Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions

Liyuan Zhang; Xuanyu Zhang; Kun Qian; Zhaorui Li; Yongqiang Cheng; Luke L. Daemen; Zili Wu; Weixin Huang

doi:10.1016/j.jechem.2020.03.038

Activation and surface reactions of CO and H₂ on ZnO powders and nanoplates under CO hydrogenation reaction conditions

Liyuan Zhang, Xuanyu Zhang, Kun Qian, Zhaorui Li, Yongqiang Cheng, Luke L. Daemen, Zili Wu, Weixin Huang

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

34 Scopus citations

Abstract

Activation and surface reactions of CO and H₂ on ZnO powders and nanoplates under CO hydrogenation reaction conditions were (quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO₂ and surface carbon adatoms, and adsorbs to form surface formate species. H₂ adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO₂ and H₂, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH₂(a), CH₃(a) and eventually gaseous CH₄. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and O-ZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH₄. These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

Original language	English
Pages (from-to)	351-357
Number of pages	7
Journal	Journal of Energy Chemistry
Volume	50
DOIs	https://doi.org/10.1016/j.jechem.2020.03.038
State	Published - Nov 2020

Funding

This work was financially supported by the National Key R & D Program of Ministry of Science and Technology of China ( 2017YFB0602205 ), the National Natural Science Foundation of China ( 21525313 , 91745202 , 91945301 ), the Chinese Academy of Sciences , and the Changjiang Scholars Program of Ministry of Education of China. Xuanyu Zhang thanks the financial support of the China Scholarship Council . Neutron scattering experiment was performed at ORNL's Spallation Neutron Source, supported by the Scientific User Facilities Division, Office of Basic Energy Sciences , US DOE, under Contract No. DE-AC0500OR22725 with UT Battelle , LLC. ZW was supported by the U.S. Department of Energy , Office of Science , Office of Basic Energy Sciences , Chemical Sciences, Geosciences, and Biosciences Division , Catalysis Science Program.

Keywords

Active species
DRIFTS
EPR
INS
Reaction mechanism
Surface intermediates
TPSR

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10.1016/j.jechem.2020.03.038

Cite this

@article{5fa95f5860dc48028d56b13950dd07d5,

title = "Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions",

abstract = "Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were (quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO2 and surface carbon adatoms, and adsorbs to form surface formate species. H2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO2 and H2, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH2(a), CH3(a) and eventually gaseous CH4. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and O-ZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH4. These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.",

keywords = "Active species, DRIFTS, EPR, INS, Reaction mechanism, Surface intermediates, TPSR",

author = "Liyuan Zhang and Xuanyu Zhang and Kun Qian and Zhaorui Li and Yongqiang Cheng and Daemen, {Luke L.} and Zili Wu and Weixin Huang",

note = "Publisher Copyright: {\textcopyright} 2020",

year = "2020",

month = nov,

doi = "10.1016/j.jechem.2020.03.038",

language = "English",

volume = "50",

pages = "351--357",

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AU - Zhang, Liyuan

AU - Zhang, Xuanyu

AU - Qian, Kun

AU - Li, Zhaorui

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Wu, Zili

AU - Huang, Weixin

PY - 2020/11

Y1 - 2020/11

N2 - Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were (quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO2 and surface carbon adatoms, and adsorbs to form surface formate species. H2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO2 and H2, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH2(a), CH3(a) and eventually gaseous CH4. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and O-ZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH4. These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

AB - Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were (quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO2 and surface carbon adatoms, and adsorbs to form surface formate species. H2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO2 and H2, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH2(a), CH3(a) and eventually gaseous CH4. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and O-ZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH4. These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

KW - Active species

KW - DRIFTS

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KW - INS

KW - Reaction mechanism

KW - Surface intermediates

KW - TPSR

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