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

Shan, Junjun; Janvelyan, Nare; Li, Hang; Liu, Jilei; Egle, Tobias M.; Ye, Jianchao; Biener, Monika M.; Biener, Juergen; Friend, Cynthia M.; Flytzani-Stephanopoulos, Maria

doi:10.1016/j.apcatb.2016.12.045

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

Journal Article · Sat Dec 31 00:00:00 EST 2016 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2016.12.045· OSTI ID:1458624

Shan, Junjun ^[1]; Janvelyan, Nare ^[2]; Li, Hang ^[1]; Liu, Jilei ^[1]; Egle, Tobias M. ^[3]; Ye, Jianchao ^[3]; Biener, Monika M. ^[3]; Biener, Juergen ^[3]; Friend, Cynthia M. ^[2]; Flytzani-Stephanopoulos, Maria ^[1]

Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Lab.

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 (Ni_0.01Cu - Ni_0.001Cu) 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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States). Center for Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC52-07NA27344; SC0012573

OSTI ID:: 1458624

Alternate ID(s):: OSTI ID: 1419112

Report Number(s):: LLNL-JRNL--741641; 896020

Journal Information:: Applied Catalysis B: Environmental, Journal Name: Applied Catalysis B: Environmental Journal Issue: C Vol. 205; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (59)

Controlling the Thickness of the Surface Oxide Layer on Cu Nanoparticles for the Fabrication of Conductive Structures by Ink-Jet Printing Jeong, Sunho; Woo, Kyoohee; Kim, Dongjo Advanced Functional Materials, Vol. 18, Issue 5 https://doi.org/10.1002/adfm.200700902	journal	March 2008
Single gold atoms stabilized on nanoscale metal oxide supports are catalytic active centers for various reactions Wang, Chongyang; Yang, Ming; Flytzani-Stephanopoulos, Maria AIChE Journal, Vol. 62, Issue 2 https://doi.org/10.1002/aic.15134	journal	December 2015
Correlation between Structural and Catalytic Properties of Copper Supported on Porous Alumina for the Ethanol Dehydrogenation Reaction Cassinelli, Wellington H.; Martins, Leandro; Passos, Aline R. ChemCatChem, Vol. 7, Issue 11 https://doi.org/10.1002/cctc.201500112	journal	May 2015
Ag/Au Mixed Sites Promote Oxidative Coupling of Methanol on the Alloy Surface Xu, Bingjun; Siler, Cassandra G. F.; Madix, Robert J. Chemistry - A European Journal, Vol. 20, Issue 16 https://doi.org/10.1002/chem.201304837	journal	March 2014
Reduction of Ni2+ by hydrazine in solution for the preparation of nickel nano-particles Li, Zhiyu; Han, Chenghui; Shen, Jianyi Journal of Materials Science, Vol. 41, Issue 11 https://doi.org/10.1007/s10853-005-5874-z	journal	April 2006
An improved procedure for estimating the metal surface area of supported copper catalysts Bond, G. Journal of Catalysis, Vol. 118, Issue 2 https://doi.org/10.1016/0021-9517(89)90339-4	journal	August 1989
Preparation of fine powders for electronic materials by freeze-drying Tachiwaki, T.; Suzuki, M.; Okajima, H. Applied Surface Science, Vol. 70-71 https://doi.org/10.1016/0169-4332(93)90615-I	journal	June 1993
Characterization of unsupported copper—chromium catalysts for ethanol dehydrogenation Tu, Yau-Jen; Chen, Yu-Wen; Li, Chiuping Journal of Molecular Catalysis, Vol. 89, Issue 1-2 https://doi.org/10.1016/0304-5102(93)E0331-A	journal	April 1994
Selective oxidation of alcohols and aldehydes on metal catalysts Besson, Michèle; Gallezot, Pierre Catalysis Today, Vol. 57, Issue 1-2 https://doi.org/10.1016/S0920-5861(99)00315-6	journal	March 2000
Dehydrogenation of ethanol over copper catalysts on rice husk ash prepared by incipient wetness impregnation Chang, Feg-Wen; Kuo, Wen-Yao; Lee, Kuen-Chan Applied Catalysis A: General, Vol. 246, Issue 2 https://doi.org/10.1016/S0926-860X(03)00050-4	journal	June 2003
Structure determination through Z-contrast microscopy Pennycook, S. J. Advances in Imaging and Electron Physics, p. 173-206 https://doi.org/10.1016/S1076-5670(02)80063-5	book	January 2002
Characterization of reduced α-alumina-supported nickel catalysts by spectroscopic and chemisorption measurements Poncelet, G.; Centeno, M. A.; Molina, R. Applied Catalysis A: General, Vol. 288, Issue 1-2 https://doi.org/10.1016/j.apcata.2005.04.052	journal	July 2005
Ethanol dehydrogenation over copper catalysts on rice husk ash prepared by ion exchange Chang, Feg-Wen; Yang, Hsien-Chang; Roselin, L. Selva Applied Catalysis A: General, Vol. 304 https://doi.org/10.1016/j.apcata.2006.02.017	journal	May 2006
Ethanol dehydrogenation by gold catalysts: The effect of the gold particle size and the presence of oxygen Guan, Yejun; Hensen, Emiel J. M. Applied Catalysis A: General, Vol. 361, Issue 1-2 https://doi.org/10.1016/j.apcata.2009.03.033	journal	June 2009
Monodispersed and nanostructrured Ni/SiO2 catalyst and its activity for non oxidative methane activation Moya, Silvia. F.; Martins, Ruth L.; Schmal, Martin Applied Catalysis A: General, Vol. 396, Issue 1-2 https://doi.org/10.1016/j.apcata.2011.02.007	journal	April 2011
Mono- and bi-metallic Au–Pd/TiO2 catalysts synthesized by one-step flame spray pyrolysis for liquid-phase hydrogenation of 1-heptyne Pongthawornsakun, Boontida; Fujita, Shin-ichiro; Arai, Masahiko Applied Catalysis A: General, Vol. 467 https://doi.org/10.1016/j.apcata.2013.07.006	journal	October 2013
Nanostructured ceria supported Pt and Au catalysts for the reactions of ethanol and formic acid Ciftci, Aysegul; Ligthart, D. A. J. Michel; Pastorino, Pietro Applied Catalysis B: Environmental, Vol. 130-131 https://doi.org/10.1016/j.apcatb.2012.10.029	journal	February 2013
Effects of the pretreatment of CuNi/SiO2 on ethanol steam reforming: Influence of bimetal morphology Chen, Li-Chung; Lin, Shawn D. Applied Catalysis B: Environmental, Vol. 148-149 https://doi.org/10.1016/j.apcatb.2013.11.031	journal	April 2014
New insights into reaction mechanisms of ethanol steam reforming on Co–ZrO2 Sun, Junming; Karim, Ayman M.; Mei, Donghai Applied Catalysis B: Environmental, Vol. 162 https://doi.org/10.1016/j.apcatb.2014.06.043	journal	January 2015
XPS study of silver, nickel and bimetallic silver–nickel nanoparticles prepared by seed-mediated growth Prieto, Pilar; Nistor, Valentin; Nouneh, Khalid Applied Surface Science, Vol. 258, Issue 22 https://doi.org/10.1016/j.apsusc.2012.05.095	journal	September 2012
Ethanol steam reforming over Ni and Ni–Cu catalysts Wang, Fagen; Li, Yong; Cai, Weijie Catalysis Today, Vol. 146, Issue 1-2 https://doi.org/10.1016/j.cattod.2009.01.027	journal	August 2009
Adsorption and decomposition of ethanol on supported Au catalysts☆ Gazsi, A.; Koós, A.; Bánsági, T. Catalysis Today, Vol. 160, Issue 1 https://doi.org/10.1016/j.cattod.2010.05.007	journal	February 2011
Selective oxidation of ethanol to acetaldehyde over Au–Cu catalysts prepared by a redox method Redina, Elena A.; Greish, Alexander A.; Mishin, Igor V. Catalysis Today, Vol. 241 https://doi.org/10.1016/j.cattod.2013.11.065	journal	March 2015
Ethanol dehydrogenation to ethyl acetate by using copper and copper chromite catalysts Santacesaria, E.; Carotenuto, G.; Tesser, R. Chemical Engineering Journal, Vol. 179 https://doi.org/10.1016/j.cej.2011.10.043	journal	January 2012
Effects of catalyst surface and hydrogen bond on ethanol dehydrogenation to ethoxy on Cu catalysts Sun, Kang; Zhang, Minhua; Wang, Lichang Chemical Physics Letters, Vol. 585 https://doi.org/10.1016/j.cplett.2013.09.005	journal	October 2013
The detailed kinetics and mechanism of ethyl ethanoate synthesis over a Cu/Cr2O3 catalyst Colley, S.; Tabatabaei, J.; Waugh, K. Journal of Catalysis, Vol. 236, Issue 1 https://doi.org/10.1016/j.jcat.2005.09.012	journal	November 2005
Bimetallic Au–Pd catalysts for selective hydrogenation of butadiene: Influence of the preparation method on catalytic properties Kolli, Nadia El; Delannoy, Laurent; Louis, Catherine Journal of Catalysis, Vol. 297 https://doi.org/10.1016/j.jcat.2012.09.022	journal	January 2013
Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion Sato, A. G.; Volanti, D. P.; Meira, D. M. Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.06.022	journal	November 2013
Exploiting basic principles to control the selectivity of the vapor phase catalytic oxidative cross-coupling of primary alcohols over nanoporous gold catalysts Wang, Lu-Cun; Stowers, Kara J.; Zugic, Branko Journal of Catalysis, Vol. 329 https://doi.org/10.1016/j.jcat.2015.04.022	journal	September 2015
Bimetallic PdAu nanoparticles as hydrogenation catalysts in imidazolium ionic liquids Dash, Priyabrat; Dehm, Nicole A.; Scott, Robert W. J. Journal of Molecular Catalysis A: Chemical, Vol. 286, Issue 1-2 https://doi.org/10.1016/j.molcata.2008.02.003	journal	May 2008
Effect of Cu content on the surface and catalytic properties of Cu/ZrO2 catalyst for ethanol dehydrogenation Freitas, I. C.; Damyanova, S.; Oliveira, D. C. Journal of Molecular Catalysis A: Chemical, Vol. 381 https://doi.org/10.1016/j.molcata.2013.09.038	journal	January 2014
Nano-structured non-platinum catalysts for automotive fuel cell application Serov, Alexey; Artyushkova, Kateryna; Niangar, Ellazar Nano Energy, Vol. 16 https://doi.org/10.1016/j.nanoen.2015.07.002	journal	September 2015
New interpretations of XPS spectra of nickel metal and oxides Grosvenor, Andrew P.; Biesinger, Mark C.; Smart, Roger St. C. Surface Science, Vol. 600, Issue 9 https://doi.org/10.1016/j.susc.2006.01.041	journal	May 2006
Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen Shan, Junjun; Lucci, Felicia R.; Liu, Jilei Surface Science, Vol. 650 https://doi.org/10.1016/j.susc.2016.02.010	journal	August 2016
Low-Temperature Dehydrogenation of Ethanol on Atomically Dispersed Gold Supported on ZnZrO _x Wang, Chongyang; Garbarino, Gabriella; Allard, Lawrence F. ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b01593	journal	December 2015
Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C═C Unsaturation on Reaction Selectivity Zugic, Branko; Karakalos, Stavros; Stowers, Kara J. ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.5b02902	journal	February 2016
Synthesis, Characterization, and Properties of Metallic Copper Nanoparticles Dhas, N. Arul; Raj, C. Paul; Gedanken, A. Chemistry of Materials, Vol. 10, Issue 5 https://doi.org/10.1021/cm9708269	journal	May 1998
Aerobic Oxidative Esterification of Aldehydes with Alcohols by Gold–Nickel Oxide Nanoparticle Catalysts with a Core–Shell Structure Suzuki, Ken; Yamaguchi, Tatsuo; Matsushita, Ken ACS Catalysis, Vol. 3, Issue 8 https://doi.org/10.1021/cs4004084	journal	July 2013
Effects of Alkali Metal Oxide Additives on Cu/SiO ₂ Catalyst in the Dehydrogenation of Ethanol Tu, Yao-Jen; Chen, Yu-Wen Industrial & Engineering Chemistry Research, Vol. 40, Issue 25 https://doi.org/10.1021/ie010272q	journal	December 2001
A Common Single-Site Pt(II)–O(OH) _x – Species Stabilized by Sodium on “Active” and “Inert” Supports Catalyzes the Water-Gas Shift Reaction Yang, Ming; Liu, Jilei; Lee, Sungsik Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/ja513292k	journal	March 2015
Tackling CO Poisoning with Single-Atom Alloy Catalysts Liu, Jilei; Lucci, Felicia R.; Yang, Ming Journal of the American Chemical Society, Vol. 138, Issue 20 https://doi.org/10.1021/jacs.6b03339	journal	May 2016
Surface and Subsurface Hydrogen: Adsorption Properties on Transition Metals and Near-Surface Alloys Greeley, Jeff; Mavrikakis, Manos The Journal of Physical Chemistry B, Vol. 109, Issue 8 https://doi.org/10.1021/jp046540q	journal	March 2005
Adsorption Dynamics of CO on Silica-Supported Cu Clusters: A Molecular Beam Scattering Study Komarneni, M.; Shan, J.; Burghaus, U. The Journal of Physical Chemistry C, Vol. 115, Issue 33 https://doi.org/10.1021/jp205120e	journal	August 2011
Mechanistic Aspects of the Ethanol Steam Reforming Reaction for Hydrogen Production on Pt, Ni, and PtNi Catalysts Supported on γ-Al ₂ O ₃ ^† Sanchez-Sanchez, Maria Cruz; Navarro Yerga, Rufino M.; Kondarides, Dimitris I. The Journal of Physical Chemistry A, Vol. 114, Issue 11 https://doi.org/10.1021/jp906531x	journal	March 2010
Influence of the support in the selectivity of nickel/clay catalysts for vegetable oil hydrogenation Anderson, J. A.; Rodrigo, M. T.; Daza, L. Langmuir, Vol. 9, Issue 10 https://doi.org/10.1021/la00034a001	journal	October 1993
Conversion of Methane to Methanol with a Bent Mono(μ-oxo)dinickel Anchored on the Internal Surfaces of Micropores Shan, Junjun; Huang, Weixin; Nguyen, Luan Langmuir, Vol. 30, Issue 28 https://doi.org/10.1021/la501184b	journal	July 2014
Molecular-Scale Perspective of Water-Catalyzed Methanol Dehydrogenation to Formaldehyde Boucher, Matthew B.; Marcinkowski, Matthew D.; Liriano, Melissa L. ACS Nano, Vol. 7, Issue 7 https://doi.org/10.1021/nn402055k	journal	June 2013
Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9550	journal	October 2015
Acetylene hydrogenation over structured Au–Pd catalysts McCue, Alan J.; Baker, Richard T.; Anderson, James A. Faraday Discussions, Vol. 188 https://doi.org/10.1039/C5FD00188A	journal	January 2016
Synergistic effect in bimetallic copper–silver (Cu _x Ag) nanoparticles enhances silicon conversion in Rochow reaction Zhang, Zailei; Ji, Yongjun; Li, Jing RSC Advances, Vol. 5, Issue 67 https://doi.org/10.1039/C5RA04575D	journal	January 2015
Time-resolved XAS/MS/Raman monitoring of mutual copper self-reduction and ethanol dehydrogenation reactions Cassinelli, Wellington H.; Martins, Leandro; Magnani, Marina RSC Advances, Vol. 6, Issue 25 https://doi.org/10.1039/C5RA27403F	journal	January 2016
A DRIFTS study of CO adsorption and hydrogenation on Cu-based core–shell nanoparticles Subramanian, Nachal D.; Kumar, Challa S. S. R.; Watanabe, Kazuo Catalysis Science & Technology, Vol. 2, Issue 3 https://doi.org/10.1039/c2cy00413e	journal	January 2012
Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions Boucher, Matthew B.; Zugic, Branko; Cladaras, George Physical Chemistry Chemical Physics, Vol. 15, Issue 29 https://doi.org/10.1039/c3cp51538a	journal	January 2013
Promotional effect of Pd single atoms on Au nanoparticles supported on silica for the selective hydrogenation of acetylene in excess ethylene Pei, Guang Xian; Liu, Xiao Yan; Wang, Aiqin New Journal of Chemistry, Vol. 38, Issue 5 https://doi.org/10.1039/c3nj01136d	journal	January 2014
Synthesis and growth mechanism of Au@Cu core–shell nanorods having excellent antioxidative properties Yoshida, Yuki; Uto, Keiko; Hattori, Masashi CrystEngComm, Vol. 16, Issue 25 https://doi.org/10.1039/c4ce00672k	journal	January 2014
Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature Wittstock, A.; Zielasek, V.; Biener, J. Science, Vol. 327, Issue 5963 https://doi.org/10.1126/science.1183591	journal	January 2010
Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions Zhai, Y.; Pierre, D.; Si, R. Science, Vol. 329, Issue 5999 https://doi.org/10.1126/science.1192449	journal	September 2010
Catalytically active Au-O(OH) _x - species stabilized by alkali ions on zeolites and mesoporous oxides Yang, Ming; Li, Sha; Wang, Yuan Science, Vol. 346, Issue 6216 https://doi.org/10.1126/science.1260526	journal	November 2014
Atomically Dispersed Supported Metal Catalysts Flytzani-Stephanopoulos, Maria; Gates, Bruce C. Annual Review of Chemical and Biomolecular Engineering, Vol. 3, Issue 1 https://doi.org/10.1146/annurev-chembioeng-062011-080939	journal	July 2012

Cited By (8)

Atomic‐Local Environments of Single‐Atom Catalysts: Synthesis, Electronic Structure, and Activity Lai, Wei‐Hong; Miao, Zongcheng; Wang, Yun‐Xiao Advanced Energy Materials, Vol. 9, Issue 43 https://doi.org/10.1002/aenm.201900722	journal	October 2019
A study of ethanol conversion over zinc aluminate catalyst Garbarino, Gabriella; Riani, Paola; Villa García, María Reaction Kinetics, Mechanisms and Catalysis, Vol. 124, Issue 2 https://doi.org/10.1007/s11144-018-1395-z	journal	March 2018
Cu–Ca–Al catalysts derived from hydrocalumite and their application to ethanol dehydrogenation Rosset, Morgana; Perez-Lopez, Oscar W. Reaction Kinetics, Mechanisms and Catalysis, Vol. 126, Issue 1 https://doi.org/10.1007/s11144-018-1513-y	journal	December 2018
First-Principle Microkinetic Modeling of Ethanol Dehydrogenation on Metal Catalyst Surfaces in Non-oxidative Environment: Design of Bimetallic Alloys Khan, Tuhin S.; Jalid, Fatima; Haider, M. Ali Topics in Catalysis, Vol. 61, Issue 18-19 https://doi.org/10.1007/s11244-018-1028-9	journal	August 2018
Palladium–gold single atom alloy catalysts for liquid phase selective hydrogenation of 1-hexyne Liu, Jilei; Shan, Junjun; Lucci, Felicia R. Catalysis Science & Technology, Vol. 7, Issue 19 https://doi.org/10.1039/c7cy00794a	journal	January 2017
Production of acetic acid from ethanol over CuCr catalysts via dehydrogenation-(aldehyde–water shift) reaction Xiang, Ning; Xu, Peng; Ran, Nianbo RSC Advances, Vol. 7, Issue 61 https://doi.org/10.1039/c7ra05922a	journal	January 2017
A nickel–iridium alloy as an efficient heterogeneous catalyst for hydrogenation of olefins Bai, Jia-qi; Tamura, Masazumi; Nakagawa, Yoshinao Chemical Communications, Vol. 55, Issue 71 https://doi.org/10.1039/c9cc04822g	journal	January 2019
Dehydrogenation of Ethanol to Acetaldehyde over Different Metals Supported on Carbon Catalysts Ob-eye, Jeerati; Praserthdam, Piyasan; Jongsomjit, Bunjerd Catalysts, Vol. 9, Issue 1 https://doi.org/10.3390/catal9010066	journal	January 2019

Similar Records

NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

Journal Article · Thu Dec 28 19:00:00 EST 2017 · Applied Catalysis B: Environmental · OSTI ID:1439883

NiAu Single Atom Alloys for the Non-oxidative Dehydrogenation of Ethanol to Acetaldehyde and Hydrogen

Journal Article · Sun Mar 18 20:00:00 EDT 2018 · Topics in Catalysis · OSTI ID:1502035

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Acetaldehyde
Copper
Ethanol dehydrogenation
Hydrogen
Nickel
Single atom alloys

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

Citation Formats

References (59)

Cited By (8)

Similar Records

Related Subjects