journal article·2025-02Open access

Electronic structure optimizing of Ru nanoparticles loaded on carbon via amorphous Pr2O3 for accelerating hydrogen production from ammonia decomposition

Rui Chen, Hongfei Pan, Zihan Meng, Haibo Tang, Qi Li, Tian Tian, Xiege Huang, Zhigang Zhan, Haolin Tang

Abstract

Green hydrogen is an effective energy countermeasure for global climate change and promoting the energy transition and CO x -free hydrogen production from ammonia decomposition provides an economic benefit of hydrogen storage and transportation which garnering widespread attention. In this study, the catalyst consisting of highly dispersed Ru nanoparticles with amorphous Pr 2 O 3 loaded on carbon supports was synthesized by the annealing of hybrid precursor in the presence of Pr and Ru ions. Benefitted from the optimized electronic structure of Ru nanoparticles stimulated by amorphous Pr 2 O 3 and carbon supports, the catalyst exhibits enhanced capability of electronic transmission which promoting the recombination and desorption of nitrogen atoms, ultimately improving the catalytic activity during the thermal ammonia decomposition. The prepared catalyst achieved a remarkable ammonia conversion rate of 99% with a hydrogen production rate of 27.7 mmol·g cat −1 ·min −1 (25,000 mL·g cat −1 ·h −1 , 500℃), an exceptional stability of catalytic activity with a degradation of less than 3% after 200 h at a space velocity of 30,000 mL·g cat −1 ·h −1 under 500℃, further facilitating the development of more efficient hydrogen production from thermal catalytic ammonia decomposition.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Ammonia Synthesis and Nitrogen Reduction · Catalytic Processes in Materials Science · Hydrogen Storage and Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (46)

Show source-provided references
1. Nagappan S, Dhandapani HN, Karmakar A, Kundu S (2023) Recent advancement of 2D Bi-metallic hydroxides with various strategical modification for the sustainable hydrogen production through water electrolysis. ES Mater Manuf. https://doi.org/10.30919/esmm5f83010.30919/esmm5f830 ↗
2. Han X, Hu M, Yu J, Xu X, Jing P, Liu B, Gao R, Zhang J (2023) Dual confinement of LaCoOx modified Co nanoparticles for superior and stable ammonia decomposition. Appl Catal B: Environ 328. https://doi.org/10.1016/j.apcatb.2023.12253410.1016/j.apcatb.2023.122534 ↗
3. Udayakumar A, Dhandapani P, Ramasamy S, Angaiah S (2023) Layered double hydroxide (LDH) – MXene nanocomposite for electrocatalytic water splitting: current status and perspective. ES Energy Environ. https://doi.org/10.30919/esee90210.30919/esee902 ↗
4. Zhao J, Bao K, Xie M, Wei D, Yang K, Zhang X, Zhang C, Wang Z, Yang X (2022) Two-dimensional ultrathin networked CoP derived from Co(OH)2 as efficient electrocatalyst for hydrogen evolution. Adv Compos Hybrid Mater 5:2421–2428. https://doi.org/10.1007/s42114-022-00455-w10.1007/s42114-022-00455-w ↗
5. Liu W, Zhang S, Almalki ASA, Fallatah AM, El-Bahy ZM, Ren J, Zhao X, Seok I, Guo Z (2024) In situ synthesis of honeycomb nanorods Ni3S2@NiCo-Layered-double hydroxide/nickel foam electrocatalysts with high performance electrocatalytic hydrogen production. ACS Appl Energy Mater 7:9223–9231. https://doi.org/10.1021/acsaem.4c0150110.1021/acsaem.4c01501 ↗
6. Liu Y, Nan J, Li L, Wang Y, Shao Q, Zhu X, Lin Z, Ren J, Algadi H, Ge R (2023) Ruthenium oxide/cobalt oxide heterojunction electrocatalyst for biomass-derivative oxidation and hydrogen evolution. Adv Compos Hybrid Mater 6. https://doi.org/10.1007/s42114-023-00743-z10.1007/s42114-023-00743-z ↗
7. Luo R, Wang R, Meng Z, Xia Y, Tang H (2023) Dysprosium-induced FeN0.0324-Dy2O3 sites with efficient bifunctional oxygen electrocatalytic reactions for Zn-air batteries. Adv Compos Hybrid Mater 6. https://doi.org/10.1007/s42114-023-00685-610.1007/s42114-023-00685-6 ↗
8. Jin C, Wu F, Tang H, Pan H, Chen Z, Wang R, Meng Z, Li J, Tang H (2023) Confined tuning of the charge distribution of Pt electrocatalyst for reinforcing anti-poisoning ability: toward efficient separation of hydrogen from gases containing ammonia. Chem Eng J 475. https://doi.org/10.1016/j.cej.2023.14613910.1016/j.cej.2023.146139 ↗
9. Magazov Y, Aliyev A, Moldabekov K, Kurbanova A, Rakymbekova A, Amze M, Ibrayev N, Kudryashov V (2024) Photoelectrochemical water splitting using cuprous oxide (Cu2O)-based photocathode – a review. ES Energy Environ. https://doi.org/10.30919/esee134710.30919/esee1347 ↗
10. Abe JO, Popoola API, Ajenifuja E, Popoola OM (2019) Hydrogen energy, economy and storage: review and recommendation. Int J Hydrogen Energy 44:15072–15086. https://doi.org/10.1016/j.ijhydene.2019.04.06810.1016/j.ijhydene.2019.04.068 ↗
11. Wang W, Herreros JM, Tsolakis A, York APE (2013) Ammonia as hydrogen carrier for transportation; investigation of the ammonia exhaust gas fuel reforming. Int J Hydrogen Energy 38:9907–9917. https://doi.org/10.1016/j.ijhydene.2013.05.14410.1016/j.ijhydene.2013.05.144 ↗
12. D’Antuono G, Galloni E, Lanni D, Fontana G (2023) A relationship for estimating the ignition delay of hydrogen-enriched ammonia-air mixtures. Eng Sci. https://doi.org/10.30919/es107410.30919/es1074 ↗
13. Lin J, Wang Y, Tian W, Zhang H, Sun H, Wang S (2023) Macroporous carbon-nitride-supported transition-metal single-atom catalysts for photocatalytic hydrogen production from ammonia splitting. ACS Catal 13:11711–11722. https://doi.org/10.1021/acscatal.3c0207610.1021/acscatal.3c02076 ↗
14. Lucentini I, Garcia X, Vendrell X, Llorca J (2021) Review of the decomposition of ammonia to generate hydrogen. Ind Eng Chem Res 60:18560–18611. https://doi.org/10.1021/acs.iecr.1c0084310.1021/acs.iecr.1c00843 ↗
15. Khan WU, Alasiri HS, Ali SA, Hossain MM (2022) Recent advances in bimetallic catalysts for hydrogen production from ammonia. Chem Rec 22:e202200030. https://doi.org/10.1002/tcr.20220003010.1002/tcr.202200030 ↗
16. Chang F, Gao W, Guo J, Chen P (2021) Emerging materials and methods toward ammonia-based energy storage and conversion. Adv Mater 33:2005721. https://doi.org/10.1002/adma.20200572110.1002/adma.202005721 ↗
17. Araia A, Wang Y, Jiang C, Brown S, Caiola A, Robinson B, Li W, Hu J (2023) Insight into enhanced microwave heating for ammonia synthesis: effects of CNT on the Cs–Ru/CeO2 catalyst. ACS Appl Mater Interfaces 15:24296–24305. https://doi.org/10.1021/acsami.3c0013210.1021/acsami.3c00132 ↗
18. Cha J, Jo YS, Jeong H, Han J, Nam SW, Song KH, Yoon CW (2018) Ammonia as an efficient COx-free hydrogen carrier: fundamentals and feasibility analyses for fuel cell applications. Appl Energy 224:194–204. https://doi.org/10.1016/j.apenergy.2018.04.10010.1016/j.apenergy.2018.04.100 ↗
19. Schüth F, Palkovits R, Schlögl R, Su DS (2012) Ammonia as a possible element in an energy infrastructure: catalysts for ammonia decomposition. Energy Environ Sci 5:6278–6289. https://doi.org/10.1039/c2ee02865d10.1039/c2ee02865d ↗
20. Tabassum H, Mukherjee S, Chen J, Holiharimanana D, Karakalos S, Yang X, Hwang S, Zhang T, Lu B, Chen M, Tang Z, Kyriakidou EA, Ge Q, Wu G (2022) Hydrogen generation via ammonia decomposition on highly efficient and stable Ru-free catalysts: approaching complete conversion at 450 °C. Energy Environ Sci 15:4190–4200. https://doi.org/10.1039/d1ee03730g10.1039/d1ee03730g ↗
21. Sun S, Jiang Q, Zhao D, Cao T, Sha H, Zhang C, Song H, Da Z (2022) Ammonia as hydrogen carrier: advances in ammonia decomposition catalysts for promising hydrogen production. Renew Sustain Energy Rev 169. https://doi.org/10.1016/j.rser.2022.11291810.1016/j.rser.2022.112918 ↗
22. Hansgen DA, Vlachos DG, Chen JG (2010) Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction. Nat Chem 2:484–489. https://doi.org/10.1038/nchem.62610.1038/nchem.626 ↗
23. Fang H, Wu S, Ayvali T, Zheng J, Fellowes J, Ho PL, Leung KC, Large A, Held G, Kato R, Suenaga K, Reyes YIA, Thang HV, Chen HT, Tsang SCE (2023) Dispersed surface Ru ensembles on MgO(111) for catalytic ammonia decomposition. Nat Commun 14:647. https://doi.org/10.1038/s41467-023-36339-w10.1038/s41467-023-36339-w ↗
24. Ganley JC, Thomas FS, Seebauer EG, Masel RI (2004) A priori catalytic activity correlations: the difficult case of hydrogen production from ammonia. Catal Lett 96:117–122. https://doi.org/10.1023/b:catl.0000030108.50691.d410.1023/b:catl.0000030108.50691.d4 ↗
25. Shin J, Jung U, Kim J, Kim KD, Song D, Park Y, An B-S, Koo KY (2024) Elucidating the effect of Ce with abundant surface oxygen vacancies on MgAl2O4-supported Ru-based catalysts for ammonia decomposition. Appl Catal B: Environ 340. https://doi.org/10.1016/j.apcatb.2023.12323410.1016/j.apcatb.2023.123234 ↗
26. Hill AK, Torrente-Murciano L (2015) Low temperature H2 production from ammonia using ruthenium-based catalysts: Synergetic effect of promoter and support. Appl Catal B 172–173:129–135. https://doi.org/10.1016/j.apcatb.2015.02.01110.1016/j.apcatb.2015.02.011 ↗
27. Chen C, Wu K, Ren H, Zhou C, Luo Y, Lin L, Au C, Jiang L (2021) Ru-based catalysts for ammonia decomposition: a mini-review. Energy Fuels 35:11693–11706. https://doi.org/10.1021/acs.energyfuels.1c0126110.1021/acs.energyfuels.1c01261 ↗
28. Yin S-F, Zhang Q-H, Xu B-Q, Zhu W-X, Ng C-F, Au C-T (2004) Investigation on the catalysis of COx-free hydrogen generation from ammonia. J Catal 224:384–396. https://doi.org/10.1016/j.jcat.2004.03.00810.1016/j.jcat.2004.03.008 ↗
29. Li L, Chen F, Dai Y, Wu J, Shao JL, Li HY (2016) Fe-assisted Ru clusters supported on porous and graphitic carbon for ammonia decomposition to COx free hydrogen. RSC Adv 6:102336–102342. https://doi.org/10.1039/c6ra21211e10.1039/c6ra21211e ↗
30. Kocer T, Oztuna F E S, Kurtoğlu S F, Unal U, Uzun A (2021) Graphene aerogel-supported ruthenium nanoparticles for COx-free hydrogen production from ammonia. Appl Catal A: Gen 610. https://doi.org/10.1016/j.apcata.2020.11796910.1016/j.apcata.2020.117969 ↗
31. Gompa TP, Ramanathan A, Rice NT, La Pierre HS (2020) The chemical and physical properties of tetravalent lanthanides: Pr, Nd, Tb, and Dy. Dalton Trans 49:15945–15987. https://doi.org/10.1039/d0dt01400a10.1039/d0dt01400a ↗
32. Malavekar DB, Magdum VV, Khot SD, Kim JH, Lokhande CD (2023) Doping of rare earth elements: towards enhancing the lelectrochemical performanceformance of pseudocapacitive materials. J Alloys Compd 960:170601. https://doi.org/10.1016/j.jallcom.2023.17060110.1016/j.jallcom.2023.170601 ↗
33. Zhang J, Xu H, Jin X, Ge Q, Li W (2005) Characterizations and activities of the nano-sized Ni/Al2O3 and Ni/La-Al2O3 catalysts for NH3 decomposition. Appl Catal A 290:87–96. https://doi.org/10.1016/j.apcata.2005.05.02010.1016/j.apcata.2005.05.020 ↗
34. Meng Q, Liu H, Xu K, Wang W, Jia C (2023) CeO2 modified Ru/γ-Al2O3 catalysts for ammonia decomposition reaction. J Rare Earths 41:801–809. https://doi.org/10.1016/j.jre.2023.01.01710.1016/j.jre.2023.01.017 ↗
35. Sing KSW (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 57:603–619. https://doi.org/10.1351/pac19855704060310.1351/pac198557040603 ↗
36. Im Y, Muroyama H, Matsui T, Eguchi K (2022) Investigation on catalytic performance and desorption behaviors of ruthenium catalysts supported on rare-earth oxides for NH3 decomposition. Int J Hydrogen Energy 47:32543–32551. https://doi.org/10.1016/j.ijhydene.2022.07.16210.1016/j.ijhydene.2022.07.162 ↗
37. Kresse F (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54:11169–11186. https://doi.org/10.1103/PhysRevB.54.1116910.1103/PhysRevB.54.11169 ↗
38. Yao L, Shi T, Li Y, Zhao J, Ji W, Au C-T (2011) Core–shell structured nickel and ruthenium nanoparticles: Very active and stable catalysts for the generation of COx-free hydrogen via ammonia decomposition. Catal Today 164:112–118. https://doi.org/10.1016/j.cattod.2010.10.05610.1016/j.cattod.2010.10.056 ↗
39. Li X, Ji W, Zhao J, Wang S, Au C (2005) Ammonia decomposition over Ru and Ni catalysts supported on fumed SiO2, MCM-41, and SBA-15. J Catal 236:181–189. https://doi.org/10.1016/j.jcat.2005.09.03010.1016/j.jcat.2005.09.030 ↗
40. Wang Z, Qu Y, Shen X, Cai Z (2019) Ruthenium catalyst supported on Ba modified ZrO2 for ammonia decomposition to COx-free hydrogen. Int J Hydrogen Energy 44:7300–7307. https://doi.org/10.1016/j.ijhydene.2019.01.23510.1016/j.ijhydene.2019.01.235 ↗
41. Cao C-F, Wu K, Zhou C, Yao Y-H, Luo Y, Chen C-Q, Lin L, Jiang L (2022) Electronic metal-support interaction enhanced ammonia decomposition efficiency of perovskite oxide supported ruthenium. Chem Eng Sci 257. https://doi.org/10.1016/j.ces.2022.11771910.1016/j.ces.2022.117719 ↗
42. Yin SF, Xu BQ, Zhu WX, Ng CF, Zhou XP, Au CT (2004) Carbon nanotubes-supported Ru catalyst for the generation of COx-free hydrogen from ammonia. Catal Today 93–95:27–38. https://doi.org/10.1016/j.cattod.2004.05.01110.1016/j.cattod.2004.05.011 ↗
43. Su Q, Gu LL, Zhong AH, Yao Y, Ji WJ, Ding WP, Au CT (2018) Layered double hydroxide derived Mg2Al-LDO supported and K-modified Ru catalyst for hydrogen production via ammonia decomposition. Catal Lett 148:894–903. https://doi.org/10.1007/s10562-017-2195-110.1007/s10562-017-2195-1 ↗
44. Choudhary TV, Sivadinarayana C, Goodman DW (2001) Catalytic ammonia decomposition: COx-free hydrogen production for fuel cell applications. Catal Lett 72:197–201. https://doi.org/10.1023/A:100902382554910.1023/A:1009023825549 ↗
45. Su Q, Gu L, Yao Y, Zhao J, Ji W, Ding W, Au C-T (2017) Layered double hydroxides derived Nix(MgyAlzOn) catalysts: Enhanced ammonia decomposition by hydrogen spillover effect. Appl Catal B 201:451–460. https://doi.org/10.1016/j.apcatb.2016.08.05110.1016/j.apcatb.2016.08.051 ↗
46. Li L, Wang Y, Xu ZP, Zhu Z (2013) Catalytic ammonia decomposition for CO-free hydrogen generation over Ru/Cr2O3 catalysts. Appl Catal A 467:246–252. https://doi.org/10.1016/j.apcata.2013.07.00310.1016/j.apcata.2013.07.003 ↗