Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Benjamin M. Moskowitz; Jisue Moon; Yuanyuan Li; Yongqiang Cheng; Luke L. Daemen; Lane Lee; Victor Fung; Aditya Savara; Anatoly I. Frenkel; Zili Wu; Israel E. Wachs

doi:10.1021/acscatal.5c03430

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Benjamin M. Moskowitz
, Jisue Moon
, Yuanyuan Li
, Yongqiang Cheng
, Luke L. Daemen
, Lane Lee
, Victor Fung
, Aditya Savara
, Anatoly I. Frenkel
, Zili Wu
, Israel E. Wachs

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH₃-TPD), and DFT calculations revealed that the supported ZnO_xphase was present as isolated surface ZnO_xsites on SiO₂, with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO)₂Zn²⁺O₂Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO_xsites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH)⁺Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH)⁺Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO)₂Zn²⁺O₂Si= sites were inactive. Greater heterogeneity among all surface ZnO_xsites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnO_xsites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO_xsites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO)₂Zn²⁺O₂Si= sites on the silica support caused a greater number of active surface ZnO_xsites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH)⁺Si) sites. Such findings suggested that inactive surface ZnO_xsites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

Original language	English
Pages (from-to)	17225-17240
Number of pages	16
Journal	ACS Catalysis
Volume	15
DOIs	https://doi.org/10.1021/acscatal.5c03430
State	Published - Jan 1 2025

Funding

The authors gratefully acknowledge the assistance of Drs. Sagar Sourav and Nebojsa (Ned) Marinkovic with XAS measurements at Brookhaven National Laboratory. The authors gratefully acknowledge the assistance of Eli Ream for DRIFTS measurement of the SiO-NHOH sample. The authors gratefully acknowledge Adhika Setiawan and Dr. Srinivas Rangarajan for DFT calculations of NH adsorption. This material is based upon work supported by the National Science Foundation under Grant No. 1605805 and by the U.S. Department of Energy (DOE), Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) Program. The SCGSR Program is administered by the Oak Ridge Institute for Science and Education for the DOE under contract number DE-SC0014664. J.M., A.S., and Z.W. acknowledge support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program. Work by L.L. was supported by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Community College Internships (CCI) Program. A.I.F. acknowledges support of his contribution to XAS data analysis by the US National Science Foundation under award 2452446. This research was conducted in part at the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, which is a DOE Office of Science User Facility. This research benefited from the use of the VISION beamline (IPTS-16527) at the Spallation Neutron Source, Oak Ridge National Laboratory (ORNL), which is supported by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. DOE. This research made use of computing resources through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium (US DOE, Office of Basic Energy Sciences, Grant No. DESC0012335). 2 4 3 The authors gratefully acknowledge the assistance of Drs. Sagar Sourav and Nebojsa (Ned) Marinkovic with XAS measurements at Brookhaven National Laboratory. The authors gratefully acknowledge the assistance of Eli Ream for DRIFTS measurement of the SiO2-NH4OH sample. The authors gratefully acknowledge Adhika Setiawan and Dr. Srinivas Rangarajan for DFT calculations of NH3 adsorption. This material is based upon work supported by the National Science Foundation under Grant No. 1605805 and by the U.S. Department of Energy (DOE), Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) Program. The SCGSR Program is administered by the Oak Ridge Institute for Science and Education for the DOE under contract number DE-SC0014664. J.M., A.S., and Z.W. acknowledge support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program. Work by L.L. was supported by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Community College Internships (CCI) Program. A.I.F. acknowledges support of his contribution to XAS data analysis by the US National Science Foundation under award 2452446. This research was conducted in part at the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, which is a DOE Office of Science User Facility. This research benefited from the use of the VISION beamline (IPTS-16527) at the Spallation Neutron Source, Oak Ridge National Laboratory (ORNL), which is supported by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. DOE. This research made use of computing resources through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium (US DOE, Office of Basic Energy Sciences, Grant No. DESC0012335).

Keywords

SiO-supported
acetaldehyde
active sites
ethanol dehydrogenation
kinetics
optical path length
sampling technique
zinc oxide

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10.1021/acscatal.5c03430

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@article{6693e5bbf3c045988734e0843233739d,

title = "Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts",

abstract = "Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH3-TPD), and DFT calculations revealed that the supported ZnOxphase was present as isolated surface ZnOxsites on SiO2, with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO)2Zn2+O2Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnOxsites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH)+Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH)+Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO)2Zn2+O2Si= sites were inactive. Greater heterogeneity among all surface ZnOxsites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnOxsites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnOxsites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO)2Zn2+O2Si= sites on the silica support caused a greater number of active surface ZnOxsites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH)+Si) sites. Such findings suggested that inactive surface ZnOxsites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.",

keywords = "SiO-supported, acetaldehyde, active sites, ethanol dehydrogenation, kinetics, optical path length, sampling technique, zinc oxide",

author = "Moskowitz, \{Benjamin M.\} and Jisue Moon and Yuanyuan Li and Yongqiang Cheng and Daemen, \{Luke L.\} and Lane Lee and Victor Fung and Aditya Savara and Frenkel, \{Anatoly I.\} and Zili Wu and Wachs, \{Israel E.\}",

note = "Publisher Copyright: {\textcopyright} 2025 The Authors. Published by American Chemical Society",

year = "2025",

month = jan,

day = "1",

doi = "10.1021/acscatal.5c03430",

language = "English",

volume = "15",

pages = "17225--17240",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

}

TY - JOUR

T1 - Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

AU - Moskowitz, Benjamin M.

AU - Moon, Jisue

AU - Li, Yuanyuan

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Lee, Lane

AU - Fung, Victor

AU - Savara, Aditya

AU - Frenkel, Anatoly I.

AU - Wu, Zili

AU - Wachs, Israel E.

PY - 2025/1/1

Y1 - 2025/1/1

N2 - Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH3-TPD), and DFT calculations revealed that the supported ZnOxphase was present as isolated surface ZnOxsites on SiO2, with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO)2Zn2+O2Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnOxsites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH)+Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH)+Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO)2Zn2+O2Si= sites were inactive. Greater heterogeneity among all surface ZnOxsites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnOxsites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnOxsites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO)2Zn2+O2Si= sites on the silica support caused a greater number of active surface ZnOxsites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH)+Si) sites. Such findings suggested that inactive surface ZnOxsites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

AB - Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH3-TPD), and DFT calculations revealed that the supported ZnOxphase was present as isolated surface ZnOxsites on SiO2, with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO)2Zn2+O2Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnOxsites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH)+Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH)+Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO)2Zn2+O2Si= sites were inactive. Greater heterogeneity among all surface ZnOxsites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnOxsites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnOxsites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO)2Zn2+O2Si= sites on the silica support caused a greater number of active surface ZnOxsites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH)+Si) sites. Such findings suggested that inactive surface ZnOxsites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

KW - SiO-supported

KW - acetaldehyde

KW - active sites

KW - ethanol dehydrogenation

KW - kinetics

KW - optical path length

KW - sampling technique

KW - zinc oxide

UR - https://www.scopus.com/pages/publications/105017548327

U2 - 10.1021/acscatal.5c03430

DO - 10.1021/acscatal.5c03430

M3 - Article

AN - SCOPUS:105017548327

SN - 2155-5435

VL - 15

SP - 17225

EP - 17240

JO - ACS Catalysis

JF - ACS Catalysis

ER -

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

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