Carbon-CeO2 interface confinement enhances the chemical stability of Pt nanocatalyst for catalytic oxidation reactions

More info
  • ReceivedMar 25, 2020
  • AcceptedApr 16, 2020
  • PublishedJul 10, 2020



the National Key Research and Development Program of China(2016YFB0701100)

the National Natural Science Foundation of China(51771047,51525101,51971059)

and the Fundamental Research Funds for the Central Universities(N180204014)


This work was supported by the National Key Research and Development Program of China (2016YFB0701100), the National Natural Science Foundation of China (51771047, 51525101 and 51971059), and the Fundamental Research Funds for the Central Universities (N180204014).

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Li S and Xu C conceived the idea and designed the experiments. Xu C, Zhang Y, and Chen J carried out the synthesis, characterization and catalytic experiments. All authors contributed to the discussion of the results and commented on the manuscript writing.

Author information

Changjin Xu received his BSc degree from Inner Mongolia Agricultural University in 2014. Currently, he is a PhD student in the School of Materials Science and Engineering at Northeastern University (China). His research interests focus on the heterogeneous nanocatalysts.

Song Li is a professor of materials science and engineering at Northeastern University, China. He received his BSc degree in 2003 from Northeastern University and PhD degree in materials physics from the University of Lorraine in 2009. His current research focuses on metal-based structured catalysts, including noble metal alloys and intermetallics, metal-oxide interfaces, and processing intensification.

Supplementary data

Supplementary information

Experimental details and supporting data are available in the online version of the paper.


[1] Nie L, Mei D, Xiong H, et al. Activation of surface lattice oxygen in single-atom Pt/CeO2 for low-temperature CO oxidation. Science, 2017, 3581419-1423 CrossRef PubMed ADS Google Scholar

[2] Wang F, He S, Chen H, et al. Active site dependent reaction mechanism over Ru/CeO2 catalyst toward CO2 methanation. J Am Chem Soc, 2016, 1386298-6305 CrossRef PubMed Google Scholar

[3] Suchorski Y, Kozlov SM, Bespalov I, et al. The role of metal/oxide interfaces for long-range metal particle activation during CO oxidation. Nat Mater, 2018, 17519-522 CrossRef PubMed ADS Google Scholar

[4] Chen G, Yang Y, Guo Z, et al. Thermally stable and highly active Pt/CeO2@SiO2 catalysts with a porous/hollow structure. Catal Sci Technol, 2018, 84413-4419 CrossRef Google Scholar

[5] Wang J, Xu M, Zhao J, et al. Anchoring ultrafine Pt electrocatalysts on TiO2-C via photochemical strategy to enhance the stability and efficiency for oxygen reduction reaction. Appl Catal B-Environ, 2018, 237228-236 CrossRef Google Scholar

[6] Cao XQ, Zhou J, Li S, et al. Ultra-stable metal nano-catalyst synthesis strategy: A perspective. Rare Met, 2020, 39113-130 CrossRef Google Scholar

[7] Dai Y, Lu P, Cao Z, et al. The physical chemistry and materials science behind sinter-resistant catalysts. Chem Soc Rev, 2018, 474314-4331 CrossRef PubMed Google Scholar

[8] Campbell CT. The energetics of supported metal nanoparticles: Relationships to sintering rates and catalytic activity. Acc Chem Res, 2013, 461712-1719 CrossRef PubMed Google Scholar

[9] Chen J, Wanyan Y, Zeng J, et al. Surface engineering protocol to obtain an atomically dispersed Pt/CeO2 catalyst with high activity and stability for CO oxidation. ACS Sustain Chem Eng, 2018, 614054-14062 CrossRef Google Scholar

[10] Hemmingson SL, Campbell CT. Trends in adhesion energies of metal nanoparticles on oxide surfaces: understanding support effects in catalysis and nanotechnology. ACS Nano, 2017, 111196-1203 CrossRef Google Scholar

[11] Cao X, Zhou J, Wang H, et al. Abnormal thermal stability of sub-10 nm Au nanoparticles and their high catalytic activity. J Mater Chem A, 2019, 710980-10987 CrossRef Google Scholar

[12] Chen G, Zhao Y, Fu G, et al. Interfacial effects in iron-nickel hydroxide-platinum nanoparticles enhance catalytic oxidation. Science, 2014, 344495-499 CrossRef PubMed ADS Google Scholar

[13] Cao K, Shi L, Gong M, et al. Nanofence stabilized platinumnanoparticles catalyst via facet-selective atomic layer deposition. Small, 2017, 131700648 CrossRef PubMed Google Scholar

[14] Zhang J, Wang L, Zhang B, et al. Sinter-resistant metal nanoparticle catalysts achieved by immobilization within zeolite crystals via seed-directed growth. Nat Catal, 2018, 1540-546 CrossRef Google Scholar

[15] Liu H, Wang H, Liu Z, et al. Confinement impact for the dynamics of supported metal nanocatalyst. Small, 2018, 141801586 CrossRef PubMed Google Scholar

[16] Zhu X, Guo Q, Sun Y, et al. Optimising surface d charge of AuPd nanoalloy catalysts for enhanced catalytic activity. Nat Commun, 2019, 101428 CrossRef PubMed ADS Google Scholar

[17] Liu Y, Chen H, Xu C, et al. Control of catalytic activity of nano-Au through tailoring the Fermi level of support. Small, 2019, 151901789 CrossRef PubMed Google Scholar

[18] Ahmadi M, Mistry H, Roldan Cuenya B. Tailoring the catalytic properties of metal nanoparticles via support interactions. J Phys Chem Lett, 2016, 73519-3533 CrossRef PubMed Google Scholar

[19] Bruix A, Rodriguez JA, Ramírez PJ, et al. A new type of strong metal-support interaction and the production of H2 through the transformation of water on Pt/CeO2 (111) and Pt/CeOx/TiO2 (110) catalysts. J Am Chem Soc, 2012, 1348968-8974 CrossRef PubMed Google Scholar

[20] Campbell CT. Electronic perturbations. Nat Chem, 2012, 4597-598 CrossRef PubMed ADS Google Scholar

[21] Klyushin AY, Jones TE, Lunkenbein T, et al. Strong metal support interaction as a key factor of Au activation in CO oxidation. ChemCatChem, 2018, 103985-3989 CrossRef Google Scholar

[22] Xu C, Wu Y, Li S, et al. Engineering the epitaxial interface of Pt-CeO2 by surface redox reaction guided nucleation for low temperature CO oxidation. J Mater Sci Tech, 2020, 4039-46 CrossRef Google Scholar

[23] Tran SBT, Choi H, Oh S, et al. Defective Nb2O5-supported Pt catalysts for CO oxidation: promoting catalytic activity via oxygen vacancy engineering. J Catal, 2019, 375124-134 CrossRef Google Scholar

[24] Lykhach Y, Kozlov SM, Skála T, et al. Counting electrons on supported nanoparticles. Nat Mater, 2016, 15284-288 CrossRef PubMed ADS Google Scholar

[25] Kim GJ, Kwon DW, Hong SC. Effect of Pt particle size and valence state on the performance of Pt/TiO2 catalysts for CO oxidation at room temperature. J Phys Chem C, 2016, 12017996-18004 CrossRef Google Scholar

[26] Ke J, Zhu W, Jiang Y, et al. Strong local coordination structure effects on subnanometer PtOx clusters over CeO2 nanowires probed by low-temperature CO oxidation. ACS Catal, 2015, 55164-5173 CrossRef Google Scholar

[27] Vayssilov GN, Lykhach Y, Migani A, et al. Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles. Nat Mater, 2011, 10310-315 CrossRef PubMed ADS Google Scholar

[28] Lu G, Hupp JT. Metal-organic frameworks as sensors: A ZIF-8 based Fabry-Pérot device as a selective sensor for chemical vapors and gases. J Am Chem Soc, 2010, 1327832-7833 CrossRef PubMed Google Scholar

[29] Rong J, Qiu F, Zhang T, et al. Non-noble metal@carbon nanosheet derived from exfoliated MOF crystal as highly reactive and stable heterogeneous catalyst. Appl Surf Sci, 2018, 447222-234 CrossRef ADS Google Scholar

[30] Horcajada P, Chalati T, Serre C, et al. Porous metal-organic-framework nanoscale carriers as a potential platform for drug delivery and imaging. Nat Mater, 2010, 9172-178 CrossRef PubMed ADS Google Scholar

[31] Zhang P, Chen C, Kang X, et al. In situ synthesis of sub-nanometer metal particles on hierarchically porous metal-organic frameworks via interfacial control for highly efficient catalysis. Chem Sci, 2018, 91339-1343 CrossRef PubMed Google Scholar

[32] deKrafft KE, Wang C, Lin W. Metal-organic framework templated synthesis of Fe2O3/TiO2 nanocomposite for hydrogen production. Adv Mater, 2012, 242014-2018 CrossRef PubMed Google Scholar

[33] Kaneti YV, Dutta S, Hossain MSA, et al. Strategies for improving the functionality of zeolitic imidazolate frameworks: Tailoring nanoarchitectures for functional applications. Adv Mater, 2017, 291700213 CrossRef PubMed Google Scholar

[34] Bai X, Chen D, Li L, et al. Fabrication of MOF thin films at miscible liquid-liquid interface by spray method. ACS Appl Mater Interfaces, 2018, 1025960-25966 CrossRef Google Scholar

[35] Kaneti YV, Zhang J, He YB, et al. Fabrication of an MOF-derived heteroatom-doped Co/CoO/carbon hybrid with superior sodium storage performance for sodium-ion batteries. J Mater Chem A, 2017, 515356-15366 CrossRef Google Scholar

[36] Tang J, Salunkhe RR, Zhang H, et al. Bimetallic metal-organic frameworks for controlled catalytic graphitization of nanoporous carbons. Sci Rep, 2016, 630295 CrossRef PubMed ADS Google Scholar

[37] Nguyen CC, Nguyen DT, Do TO. A novel route to synthesize C/Pt/TiO2 phase tunable anatase-rutile TiO2 for efficient sunlight-driven photocatalytic applications. Appl Catal B-Environ, 2018, 22646-52 CrossRef Google Scholar

[38] Ning X, Li Y, Dong B, et al. Electron transfer dependent catalysis of Pt on N-doped carbon nanotubes: Effects of synthesis method on metal-support interaction. J Catal, 2017, 348100-109 CrossRef Google Scholar

[39] Isaeva VI, Belyaeva EV, Fitch AN, et al. Synthesis and structural characterization of a series of novel Zn(II)-based MOFs with pyridine-2,5-dicarboxylate linkers. Cryst Growth Des, 2013, 135305-5315 CrossRef Google Scholar

[40] Zhao P, Qin F, Huang Z, et al. MOF-derived hollow porous Ni/CeO2 octahedron with high efficiency for N2O decomposition. Chem Eng J, 2018, 34972-81 CrossRef Google Scholar

[41] Cao F, Zhang S, Gao W, et al. Facile synthesis of highly-dispersed Pt/CeO2 by a spontaneous surface redox chemical reaction for CO oxidation. Catal Sci Technol, 2018, 83233-3237 CrossRef Google Scholar

[42] Liu H, Wang J, Feng Z, et al. Facile synthesis of Au nanoparticles embedded in an ultrathin hollow graphene nanoshell with robust catalytic performance. Small, 2015, 115059-5064 CrossRef PubMed Google Scholar

[43] Li WZ, Kovarik L, Mei D, et al. Stable platinum nanoparticles on specific MgAl2O4 spinel facets at high temperatures in oxidizing atmospheres. Nat Commun, 2013, 42481 CrossRef PubMed ADS Google Scholar

[44] Ouyang R, Liu JX, Li WX. Atomistic theory of ostwald ripening and disintegration of supported metal particles under reaction conditions. J Am Chem Soc, 2013, 1351760-1771 CrossRef PubMed Google Scholar

[45] Naumann d’Alnoncourt R, Friedrich M, Kunkes E, et al. Strong metal-support interactions between palladium and iron oxide and their effect on CO oxidation. J Catal, 2014, 317220-228 CrossRef Google Scholar

[46] Yu X, Wang Y, Kim A, et al. Observation of temperature-dependent kinetics for catalytic CO oxidation over TiO2-supported Pt catalysts. Chem Phys Lett, 2017, 685282-287 CrossRef ADS Google Scholar

[47] Gracia FJ, Bollmann L, Wolf EE, et al. In situ FTIR, EXAFS, and activity studies of the effect of crystallite size on silica-supported Pt oxidation catalysts. J Catal, 2003, 220382-391 CrossRef Google Scholar

[48] Bera P, Priolkar KR, Gayen A, et al. Ionic dispersion of Pt over CeO2 by the combustion method: structural investigation by XRD, TEM, XPS, and EXAFS. Chem Mater, 2003, 152049-2060 CrossRef Google Scholar

[49] Liu J, Ding T, Zhang H, et al. Engineering surface defects and metal-support interactions on Pt/TiO2 (B) nanobelts to boost the catalytic oxidation of CO. Catal Sci Technol, 2018, 84934-4944 CrossRef Google Scholar

[50] Li QQ, Zhang X, Han WP, et al. Raman spectroscopy at the edges of multilayer graphene. Carbon, 2015, 85221-224 CrossRef Google Scholar

[51] Fu Y, Yu HY, Jiang C, et al. NiCo alloy nanoparticles decorated on N-doped carbon nanofibers as highly active and durable oxygen electrocatalyst. Adv Funct Mater, 2018, 281705094 CrossRef Google Scholar

[52] Liu J, Yue Y, Liu H, et al. Origin of the robust catalytic performance of nanodiamond-graphene-supported Pt nanoparticles used in the propane dehydrogenation reaction. ACS Catal, 2017, 73349-3355 CrossRef Google Scholar

[53] Jia Z, Huang F, Diao J, et al. Pt NPs immobilized on a N-doped graphene@Al2O3 hybrid support as robust catalysts for low temperature CO oxidation. Chem Commun, 2018, 5411168-11171 CrossRef PubMed Google Scholar

[54] Sun X, Wang R, Zhang B, et al. Evolution and reactivity of active oxygen species on sp2@sp3 core-shell carbon for the oxidative dehydrogenation reaction. ChemCatChem, 2014, 62270-2275 CrossRef Google Scholar

[55] Padilla R, Benito M, Rodríguez L, et al. Platinum supported catalysts for carbon monoxide preferential oxidation: Study of support influence. J Power Sources, 2009, 192114-119 CrossRef ADS Google Scholar

[56] Jardim EO, Rico-Francés S, Coloma F, et al. Influence of the metal precursor on the catalytic behavior of Pt/ceria catalysts in the preferential oxidation of CO in the presence of H2 (PROX). J Colloid Interface Sci, 2015, 44345-55 CrossRef PubMed ADS Google Scholar

[57] Kopelent R, van Bokhoven JA, Szlachetko J, et al. Catalytically active and spectator Ce3+ in ceria-supported metal catalysts. Angew Chem Int Ed, 2015, 548728-8731 CrossRef PubMed Google Scholar

  • Figure 1

    (a) Scheme for preparation of porous CeO2 support by an MOF-assisted strategy. TEM images of Ce-BDC MOFs (b), CeO2-P (c), and CeO2-C (d). (e) TG curves.

  • Figure 2

    HAADF-STEM, TEM-EDX mapping and HRTEM images of Pt/CeO2-C (a, a1–a3), and Pt/CeO2-P (b, b1–b3), respectively. The crystal lattice fringes d=0.31 and 0.23 nm are attributed to (111) facets of CeO2 and (111) planes of Pt, respectively. The white dash circles mark the Pt NPs.

  • Figure 3

    Catalytic performance of the Pt/CeO2 catalysts. (a) CO conversion as function of reaction temperature. (b) CO conversion for stability test at 90°C (mass of catalysts: 70 mg for both catalysts and 25 mg for Pt/CeO2-C to lower the CO conversion). TEM (c, e) and HAADF-STEM (d, f) images of the Pt/CeO2-C (c, d) and Pt/CeO2-P (e,f) catalysts after 20 h stability test.

  • Figure 4

    XPS spectra of Pt 4f peak of the as-prepared fresh Pt/CeO2 catalysts (a) and after the 20 h stability test (b). The ratios of Pt0 in the catalysts are displayed. Raman spectra (c) and Ce 3d XPS spectra (d) of the as-prepared Pt/CeO2 catalysts.

  • Figure 5

    In situ DRIFTS of CO adsorbed on the Pt/CeO2-C (a) and Pt/CeO2-P (b) catalysts recorded under 1% CO, 20% O2, and N2 as balance.


Contact and support