In Situ Formation of FeRh Nanoalloys for Oxygenate Synthesis

Carrillo, Pamela; Shi, Rui; Teeluck, Krishani; Senanayake, Sanjaya D.; White, Michael G.

doi:10.1021/acscatal.8b02235

Title: In Situ Formation of FeRh Nanoalloys for Oxygenate Synthesis

Journal Article · Wed Jun 27 00:00:00 EDT 2018 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.8b02235· OSTI ID:1462400

Carrillo, Pamela ^[1]; Shi, Rui ^[1]; Teeluck, Krishani ^[1];

^[2];

^[3]

Stony Brook Univ., NY (United States). Dept. of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division; Stony Brook Univ., NY (United States). Dept. of Chemistry

Early and late transition metals are often combined as a strategy to tune the selectivity of catalysts for the conversion of syngas (CO/H₂) to C₂₊ oxygenates, such as ethanol. Here we show how the use of a highly reducible Fe₂O₃ support for Rh leads to the in situ formation of supported FeRh nanoalloy catalysts that exhibit high selectivity for ethanol synthesis. In situ characterizations by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) reveal the coexistence of iron oxide, iron carbide, metallic iron, and FeRh alloy phases depending on reaction conditions and Rh loading. Structural analysis coupled with catalytic testing indicates that oxygenate formation is correlated to the presence of FeRh alloys, while the iron oxide and carbide phases lead mainly to hydrocarbons. Finally, the formation of nanoalloys by in situ reduction of a metal oxide support under working conditions represents a simple approach for the preparation bimetallic catalysts with enhanced catalytic properties.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1462400

Report Number(s):: BNL-207863-2018-JAAM

Journal Information:: ACS Catalysis, Vol. 8; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 22 works

Citation information provided by
Web of Science

References (37)

Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas Spivey, James J.; Egbebi, Adefemi Chemical Society Reviews, Vol. 36, Issue 9 https://doi.org/10.1039/b414039g	journal	January 2007
A Review of Recent Literature to Search for an Efficient Catalytic Process for the Conversion of Syngas to Ethanol Subramani, Velu; Gangwal, Santosh K. Energy & Fuels, Vol. 22, Issue 2 https://doi.org/10.1021/ef700411x	journal	March 2008
Status and prospects in higher alcohols synthesis from syngas Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla Chemical Society Reviews, Vol. 46, Issue 5 https://doi.org/10.1039/C6CS00324A	journal	January 2017
Heterogeneous Catalytic Conversion of Dry Syngas to Ethanol and Higher Alcohols on Cu-Based Catalysts Gupta, Mayank; Smith, Miranda L.; Spivey, James J. ACS Catalysis, Vol. 1, Issue 6 https://doi.org/10.1021/cs2001048	journal	May 2011
Mechanism of Ethanol Synthesis from Syngas on Rh(111) Choi, YongMan; Liu, Ping Journal of the American Chemical Society, Vol. 131, Issue 36 https://doi.org/10.1021/ja903013x	journal	September 2009
Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C ₂₊ Oxygenate Production Yang, Nuoya; Medford, Andrew J.; Liu, Xinyan Journal of the American Chemical Society, Vol. 138, Issue 11 https://doi.org/10.1021/jacs.5b12087	journal	March 2016
Ethanol Synthesis from Syngas on Transition Metal-Doped Rh(111) Surfaces: A Density Functional Kinetic Monte Carlo Study Yang, Liu; Liu, Ping Topics in Catalysis, Vol. 57, Issue 1-4 https://doi.org/10.1007/s11244-013-0168-1	journal	October 2013
The effect of Fe–Rh alloying on CO hydrogenation to C2+ oxygenates Palomino, Robert M.; Magee, Joseph W.; Llorca, Jordi Journal of Catalysis, Vol. 329 https://doi.org/10.1016/j.jcat.2015.04.033	journal	September 2015
The Preparation and Characterisation of Fe-Promoted Al2O3-Supported Rh Catalysts for the Selective Production of Ethanol from Syngas Burch, R.; Hayes, M. J. Journal of Catalysis, Vol. 165, Issue 2 https://doi.org/10.1006/jcat.1997.1482	journal	January 1997
Fe-promotion of supported Rh catalysts for direct conversion of syngas to ethanol Haider, M.; Gogate, M.; Davis, R. Journal of Catalysis, Vol. 261, Issue 1 https://doi.org/10.1016/j.jcat.2008.10.013	journal	January 2009
Comparative study of CO and CO2 hydrogenation over supported Rh–Fe catalysts Gogate, Makarand R.; Davis, Robert J. Catalysis Communications, Vol. 11, Issue 10 https://doi.org/10.1016/j.catcom.2010.03.020	journal	May 2010
Performance of Promoted Rh-Fe/Al₂O₃ Catalysts for CO Hydrogenation to Ethanol: Performance of Promoted Rh-Fe/Al₂O₃ Catalysts for CO Hydrogenation to Ethanol Chen, Weimiao; Ding, Yunjie; Song, Xiangeng CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Vol. 33, Issue 6 https://doi.org/10.3724/SP.J.1088.2012.11215	journal	June 2012
EXAFS evidence for direct rhodium-iron bonding in silica-supported rhodium-iron bimetallic catalysts Ichikawa, Masaru; Fukushima, Takakazu; Yokoyama, Toshihiko The Journal of Physical Chemistry, Vol. 90, Issue 7 https://doi.org/10.1021/j100398a003	journal	March 1986
Rh-Fe alloy derived from YRh0.5Fe0.5O3/ZrO2 for higher alcohols synthesis from syngas Han, Tong; Zhao, Lin; Liu, Guilong Catalysis Today, Vol. 298 https://doi.org/10.1016/j.cattod.2017.05.057	journal	December 2017
Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn Liu, Yifei; Göeltl, Florian; Ro, Insoo ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b01381	journal	June 2017
A versatile sample-environment cell for non-ambient X-ray scattering experiments Chupas, Peter J.; Chapman, Karena W.; Kurtz, Charles Journal of Applied Crystallography, Vol. 41, Issue 4 https://doi.org/10.1107/S0021889808020165	journal	July 2008
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Investigation of the synthesis of oxygenates from carbon monoxide/hydrogen mixtures on supported rhodium catalysts Burch, R.; Petch, M. I. Applied Catalysis A: General, Vol. 88, Issue 1 https://doi.org/10.1016/0926-860X(92)80195-I	journal	September 1992
Fischer-Tropsch synthesis over reduced and unreduced iron oxide catalysts Dictor, Ronald A.; Bell, Alexis T. Journal of Catalysis, Vol. 97, Issue 1, p. 121-136 https://doi.org/10.1016/0021-9517(86)90043-6	journal	January 1986
X-ray Absorption Spectroscopy of an Fe-Promoted Rh/TiO ₂ Catalyst for Synthesis of Ethanol from Synthesis Gas Gogate, Makarand R.; Davis, Robert J. ChemCatChem, Vol. 1, Issue 2 https://doi.org/10.1002/cctc.200900104	journal	October 2009
Genesis of Surface and Bulk Phases in Rhodium−Copper Catalysts Fernández-García, M.; Martínez-Arias, A.; Rodríguez-Ramos, I. Langmuir, Vol. 15, Issue 16 https://doi.org/10.1021/la980689+	journal	June 1999
EXAFS and FT-IR Characterization of Mn and Li Promoted Titania-Supported Rh Catalysts for CO Hydrogenation Schwartz, Viviane; Campos, Andrew; Egbebi, Adefemi ACS Catalysis, Vol. 1, Issue 10 https://doi.org/10.1021/cs200281g	journal	August 2011
Fischer−Tropsch Synthesis: An In-Situ TPR-EXAFS/XANES Investigation of the Influence of Group I Alkali Promoters on the Local Atomic and Electronic Structure of Carburized Iron/Silica Catalysts Ribeiro, Mauro C.; Jacobs, Gary; Davis, Burtron H. The Journal of Physical Chemistry C, Vol. 114, Issue 17 https://doi.org/10.1021/jp911856q	journal	April 2010
Stability and Reactivity of ϵ−χ−θ Iron Carbide Catalyst Phases in Fischer−Tropsch Synthesis: Controlling μ _C de Smit, Emiel; Cinquini, Fabrizio; Beale, Andrew M. Journal of the American Chemical Society, Vol. 132, Issue 42 https://doi.org/10.1021/ja105853q	journal	October 2010
Hydrogen Spillover. Facts and Fiction Prins, R. Chemical Reviews, Vol. 112, Issue 5 https://doi.org/10.1021/cr200346z	journal	February 2012
ε-Iron carbide as a low-temperature Fischer–Tropsch synthesis catalyst Xu, Ke; Sun, Bo; Lin, Jun Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6783	journal	December 2014
Iron Carbides in Fischer–Tropsch Synthesis: Theoretical and Experimental Understanding in Epsilon-Iron Carbide Phase Assignment Liu, Xing-Wu; Cao, Zhi; Zhao, Shu The Journal of Physical Chemistry C, Vol. 121, Issue 39 https://doi.org/10.1021/acs.jpcc.7b06104	journal	September 2017
Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure Ankudinov, A. L.; Ravel, B.; Rehr, J. J. Physical Review B, Vol. 58, Issue 12 https://doi.org/10.1103/PhysRevB.58.7565	journal	September 1998
Local structural change under antiferro- and ferromagnetic transition in FeRh alloy Miyanaga, Takafumi; Itoga, Tatsunori; Okazaki, Teiko Journal of Physics: Conference Series, Vol. 190 https://doi.org/10.1088/1742-6596/190/1/012097	journal	November 2009
Determination of metal particle size of highly dispersed Rh, Ir, and Pt catalysts by hydrogen chemisorption and EXAFS Kip, B. Journal of Catalysis, Vol. 105, Issue 1 https://doi.org/10.1016/0021-9517(87)90005-4	journal	May 1987
Comparative study of Rh/MgO modified with Fe, Co or Ni for the catalytic partial oxidation of methane at short contact time. Part I: Characterization of catalysts Tanaka, Hisanori; Kaino, Rie; Okumura, Kazu Applied Catalysis A: General, Vol. 378, Issue 2 https://doi.org/10.1016/j.apcata.2010.02.017	journal	April 2010
Elucidating the Copper–Hägg Iron Carbide Synergistic Interactions for Selective CO Hydrogenation to Higher Alcohols Lu, Yongwu; Zhang, Riguang; Cao, Baobao ACS Catalysis, Vol. 7, Issue 8 https://doi.org/10.1021/acscatal.7b01469	journal	July 2017
Rh-MnO Interface Sites Formed by Atomic Layer Deposition Promote Syngas Conversion to Higher Oxygenates Yang, Nuoya; Yoo, Jong Suk; Schumann, Julia ACS Catalysis, Vol. 7, Issue 9 https://doi.org/10.1021/acscatal.7b01851	journal	August 2017
γ-Fe2O3 nanoparticle surface controls PtFe nanoparticle growth and catalytic properties Gumina, Gregory; Easterday, Rosemary; Malyutin, Andrey G. Nanoscale, Vol. 5, Issue 7 https://doi.org/10.1039/c3nr33879g	journal	January 2013
Rhodium-Catalyzed Methanation and Methane Steam Reforming Reactions on Rhodium-Perovskite Systems: Metal-Support Interaction Thalinger, Ramona; Götsch, Thomas; Zhuo, Chen ChemCatChem, Vol. 8, Issue 12 https://doi.org/10.1002/cctc.201600262	journal	May 2016
A New Class of Tunable Heterojunction by using Two Support Materials for the Synthesis of Supported Bimetallic Catalysts Liao, Fenglin; Lo, Ben Tsz; Sexton, Douglas ChemCatChem, Vol. 7, Issue 2 https://doi.org/10.1002/cctc.201402710	journal	November 2014

Cited By (3)

Switching Between Oxidation Types Using Molybdenum Phosphate Catalysts for Paraffin Activation Using Doped Fe as Surface Acidity Modifier and MoOx as an Oxygen Insertion Tool Mncwabe, Zibuyile; Farahani, Majid D.; Friedrich, Holger B. Catalysis Letters, Vol. 150, Issue 3 https://doi.org/10.1007/s10562-019-02943-z	journal	September 2019
Single-pass transformation of syngas into ethanol with high selectivity by triple tandem catalysis Kang, Jincan; He, Shun; Zhou, Wei Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14672-8	journal	February 2020
One-pass selective conversion of syngas to para -xylene Zhang, Peipei; Tan, Li; Yang, Guohui Chemical Science, Vol. 8, Issue 12 https://doi.org/10.1039/C7SC03427J	journal	January 2017

Similar Records

Composition–Structure–Activity Correlation of Platinum–Ruthenium Nanoalloy Catalysts for Ethanol Oxidation Reaction

Journal Article · Thu Aug 03 00:00:00 EDT 2017 · Journal of Physical Chemistry. C · OSTI ID:1462400

Zhao, Yinguang; Maswadeh, Yazan; Shan, Shiyao; +6 more

Catalytic Oxidation of Propane over Palladium Alloyed with Gold: An Assessment of the Chemical and Intermediate Species

Journal Article · Wed Nov 14 00:00:00 EST 2018 · Catalysis Science and Technology · OSTI ID:1462400

Kareem, Haval; Shan, Shiyao; Wu, Zhi-Peng; +11 more

Role of support-nanoalloy interactions in the atomic-scale structural and chemical ordering for tuning catalytic sites

Journal Article · Wed Sep 12 00:00:00 EDT 2012 · Journal of the American Chemical Society, 134(36):15048-15060 · OSTI ID:1462400

Yang, Lefu; Shan, Shiyao; Loukrakpam, Rameshwori; +8 more

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CO hydrogenation
heterogeneous catalysis
in situ characterization
iron−rhodium alloy
oxygenate synthesis
supported catalysts

Title: In Situ Formation of FeRh Nanoalloys for Oxygenate Synthesis

Citation Formats

References (37)

Cited By (3)

Similar Records

Related Subjects