Mechanism Study on the Difference in Ammonia Decomposition Performance between Co Catalysts Supported on Y2O3 and Al2O3

doi:10.12422/j.issn.1006-396X.2026.04.002

Journal of Petrochemical Universities ›› 2026, Vol. 39 ›› Issue (4): 13-21.DOI: 10.12422/j.issn.1006-396X.2026.04.002

• Catalysts and Catalytic Materials • Previous Articles Next Articles

Mechanism Study on the Difference in Ammonia Decomposition Performance between Co Catalysts Supported on Y₂O₃ and Al₂O₃

Yiru CAO¹(), Huilin XU¹, Jianyu LI¹, Yingying JIN¹, Yan LUO², Hongfeng CHEN², Yong CHEN³, Xuesong LIU¹()

^1.College of Chemistry and Chemical Engineering，Shaoxing University，Shaoxing Zhejiang 312000，China
^2.Shaoxing Institute of Quality & Technical Supervision and Testing，Shaoxing Zhejiang 312000，China
^3.Zhejiang Hailiang Environmental Materials Co. ，Ltd. ，Zhuji Zhejiang 311800，China

Received:2025-10-20 Revised:2025-12-08 Published:2026-08-25 Online:2026-07-20
Contact: Xuesong LIU

Y₂O₃与Al₂O₃负载钴催化剂的氨分解性能差异机理研究

曹艺茹¹(), 许慧琳¹, 李建宇¹, 金莹莹¹, 罗燕², 陈洪锋², 陈勇³, 刘雪松¹()

^1.绍兴大学化学化工学院，浙江绍兴 312000
^2.绍兴市质量技术监督检测院，浙江绍兴 312000
^3.浙江海亮环境材料有限公司，浙江诸暨 311800

通讯作者: 刘雪松
作者简介:曹艺茹（2003-），女，硕士研究生，从事能源环境材料方面的研究；E-mail：1007003320@qq.com。
基金资助:
国家自然科学基金项目(52370115);国家级大学生创新项目(202410349068);浙江省基础公益研究计划项目(LTGS23B070002);诸暨市科技计划项目(2023J07)

Abstract

Abstract:

Hydrogen production via ammonia decomposition is a crucial pathway toward achieving a "carbon-neutral society", and its catalytic efficiency is significantly influenced by the regulation of support materials. Based on the similar electronic structures of Al and Y elements, which belong to the main group and the subgroup (transition metal group) respectively, the differentiation mechanisms of Y?O? and Al?O? supports in cobalt-based catalysts were systematically compared.Catalyst characterization was performed using XRD, BET, SEM, XPS, H₂-TPR, and NH₃-TPD. The results show that although both Al and Y are trivalent, Y, as a rare-earth transition element, possesses a unique 4f electron configuration, which endows Y₂O₃ with richer oxygen vacancies and stronger electron-donating ability, significantly promoting the formation and dispersion of active Co²⁺ species. The 10Co/Y₂O₃ catalyst achieves an ammonia conversion of 100% at 700 ℃, and its specific surface area activity is 3.2 times that of 10Co/Al₂O₃. Although Al₂O₃ exhibits higher specific surface area and thermal stability, the spinel phase CoAl₂O₄ formed between the main-group element Al and Co shows low activity. This study provided new insights for the rational design of catalysts based on the periodic law.

Key words: Ammonia decomposition, Cobalt-based catalyst, Support effect, Y₂O₃, Main and subgroup elements

摘要：

氨分解制氢是实现“碳中和社会”的重要路径，其催化效率受载体材料调控作用的显著影响。基于Al和Y元素电子结构相似但分属主族和副族的特性，系统对比了Y₂O₃和Al₂O₃载体在Co基催化剂中的差异化机制；通过XRD、BET、SEM、XPS、H₂-TPR、NH₃-TPD对催化剂进行了表征。结果表明，虽然Al和Y均为+3价，但Y作为稀土副族元素，其独特的4f电子构型使Y₂O₃载体具有更丰富的氧空位和更强的电子给体能力，显著促进了活性Co²⁺物种的形成和分散；虽然Al₂O₃具有更高的比表面积和热稳定性，但主族元素Al与Co形成的CoAl₂O₄尖晶石相活性较低；10Co/Y₂O₃在700 ℃时氨转化率达100%，单位比表面积活性为10Co/Al₂O₃的3.2倍。研究结果为基于元素周期律的理性设计催化剂提供了新思路。

关键词: 氨分解, Co基催化剂, 载体效应, Y₂O₃, 主副族元素

CLC Number:

TQ032.4

Yiru CAO, Huilin XU, Jianyu LI, Yingying JIN, Yan LUO, Hongfeng CHEN, Yong CHEN, Xuesong LIU. Mechanism Study on the Difference in Ammonia Decomposition Performance between Co Catalysts Supported on Y₂O₃ and Al₂O₃[J]. Journal of Petrochemical Universities, 2026, 39(4): 13-21.

曹艺茹, 许慧琳, 李建宇, 金莹莹, 罗燕, 陈洪锋, 陈勇, 刘雪松. Y₂O₃与Al₂O₃负载钴催化剂的氨分解性能差异机理研究[J]. 石油化工高等学校学报, 2026, 39(4): 13-21.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2026.04.002

https://journal.lnpu.edu.cn/syhg/EN/Y2026/V39/I4/13

Figures/Tables 11

Fig.1 Ammonia conversion rate curves of the catalyst before and after aging as a function of temperature

Fig.2 XRD spectra of oxides and catalysts before and after aging

Table 1 Cell parameters, cell volume and average grain size of 10Co/Y2O3 before and after aging

催化剂

晶胞参数/nm

晶胞体积/nm³

平均晶粒

尺寸/nm

10Co/Y₂O₃

10Co/Y₂O₃-A

Fig.3 SEM image of the catalyst

Table 2 BET specific surface area of catalysts and carriers

催化剂及载体	BET比表面积/（m²·g^-1）
10Co/Al₂O₃	142.5
10Co/Y₂O₃	36.1
10Co/Y₂O₃-A	4.6
Al₂O₃	126.5
Y₂O₃	82.2

Fig.4 Raman spectra of oxides and catalysts before and after aging

Fig.5 XPS spectra of the catalysts

Fig.6 H2-TPR curves of catalysts before and after aging

Fig.7 H2 consumption chart of catalyst before and after aging

Fig.8 NH3-TPD curves for catalysts before and

Fig.9 NH3 desorption from catalysts before and

References 25

[1]	MUKHERJEE S， DEVAGUPTAPU S V， SVIRIPA A， et al. Low-temperature ammonia decomposition catalysts for hydrogen generation［J］. Applied Catalysis B： Environmental， 2018， 226： 162-181.
[2]	GENUS A， THEOBALD K. Creating low-carbon neighbourhoods： A critical discourse analysis［J］. European Urban and Regional Studies， 2016， 23（4）： 782-797.
[3]	HU X C， FU X P， WANG W W， et al. Ceria-supported ruthenium clusters transforming from isolated single atoms for hydrogen production via decomposition of ammonia［J］. Applied Catalysis B： Environmental， 2020， 268： 118424.
[4]	BELL T E， TORRENTE-MURCIANO L. H₂ production via ammonia decomposition using non-noble metal catalysts： A review［J］. Topics in Catalysis， 2016， 59（15）： 1438-1457.
[5]	胡利华，陈境烨，童金明，等. Fe/Co/Ni基催化剂制备及氨分解制氢性能［J］. 洁净煤技术， 2024， 30（8）： 1-10.
	HU L H， CHEN J Y， TONG J M， et al. Synthesis of Fe/Co/Ni based catalysts and NH₃ cracking performance for H₂ production［J］. Clean Coal Technology， 2024， 30（8）： 1-10.
[6]	JU M， WANG J J， HUANG J， et al. The microstructure and electronic properties of yttrium oxide doped with cerium： A theoretical insight［J］. Front Chem， 2020， 8： 338.
[7]	LU Y， WANG H， LIU Y， et al. Novel microfibrous composite bed reactor： High efficiency H₂ production from NH₃ with potential for portable fuel cell power supplies［J］. Lab on a Chip， 2007， 7（1）： 133-140.
[8]	AGUILAR-ELGUÉZABAL A， ROMÁN-AGUIRRE M， DE LA TORRE-SÁENZ L， et al. Synthesis of CoAl₂O₄/Al₂O₃ nanoparticles for ceramic blue pigments［J］. Ceramics International， 2017， 43（17）： 15254-15257.
[9]	李国儒. 面向氨催化分解制氢Ni、Co基催化剂的构筑及催化性能研究［D］. 马鞍山：安徽工业大学， 2023.
[10]	韩建，孔熙瑞，张立波. Ni/Al₂O₃催化剂的制备及其催化NH₃分解性能研究［J］. 现代化工， 2019， 39（3）： 127-130.
	HAN J， KONG X R， ZHANG L B. Preparation of Ni/Al₂O₃ catalyst and its catalytic performance in ammonia decomposition［J］. Modern Chemical Industry， 2019， 39（3）： 127-130.
[11]	ZHANG Z S， FU X P， WANG W W， et al. Promoted porous Co₃O₄-Al₂O₃ catalysts for ammonia decomposition［J］. Science China Chemistry， 2018， 61（11）： 1389-1398.
[12]	ZHU Y， PAN H F， LI Q， et al. Dynamic reconstruction of yttrium oxide-stabilized cobalt-loaded carbon‐based catalysts during thermal ammonia decomposition［J］. Advanced Science， 2024， 11（43）： 2406659.
[13]	ALVAREZ A， IVANOVA S， CENTENO M A， et al. Sub-ambient CO oxidation over mesoporous Co₃O₄： Effect of morphology on its reduction behavior and catalytic performance［J］. Applied Catalysis A： General， 2012， 431-432： 9-17.
[14]	ZHANG Y， HUANG J W， DING Y. Porous Co₃O₄/CuO hollow polyhedral nanocages derived from metal-organic frameworks with heterojunctions as efficient photocatalytic water oxidation catalysts［J］. Applied Catalysis B： Environmental， 2016， 198： 447-456.
[15]	龚绍峰，杜泽学，慕旭宏. 氨分解制氢催化剂的研究进展［J］. 石油学报（石油加工）， 2022， 38（6）： 1506-1519.
	GONG S F， DU Z X， MU X H. Research progress of ammonia decomposition catalysts for hydrogen generation［J］. Acta Petrolei Sinica （Petroleum Processing Section）， 2022， 38（6）： 1506-1519.
[16]	RAZZAQ R， ZHU H W， JIANG L， et al. Catalytic methanation of CO and CO₂ in coke oven gas over Ni-Co/ZrO₂-CeO₂［J］. Industrial & Engineering Chemistry Research， 2013， 52（6）： 2247-2256.
[17]	BELL T E， MÉNARD H， GONZÁLEZ CARBALLO J M， et al. Hydrogen production from ammonia decomposition using Co/γ-Al₂O₃ catalysts-insights into the effect of synthetic method［J］. International Journal of Hydrogen Energy， 2020， 45（51）： 27210-27220.
[18]	LI J W， SONG Q， LI J B， et al. La-enhanced Ni nanoparticles highly dispersed on SiC for low-temperature CO methanation performance［J］. Rare Metals， 2021， 40（7）： 1753-1761.
[19]	MCINTYRE N S， COOK M G. X-ray photoelectron studies on some oxides and hydroxides of cobalt， nickel， and copper［J］. Analytical Chemistry， 1975， 47（13）： 2208-2213.
[20]	LENDZION-BIELUN Z， NARKIEWICZ U， ARABCZYK W. Cobalt-based catalysts for ammonia decomposition［J］. Materials， 2013， 6（6）： 2400-2409.
[21]	DE BEER M， KUNENE A， NABAHO D， et al. Technical and economic aspects of promotion of cobalt-based fischer-tropsch catalysts by noble metals——A review［J］. Journal of the Southern African Institute of Mining and Metallurgy， 2014， 114（2）： 157-165.
[22]	TAKAHASHI A， FUJITANI T. Kinetic analysis of decomposition of ammonia over nickel and ruthenium catalysts［J］. Journal of Chemical Engineering of Japan， 2016， 49（1）： 22-28.
[23]	GU Y Q， XU D， HUANG Y， et al. COx-free hydrogen production via ammonia decomposition over mesoporous Co/Al₂O₃ catalysts with highly dispersed Co species synthesized by a facile method［J］. Dalton Transactions， 2021， 50（4）： 1443-1452.
[24]	CHEN X， CAI H， TANG Q， et al. Eggshell membrane templated Y₂O₃@Pd catalyst for enhanced methanol oxidation and CO tolerance［J］. Materials Research Innovations， 2014， 18（4）： 300-306.
[25]	李世刚，李冰，刘晓晖，等. 氨分解催化剂研究进展［J］. 石油炼制与化工， 2024， 55（2）： 10-22.
	LI S G， LI B， LIU X H， et al. Progress on catalysts for ammonia decomposition［J］. Petroleum Processing and Petrochemicals， 2024， 55（2）： 10-22.