Proton Ceramic Membrane Reactor: Preparation and Low-temperature Ammonia Decomposition Performance

doi:10.15541/jim20250057

Abstract

Abstract:

Ammonia (NH₃) has been considered as a hydrogen storage material due to high hydrogen storage density and ease of liquefaction, thus hydrogen (H₂) production by ammonia decomposition is an ideal method for hydrogen preparation. However, traditional ammonia decomposition technologies face challenges such as high operating temperatures, low efficiency at moderate temperatures, and difficulties in hydrogen purification. In this study, proton ceramic membrane reactor (PCMR) with symmetric structure of porous electrode Ni-BZCY/BZCY/Ni-BZCY (BZCY: BaZr_0.1Ce_0.7Y_0.2O_3-_δ) was prepared by co-pressing method. At 600 ℃, PCMR exhibited polarization resistances (R_p) of 0.11 and 0.23 Ω·cm² in H₂ and NH₃ atmospheres, respectively, with corresponding current densities of 1.87 and 1.56 A·cm^-2 at an applied voltage of 0.8 V. Even at 300 ℃ and 0.8 V, the current densities in H₂ and NH₃ remained at 0.16 and 0.06 A·cm^-2, respectively. The NH₃ conversion efficiency of PCMR reached 80% at 600 ℃, improving by 8% compared to bare catalyst material. Even at 350 ℃, an additional improvement of 0.3% can still be attained, and the NH₃ conversion efficiency of about 1% was demonstrated even at 300 ℃. This study provides a novel approach to low-temperature ammonia decomposition for hydrogen production.

Key words: hydrogen production, ammonia decomposition, low-temperature, proton ceramic membrane reactor, electrochemical property, proton transport

CLC Number:

TK91

TANG Yang, LIU Limin, ZHOU Xiaoliang, ZHANG Bo, JIANG Xingzhou, JIA Haoyi, LUO Yanlinqing. Proton Ceramic Membrane Reactor: Preparation and Low-temperature Ammonia Decomposition Performance[J]. Journal of Inorganic Materials, 2025, 40(11): 1277-1284.

Figures/Tables 12

Fig. 1 Schematic diagram of the PCMR test setup

Fig. 2 XRD patterns of samples (a) BZCY calcined at 1000 ℃ for 5 h in air and calcined at 400 and 600 ℃ for 4 h in NH3; (b) NiO-BZCY and Ni-BZCY treated with H2 and NH3 for 4 h at 400 ℃

Fig. 3 SEM images of (a) cross-section, (b) electrolyte, and (c, d) electrodes on both sides of PCMR, and (e-j) EDS elemental mappings of NiO-BZCY electrode

Fig. 4 LSV results under (a) H2 and (b) NH3 environments for PCMR

Table 1 Current density of partially symmetrical PCMR

Reactor structure	Temperature/℃, gas environment	Voltage/V	Current density/ (A·cm^-2)	Ref.
Ni-BZCY/BZCY/Ni-BZCY	650, 50% H₂-N₂(measured at only 650 ℃)	0.8	2.0	[18]
LSV-Ce-Pd/BZCYCu/LSV-Ce-Pd	600, H₂(3% H₂O)	1.0	0.92	[31]
Ni-BZCY/BZCY/Ni-BZCY	450, 60% H₂(maximum testing temperature of 450 ℃)	1.0	0.53	[32]
Ni-BZCYYb/BZCYYb/Ni-BZCYYb	600, 50% H₂-N₂	0.8	1.78	[30]
Ni-BZCY/BZCY/Ni-BZCY	600, H₂(3% H₂O)	0.8	1.87	This work
Ni-BZCY/BZCY/Ni-BZCY	600, NH₃	0.8	1.56	This work

Fig. 5 EIS plots under (a) H2 and (b) NH3 environments for PCMR

Table 2 Resistances under H2 and NH3 environments for PCMR (Ω·cm2)

Temperature/℃	H₂			NH₃
Temperature/℃	R_total	R_Ω	R_p	R_total	R_Ω	R_p
600	0.48	0.37	0.11	0.67	0.44	0.23
500	0.72	0.47	0.25	1.28	0.61	0.67
400	1.98	0.81	1.17	3.31	1.09	2.22
300	9.23	1.54	7.69	17.31	2.80	14.51

Fig. 6 Arrhenius curves of temperature vs. Rp, RΩ and Rtotal of PCMR under (a) H2 and (b) NH3 environments

Fig. 7 Stability testing in different gas environments at 400 ℃ and 0.6 V for PCMR

Fig. 8 Variation in impedance before and after stability testing under NH3 environment for PCMR

Fig. 9 DRT curves before and after stability testing under NH3 environment for PCMR

Fig. 10 NH3 conversion efficiency of Ni-BZCY powder and PCMR operated at 0.8 V

References 12

[13]	LI Y F, ZHANG W S, REN J, et al. Ammonia decomposition for carbon-free hydrogen production over Ni/Al-Ce catalysts: synergistic effect between Al and Ce. Fuel, 2024, 358: 130176. DOI URL
[14]	BUONOMENNA M G. Proton-conducting ceramic membranes for the production of hydrogen via decarbonized heat: overview and prospects. Hydrogen, 2023, 4(4): 807. DOI URL
[15]	WANG H N, WANG X B, MENG B, et al. Perovskite-based mixed protonic-electronic conducting membranes for hydrogen separation: recent status and advances. Journal of Industrial and Engineering Chemistry, 2018, 60: 297. DOI URL
[16]	LI N N, ZARKADOULAS A, KYRIAKOU V. Opportunities and challenges for direct electrification of chemical processes with protonic ceramic membrane reactors. Progress in Energy, 2024, 6(4): 043007. DOI
[17]	LI F R, DUAN G X, WANG Z G, et al. Highly efficient recovery of hydrogen from dilute H₂-streams using BaCe_0.7Zr_0.1Y_0.2O_3-_δ/ Ni-BaCe_0.7Zr_0.1Y_0.2O_3-_δ dual-layer hollow fiber membrane. Separation and Purification Technology, 2022, 287: 120602. DOI URL
[18]	WANG Q J, LUO T, TONG Y C, et al. Large-area protonic ceramic cells for hydrogen purification. Separation and Purification Technology, 2022, 295: 121301. DOI URL
[19]	TONG Y C, WANG Y, CUI C S, et al. Preparation and characterization of symmetrical protonic ceramic fuel cells as electrochemical hydrogen pumps. Journal of Power Sources, 2020, 457: 228036. DOI URL
[20]	LIANG M Z, SONG Y F, XIONG B C, et al. In situ exsolved CoFeRu alloy decorated perovskite as an anode catalyst layer for high-performance direct-ammonia protonic ceramic fuel cells. Advanced Functional Materials, 2024, 34(48): 2408756. DOI URL
[21]	曹希文, 罗凌虹, 曾小军, 等. 固体氧化物燃料电池Ni基阳极抗积碳的研究进展. 陶瓷学报, 2024, 45(1): 72.
[22]	蓝海洋, 陈星余, 张博, 等. 固体氧化物直接氨燃料电池阳极材料的研究进展. 陶瓷学报, 2023, 44(6): 1078.
[23]	PENG C X, ZHAO B X, MENG X, et al. Effect of NiO addition on the sintering and electrochemical properties of BaCe_0.55Zr_0.35Y_0.1O_3-_δ proton-conducting ceramic electrolyte. Membranes, 2024, 14(3): 61. DOI URL
[24]	DANILOV N A, STAROSTINA I A, STAROSTIN G N, et al. Fundamental understanding and applications of protonic Y- and Yb-coped Ba(Ce, Zr)O₃ perovskites: state-of-the-art and perspectives. Advanced Energy Materials, 2023, 13(47): 2302175. DOI URL
[25]	YANG Y M, LU J C, ZHANG X Y, et al. Symmetry-induced modulation of proton conductivity in Y-doped Ba(Zr, Ce)O₃: insights from Raman spectroscopy. Journal of Materials Chemistry A, 2024, 12(21): 12599. DOI URL
[26]	ZHANG J H, LU X T, MAO H Y, et al. Effect of sintering additives on sintering behavior and conductivity of BaZr_0.1Ce_0.7Y_0.2O_3-_δ electrolytes. Journal of Inorganic Materials, 2025, 40(1): 84. DOI URL
[27]	ZHU D C, LIU Z Q, ZHU C J, et al. Construction of a novel BaZr_0.1Ce_0.7Y_0.2O_3-_δ-SnO₂ heterojunction composite electrolyte for advanced semiconductor ion fuel cells operating at lower temperature down to 350 ℃. Chemical Engineering Journal, 2025, 505: 159368. DOI URL
[28]	HOU J, GONG J Y, BI L. Advancing cathodic electrocatalysis via an in situ generated dense active interlayer based on CuO₅ pyramid-structured Sm₂Ba_1.33Ce_0.67Cu₃O₉. Journal of Materials Chemistry A, 2022, 10(30): 15949. DOI URL
[29]	HOU J, DONG K, MIAO L N, et al. Rationally structuring proton-conducting solid oxide fuel cell anode with Ni metal catalyst and porous skeleton. Ceramics International, 2020, 46(15): 24038. DOI URL
[30]	ZHANG G J, CHEN T, GUO Z Z, et al. A 10 × 10 cm² protonic ceramic electrochemical hydrogen pump for efficient and durable hydrogen purification. Chemical Engineering Journal, 2024, 495: 153521. DOI URL
[31]	CHOI J, SHIN M, KIM B, et al. High-performance ceramic composite electrodes for electrochemical hydrogen pump using protonic ceramics. International Journal of Hydrogen Energy, 2017, 42(18): 13092. DOI URL
[32]	MUSHTAQ U, WELZEL S, SHARMA R K, et al. Development of electrode-supported proton conducting solid oxide cells and their evaluation as electrochemical hydrogen pumps. ACS Applied Materials & Interfaces, 2022, 14(34): 38938.
[1]	SADEQ A M, HOMOD R Z, HUSSEIN A K, et al. Hydrogen energy systems: technologies, trends, and future prospects. Science of the Total Environment, 2024, 939: 173622. DOI URL
[2]	YUE M L, LAMBERT H, PAHON E, et al. Hydrogen energy systems: a critical review of technologies, applications, trends and challenges. Renewable and Sustainable Energy Reviews, 2021, 146: 111180. DOI URL
[3]	AGYEKUM E B, ODOI-YORKE F, ABBEY A A, et al. A review of the trends, evolution, and future research prospects of hydrogen fuel cells-a focus on vehicles. International Journal of Hydrogen Energy, 2024, 72: 918. DOI URL
[4]	LI N, ZHANG C, LI D, et al. Review of reactor systems for hydrogen production via ammonia decomposition. Chemical Engineering Journal, 2024, 495: 153125. DOI URL
[5]	ZAINAL N A, ZULKIFLI N W M, GULZAR M, et al. A review on the chemistry, production, and technological potential of bio-based lubricants. Renewable and Sustainable Energy Reviews, 2018, 82: 80. DOI URL
[6]	LIANG D T, FENG C, XU L, et al. Promotion effects of different methods in CO_x-free hydrogen production from ammonia decomposition. Catalysis Science & Technology, 2023, 13(12): 3614.
[7]	ZHANG X S, LIU Y T, WANG Y Y, et al. Self-assembled platinum-iridium alloy aerogels and their efficient electrocatalytic ammonia oxidation performance. Journal of Inorganic Materials, 2023, 38(5): 511. DOI
[8]	MUKHERJEE S, DEVAGUPTAPU S V, SVIRIPA A, et al. Low-temperature ammonia decomposition catalysts for hydrogen generation. Applied Catalysis B: Environmental, 2018, 226: 162. DOI URL
[9]	LIAN M L, SU J X, HUANG H Y, et al. Supported Ni catalysts from Ni-Mg-Al hydrotalcite-like compounds: preparation and catalytic performance for ammonia decomposition. Journal of Inorganic Materials, 2025, 40(1): 53. DOI URL
[10]	SUN S C, JIANG Q Q, ZHAO D Y, et al. Ammonia as hydrogen carrier: advances in ammonia decomposition catalysts for promising hydrogen production. Renewable and Sustainable Energy Reviews, 2022, 169: 112918. DOI URL
[33]	YUN J, XIONG G, KIM S, et al. Understanding direct-ammonia protonic ceramic fuel cells: high-performance in the absence of precious metal catalysts. ACS Energy Letters, 2024, 9(11): 5520. DOI URL
[34]	ZHOU Y C, LIU E Z, CHEN Y, et al. An active and robust air electrode for reversible protonic ceramic electrochemical cells. ACS Energy Letters, 2021, 6(4): 1511.
[11]	CECHETTO V, DI FELICE L, MARTINEZ G R, et al. Ultra-pure hydrogen production via ammonia decomposition in a catalytic membrane reactor. International Journal of Hydrogen Energy, 2022, 47(49): 21220. DOI URL
[12]	SHEN M H, AI F J, MA H L, et al. Progress and prospects of reversible solid oxide fuel cell materials. iScience, 2021, 24(12): 103464. DOI URL