Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports

Megan E. Strayer, Jason M. Binz, Mihaela Tanase, Seyed Mehdi Kamali Shahri, Renu Sharma, Robert Martin Rioux, Jr., Thomas E. Mallouk

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb 3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al 0.02)O10.02F1.96), and α-Zr(HPO 4)2·H2O. High surface area SiO 2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with "H values in the range -32 kJ·mol-1 Rh to -37 kJ·mol-1 Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports.

Original languageEnglish (US)
Pages (from-to)5687-5696
Number of pages10
JournalJournal of the American Chemical Society
Volume136
Issue number15
DOIs
StatePublished - Apr 16 2014

Fingerprint

Rhodium
Nanoparticles
Oxides
Calorimetry
Nanosheets
Titration
Metal Nanoparticles
Metal nanoparticles
Transmission Electron Microscopy
X-Ray Absorption Spectroscopy
Transmission electron microscopy
Synchrotrons
X ray absorption spectroscopy
X ray absorption
Coarsening
X ray scattering
Distribution functions
Enthalpy
Metals
X-Rays

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Strayer, Megan E. ; Binz, Jason M. ; Tanase, Mihaela ; Kamali Shahri, Seyed Mehdi ; Sharma, Renu ; Rioux, Jr., Robert Martin ; Mallouk, Thomas E. / Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 15. pp. 5687-5696.
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Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports. / Strayer, Megan E.; Binz, Jason M.; Tanase, Mihaela; Kamali Shahri, Seyed Mehdi; Sharma, Renu; Rioux, Jr., Robert Martin; Mallouk, Thomas E.

In: Journal of the American Chemical Society, Vol. 136, No. 15, 16.04.2014, p. 5687-5696.

Research output: Contribution to journalArticle

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T1 - Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports

AU - Strayer, Megan E.

AU - Binz, Jason M.

AU - Tanase, Mihaela

AU - Kamali Shahri, Seyed Mehdi

AU - Sharma, Renu

AU - Rioux, Jr., Robert Martin

AU - Mallouk, Thomas E.

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N2 - Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb 3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al 0.02)O10.02F1.96), and α-Zr(HPO 4)2·H2O. High surface area SiO 2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with "H values in the range -32 kJ·mol-1 Rh to -37 kJ·mol-1 Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports.

AB - Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb 3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al 0.02)O10.02F1.96), and α-Zr(HPO 4)2·H2O. High surface area SiO 2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with "H values in the range -32 kJ·mol-1 Rh to -37 kJ·mol-1 Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports.

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