Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co1–xPtx Clusters under H2 and CO + H2 Atmospheres

doi:10.1021/acs.jpcc.6b06483

Title: Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co _1–xPt _x Clusters under H ₂ and CO + H ₂ Atmospheres

Full Record
Other Related Research

Abstract

In this study, Co _1–xPt _x clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al ₂O ₃ was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged cluster samples were characterized by grazing-incidence X-ray absorption spectroscopy (GIXAS) and then pretreated with diluted hydrogen and further exposed to the mixture of diluted CO and H ₂ up to 225°C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the clusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the clusters. For example, a low Pt/Co ratio (x ≤ 0.5) facilitates the formation of Co(OH) ₂, whereas a high Pt/Comore »« less

Authors:

Yang, Bing ^[1]; Khadra, Ghassan ^[2]; Tuaillon-Combes, Juliette ^[2]; Tyo, Eric C. ^[1]; Pellin, Michael J. ^[1]; Reinhart, Benjamin ^[3]; Seifert, Sönke ^[3]; Chen, Xinqi ^[4]; Dupuis, Veronique ^[2]; Vajda, Stefan ^[5]

Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
University Lyon & CNRS, Lyon (France). Institut Lumiere Matiere
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
Northwestern Univ., Evanston, IL (United States). Department of Mechanical Engineering
Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division and Nanoscience and Technology Division; Yale Univ., New Haven, CT (United States). Department of Chemical and Environmental Engineering; Univ. of Chicago, IL (United States). Institute for Molecular Engineering

Publication Date:: 2016-08-25

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1352595

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 120; Journal Issue: 38; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Yang, Bing, Khadra, Ghassan, Tuaillon-Combes, Juliette, Tyo, Eric C., Pellin, Michael J., Reinhart, Benjamin, Seifert, Sönke, Chen, Xinqi, Dupuis, Veronique, and Vajda, Stefan. Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co1–xPtx Clusters under H2 and CO + H2 Atmospheres.  United States: N. p., 2016. 
        Web.  doi:10.1021/acs.jpcc.6b06483.

Copy to clipboard


                    Yang, Bing, Khadra, Ghassan, Tuaillon-Combes, Juliette, Tyo, Eric C., Pellin, Michael J., Reinhart, Benjamin, Seifert, Sönke, Chen, Xinqi, Dupuis, Veronique, & Vajda, Stefan. Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co1–xPtx Clusters under H2 and CO + H2 Atmospheres.  United States.  doi:10.1021/acs.jpcc.6b06483.

Copy to clipboard


                    Yang, Bing, Khadra, Ghassan, Tuaillon-Combes, Juliette, Tyo, Eric C., Pellin, Michael J., Reinhart, Benjamin, Seifert, Sönke, Chen, Xinqi, Dupuis, Veronique, and Vajda, Stefan. Thu .  
        "Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co1–xPtx Clusters under H2 and CO + H2 Atmospheres".  United States.  doi:10.1021/acs.jpcc.6b06483.  https://www.osti.gov/servlets/purl/1352595.

Copy to clipboard


                    
@article{osti_1352595,

  title        = {Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co1–xPtx Clusters under H2 and CO + H2 Atmospheres},

  author       = {Yang, Bing and Khadra, Ghassan and Tuaillon-Combes, Juliette and Tyo, Eric C. and Pellin, Michael J. and Reinhart, Benjamin and Seifert, Sönke and Chen, Xinqi and Dupuis, Veronique and Vajda, Stefan},

  abstractNote = {In this study, Co1–xPtx clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al2O3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged cluster samples were characterized by grazing-incidence X-ray absorption spectroscopy (GIXAS) and then pretreated with diluted hydrogen and further exposed to the mixture of diluted CO and H2 up to 225°C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the clusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the clusters. For example, a low Pt/Co ratio (x ≤ 0.5) facilitates the formation of Co(OH)2, whereas a high Pt/Co ratio (x = 0.75) stabilizes the Co3O4 composition instead through the formation of a Co–Pt core–shell structure where the platinum shell inhibits the reduction of cobalt in the core of the Co1–xPtx alloy clusters. Finally, the obtained results indicate methods for optimizing the composition and structure of binary alloy clusters for catalysis.},

  doi          = {10.1021/acs.jpcc.6b06483},

  journal      = {Journal of Physical Chemistry. C},

  number       = 38,

  volume       = 120,

  place        = {United States},

  year         = {2016},

  month        = {8}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acs.jpcc.6b06483

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co _1–x Pt _x Clusters under H ₂ and CO + H ₂ Atmospheres

Journal Article Yang, Bing ; Khadra, Ghassan ; Tuaillon-Combes, Juliette ; ... - Journal of Physical Chemistry. C

Co1-xPtx clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al2O3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged duster samples were characterized by grazing-incidence X-ray absorption spectroscopy (GIXAS) and then pretreated with diluted hydrogenmore »« less
DOI: 10.1021/acs.jpcc.6b06483
Rhenium-platinum mixed-metal spiked-triangle clusters. Synthesis and X-ray characterization of the cluster anions [Re{sub 2}Pt({mu}-H){sub 2}(CO){sub 9}[Re(CO){sub 5}]]{sup -} and [Re{sub 2}Pt({mu}-H){sub 2}(CO){sub 9}[Re{sub 2}(CO){sub 9}]]RB{sup -}

Journal Article Bergamo, M. ; Beringhelli, T. ; D`Alfonso, G. ; ... - Organometallics

The spiked-triangle cluster [Re{sub 2}Pt({mu}-H){sub 2}(CO){sub 9}[Re(CO){sub 5}]] B@ (1), which contains a HRe(CO){sub 5} molecule bound to the Pt vertex of a Re{sub 2}Pt triangle, reacts with methanolic NEt{sub 4}OH to give the red anion [Re{sub 2}Pt({mu}-H){sub 2}(CO){sub 9}[Re(CO){sub 5}]]{sup -} (2), whose structure has been determined by single-crystal X-ray analysis of its NEt{sub 4}{sup +} salt. NMR monitoring showed the intermediate formation of a carbomethoxy derivative 3, arising from the attack of OMe{sup -} on a carbonyl of the HRe(CO){sub 5} group. The deprotonation of 1 can be performed also by a base as weak as pyridine. Themore »« less
DOI: 10.1021/om9507080
Structural Evolution of Li _xNi _yMn _zCo _1-y-zO ₂ Cathode Materials during High-Rate Charge and Discharge

Journal Article Hwang, Sooyeon ; Jo, Eunmi ; Chung, Kyung Yoon ; ... - Journal of Physical Chemistry Letters

Ni-rich lithium transition metal oxides have received significant attention due to their high capacities and rate capabilities determined via theoretical calculations. Although the structural properties of these materials are strongly correlated with the electrochemical performance, their structural stability during the high-rate electrochemical reactions has not been fully evaluated yet. In this work, transmission electron microscopy is used to investigate the crystallographic and electronic structural modifications of Ni-based cathode materials at a high charge/discharge rate of 10 C. It is found that the high-rate electrochemical reactions induce structural inhomogeneity near the surface of Ni-rich cathode materials, which limits Li transport andmore »« less
Cited by 1
DOI: 10.1021/acs.jpclett.7b02579

Full Text Available
Cluster synthesis. 40. New high-nuclearity platinum-ruthenium carbonyl cluster complexes. Synthesis and structural characterizations of Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2], Ru[sub 7]Pt[sub 3](CO)[sub 22]([mu][sub 3]-H)[sub 2], and Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-[eta][sup 2]-CO)[sub 2](dppe)([mu]-H)[sub 2] with a new type of triply bridging CO ligand and the new layered cluster complex Ru[sub 6]Pt[sub 3](CO)[sub 21]([mu]-CO)([mu][sub 3]-H)[sub 2]

Journal Article Adams, R.D. ; Zhaoyang Li ; Jauching Lii ; ... - Organometallics; (United States)

The reaction of Ru[sub 4]Pt[sub 2](CO)[sub 18] with Ru[sub 4](CO)[sub 13]([mu]-H)[sub 2] at 97[degrees]C yielded the new decanuclear platinum-ruthenium carbonyl cluster complex Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2] 1 (22%). In a similar manner the reaction of Ru[sub 4]Pt[sub 2](CO)[sub 18] with Ru[sub 3]Pt(CO)[sub 10](COD)([mu]-H)[sub 2], 2, in 25% yield. Both compounds were characterized by IR, [sup 1]H NMR, and single-crystal X-ray diffraction analyses, and both were bound to consist of similar edge-fused bioctahedral clusters with platinum atoms along the edge-sharing sites. There are strong metal-metal bonds between the apices of the adjacent octahedra. Both compounds are electron deficient, andmore »« less
DOI: 10.1021/om00060a014
Characterization of Electronic and Ionic Transport in Li _1- _xNi _0.33Mn _0.33Co _0.33O ₂ (NMC ₃₃₃) and Li _1- _xNi _0.50Mn _0.20Co _0.30O ₂ (NMC ₅₂₃) as a Function of Li Content

Journal Article Amin, Ruhul ; Chiang, Yet -Ming - Journal of the Electrochemical Society

Despite the extensive commercial use of Li _1-xNi _1-y-zMn _zCo _yO ₂ (NMC) as the positive electrode in Li-ion batteries, and its long research history, its fundamental transport properties are poorly understood. These properties are crucial for designing high energy density and high power Li-ion batteries. Here, the transport properties of NMC ₃₃₃ and NMC ₅₂₃ are investigated using impedance spectroscopy and DC polarization and depolarization techniques. The electronic conductivity is found to increase with decreasing Li-content (increasing state-of-charge) from ~10 ^–7 Scm ^–1 to ~10 ^–2 Scm ^–1 over Li concentrations x = 0.00 to 0.75, corresponding to anmore »« less
Cited by 27
DOI: 10.1149/2.0131608jes

Full Text Available

Similar Records

Title: Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co 1–xPt x Clusters under H 2 and CO + H 2 Atmospheres

Abstract

Citation Formats

Title: Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co _1–xPt _x Clusters under H ₂ and CO + H ₂ Atmospheres