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

Shan, Junjun; Liu, Jilei; Li, Mengwei; Lustig, Sylvia; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

doi:10.1016/j.apcatb.2017.12.059

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

Abstract

Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO₂ monometallic nanoparticles, while in the NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.

Authors:

Shan, Junjun ^[1]; Liu, Jilei ^[2]; Li, Mengwei ^[2]; Lustig, Sylvia ^[2]; Lee, Sungsik ^[3]; Flytzani-Stephanopoulos, Maria ^[2]

Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering; NICE America Research, Inc, Mountain View, CA (United States)
Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division

Publication Date:: Fri Dec 29 00:00:00 EST 2017

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Harvard Univ., Boston, MA (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)

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

OSTI Identifier:: 1439883

Alternate Identifier(s):: OSTI ID: 1496353

Grant/Contract Number:: AC02-06CH11357; SC0012573; DESC0012573

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Applied Catalysis B: Environmental

Additional Journal Information:: Journal Volume: 226; Journal Issue: C; Journal ID: ISSN 0926-3373

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; Copper; Nickel; ethanol dehydrogenation; single atom alloys; C-H bond activation

Citation Formats


                    Shan, Junjun, Liu, Jilei, Li, Mengwei, Lustig, Sylvia, Lee, Sungsik, and Flytzani-Stephanopoulos, Maria. NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction.  United States: N. p., 2017. 
        Web.  doi:10.1016/j.apcatb.2017.12.059.

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                    Shan, Junjun, Liu, Jilei, Li, Mengwei, Lustig, Sylvia, Lee, Sungsik, & Flytzani-Stephanopoulos, Maria. NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction.  United States.  https://doi.org/10.1016/j.apcatb.2017.12.059

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                    Shan, Junjun, Liu, Jilei, Li, Mengwei, Lustig, Sylvia, Lee, Sungsik, and Flytzani-Stephanopoulos, Maria. 2017.  
        "NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction".  United States.  https://doi.org/10.1016/j.apcatb.2017.12.059.  https://www.osti.gov/servlets/purl/1439883.

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@article{osti_1439883,

  title        = {NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction},

  author       = {Shan, Junjun and Liu, Jilei and Li, Mengwei and Lustig, Sylvia and Lee, Sungsik and Flytzani-Stephanopoulos, Maria},

  abstractNote = {Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO2 monometallic nanoparticles, while in the NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.},

  doi          = {10.1016/j.apcatb.2017.12.059},

  url          = {https://www.osti.gov/biblio/1439883},
  journal      = {Applied Catalysis B: Environmental},

  issn         = {0926-3373},

  number       = C,

  volume       = 226,

  place        = {United States},

  year         = {Fri Dec 29 00:00:00 EST 2017},

  month        = {Fri Dec 29 00:00:00 EST 2017}

}

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https://doi.org/10.1016/j.apcatb.2017.12.059

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Cited by: 95 works

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Figures / Tables:

Fig. 1: XRD patterns of unsupported np-Cu, unsupported np-Ni_0.01Cu, and unsupported np-Ni_0.01Cu after the ethanol dehydrogenation reaction at 250 °C for 8 h.

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

Abstract

Citation Formats

Figures / Tables:

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

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Atomic Structure of Pt 3 Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy journal, December 2015

X-Ray Absorption Fine Structure Spectra and the Oxidation State of Nickel in Some of Its Oxycompounds journal, January 1994

Speciation and fractionation of nickel in airborne particulate matter: comparison between selective leaching and XASspectroscopy journal, January 2011

Synergetic Effect of Surface and Subsurface Ni Species at Pt−Ni Bimetallic Catalysts for CO Oxidation journal, February 2011

Electronic structure of Ni-Cu alloys: The d -electron charge distribution journal, June 1998

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

Bond-Length Change as a Tool to Determine Charge Transfer and Electron-Phonon Coupling in Graphite Intercalation Compounds journal, August 1981

Microcalorimetric, FTIR, and DFT Studies of the Adsorption of Methanol, Ethanol, and 2,2,2-Trifluoroethanol on Silica journal, April 1998

Ultra-broadband sum-frequency spectrometer of aqueous interfaces based on a non-collinear optical parametric amplifier journal, December 2011

Surface species and gas phase products in steam reforming of ethanol on TiO2 and Rh/TiO2 journal, August 2004

Binary combination and overtone modes in the C–H stretch region in ethoxy adsorbed on Cu(100): Experimental and calculated vibrational spectra journal, July 2000

In situ DRIFTS Studies on Cu, Ni and CuNi catalysts for Ethanol Decomposition Reaction journal, February 2016

Combined DFT, Microkinetic, and Experimental Study of Ethanol Steam Reforming on Pt journal, February 2013

Recent advances in homogeneous nickel catalysis journal, May 2014

Recent advances on nickel-catalyzed C–H bonds functionalized reactions journal, February 2015

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

Graphene Supported Single Atom Transition Metal Catalysts for Methane Activation journal, May 2018

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

Anchoring ultrafine PtNi nanoparticles on N-doped graphene for highly efficient hydrogen evolution reaction journal, January 2019

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies journal, January 2020

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

Ultrafine PtRu Dilute Alloy Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation journal, October 2019

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

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

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

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

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

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

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

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

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

Mechanistic Study of Ethanol Dehydrogenation over Silica-Supported Silver
journal, May 2013

Oxidant-Free Dehydrogenation of Alcohols Heterogeneously Catalyzed by Cooperation of Silver Clusters and Acid-Base Sites on Alumina
journal, February 2009

Dehydrogenation of isopropyl alcohol on carbon-supported Pt and Cu–Pt catalysts
journal, July 2005

Dehydrogenation of cyclohexanol on copper-containing catalysts II. The pathways of the cyclohexanol dehydrogenation reaction to cyclohexanone on copper-active sites in oxidation state Cu0 and Cu+
journal, March 2004

Reaction Mechanism of 2-Propanol Dehydrogenation with a Carbon-Supported Ru–Pt Composite Catalyst in the Liquid Phase
journal, October 2003

Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts
journal, August 2003

Atomically Dispersed Supported Metal Catalysts
journal, July 2012

Gold Atoms Stabilized on Various Supports Catalyze the Water–Gas Shift Reaction
journal, November 2013

Catalysis by Supported Single Metal Atoms
journal, November 2016

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

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

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

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

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

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

Selective Formic Acid Dehydrogenation on Pt-Cu Single-Atom Alloys
journal, December 2016

Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys
journal, May 2017

Controlling a spillover pathway with the molecular cork effect
journal, April 2013

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

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

Early and transient stages of Cu oxidation: Atomistic insights from theoretical simulations and in situ experiments
journal, October 2016

Atomic Structure of Pt ₃ Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy
journal, December 2015

X-Ray Absorption Fine Structure Spectra and the Oxidation State of Nickel in Some of Its Oxycompounds
journal, January 1994

Speciation and fractionation of nickel in airborne particulate matter: comparison between selective leaching and XASspectroscopy
journal, January 2011

Synergetic Effect of Surface and Subsurface Ni Species at Pt−Ni Bimetallic Catalysts for CO Oxidation
journal, February 2011

Electronic structure of Ni-Cu alloys: The $d$ -electron charge distribution
journal, June 1998

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

Bond-Length Change as a Tool to Determine Charge Transfer and Electron-Phonon Coupling in Graphite Intercalation Compounds
journal, August 1981

Microcalorimetric, FTIR, and DFT Studies of the Adsorption of Methanol, Ethanol, and 2,2,2-Trifluoroethanol on Silica
journal, April 1998

Ultra-broadband sum-frequency spectrometer of aqueous interfaces based on a non-collinear optical parametric amplifier
journal, December 2011

Surface species and gas phase products in steam reforming of ethanol on TiO2 and Rh/TiO2
journal, August 2004

Binary combination and overtone modes in the C–H stretch region in ethoxy adsorbed on Cu(100): Experimental and calculated vibrational spectra
journal, July 2000

In situ DRIFTS Studies on Cu, Ni and CuNi catalysts for Ethanol Decomposition Reaction
journal, February 2016

Combined DFT, Microkinetic, and Experimental Study of Ethanol Steam Reforming on Pt
journal, February 2013

Recent advances in homogeneous nickel catalysis
journal, May 2014

Recent advances on nickel-catalyzed C–H bonds functionalized reactions
journal, February 2015

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

Graphene Supported Single Atom Transition Metal Catalysts for Methane Activation
journal, May 2018

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

Anchoring ultrafine PtNi nanoparticles on N-doped graphene for highly efficient hydrogen evolution reaction
journal, January 2019

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies
journal, January 2020

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

Ultrafine PtRu Dilute Alloy Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation
journal, October 2019