氨合成及分解用钌基催化剂的研究现状

摘要/Abstract

摘要： 氢气因在其燃烧过程无碳排放且比能量密度高，被认为是未来最具潜力的清洁能源之一；而氨作为一种高效的氢载体，在储氢技术中展现出广阔的应用前景。钌基催化剂凭借卓越的催化性能，在氨合成及分解领域备受关注。基于此，综述了近年来钌基催化剂的合成方法及其性能关键影响因素，探讨了钌基催化剂在氨合成和氨分解过程中的催化机理，重点分析了颗粒大小、载体类型及助剂对催化活性的影响，以期为高效钌基催化剂的开发提供参考。

关键词: 钌基催化剂, 催化剂合成, 氢气, 氨合成, 氨分解

Abstract: Hydrogen is regarded as one of the most promising clean energy sources for the future due to its high energy density and zero carbon emissions during combustion. Ammonia, as an efficient hydrogen carrier, has demonstrated broad application prospects in hydrogen storage technologies. Ruthenium-based catalysts have attracted significant attention in the fields of ammonia synthesis and decomposition owing to their outstanding catalytic performance. Based on this, this review summarizes recent advances in the synthesis methods of ruthenium-based catalysts and the key factors influencing their performance. It further explores the catalytic mechanisms of ruthenium-based catalysts in ammonia synthesis and decomposition processes, with a particular focus on the effects of particle size, support type, and promoters on catalytic activity, aiming to provide a reference for the development of efficient ruthenium-based catalysts.

Key words: ruthenium-based catalysts, catalyst synthesis, hydrogen, ammonia synthesis, ammonia decomposition

陈文睿刘俊龙军. 氨合成及分解用钌基催化剂的研究现状[J]. 石油炼制与化工, 2025, 56(10): 140-151.

参考文献

[1] Staffell I, Scamman D, Velazquez Abad A, et al. The role of hydrogen and fuel cells in the global energy system. Energy Environ Sci 2019;12(2):463e91.
[2] Su YL, Wang SB, Song GX, et al. Development in catalysts for hydrogen production by ammonia decomposition. Ship Sci technology 2010;32(4):138e43.
[3] Bell TE, Torrente-Murciano L. H2 production via ammonia decomposition using non-noble metal catalysts: a review. Top Catal 2016;59(15e16):1438e57.
[4] Mukherjee S, Devaguptapu SV, Sviripa A, et al. Low- temperature ammonia decomposition catalysts for hydrogen generation. Appl Catal B Environ 2018;226:162e81.
[5] Cao CF, Wu K, Zhou C, Yao YH, et al. Electronic metal-support interaction enhanced ammonia decomposition efficiency of perovskite oxide supported ruthenium. Chem Eng Sci 2022;257: 117719e26.
[6] Cha J, Lee T, Lee YJ, et al. Highly monodisperse sub-nanometer and nanometer Ru particles confined in alkali-exchanged zeolite Y for ammonia decomposition. Appl Catal B Environ 2021;283:119627e38.
[7] V.S. Marakatti, E.M. Gaigneaux, Recent advances in heterogeneous catalysis for ammonia synthesis, ChemCatChem 12 (23) (2020) 5838–5857,
[8] X. Peng, X. Chen, Y. Zhou, et al.,Size-dependent activity of supported Ru catalysts for ammonia synthesis at mild conditions, J. Catal. 408 (2022) 98–108,
[9] L. Zhao, J. Zhao, J. Zhao, et al.Artificial N2 fixation to NH3 by electrocatalytic Ru NPs at low overpotential, Nanotechnology 31 (29) (2020) 29LT01,
[10] Mazzone S, Goklany T, Zhang G, et al. Ruthenium-based catalysts supported on carbon xerogels for hydrogen production via ammonia decomposition. Appl Catal Gen 2022;632:118484e99.
[11] H. Hosono, Catalytic activation of molecular nitrogen for green ammonia synthesis: Introduction and current status, Faraday Discuss. (2023),
[12] Jiang W, Cao J-P, Zhu C, et al. Catalytic hydrogenation of aromatic ring over ruthenium nanoparticles supported on α-Al2O3 at room temperature. Appl Catal B 2022;307:121137.
[13] Amar Al-khawlani, Jiehua Bao, Xiaoli Sheng, et al.SSZ-39 zeolite-based Ru catalysts for selective hydrogenation of levulinic acid to γ-valerolactone: Influence of synthesis method and zeolite acidity, Microporous and Mesoporous Materials,Volume 372,2024,113112,ISSN 1387-1811,
[14] Wang J-b, Ren Z, Hou Y, et al. A review of graphene synthesisatlow temperatures by CVD methods. New Carbon Mater 2020;35: 193–208.
[15] Wu Y, Yu H, Guo Y, Jiang X, Qi Y, Sun B, et al. A rare earth hydride supported ruthenium catalyst for the hydrogenation of N-heterocycles: boosting the activity via a new hydrogen transfer path and controlling the stereoselectivity. Chem Sci 2019;10:10459–65.
[16] Moujie Huang, Yongsong Ma, Jingbo Yang, et al Ultrafine Ru nanoparticles on nitrogen-doped CNT arrays for HER: A CVD-based protocol achieving microstructure design and strong catalyst-support interaction, Applied Surface Science, Volume 645,2024,158834,ISSN 0169-4332,
[17] Feltes TC, Espinosa-Alonso L, Smit E, et al.Weckhuysen BM, Regalbuto JR. J Catal 2010;270:95.
[18] Fujitani T, Nakamura I, Hashiguchi Y, et al. Effect of catalyst preparation method on ammonia decomposition reaction over Ru/MgO catalyst. Bull Chem Soc Jpn 2020;93(10):1186e92.
[19] Ju X, Liu L, Zhang X, et al. Highly ef?cient Ru/MgO catalyst with surface-enriched basic sites for production of hydrogen from ammonia decomposition. ChemCatChem2019; 11(16): 4161e70.
[20] Zhao X, Kong X, Li G, et al. Ru-based catalysts for hydrogenation of N-ethylcarbazole: Progress and prospects[J]. Fuel: A journal of fuel science, 2024(Mar.15): 360.
[21] Kee Young Koo, Hyo Been Im, Dahye Song, et al. Ammonia decomposition over Ru-coated metal-structured catalysts for COx-free hydrogen production, International Journal of Hydrogen Energy, Volume52, Part D, 2024,
[22] Liu X, Bai X, Wu W. Ultrasound-assisted green synthesis of Ru supported on LDH-CNT composites as an efficient catalyst for N-ethylcarbazole hydrogenation. Ultrason Sonochem2022; 91.
[23] Qin Y, Shi J, Bai X. Preparing ultra-stable Ru nanocatalysts supported on partially graphitized biochar via carbothermal reduction for hydrogen storage of N-ethylcarbazole. Int J Hydrogen Energy2021; 46: 25543–54.
[24] Y. Zhou, J. Wang, L. Liang, et al. Unraveling the size-dependent effect of Ru-based catalysts on ammonia synthesis at mild conditions, J. Catal.404(2021) 501–511,
[25] X. Wang, L. Li, Z. Fang, Y et al.Atomically dispersed Ru catalyst for low-temperature nitrogen activation to ammonia via an associative mechanism, ACS Catal.10(16)(2020) 9504–9514,
[26] Ju, X, Liu, L, Yu, P, et al.2017. Mesoporous Ru/MgO prepared by a deposition-precipitation method as highly active catalyst for producing COx-free hydrogen from ammonia decomposition. Appl. Catal. B Environ.211, 167–175.
[27] Kishida K, Kitano M, Inoue Y, et al. Large oblatehemispheroidal ruthenium particles supported on calciumamide as ef?cient catalysts for ammonia decomposition. Chemistry2018; 24(31): 7976e84.
[28] Zhao, M.; Xia, Y. Crystal-Phase and Surface-StructureEngineering of Ruthenium Nanocrystals. Nat. Rev. Mater.2020, 5, 440?459.
[29] Sanil E. Sivan, Ki Hyuk Kang, Seung Ju Han, et al, Facile MOF-derived one-pot synthetic approach toward Ru single atoms, nanoclusters, and nanoparticles dispersed on CeO2supports for enhanced ammonia synthesis, Journal of Catalysis, Volume408, 2022, Pages316-328, ISSN0021-9517,
[30] Lingling Li, Ya-Fei Jiang, Tianhua Zhang, et al, Size sensitivity of supported Ru catalysts for ammonia synthesis: From nanoparticles to subnanometric clusters and atomic clusters, Chem, Volume8, Issue3, 2022, Pages749-768, ISSN2451-9294,
[31] Zhang C, Sun L, Ouyang Y, et al. Improved electrochemical water splitting by RuNi nanoparticles supported on rGO@mesoporous N-doped carbon nanosheets. J Alloy Compd2023; 937: 168334.
[32] Chen, C., Wu, K., Ren, H et al.2021. Ru-based catalysts for ammonia decomposition: a mini-review. Energy&Fuels35(15), 11693–11706.
[33] Simonsen SB, Chakraborty D, Chorkendorff I, et al. Alloyed Ni-Fe nanoparticles as catalysts for NH3decomposition. Appl Catal Gen2012; 447e448: 22e31.
[34] Ilaria Lucentini, Germán García Colli, Carlos D et al. Catalytic ammonia decomposition over Ni-Ru supported on CeO2for hydrogen production: Effect of metal loading and kinetic analysis, Applied Catalysis B: Environmental, Volume286, 2021, 119896,
[35] Chen, J.; Zhu, Z. H.; Wang, S et al. Effects of Nitrogen Doping on the Structure of Carbon Nanotubes(CNTs) and Activity of Ru/CNTs in Ammonia Decomposition. Chem. Eng. J.2010, 156(2), 404?410.
[36] Bell TE, Zhan G, Wu K, et al. Modi?cation of ammonia decomposition activity of ruthenium nanoparticles by N-doping of CNT supports. Top Catal2017; 60(15): 1251e9.
[37] Xuezhi DUAN, Jinghong ZHOU, Gang QIAN, et al.Carbon Nanofiber-Supported Ru Catalysts for Hydrogen Evolution by Ammonia Decomposition, Chinese Journal of Catalysis, Volume31, Issue8, 2010, Pages979-986, ISSN1872-2067,
[38] Mirzaei F, Rezaei M, Meshkani F, et al. Carbon dioxide reforming of methane for syngas production over Co-MgO mixed oxide nanocatalysts. J Ind Eng Chem2015; 21: 662e7.
[39] Ju, X.; Liu, L.; Zhang, X et al. Highly Efficient Ru/MgO Catalyst with Surface-Enriched Basic Sites for Production of Hydrogen from Ammonia Decomposition. Chem-CatChem2019, 11(16), 4161?4170.
[40] S. Y. Chen, C. L. Chang, M. Nishi, et al. Unraveling the active sites of Cs-promoted Ru/c-Al2O3catalysts for ammonia synthesis, Appl. Catal. B Environ.310(2022) 121269.
[41] Mostafa El-Shafie, Shinji Kambara, Yukio Hayakawa, Plasma-enhanced catalytic ammonia decomposition over ruthenium(Ru/Al2O3) and soda glass(SiO2) materials, Journal of the Energy Institute, Volume99, 2021, Pages145-153,
[42] Armenise, S.; Cazan?a, F.; Monzón, A. et al. In Situ Generation of COx-Free H2by Catalytic Ammonia Decom-position over Ru-Al-Monoliths. Fuel2018, 233, 851?859.
[43] 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. Appl. Catal. B: Environ.2020, 268, 118424.
[44] Saadatjou, N.; Jafari, A.; Sahebdelfar, S. Ruthenium Nano-catalysts for Ammonia Synthesis: A Review. Chem. Eng. Commun.2015, 202, 420?448.
[45] Y. Zhao, R. Shi, X. Bian, et al.Ammonia detection methods in photocatalytic and electrocatalytic experiments: How to improve the reliability of NH3production rates? Adv. Sci.6(8)(2019) 1802109,
[46] F. Chang, W. Gao, J. Guo, P. Chen, Emerging materials and methods toward ammonia-based energy storage and conversion, Adv. Mater.33(50)(2021) 2005721,
[47] Y. Zhang, M. Zhang, Y. Zhou, et al. Insight into the critical role of strong interaction between Ru and Co in RuCo single-atom alloy structure for significant enhancement of ammonia synthesis performance, J. Catal.410(2022) 256–265,
[48] H. Liu, Ammonia synthesis catalysts: Innovation and practice, World Scientific, 2013.
[49] E. Zambrzycka, D. Roszko, B. Le′sniewska, et al. Studies of ion-imprinted polymers for solid-phase extraction of ruthenium from environmental samples before its determination by electrothermal atomic absorption spectrometry, Spectrochim. Acta B At. Spectrosc.66(7)(2011) 508–516,
[50] Z. Han, P. Wu, M. He, et al.Ammonia synthesis by electrochemical nitrogen reduction reaction-A novel energy storage way, J. Energy Storage55(2022), 105684,
[51] B. Lin, B. Fang, Y. Wu, et al. Enhanced ammonia synthesis activity of ceria-supported ruthenium catalysts induced by CO activation, ACS Catal.11(3)(2021) 1331–1339,
[52] S. Qureshi, M. Mumtaz, F. K. Chong, et al.A review on sensing and catalytic activity of nano-catalyst for synthesis of one-step ammonia and urea: Challenges and perspectives, Chemosphere291(2022), 132806,
[53] Y. Zhang, S. Li, C. Sun, et al.Defective g-C3N4supported Ru3single-cluster catalyst for ammonia synthesis through parallel reaction pathways, Nano Res.16(2)(2023) 3580–3587.
[54] H. Shen, C. Choi, J. Masa, et al. Electrochemical ammonia synthesis: Mechanistic understanding and catalyst design, Chem.7(7)(2021) 1708–1754,
[55] C. Li, S. Yu, Y. Shi, et al.Combining silica to boost the ammonia synthesis activity of ceria-supported Ru catalyst, Chem. Eng. Sci.262(2022), 118045,
[56] C. Foo, J. Fellowes, H. Fang, et al.Importance of hydrogen migration in catalytic ammonia synthesis over yttrium-doped barium zirconate-supported ruthenium nanoparticles: Visualization of proton trap sites, J. Phys. Chem. C125(42)(2021) 23058–23070,
[57] L. Li, T. Zhang, Y. Zhou, et al. Review on catalytic roles of rare earth elements in ammonia synthesis: Development and perspective, J. Rare Earths40(1)(2022) 1–10,
[58] L. Shi, Y. Yin, S. Wang, et al. Rational catalyst design for N2reduction under ambient conditions: Strategies toward enhanced conversion efficiency, ACS Catal.10(12)(2020) 6870–6899,
[59] J. Wang, L. Liu, X. Zhang, et al.Sub-nanometer Ru clusters on Sm2O3obtained from a room temperature ion adsorption method for ammonia synthesis, Cat. Sci. Technol.12(24)(2022) 7501–7509,
[60] Ni, J.; Tan, Z.; Sai, Q et al. Target-Oriented Confinement of Ru-Co Nanoparticlesinside N-Doped Carbon Spheres via a Benzoic Acid Guided Processfor High-Efficient Low-Temperature Ammonia Synthesis. J. Energ. Chem.2021, 57, 140?146
[61] Chen C, et al. Bimetallic Ru-Fe nanoparticles supported on carbon nanotubes for ammonia decomposition and synthesis. Chem Eng Technol2020; 43(4): 719e30.
[62] Chunyan Li, Zecheng Zhang, Yiping Zheng, et al. Titanium modified Ru/CeO2catalysts for ammonia synthesis, Chemical Engineering Science, Volume251, 2022, 117434,
[63] Ma Y, et al. Role of surface defects of carbon nanotubes on catalytic performance of barium promoted ruthenium catalyst forammoniasynthesis. J EnergyChem2020; 41: 79e86.
[64] Shih-Yuan Chen, Li-Yu Wang, Kai-Chun Chen, et al. Ammonia synthesis over cesium-promoted mesoporous-carbon-supported ruthenium catalysts: Impact of graphitization degree of the carbon support,
[65] Masayasu Nishi, Shih-Yuan Chen, Hiroyuki Tateno, et al.A super-growth carbon nanotubes-supported, Cs-promoted Ru catalyst for0.1–8MPaG ammonia synthesis, Journal of Catalysis, Volume413, 2022, Pages623-635,
[66] Kyungho Lee, Rayoon Woo, Hee Chahng Woo, et al.Unraveling the role of MgO in the Ru-Ba/MgO catalyst for boosting ammonia synthesis: Comparative study of MgO and MgAlOx supports, Journal of Catalysis, Volume434, 2024, 115530,
[67] Bingyu Lin, Yuyuan Wu, Biyun Fang, et al.Ru surface density effect on ammonia synthesis activity and hydrogen poisoning of ceria-supported Ru catalysts, Chinese Journal of Catalysis, Volume42, Issue10, 2021, Pages1712-1723,
[68] A. Daisley, J. S. J. Hargreaves, R. Hermann, et al. A comparison of the activities of various supported catalysts for ammonia synthesis, Catalysis Today, Volume357, 2020, Pages534-540,
[69] Ji Feng, Lin Liu, Xilun Zhang, J et al.Ru nanoparticles on Y2O3with enhanced metal–support interactions for efficient ammonia synthesis??Electronic supplementary information(ESI) available.
[70] Xuanbei Peng, Yongjin Luo, Tianhua Zhang, et al.Potassium promoter regulates electronic structure and hydrogen spillover of ultrasmall Ru nanoclusters catalyst for ammonia synthesis, Chemical Engineering Science, Volume292, 2024, 120021,
[71] Chunyan Li, Shitong Yu, Yuying Shi, et al.Combining silica to boost the ammonia synthesis activity of ceria-supported Ru catalyst, Chemical Engineering Science, Volume262, 2022, 118045,
[72] Chunyan Li, Yuying Shi, Zecheng Zhang, J et al.Improving the ammonia synthesis activity of Ru/CeO2through enhancement of the metal–support interaction, Journal of Energy Chemistry, Volume60, 2021, Pages403-409,
[73] Jun Ni, Baoqiang Jing, Jianxin Lin et al. Effect of rare earth on the performance of Ru/MgAl-LDO catalysts for ammonia synthesis, Journal of Rare Earths, Volume36, Issue2, 2018, Pages135-141,
[74] Mami Osozawa, Ayane Hori, Kosuke Fukai, T et al. Improvement in ammonia synthesis activity on ruthenium catalyst using ceria support modified a large amount of cesium promoter, International Journal of Hydrogen Energy, Volume47, Issue4, 2022, Pages2433-2441,
[75] Shih-Yuan Chen, Chih-Li Chang, Masayasu Nishi, el at.Unraveling the active sites of Cs-promoted Ru/γ-Al2O3catalysts for ammonia synthesis, Applied Catalysis B: Environmental, Volume310, 2022, 121269,
[76] Wang Y, et al. Effects of support and promoter on Ru catalyst activity in microwave-assisted ammonia synthesis. Chem Eng J2021; 425: 130546.
[77] Bajus, S., Agel, F., Kusche, M., et al. 2016. Alkali hydroxide-modified Ru/γ-Al2O3catalysts for ammonia decomposition. Appl. Catal. Gen.510, 189–195.
[78] Fang, H., Liu, D., Luo, Y., et al., 2022. Challenges and opportunities of Ru-based catalysts toward the synthesis and utilization ofammonia. ACS Catal.12(7), 3938–3954.
[79] Antunes R, Steiner R, Marot L, et al. Decomposition studies of NH3and ND3in presence of H2and D2with Pt/Al2O3and Ru/Al2O3catalysts. Int J Hydrogen Energy2022; 47(30): 14130e40.
[80] Jie, X., Gonzalez-Cortes, S., Xiao, et al., 2019. The decarbonisation of petroleum and other fossil hydrocarbon fuels for the facile production and safe storage of hydrogen. Energy Environ. Sci.12(1), 238–249.
[81] Ojelade OA, Zaman SF. Ammonia decomposition for hydrogen production: a thermodynamic study. Chem Paper2020; 75(1): 57e65.
[82] Bao JL, Carter EA. Rationalizing the hot-carrier-mediated reaction mechanisms and kinetics for ammonia decomposition on ruthenium-doped copper nanoparticles. J Am Chem Soc2019; 141(34): 13320e3.
[83] Yi, Y., Wang, L., Guo, Y., et al. 2018. Plasma-Assisted ammonia decomposition over Fe-Ni alloy catalysts for COx-Free hydrogen. AIChE J.65(2), 691–701.
[84] Zhang H, Gong Q, Ren S, et al. Implication of iron nitride species to enhance the catalytic activity and stability of carbon nanotubes supported Fe catalysts for carbon-free hydrogen production via low-temperature ammonia decomposition. Catal Sci Technol2018; 8(3): 907e15.
[85] Jiuling Chen, Zhong Hua Zhu, Shaobin Wang, et al.Effects of nitrogen doping on the structure of carbon nanotubes(CNTs) and activity of Ru/CNTs in ammonia decomposition, Chemical Engineering Journal, Volume156, Issue2, 2010, Pages404-410, ISSN1385-8947,
[86] Marco Y, Rold an L, Armenise S, et al. Support-induced oxidation state of catalytic Ru nanoparticles on carbon nano?bers that were doped with heteroatoms(O, N) for the decomposition of NH3. ChemCatChem2013; 5(12): 3829e34.
[87] Armenise S, Rold an L, Marco Y, et al. Elucidation of catalyst support effect for NH3decomposition using Ru nanoparticles on nitrogen-functionalized carbon nano?ber monoliths. J Phys Chem C2012; 116(50): 26385e95.
[88] Zheng, W.; Zhang, J.; Zhu, B.; et al. Structure-Function Correlations for Ru/CNT in the Catalytic Decomposition of Ammonia. ChemSusChem2010, 3(2), 226?230
[89] Wang, L.; Chen, J.; Ge, L.; et al. Difference in the Cooperative Interaction between Carbon Nanotubes and Ru Particles Loaded on Their Internal/External Surface. RSC Adv.2013, 3(31), 12641?12647
[90] Hu, X. C.; Wang, W. W.; Si, R.; et al. Hydrogen Production via Catalytic Decomposition of NH3Using Promoted MgO-Supported Ruthenium Catalysts. Sci. China Chem.2019, 62(12), 1625?1633.
[91] Borisov VA, Iost KN, Temerev VL, et al. Ammonia decomposition Ru catalysts supported on alumina nanofibers for hydrogen generation. Mater Lett2022; 306: 130842e5.
[92] Ranlei Shao, Lu Zhang, Luyuan Wang, et al.Cerium oxide-based catalyst for low-temperature and efficient ammonia decomposition for hydrogen production research, International Journal of Hydrogen Energy, Volume68, 2024, Pages311-320,
[93] Fu ZQ, Wang ZQ, Li DX, et al. Catalytic ammonia decomposition to COx-free hydrogen over ruthenium catalyst supported on alkali silicates. Fuel2022; 326: 125094e102.
[94] Nagaoka K, Eboshi T, Abe N, et al. In?uence of basic dopants on the activity of Ru/Pr6O11for hydrogen production by ammonia decomposition. Int J Hydrogen Energy2014; 39: 20731e5.
[95] Garc?′a-Garc?′a FR, Gallegos-Suarez E, Fern andez-Garc?′a M, et al. Understanding the role of oxygen surface groups: the key for a smart ruthenium-based carbon-supported heterogeneous catalyst design and synthesis. Appl Catal Gen2017; 544: 66e76.
[96] Sayas S, Morlan es N, Katikaneni SP, et al. High pressure ammonia decomposition on Ru-K/CaO catalysts. Catal Sci Technol2020; 10(15): 5027e35.
[97] Wang F, Deng LD, Wu ZW, et al. The dispersed SiO2microspheres supported Ru catalyst with enhanced activity for ammonia decomposition. Int J Hydrogen Energy2021; 46(40): 20815e24.
[98] Chang F, Wu H, Pluijm RV, et al. Effect of pore con?nement of NaNH2and KNH2on hydrogen generation from ammonia. J Phys Chem C Nanomater Interfaces2019; 123(35): 21487e96.
[99] Wang Z, Qu Y, Shen X, et al. Ruthenium catalyst supported on Ba modi?ed ZrO2for ammonia decomposition to COx-free hydrogen. Int J Hydrogen Energy2019; 44(14): 7300e7.
[100] Guo, J.; Chen, Z.; Wu, A.; et al.Electronic Promoter or Reacting Species? The Role of LiNH2on Ru in Catalyzing NH3Decomposition. Chem. Commun.2015, 51(82), 15161?15164.
[101] Huang, C., Yu, Y., Yang, J., et al., 2019a. Ru/La2O3catalyst for ammonia decomposition to hydrogen. Appl. Surf. Sci.476, 928–936.
[102] Furusawa T, Sugiyama K, Kuribara H, et al. Effect of alkali metal addition to a Ru/CeO2catalyst prepared by NaBH4reduction on the catalytic performance for H2production via NH3decomposition. J Chem Eng Jpn2021; 54: 77e86.
[103] W Hu Z, Mahin J, Datta S, et al. Ru-based catalysts for H2production from ammonia: effect of1D Support. Top Catal2018; 62(17e20): 1169e77.
[104] Wang, Z., Qu, Y., Shen, X., Cai, Z., 2019c. Ruthenium catalyst supported on Ba modified ZrO2for ammonia decomposition to COx-free hydrogen. Int. J. Hydrogen Energy44(14), 7300–7307.
[105] Furusawa T, Kuribara H, Kimura K, et al. Development of a Cs-Ru/CeO2spherical catalyst prepared by impregnation and washing processes for low-temperature decomposition of NH3: characterization and kinetic analysis results. Ind Eng Chem Res2020; 59: 18460e70.
[106] Hill, A. K.; Torrente-Murciano, L. Low Temperature H2Production from Ammonia Using Ruthenium-Based Catalysts: Synergetic Effect of Promoter and Support. Appl. Catal. B: Environ.2015, 172?173, 129?135.
[107] Isao Nakamura, Hidehito Kubo, Tadahiro Fujitani, Critical role of Cs doping in the structure and NH3decomposition performance of Ru/MgO catalysts, Applied Catalysis A: General, Volume644, 2022, 118806,
[108] Le TA, Kim Y, Kim HW, et al. Ru-supported lanthania-ceria composite as an ef?cient catalyst for COx-free H2production from ammonia decomposition. Appl Catal B Environ2021; 285: 119831e41.
[109] Miyamoto M, Hamajima A, Oumi Y, et al. Effect of basicity of metal doped ZrO2supports on hydrogen production reactions. Int J Hydrogen Energy2018; 43: 730e8.
[110] JungHun Shin, Unho Jung, Jiyu Kim, et al.Elucidating the effect of Ce with abundant surface oxygen vacancies on MgAl2O4-supported Ru-based catalysts for ammonia decomposition, Applied Catalysis B: Environmental, Volume340, 2024, 123234,
[111] Qinglu Meng, Haoxin Liu, Kai Xu, et al. CeO2?x modified Ru/γ-Al2O3catalysts for ammonia decomposition reaction, Journal of Rare Earths, Volume41, Issue6, 2023,