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Title: Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys

Abstract

The non-oxidative dehydrogenation of ethanol to acetaldehyde has long been considered as an important method to produce acetaldehyde and clean hydrogen gas. Although monometallic Cu nanoparticles have high activity in the non-oxidative dehydrogenation of ethanol, they quickly deactivate due to sintering of Cu. In this paper, we show that adding a small amount of Ni (Ni0.01Cu - Ni0.001Cu) into Cu to form highly dilute NiCu alloys dramatically increases the catalytic activity and increases their long-term stability. The kinetic studies show that the apparent activation energy decreases from ~70 kJ/mol over Cu to ~45 kJ/mol over the dilute NiCu alloys. The improved performance is observed both for nanoparticles and nanoporous NiCu alloys. The improvement in the long-term stability of the catalysts is attributed to the stabilization of Cu against sintering. Our characterization data show that Ni is atomically dispersed in Cu. The comparison of the catalytic performance of highly dilute alloy nanoparticles with nanoporous materials is useful to guide the design of novel mesoporous catalyst architectures for selective dehydrogenation reactions.

Authors:
 [1];  [2];  [1];  [1];  [3];  [3];  [3];  [3];  [2];  [1]
  1. Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
  2. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Lab.
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Harvard Univ., Cambridge, MA (United States). Center for Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1458624
Alternate Identifier(s):
OSTI ID: 1419112
Report Number(s):
LLNL-JRNL-741641
Journal ID: ISSN 0926-3373; 896020
Grant/Contract Number:  
AC52-07NA27344; SC0012573; 1541959
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis B: Environmental
Additional Journal Information:
Journal Volume: 205; Journal Issue: C; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Single atom alloys; Nickel; Copper; Ethanol dehydrogenation; Acetaldehyde; Hydrogen

Citation Formats

Shan, Junjun, Janvelyan, Nare, Li, Hang, Liu, Jilei, Egle, Tobias M., Ye, Jianchao, Biener, Monika M., Biener, Juergen, Friend, Cynthia M., and Flytzani-Stephanopoulos, Maria. Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys. United States: N. p., 2016. Web. doi:10.1016/j.apcatb.2016.12.045.
Shan, Junjun, Janvelyan, Nare, Li, Hang, Liu, Jilei, Egle, Tobias M., Ye, Jianchao, Biener, Monika M., Biener, Juergen, Friend, Cynthia M., & Flytzani-Stephanopoulos, Maria. Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys. United States. https://doi.org/10.1016/j.apcatb.2016.12.045
Shan, Junjun, Janvelyan, Nare, Li, Hang, Liu, Jilei, Egle, Tobias M., Ye, Jianchao, Biener, Monika M., Biener, Juergen, Friend, Cynthia M., and Flytzani-Stephanopoulos, Maria. Sat . "Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys". United States. https://doi.org/10.1016/j.apcatb.2016.12.045. https://www.osti.gov/servlets/purl/1458624.
@article{osti_1458624,
title = {Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys},
author = {Shan, Junjun and Janvelyan, Nare and Li, Hang and Liu, Jilei and Egle, Tobias M. and Ye, Jianchao and Biener, Monika M. and Biener, Juergen and Friend, Cynthia M. and Flytzani-Stephanopoulos, Maria},
abstractNote = {The non-oxidative dehydrogenation of ethanol to acetaldehyde has long been considered as an important method to produce acetaldehyde and clean hydrogen gas. Although monometallic Cu nanoparticles have high activity in the non-oxidative dehydrogenation of ethanol, they quickly deactivate due to sintering of Cu. In this paper, we show that adding a small amount of Ni (Ni0.01Cu - Ni0.001Cu) into Cu to form highly dilute NiCu alloys dramatically increases the catalytic activity and increases their long-term stability. The kinetic studies show that the apparent activation energy decreases from ~70 kJ/mol over Cu to ~45 kJ/mol over the dilute NiCu alloys. The improved performance is observed both for nanoparticles and nanoporous NiCu alloys. The improvement in the long-term stability of the catalysts is attributed to the stabilization of Cu against sintering. Our characterization data show that Ni is atomically dispersed in Cu. The comparison of the catalytic performance of highly dilute alloy nanoparticles with nanoporous materials is useful to guide the design of novel mesoporous catalyst architectures for selective dehydrogenation reactions.},
doi = {10.1016/j.apcatb.2016.12.045},
journal = {Applied Catalysis B: Environmental},
number = C,
volume = 205,
place = {United States},
year = {Sat Dec 31 00:00:00 EST 2016},
month = {Sat Dec 31 00:00:00 EST 2016}
}

Journal Article:

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Cited by: 110 works
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Works referenced in this record:

Ethanol dehydrogenation by gold catalysts: The effect of the gold particle size and the presence of oxygen
journal, June 2009


Ethanol dehydrogenation over copper catalysts on rice husk ash prepared by ion exchange
journal, May 2006


Mechanistic Aspects of the Ethanol Steam Reforming Reaction for Hydrogen Production on Pt, Ni, and PtNi Catalysts Supported on γ-Al 2 O 3
journal, March 2010

  • Sanchez-Sanchez, Maria Cruz; Navarro Yerga, Rufino M.; Kondarides, Dimitris I.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 11
  • DOI: 10.1021/jp906531x

New insights into reaction mechanisms of ethanol steam reforming on Co–ZrO2
journal, January 2015


Effects of Alkali Metal Oxide Additives on Cu/SiO 2 Catalyst in the Dehydrogenation of Ethanol
journal, December 2001

  • Tu, Yao-Jen; Chen, Yu-Wen
  • Industrial & Engineering Chemistry Research, Vol. 40, Issue 25
  • DOI: 10.1021/ie010272q

Selective oxidation of alcohols and aldehydes on metal catalysts
journal, March 2000


Selective oxidation of ethanol to acetaldehyde over Au–Cu catalysts prepared by a redox method
journal, March 2015


Effect of Cu content on the surface and catalytic properties of Cu/ZrO2 catalyst for ethanol dehydrogenation
journal, January 2014


Correlation between Structural and Catalytic Properties of Copper Supported on Porous Alumina for the Ethanol Dehydrogenation Reaction
journal, May 2015

  • Cassinelli, Wellington H.; Martins, Leandro; Passos, Aline R.
  • ChemCatChem, Vol. 7, Issue 11
  • DOI: 10.1002/cctc.201500112

Time-resolved XAS/MS/Raman monitoring of mutual copper self-reduction and ethanol dehydrogenation reactions
journal, January 2016

  • Cassinelli, Wellington H.; Martins, Leandro; Magnani, Marina
  • RSC Advances, Vol. 6, Issue 25
  • DOI: 10.1039/C5RA27403F

The detailed kinetics and mechanism of ethyl ethanoate synthesis over a Cu/Cr2O3 catalyst
journal, November 2005


Dehydrogenation of ethanol over copper catalysts on rice husk ash prepared by incipient wetness impregnation
journal, June 2003


Characterization of unsupported copper—chromium catalysts for ethanol dehydrogenation
journal, April 1994


Ethanol dehydrogenation to ethyl acetate by using copper and copper chromite catalysts
journal, January 2012


Low-Temperature Dehydrogenation of Ethanol on Atomically Dispersed Gold Supported on ZnZrO x
journal, December 2015

  • Wang, Chongyang; Garbarino, Gabriella; Allard, Lawrence F.
  • ACS Catalysis, Vol. 6, Issue 1
  • DOI: 10.1021/acscatal.5b01593

Adsorption and decomposition of ethanol on supported Au catalysts☆
journal, February 2011


Nanostructured ceria supported Pt and Au catalysts for the reactions of ethanol and formic acid
journal, February 2013

  • Ciftci, Aysegul; Ligthart, D. A. J. Michel; Pastorino, Pietro
  • Applied Catalysis B: Environmental, Vol. 130-131
  • DOI: 10.1016/j.apcatb.2012.10.029

Atomically Dispersed Supported Metal Catalysts
journal, July 2012


Single gold atoms stabilized on nanoscale metal oxide supports are catalytic active centers for various reactions
journal, December 2015

  • Wang, Chongyang; Yang, Ming; Flytzani-Stephanopoulos, Maria
  • AIChE Journal, Vol. 62, Issue 2
  • DOI: 10.1002/aic.15134

A Common Single-Site Pt(II)–O(OH) x – Species Stabilized by Sodium on “Active” and “Inert” Supports Catalyzes the Water-Gas Shift Reaction
journal, March 2015

  • Yang, Ming; Liu, Jilei; Lee, Sungsik
  • Journal of the American Chemical Society, Vol. 137, Issue 10
  • DOI: 10.1021/ja513292k

Catalytically active Au-O(OH) x - species stabilized by alkali ions on zeolites and mesoporous oxides
journal, November 2014


Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions
journal, September 2010


Bimetallic Au–Pd catalysts for selective hydrogenation of butadiene: Influence of the preparation method on catalytic properties
journal, January 2013


Promotional effect of Pd single atoms on Au nanoparticles supported on silica for the selective hydrogenation of acetylene in excess ethylene
journal, January 2014

  • Pei, Guang Xian; Liu, Xiao Yan; Wang, Aiqin
  • New Journal of Chemistry, Vol. 38, Issue 5
  • DOI: 10.1039/c3nj01136d

Acetylene hydrogenation over structured Au–Pd catalysts
journal, January 2016

  • McCue, Alan J.; Baker, Richard T.; Anderson, James A.
  • Faraday Discussions, Vol. 188
  • DOI: 10.1039/C5FD00188A

Mono- and bi-metallic Au–Pd/TiO2 catalysts synthesized by one-step flame spray pyrolysis for liquid-phase hydrogenation of 1-heptyne
journal, October 2013


Bimetallic PdAu nanoparticles as hydrogenation catalysts in imidazolium ionic liquids
journal, May 2008

  • Dash, Priyabrat; Dehm, Nicole A.; Scott, Robert W. J.
  • Journal of Molecular Catalysis A: Chemical, Vol. 286, Issue 1-2
  • DOI: 10.1016/j.molcata.2008.02.003

Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature
journal, January 2010


Ag/Au Mixed Sites Promote Oxidative Coupling of Methanol on the Alloy Surface
journal, March 2014

  • Xu, Bingjun; Siler, Cassandra G. F.; Madix, Robert J.
  • Chemistry - A European Journal, Vol. 20, Issue 16
  • DOI: 10.1002/chem.201304837

Aerobic Oxidative Esterification of Aldehydes with Alcohols by Gold–Nickel Oxide Nanoparticle Catalysts with a Core–Shell Structure
journal, July 2013

  • Suzuki, Ken; Yamaguchi, Tatsuo; Matsushita, Ken
  • ACS Catalysis, Vol. 3, Issue 8
  • DOI: 10.1021/cs4004084

Surface and Subsurface Hydrogen:  Adsorption Properties on Transition Metals and Near-Surface Alloys
journal, March 2005

  • Greeley, Jeff; Mavrikakis, Manos
  • The Journal of Physical Chemistry B, Vol. 109, Issue 8
  • DOI: 10.1021/jp046540q

Tackling CO Poisoning with Single-Atom Alloy Catalysts
journal, May 2016

  • Liu, Jilei; Lucci, Felicia R.; Yang, Ming
  • Journal of the American Chemical Society, Vol. 138, Issue 20
  • DOI: 10.1021/jacs.6b03339

Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit
journal, October 2015

  • Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9550

Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions
journal, January 2013

  • Boucher, Matthew B.; Zugic, Branko; Cladaras, George
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 29
  • DOI: 10.1039/c3cp51538a

Molecular-Scale Perspective of Water-Catalyzed Methanol Dehydrogenation to Formaldehyde
journal, June 2013

  • Boucher, Matthew B.; Marcinkowski, Matthew D.; Liriano, Melissa L.
  • ACS Nano, Vol. 7, Issue 7
  • DOI: 10.1021/nn402055k

Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen
journal, August 2016


Reduction of Ni2+ by hydrazine in solution for the preparation of nickel nano-particles
journal, April 2006


Nano-structured non-platinum catalysts for automotive fuel cell application
journal, September 2015


Preparation of fine powders for electronic materials by freeze-drying
journal, June 1993


Synthesis, Characterization, and Properties of Metallic Copper Nanoparticles
journal, May 1998

  • Dhas, N. Arul; Raj, C. Paul; Gedanken, A.
  • Chemistry of Materials, Vol. 10, Issue 5
  • DOI: 10.1021/cm9708269

Controlling the Thickness of the Surface Oxide Layer on Cu Nanoparticles for the Fabrication of Conductive Structures by Ink-Jet Printing
journal, March 2008

  • Jeong, Sunho; Woo, Kyoohee; Kim, Dongjo
  • Advanced Functional Materials, Vol. 18, Issue 5
  • DOI: 10.1002/adfm.200700902

Synergistic effect in bimetallic copper–silver (Cu x Ag) nanoparticles enhances silicon conversion in Rochow reaction
journal, January 2015

  • Zhang, Zailei; Ji, Yongjun; Li, Jing
  • RSC Advances, Vol. 5, Issue 67
  • DOI: 10.1039/C5RA04575D

Synthesis and growth mechanism of Au@Cu core–shell nanorods having excellent antioxidative properties
journal, January 2014

  • Yoshida, Yuki; Uto, Keiko; Hattori, Masashi
  • CrystEngComm, Vol. 16, Issue 25
  • DOI: 10.1039/c4ce00672k

An improved procedure for estimating the metal surface area of supported copper catalysts
journal, August 1989


New interpretations of XPS spectra of nickel metal and oxides
journal, May 2006

  • Grosvenor, Andrew P.; Biesinger, Mark C.; Smart, Roger St. C.
  • Surface Science, Vol. 600, Issue 9
  • DOI: 10.1016/j.susc.2006.01.041

Conversion of Methane to Methanol with a Bent Mono(μ-oxo)dinickel Anchored on the Internal Surfaces of Micropores
journal, July 2014

  • Shan, Junjun; Huang, Weixin; Nguyen, Luan
  • Langmuir, Vol. 30, Issue 28
  • DOI: 10.1021/la501184b

XPS study of silver, nickel and bimetallic silver–nickel nanoparticles prepared by seed-mediated growth
journal, September 2012


Adsorption Dynamics of CO on Silica-Supported Cu Clusters: A Molecular Beam Scattering Study
journal, August 2011

  • Komarneni, M.; Shan, J.; Burghaus, U.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 33
  • DOI: 10.1021/jp205120e

A DRIFTS study of CO adsorption and hydrogenation on Cu-based core–shell nanoparticles
journal, January 2012

  • Subramanian, Nachal D.; Kumar, Challa S. S. R.; Watanabe, Kazuo
  • Catalysis Science & Technology, Vol. 2, Issue 3
  • DOI: 10.1039/c2cy00413e

Monodispersed and nanostructrured Ni/SiO2 catalyst and its activity for non oxidative methane activation
journal, April 2011


Characterization of reduced α-alumina-supported nickel catalysts by spectroscopic and chemisorption measurements
journal, July 2005


Influence of the support in the selectivity of nickel/clay catalysts for vegetable oil hydrogenation
journal, October 1993

  • Anderson, J. A.; Rodrigo, M. T.; Daza, L.
  • Langmuir, Vol. 9, Issue 10
  • DOI: 10.1021/la00034a001

Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion
journal, November 2013


Effects of catalyst surface and hydrogen bond on ethanol dehydrogenation to ethoxy on Cu catalysts
journal, October 2013


Effects of the pretreatment of CuNi/SiO2 on ethanol steam reforming: Influence of bimetal morphology
journal, April 2014


Ethanol steam reforming over Ni and Ni–Cu catalysts
journal, August 2009


Works referencing / citing this record:

Atomic‐Local Environments of Single‐Atom Catalysts: Synthesis, Electronic Structure, and Activity
journal, October 2019

  • Lai, Wei‐Hong; Miao, Zongcheng; Wang, Yun‐Xiao
  • Advanced Energy Materials, Vol. 9, Issue 43
  • DOI: 10.1002/aenm.201900722

A study of ethanol conversion over zinc aluminate catalyst
journal, March 2018

  • Garbarino, Gabriella; Riani, Paola; Villa García, María
  • Reaction Kinetics, Mechanisms and Catalysis, Vol. 124, Issue 2
  • DOI: 10.1007/s11144-018-1395-z

Cu–Ca–Al catalysts derived from hydrocalumite and their application to ethanol dehydrogenation
journal, December 2018

  • Rosset, Morgana; Perez-Lopez, Oscar W.
  • Reaction Kinetics, Mechanisms and Catalysis, Vol. 126, Issue 1
  • DOI: 10.1007/s11144-018-1513-y

First-Principle Microkinetic Modeling of Ethanol Dehydrogenation on Metal Catalyst Surfaces in Non-oxidative Environment: Design of Bimetallic Alloys
journal, August 2018


Production of acetic acid from ethanol over CuCr catalysts via dehydrogenation-(aldehyde–water shift) reaction
journal, January 2017

  • Xiang, Ning; Xu, Peng; Ran, Nianbo
  • RSC Advances, Vol. 7, Issue 61
  • DOI: 10.1039/c7ra05922a

A nickel–iridium alloy as an efficient heterogeneous catalyst for hydrogenation of olefins
journal, January 2019

  • Bai, Jia-qi; Tamura, Masazumi; Nakagawa, Yoshinao
  • Chemical Communications, Vol. 55, Issue 71
  • DOI: 10.1039/c9cc04822g

Dehydrogenation of Ethanol to Acetaldehyde over Different Metals Supported on Carbon Catalysts
journal, January 2019

  • Ob-eye, Jeerati; Praserthdam, Piyasan; Jongsomjit, Bunjerd
  • Catalysts, Vol. 9, Issue 1
  • DOI: 10.3390/catal9010066