan, Joule, 2023, 7, 1308-1332.
[16]	T. Tan, Z. Wang, K. Huang, C. Yang, ACS Nano, 2023, 17, 13985-13996.
[17]	L. Yang, Y. Choi, W. Qin, H. Chen, K. Blinn, M. Liu, P. Liu, J. Bai, T. A. Tyson, M. Liu, Nat. Commun., 2011, 2, 357.
[18]	S. De, J. Zhang, R. Luque, N. Yan, Energy Environ. Sci., 2016, 9, 3314-3347.
[19]	S. Zha, A. Moore, H. Abernathy, M. Liu, J. Electrochem. Soc., 2004, 151, A1128-A1133.
[20]	K. Hong, M. Choi, Y. Bae, J. Min, J. Lee, D. Kim, S. Bang, H.-K. Lee, W. Lee, J. Hong, Nat. Commun., 2023, 14, 7485.
[21]	P. Schwach, X. Pan, X. Bao, Chem. Rev., 2017, 117, 8497-8520.
[22]	J.-C. Zhang, B.-H. Ge, T.-F. Liu, Y.-Z. Yang, B. Li, W.-Z. Li, ACS Catal., 2020, 10, 783-791.
[23]	D. Pakhare, J. Spivey, Chem. Soc. Rev., 2014, 43, 7813-7837.
[24]	N. Bion, D. Duprez, F. Epron, ChemSusChem, 2012, 5, 76-84.
[25]	V. L. Dagle, R. Dagle, L. Kovarik, A. Genc, Y.-G. Wang, M. Bowden, H. Wan, M. Flake, V.-A. Glezakou, D. L. King, R. Rousseau, Appl. Catal. B, 2016, 184, 142-152.
[26]	J. Ashok, N. Dewangan, S. Das, P. Hongmanorom, M.-H. Wai, K. Tomishige, S. Kawi, Fuel Process. Technol., 2020, 199, 106252.
[27]	A. Yamaguchi, E. Iglesia, J. Catal., 2010, 274, 52-63.
[28]	M. Li, A. C. van Veen, Appl. Catal. B, 2018, 237, 641-648.
[29]	B. Steinhauer, M. R. Kasireddy, J. Radnik, A. Martin, Appl. Catal. A, 2009, 366, 333-341.
[30]	J. Lucas, N. S. Padmanabha Naveen, M. J. Janik, K. Alexopoulos, G. Noh, D. Aireddy, K. Ding, J. A. Dorman, K. M. Dooley, ACS Catal., 2024, 14, 9115-9133.
[31]	L. R. Winter, R. Chen, X. Chen, K. Chang, Z. Liu, S. D. Senanayake, A. M. Ebrahim, J. G. Chen, Appl. Catal. B, 2019, 245, 360-366.
[32]	M. Zhu, P. Tian, X. Cao, J. Chen, T. Pu, B. Shi, J. Xu, J. Moon, Z. Wu, Y.-F. Han, Appl. Catal. B, 2021, 282, 119561.
[33]	T. Zheng, J. He, Y. Zhao, W. Xia, J. He, J. Rare Earths, 2014, 32, 97-107.
[34]	Y. Song, Y. Zhao, G. Nan, W. Chen, Z. Guo, S. Li, Z. Tang, W. Wei, Y. Sun, Appl. Catal. B, 2020, 270, 118888.
[35]	S. Chen, S. Li, R. You, Z. Guo, F. Wang, G. Li, W. Yuan, B. Zhu, Y. Gao, Z. Zhang, H. Yang, Y. Wang, ACS Catal., 2021, 11, 5666-5677.
[36]	H. Wang, G. Cui, H. Lu, Z. Li, L. Wang, H. Meng, J. Li, H. Yan, Y. Yang, M. Wei, Nat. Commun., 2024, 15, 3765.
[37]	F. Jiang, S. Wang, B. Liu, J. Liu, L. Wang, Y. Xiao, Y. Xu, X. Liu, ACS Catal., 2020, 10, 11493-11509.
[38]	B. Safavinia, Y. Wang, C. Jiang, C. Roman, P. Darapaneni, J. Larriviere, D. A. Cullen, K. M. Dooley, J. A. Dorman, ACS Catal., 2020, 10, 4070-4079.
[39]	J. Li, Z. Liu, D. A. Cullen, W. Hu, J. Huang, L. Yao, Z. Peng, P. Liao, R. Wang, ACS Catal., 2019, 9, 11088-11103.
[40]	R. K. Singha, A. Yadav, A. Shukla, M. Kumar, R. Bal, Catal. Commun., 2017, 92, 19-22.
[41]	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.
[42]	J.-S. Park, N. H. Hao, Int. J. Hydrogen Energy, 2023, 48, 19207-19216.
[43]	X. Yin, L. Shen, S. Wang, B. Wang, C. Shen, Appl. Catal. B, 2022, 301, 120816.
[44]	S. Sun, O. Awadallah, Z. Cheng, J. Power Sources, 2018, 378, 255-263.
[45]	S. Choi, C. J. Kucharczyk, Y. Liang, X. Zhang, I. Takeuchi, H.-I. Ji, S. M. Haile, Nat. Energy, 2018, 3, 202-210.
[46]	L. Lei, J. M. Keels, Z. Tao, J. Zhang, F. Chen, Appl. Energy, 2018, 224, 280-288.
[47]	X. Zhang, K. Yim, J. Kim, D. Wu, S. Ha, Appl. Catal. B, 2022, 310, 121250.
[48]	V. Sonn, A. Leonide, E. Ivers-Tiffée, J. Electrochem. Soc., 2008, 155, B675-B679.
[49]	Y. Wang, Q. Shen, Y. Tong, Z. Zhan, Int. J. Hydrogen Energy, 2022, 47, 6827-6836.
[50]	X. Meng, Z. Zhan, X. Liu, H. Wu, S. Wang, T. Wen, J. Power Sources, 2011, 196, 9961-9964.
[51]	M. Liu, R. Peng, D. Dong, J. Gao, X. Liu, G. Meng, J. Power Sources, 2008, 185, 188-192.
[52]	K. Xu, H. Zhang, W. Deng, Y. Liu, Y. Ding, Y. Zhou, M. Liu, Y. Chen, Sci. Bull., 2023, 68, 2574-2582.