PHOTOLUMINESCENCE FROM ZINC-OXIDE POWDER TO PROBE ADSORPTION AND REACTION OF O2, CO, H-2, HCOOH, AND CH3OH

Hicham Idriss, M A BARTEAU

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Abstract

Two emissions were observed at room temperature from zinc oxide powder excited with photons of higher energy than its band gap (3.2 eV). The sharp UV emission at 383 nm corresponded to band gap emission, and a broad visible (green) emission at ca. 500 nm corresponded to sub-band gap emission. Adsorption of O2, H-2, CO, methanol, and carboxylic acids (formic acid and acetic acid) changed the intensities of both emissions. At room temperature, O2, H-2, and CO exposure decreased the emission intensities; after evacuation at 10(-6) Torr the effect of O2 adsorption was only partially reversible, while those of H-2 and CO were virtually completely reversible. In contrast, adsorption of methanol and formic acid (and acetic acid) caused an irreversible increase of both emissions. Surface formate species were formed by dissociative adsorption of formic acid as well as by oxidation of methanol, as shown by temperature-programmed desorption and FT-IR. The decomposition of formate intermediates further increased the intensity of both emissions. Moreover, the increase of the visible emission intensity was more pronounced in the case of the decomposition of formates produced by methanol oxidation than of those resulting from formic acid dissociation. The increase of the visible emission intensity upon formate decomposition may be related to the creation of oxygen vacancies in the course of this reaction. These vacancies act as acceptor centers for deexcited electrons from the conduction band. This study demonstrates that photoluminescence can be used to probe adsorption, both reversible and irreversible, and reaction phenomena on the surface of zinc oxide.

Original languageEnglish
Pages (from-to)3382-3388
Number of pages7
JournalJournal of Physical Chemistry
Volume96
Issue number8
DOIs
Publication statusPublished - 16 Apr 1992

Keywords

  • ZNO SURFACE PROPERTIES
  • METHANOL DECOMPOSITION
  • INFRARED-SPECTROSCOPY
  • STRUCTURE SENSITIVITY
  • ROOM-TEMPERATURE
  • CADMIUM SELENIDE
  • POLAR SURFACES
  • METAL-OXIDES
  • FORMIC-ACID
  • FORMALDEHYDE

Cite this

PHOTOLUMINESCENCE FROM ZINC-OXIDE POWDER TO PROBE ADSORPTION AND REACTION OF O2, CO, H-2, HCOOH, AND CH3OH. / Idriss, Hicham; BARTEAU, M A .

In: Journal of Physical Chemistry, Vol. 96, No. 8, 16.04.1992, p. 3382-3388.

Research output: Contribution to journalArticle

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abstract = "Two emissions were observed at room temperature from zinc oxide powder excited with photons of higher energy than its band gap (3.2 eV). The sharp UV emission at 383 nm corresponded to band gap emission, and a broad visible (green) emission at ca. 500 nm corresponded to sub-band gap emission. Adsorption of O2, H-2, CO, methanol, and carboxylic acids (formic acid and acetic acid) changed the intensities of both emissions. At room temperature, O2, H-2, and CO exposure decreased the emission intensities; after evacuation at 10(-6) Torr the effect of O2 adsorption was only partially reversible, while those of H-2 and CO were virtually completely reversible. In contrast, adsorption of methanol and formic acid (and acetic acid) caused an irreversible increase of both emissions. Surface formate species were formed by dissociative adsorption of formic acid as well as by oxidation of methanol, as shown by temperature-programmed desorption and FT-IR. The decomposition of formate intermediates further increased the intensity of both emissions. Moreover, the increase of the visible emission intensity was more pronounced in the case of the decomposition of formates produced by methanol oxidation than of those resulting from formic acid dissociation. The increase of the visible emission intensity upon formate decomposition may be related to the creation of oxygen vacancies in the course of this reaction. These vacancies act as acceptor centers for deexcited electrons from the conduction band. This study demonstrates that photoluminescence can be used to probe adsorption, both reversible and irreversible, and reaction phenomena on the surface of zinc oxide.",
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T1 - PHOTOLUMINESCENCE FROM ZINC-OXIDE POWDER TO PROBE ADSORPTION AND REACTION OF O2, CO, H-2, HCOOH, AND CH3OH

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AU - BARTEAU, M A

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N2 - Two emissions were observed at room temperature from zinc oxide powder excited with photons of higher energy than its band gap (3.2 eV). The sharp UV emission at 383 nm corresponded to band gap emission, and a broad visible (green) emission at ca. 500 nm corresponded to sub-band gap emission. Adsorption of O2, H-2, CO, methanol, and carboxylic acids (formic acid and acetic acid) changed the intensities of both emissions. At room temperature, O2, H-2, and CO exposure decreased the emission intensities; after evacuation at 10(-6) Torr the effect of O2 adsorption was only partially reversible, while those of H-2 and CO were virtually completely reversible. In contrast, adsorption of methanol and formic acid (and acetic acid) caused an irreversible increase of both emissions. Surface formate species were formed by dissociative adsorption of formic acid as well as by oxidation of methanol, as shown by temperature-programmed desorption and FT-IR. The decomposition of formate intermediates further increased the intensity of both emissions. Moreover, the increase of the visible emission intensity was more pronounced in the case of the decomposition of formates produced by methanol oxidation than of those resulting from formic acid dissociation. The increase of the visible emission intensity upon formate decomposition may be related to the creation of oxygen vacancies in the course of this reaction. These vacancies act as acceptor centers for deexcited electrons from the conduction band. This study demonstrates that photoluminescence can be used to probe adsorption, both reversible and irreversible, and reaction phenomena on the surface of zinc oxide.

AB - Two emissions were observed at room temperature from zinc oxide powder excited with photons of higher energy than its band gap (3.2 eV). The sharp UV emission at 383 nm corresponded to band gap emission, and a broad visible (green) emission at ca. 500 nm corresponded to sub-band gap emission. Adsorption of O2, H-2, CO, methanol, and carboxylic acids (formic acid and acetic acid) changed the intensities of both emissions. At room temperature, O2, H-2, and CO exposure decreased the emission intensities; after evacuation at 10(-6) Torr the effect of O2 adsorption was only partially reversible, while those of H-2 and CO were virtually completely reversible. In contrast, adsorption of methanol and formic acid (and acetic acid) caused an irreversible increase of both emissions. Surface formate species were formed by dissociative adsorption of formic acid as well as by oxidation of methanol, as shown by temperature-programmed desorption and FT-IR. The decomposition of formate intermediates further increased the intensity of both emissions. Moreover, the increase of the visible emission intensity was more pronounced in the case of the decomposition of formates produced by methanol oxidation than of those resulting from formic acid dissociation. The increase of the visible emission intensity upon formate decomposition may be related to the creation of oxygen vacancies in the course of this reaction. These vacancies act as acceptor centers for deexcited electrons from the conduction band. This study demonstrates that photoluminescence can be used to probe adsorption, both reversible and irreversible, and reaction phenomena on the surface of zinc oxide.

KW - ZNO SURFACE PROPERTIES

KW - METHANOL DECOMPOSITION

KW - INFRARED-SPECTROSCOPY

KW - STRUCTURE SENSITIVITY

KW - ROOM-TEMPERATURE

KW - CADMIUM SELENIDE

KW - POLAR SURFACES

KW - METAL-OXIDES

KW - FORMIC-ACID

KW - FORMALDEHYDE

U2 - 10.1021/j100187a037

DO - 10.1021/j100187a037

M3 - Article

VL - 96

SP - 3382

EP - 3388

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 8

ER -