skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Atomically Dispersed Reduced Graphene Aerogel-Supported Iridium Catalyst with an Iridium Loading of 14.8 wt %

Abstract

Atomically dispersed iridium complexes were anchored on a reduced graphene aerogel (rGA) by the reaction of Ir(CO)2(acac) [acac = acetonylacetonato] with oxygen-containing groups on the rGA. Characterization by X-ray absorption, infrared, and X-ray photoelectron spectroscopies and atomic resolution aberration-corrected scanning transmission electron microscopy demonstrates atomically dispersed iridium, at the remarkably high loading of 14.8 wt %. The rGA support offers sites for metal bonding comparable to those of metal oxides, but with the advantages of high density and a relatively high degree of uniformity, as indicated by the same turnover frequencies for catalytic hydrogenation of ethylene at low and high iridium loadings. We note the atomic dispersion at a high metal loading—and the high density of catalytic sites per unit of reactor volume, a key criterion for practical catalysts—set this catalyst apart from those reported.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [3];  [3]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Koç Univ., Istanbul (Turkey)
  2. Univ. of California, Davis, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Scientific and Technological Research Council of Turkey (TUBITAK)
OSTI Identifier:
1598414
Grant/Contract Number:  
AC02-76SF00515; FG02-04ER15513; 217M547
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 11; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; single-site; catalyst; iridium; noble metal; graphene; high metal loading; atomic dispersion

Citation Formats

Babucci, Melike, Sarac Oztuna, F. Eylul, Debefve, Louise M., Boubnov, Alexey, Bare, Simon R., Gates, Bruce C., Unal, Ugur, and Uzun, Alper. Atomically Dispersed Reduced Graphene Aerogel-Supported Iridium Catalyst with an Iridium Loading of 14.8 wt %. United States: N. p., 2019. Web. https://doi.org/10.1021/acscatal.9b02231.
Babucci, Melike, Sarac Oztuna, F. Eylul, Debefve, Louise M., Boubnov, Alexey, Bare, Simon R., Gates, Bruce C., Unal, Ugur, & Uzun, Alper. Atomically Dispersed Reduced Graphene Aerogel-Supported Iridium Catalyst with an Iridium Loading of 14.8 wt %. United States. https://doi.org/10.1021/acscatal.9b02231
Babucci, Melike, Sarac Oztuna, F. Eylul, Debefve, Louise M., Boubnov, Alexey, Bare, Simon R., Gates, Bruce C., Unal, Ugur, and Uzun, Alper. Tue . "Atomically Dispersed Reduced Graphene Aerogel-Supported Iridium Catalyst with an Iridium Loading of 14.8 wt %". United States. https://doi.org/10.1021/acscatal.9b02231. https://www.osti.gov/servlets/purl/1598414.
@article{osti_1598414,
title = {Atomically Dispersed Reduced Graphene Aerogel-Supported Iridium Catalyst with an Iridium Loading of 14.8 wt %},
author = {Babucci, Melike and Sarac Oztuna, F. Eylul and Debefve, Louise M. and Boubnov, Alexey and Bare, Simon R. and Gates, Bruce C. and Unal, Ugur and Uzun, Alper},
abstractNote = {Atomically dispersed iridium complexes were anchored on a reduced graphene aerogel (rGA) by the reaction of Ir(CO)2(acac) [acac = acetonylacetonato] with oxygen-containing groups on the rGA. Characterization by X-ray absorption, infrared, and X-ray photoelectron spectroscopies and atomic resolution aberration-corrected scanning transmission electron microscopy demonstrates atomically dispersed iridium, at the remarkably high loading of 14.8 wt %. The rGA support offers sites for metal bonding comparable to those of metal oxides, but with the advantages of high density and a relatively high degree of uniformity, as indicated by the same turnover frequencies for catalytic hydrogenation of ethylene at low and high iridium loadings. We note the atomic dispersion at a high metal loading—and the high density of catalytic sites per unit of reactor volume, a key criterion for practical catalysts—set this catalyst apart from those reported.},
doi = {10.1021/acscatal.9b02231},
journal = {ACS Catalysis},
number = 11,
volume = 9,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: FESEM images of bare rGA at a magnification of (a) 70 kX and (b) 550 kX.

Save / Share:

Works referenced in this record:

Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts
journal, June 2018


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


The electronic structure of iridium and its oxides: The electronic structure of iridium and its oxides
journal, December 2015

  • Pfeifer, Verena; Jones, Travis E.; Velasco Vélez, Juan J.
  • Surface and Interface Analysis, Vol. 48, Issue 5
  • DOI: 10.1002/sia.5895

Probing the Thermal Deoxygenation of Graphene Oxide Using High-Resolution In Situ X-ray-Based Spectroscopies
journal, August 2011

  • Ganguly, Abhijit; Sharma, Surbhi; Papakonstantinou, Pagona
  • The Journal of Physical Chemistry C, Vol. 115, Issue 34
  • DOI: 10.1021/jp203741y

Isolated Metal Atom Geometries as a Strategy for Selective Heterogeneous Hydrogenations
journal, March 2012

  • Kyriakou, Georgios; Boucher, Matthew B.; Jewell, April D.
  • Science, Vol. 335, Issue 6073
  • DOI: 10.1126/science.1215864

Operando study of iridium acetylacetonate decomposition on amorphous silica–alumina for bifunctional catalyst preparation
journal, January 2010

  • Nassreddine, Salim; Bergeret, Gérard; Jouguet, Bernadette
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 28
  • DOI: 10.1039/b925062j

Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra
journal, September 2016

  • Hoffman, Adam S.; Fang, Chia-Yu; Gates, Bruce C.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
  • DOI: 10.1021/acs.jpclett.6b01825

A new method for parameterization of phase shift and backscattering amplitude
journal, March 1995

  • Vaarkamp, Marius; Linders, Johannes C.; Koningsberger, Diek C.
  • Physica B: Condensed Matter, Vol. 208-209
  • DOI: 10.1016/0921-4526(94)00658-I

Layer-by-Layer Grown Electrodes Composed of Cationic Fe 3 O 4 Nanoparticles and Graphene Oxide Nanosheets for Electrochemical Energy Storage Devices
journal, January 2019

  • Sarac Oztuna, F. Eylul; Unal, Ozlem; Erdem, Emre
  • The Journal of Physical Chemistry C, Vol. 123, Issue 6
  • DOI: 10.1021/acs.jpcc.8b11772

Self-Assembled Three-Dimensional Graphene-Based Aerogel with Embedded Multifarious Functional Nanoparticles and Its Excellent Photoelectrochemical Activities
journal, January 2014

  • Han, Weijia; Ren, Long; Gong, Lunjun
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 4
  • DOI: 10.1021/sc400417u

Catalysis by Supported Single Metal Atoms
journal, November 2016


Synthesis and Characterization of Highly Crystalline Graphene Aerogels
journal, October 2014

  • Worsley, Marcus A.; Pham, Thang T.; Yan, Aiming
  • ACS Nano, Vol. 8, Issue 10, p. 11013-11022
  • DOI: 10.1021/nn505335u

Nature of the metal-support interface in supported metal catalysts: Results from X-ray absorption spectroscopy
journal, January 1992

  • Koningsberger, D. C.; Gates, B. C.
  • Catalysis Letters, Vol. 14, Issue 3-4
  • DOI: 10.1007/BF00769664

Stability investigation of a high number density Pt 1 /Fe 2 O 3 single-atom catalyst under different gas environments by HAADF-STEM
journal, March 2018


Controlling catalytic activity and selectivity for partial hydrogenation by tuning the environment around active sites in iridium complexes bonded to supports
journal, January 2019

  • Babucci, Melike; Fang, Chia-Yu; Perez-Aguilar, Jorge E.
  • Chemical Science, Vol. 10, Issue 9
  • DOI: 10.1039/C8SC05287E

Beating Heterogeneity of Single-Site Catalysts: MgO-Supported Iridium Complexes
journal, March 2018


Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013

  • Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300361m

Fabrication of Single-Atom Catalysts with Precise Structure and High Metal Loading
journal, October 2018


Transmission and fluorescence X-ray absorption spectroscopy cell/flow reactor for powder samples under vacuum or in reactive atmospheres
journal, July 2016

  • Hoffman, A. S.; Debefve, L. M.; Bendjeriou-Sedjerari, A.
  • Review of Scientific Instruments, Vol. 87, Issue 7
  • DOI: 10.1063/1.4958824

Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011

  • Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
  • Nature Chemistry, Vol. 3, Issue 8
  • DOI: 10.1038/nchem.1095

Multiple-scattering calculations of x-ray-absorption spectra
journal, July 1995


Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles
journal, April 2018


Unusual infrared-absorption mechanism in thermally reduced graphene oxide
journal, September 2010

  • Acik, M.; Lee, G.; Mattevi, C.
  • Nature Materials, Vol. 9, Issue 10
  • DOI: 10.1038/nmat2858

The Role of Intercalated Water in Multilayered Graphene Oxide
journal, October 2010

  • Acik, Muge; Mattevi, Cecilia; Gong, Cheng
  • ACS Nano, Vol. 4, Issue 10
  • DOI: 10.1021/nn101844t

Avogadro: an advanced semantic chemical editor, visualization, and analysis platform
journal, August 2012

  • Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C.
  • Journal of Cheminformatics, Vol. 4, Issue 1
  • DOI: 10.1186/1758-2946-4-17

High-rate capacitive performance of graphene aerogel with a superhigh C/O molar ratio
journal, January 2012

  • Wu, Xiaozhong; Zhou, Jin; Xing, Wei
  • Journal of Materials Chemistry, Vol. 22, Issue 43
  • DOI: 10.1039/c2jm35278h

Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids
journal, September 2017


Graphene Aerogel Supported Pt Electrocatalysts for Oxygen Reduction Reaction by Supercritical Deposition
journal, October 2017


    Works referencing / citing this record:

    One‐Pot Cooperation of Single‐Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization‐Hydrosilylation Process
    journal, February 2020

    • Sarma, Bidyut B.; Kim, Jonglack; Amsler, Jonas
    • Angewandte Chemie, Vol. 132, Issue 14
    • DOI: 10.1002/ange.201915255

    One‐Pot Cooperation of Single‐Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization‐Hydrosilylation Process
    journal, February 2020

    • Sarma, Bidyut B.; Kim, Jonglack; Amsler, Jonas
    • Angewandte Chemie International Edition, Vol. 59, Issue 14
    • DOI: 10.1002/anie.201915255