Stabilization of Sub-Nanometer Pt Clusters on CoO x Nano-Islands by Area-Selective Atomic Layer Deposition and Machine Learning Insights

Rongli Ye; Fangwen Ye; Junyang Chen; Xianbao Duan; Yaohui Dun; Bin Shan; Kun Cao; Rong Chen

doi:10.1016/j.eng.2025.10.037

Engineering ›› :202510037 DOI: 10.1016/j.eng.2025.10.037

Article

research-article

Stabilization of Sub-Nanometer Pt Clusters on CoO x Nano-Islands by Area-Selective Atomic Layer Deposition and Machine Learning Insights

Author information +

History +

PDF (3672KB)

Abstract

Sub-nanometer metallic clusters have attracted considerable interest owing to their high surface area and size-dependent properties. However, their high surface energies cause thermal instability, leading to aggregation and sintering that limit practical applications. In this study, we obtained sub-nanometer Pt clusters (average size ~0.76 nm) with highly stable configuration, deposited on CoO x nano-islands by area-selective deposition (ASD). The Pt-CoO x structures exhibited low Pt loading and high deposition selectivity. During ASD, Pt clusters were selectively deposited on CoO x regions, where strong metal-support interactions (MSI) between Pt and CoO x supported effective anchoring. Subsequent H₂ post-treatment promoted electron transfer between Pt and CoO x as well as Pt cluster migration from the Al₂O₃ substrate to the CoO x nano-islands, particularly at the Al₂O₃-CoO x interface, further improving selectivity. Potential simulations by machine learning revealed directional Pt migration and provided atomic-level insights into stabilization mechanisms. After high-temperature (at 600 °C) aging, Pt clusters remained highly dispersed without noticeable sintering, owing to the synergistic effects of physical isolation by CoO x nano-islands and strong MSI. This synergistic strategy holds practical relevance for industrial applications and provides a robust framework for designing durable catalytic structures.

Keywords

Sub-nanometer Pt clusters / Thermal stability / Area-selective deposition / Interfacial interaction / Machine learning potential

Cite this article

Download citation ▾

Rongli Ye, Fangwen Ye, Junyang Chen, Xianbao Duan, Yaohui Dun, Bin Shan, Kun Cao, Rong Chen. Stabilization of Sub-Nanometer Pt Clusters on CoO x Nano-Islands by Area-Selective Atomic Layer Deposition and Machine Learning Insights. Engineering 202510037 DOI:10.1016/j.eng.2025.10.037

登录浏览全文

4963

注册一个新账户忘记密码

References

Publishing order | Descend order by publishing year | Descend order by cited within

[1]	Zhou T, Li X, Zhao J, Luo L, Wang Y, Xiao Z, et al. Ultrafine metal nanoparticles isolated on oxide nano-islands as exceptional sintering-resistant catalysts. Nat Mater 2025; 24(6):891-9.

[2]	Min J, Seo H, Shin J, Park MY, Park SY, Choi H, et al. Atomically dispersed platinum electrocatalysts supported on gadolinia-doped ceria nanoparticles for practical high-temperature solid oxide cells. J Mater Chem A 2023; 11(46):25298-307.

[3]	Gao Y, Li Q, Wang C, Yan D, Chen J, Jia H. Light-driven efficient dry reforming of methane over Pt/La₂O₃ with long-term durability. J Mater Chem A 2022; 10(30):16016-28.

[4]	Liang L, Jin H, Zhou H, Liu B, Hu C, Chen D, et al. Cobalt single atom site isolated Pt nanoparticles for efficient ORR and HER in acid media. Nano Energy 2021; 88:106221.

[5]	Ren Y, Chen K, Zhang Y, Shi D, Wu Q, Liang D, et al. N-doped carbon confined CoFe@Pt nanoparticles with robust catalytic performance for the methanol oxidation reaction. J Mater Chem A Mater Energy Sustain 2022;10(25):13345-54.

[6]	Campbell CT, Mao Z. Chemical potential of metal atoms in supported nanoparticles: dependence upon particle size and support. ACS Catal 2017; 7(12):8460-6.

[7]	Xiao Y, Zhang J, Liu T, Xu M, Dong Y, Wang CA. Constructing morphologically stable supported noble metal catalysts in heterogeneous catalysis: mechanisms and strategies. Nano Energy 2024;129(Pt A):109975.

[8]	Hu S, Li W. Influence of particle size distribution on lifetime and thermal stability of ostwald ripening of supported particles. ChemCatChem 2018; 10(13):2900-7.

[9]	Sarnello E, Lu Z, Seifert S, Winans RE, Li T. Design and characterization of ALD-based overcoats for supported metal nanoparticle catalysts. ACS Catal 2021; 11(5):2605-19.

[10]	Solano E, Dendooven J, Feng JY, Brüner P, Minjauw MM, Ramachandran RK, et al. In situ study of the thermal stability of supported Pt nanoparticles and their stabilization via atomic layer deposition overcoating. Nanoscale 2020; 12(21):11684-93.

[11]	Cargnello M, Delgado Jaén JJ, Hernández Garrido JC, Bakhmutsky K, Montini T, Calvino Gámez JJ, et al. Exceptional activity for methane combustion over modular Pd@CeO₂ subunits on functionalized Al₂O₃. Science 2012; 337(6095):713-7.

[12]	Adijanto L, Bennett DA, Chen C, Yu AS, Cargnello M, Fornasiero P, et al. Exceptional thermal stability of Pd@CeO₂ core-shell catalyst nanostructures grafted onto an oxide surface. Nano Lett 2013; 13(5):2252-7.

[13]	Cao A, Veser G. Exceptional high-temperature stability through distillation-like self-stabilization in bimetallic nanoparticles. Nat Mater 2010; 9(1):75-81.

[14]	Carrillo C, DeLaRiva A, Xiong H, Peterson EJ, Spilde MN, Kunwar D, et al. Regenerative trapping: how Pd improves the durability of Pt diesel oxidation catalysts. Appl Catal B 2017; 218:581-90.

[15]	Chen R, Li YC, Cai JM, Cao K, Lee HBR. Atomic level deposition to extend Moore’s law and beyond. Int J Extreme Manuf 2020; 2(2):022002.

[16]	Chen R, Gu E, Cao K, Zhang J. Area selective deposition for bottom-up atomic-scale manufacturing. Int J Mach Tools Manuf 2024; 199:104173.

[17]	Chen R, Cao K, Wen Y, Yang F, Wang J, Liu X, et al. Atomic layer deposition in advanced display technologies: from photoluminescence to encapsulation. Int J Extreme Manuf 2024; 6(2):022003.

[18]	Li Y, Qi Z, Lan Y, Cao K, Wen Y, Zhang J, et al. Self-aligned patterning of tantalum oxide on Cu/SiO₂ through redox-coupled inherently selective atomic layer deposition. Nat Commun 2023; 14(1):4493.

[19]	Cheng N, Banis MN, Liu J, Riese A, Li X, Li R, et al. Extremely stable platinum nanoparticles encapsulated in a zirconia nanocage by area-selective atomic layer deposition for the oxygen reduction reaction. Adv Mater 2015; 27(2):277-81.

[20]	Aitbekova A, Zhou C, Stone ML, Lezama-Pacheco JS, Yang AC, Hoffman AS, et al. Templated encapsulation of platinum-based catalysts promotes high-temperature stability to 1,100 °C. Nat Mater 2022; 21(11):1290-7.

[21]	Cao K, Shi L, Gong M, Cai J, Liu X, Chu S, et al. Nanofence stabilized platinum nanoparticles catalyst via facet-selective atomic layer deposition. Small 2017; 13(32):1700648.

[22]	Liu X, Zhu Q, Lang Y, Cao K, Chu S, Shan B, et al. Oxide-nanotrap-anchored platinum nanoparticles with high activity and sintering resistance by area-selective atomic layer deposition. Angew Chem Int Ed Engl 2017; 56(6):1648-52.

[23]	Li X, Pereira-Hernández XI, Chen Y, Xu J, Zhao J, Pao CW, et al. Functional CeO x nanoglues for robust atomically dispersed catalysts. Nature 2022; 611(7935):284-8.

[24]	Hu S, Li WX. Sabatier principle of metal-support interaction for design of ultrastable metal nanocatalysts. Science 2021; 374(6573):1360-5.

[25]	Jones J, Xiong H, DeLaRiva AT, Peterson EJ, Pham H, Challa SR, et al. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping. Science 2016; 353(6295):150-4.

[26]	Li Z, Li B, Li Q. Single-atom nano-islands (SANIs): a robust atomic-nano system for versatile heterogeneous catalysis applications. Adv Mater 2023; 35(20):2211103.

[27]	Liu JC, Luo L, Xiao H, Zhu J, He Y, Li J. Metal affinity of support dictates sintering of gold catalysts. J Am Chem Soc 2022; 144(45):20601-9.

[28]	Cai J, Liu Z, Cao K, Lang Y, Chu S, Shan B, et al. Highly dispersed Pt studded on CoO x nanoclusters for CO preferential oxidation in H₂. J Mater Chem 2020; 8(20):10180-7.

[29]	Bobb-Semple D, Nardi KL, Draeger N, Hausmann DM, Bent SF. Area-selective atomic layer deposition assisted by self-assembled monolayers: a comparison of Cu, Co, W, and Ru. Chem Mater 2019; 31(5):1635-45.

[30]	Gladfelter WL. Selective metalization by chemical vapor deposition. Chem Mater 1993; 5(10):1372-88.

[31]	Yu X, Yu W, Li H, Tu ST, Han YF. Preparation, characterization and application of K-PtCo/Al₂O₃ catalyst coatings for preferential CO oxidation. Appl Catal B 2013;140-141:588-97.

[32]	Choya A, de Rivas B, Gutiérrez-Ortiz JI, López-Fonseca R. Comparative study of strategies for enhancing the performance of Co₃O₄/Al₂O₃ catalysts for lean methane combustion. Catalysts 2020; 10(7):757.

[33]	Dong Y, He K, Yin L, Zhang A. A facile route to controlled synthesis of Co₃O₄ nanoparticles and their environmental catalytic properties. Nanotechnology 2007; 18(43):435602.

[34]	Zhao R, Cao K, Ye R, Tang Y, Du C, Liu F, et al. Deciphering the stability mechanism of Pt-Ni/Al₂O₃ catalysts in syngas production via DRM. Chem Eng J 2024; 491:151966.

[35]	Xiong G, Feng C, Chen HC, Li J, Jiang F, Tao S, et al. Atomically dispersed Pt-doped Co₃O₄ spinel nanoparticles embedded in polyhedron frames for robust propane oxidation at low temperature. Small Methods 2023; 7(7):2300121.

[36]	Lin J, Zhao S, Yang J, Huang W, Chen C, Chen T, et al. Hydrogen spillover induced PtCo/CoO x interfaces with enhanced catalytic activity for CO oxidation at low temperatures in humid conditions. Small 2024; 20(22):2309181.

[37]	Raskó J. CO-induced surface structural changes of Pt on oxide-supported Pt catalysts studied by DRIFTS. J Catal 2003; 217(2):478-86.

[38]	Macino M, Barnes AJ, Althahban SM, Qu R, Gibson EK, Morgan DJ, et al. Tuning of catalytic sites in Pt/TiO₂ catalysts for the chemoselective hydrogenation of 3-nitrostyrene. Nat Catal 2019; 2(10):873-81.

[39]	Pham HN, DeLaRiva A, Peterson EJ, Alcala R, Khivantsev K, Szanyi J, et al. Designing ceria/alumina for efficient trapping of Platinum single atoms. ACS Sustain Chem Eng 2022; 10(23):7603-12.

[40]	Han B, Guo Y, Huang Y, Xi W, Xu J, Luo J, et al. Strong metal-support interactions between Pt single atoms and TiO₂. Angew Chem Int Ed Engl 2020; 59(29):11824-9.

[41]	Lee HBR, Pickrahn KL, Bent SF. Effect of O₃ on growth of Pt by atomic layer deposition. J Phys Chem C 2014; 118(23):12325-32.

[42]	Erkens IJM, Mackus AJM, Knoops HCM, Smits P, van de Ven THM, Roozeboom F, et al. Mass spectrometry study of the temperature dependence of Pt film growth by atomic layer deposition. ECS J Solid State Sci Technol 2012; 1(6):P255.

[43]	Baker L, Cavanagh AS, Seghete D, George SM, Mackus AJM, Kessels WMM, et al. Nucleation and growth of Pt atomic layer deposition on Al₂O₃ substrates using (methylcyclopentadienyl)-trimethyl platinum and O₂ plasma. J Appl Phys 2011; 109(8):084333.

[44]	Knoops HCM, Mackus AJM, Donders ME, van de Sanden MCM, Notten PHL, Kessels WMM. Remote plasma ALD of platinum and platinum oxide films. Electrochem Solid-State Lett 2009; 12(7):G34.

[45]	Knoops HC, Mackus A, Donders M, Van de Sanden MC, Notten P, Kessels WM. Remote plasma and thermal ALD of platinum and platinum oxide films. ECS Trans 2008; 16(4):209.

[46]	Wang W, Chen X, Cai Q, Mo G, Jiang LS, Zhang K, et al. In situ SAXS study on size changes of platinum nanoparticles with temperature. Eur Phys J B 2008; 65(1):57-64.

[47]	Dinh KHT, Ta HTT, Nguyen NL, Le VT, Nguyen VH, Van Bui H. Dimension control of Platinum nanostructures by atomic layer deposition: from surface chemical reactions to applications. Chem Mater 2023; 35(6):2248-80.

[48]	Lentz C, Jand SP, Melke J, Roth C, Kaghazchi P. DRIFTS study of CO adsorption on Pt nanoparticles supported by DFT calculations. J Mol Catal A 2017;426(Part A):1-9.

[49]	Wang Y, Zhu B, Cheng B, Macyk W, Kuang P, Yu J. Hollow carbon sphere-supported Pt/CoO x hybrid with excellent hydrogen evolution activity and stability in acidic environment. Appl Catal B 2022; 314:121503.