Polyelectrolyte-Assisted Oxygen Vacancies : A New Route to Defect Engineering in Molybdenum Oxide
The presence of oxygen vacancy sites fundamentally affects physical and chemical properties of materials. In this study, a dipole-containing interaction between poly(diallyldimethylammonium chloride) PDDA and α-MoO3 is found to enable high-concentrations of surface oxygen vacancies. Thermal annealin...
| Veröffentlicht in: | Langmuir : the ACS journal of surfaces and colloids. - 1992. - 34(2018), 21 vom: 29. Mai, Seite 6296-6306 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2018
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| Zugriff auf das übergeordnete Werk: | Langmuir : the ACS journal of surfaces and colloids |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't Research Support, U.S. Gov't, Non-P.H.S. |
| Zusammenfassung: | The presence of oxygen vacancy sites fundamentally affects physical and chemical properties of materials. In this study, a dipole-containing interaction between poly(diallyldimethylammonium chloride) PDDA and α-MoO3 is found to enable high-concentrations of surface oxygen vacancies. Thermal annealing under Ar resulted in negligible reduction of MoO3 to MoO3- x with x = 0.03 at 600 °C. In contrast, we show that the thermochemical reaction with PDDA polyelectrolyte under Ar can significantly reduce MoO3 to MoO3- x with x = 0.36 (MoO2.64) at 600 °C. Thermal annealing under H2 gas enhanced the substoichiometry of MoO3- x from x = 0.62 to 0.98 by using PDDA at the same conditions. Density functional theory calculations, supported by experimental analysis, suggest that the vacancy sites are created through absorption of terminal site oxygen (Ot) upon decomposition of the N-C bond in the pentagonal ring of PDDA during the thermal treatment. Ot atoms are absorbed as ionic O- and neutral O2-, creating Mo5+-vO· and Mo4+-vO·· vacancy bipolarons and polarons, respectively. X-ray photoemission spectroscopy peak analysis indicates the ratio of charged to neutral molybdenum ions in the PDDA-processed samples increased from Mo4+/Mo6+ = 1.0 and Mo5+/Mo6+ = 3.3 when reduced at 400 °C to Mo4+/Mo6+ = 3.7 and Mo5+/Mo6+ = 2.6 when reduced at 600 °C. This is consistent with our ab initio calculation where the Mo4+-vO·· formation energy is 0.22 eV higher than that for Mo5+-vO· in the bulk of the material and 0.02 eV higher on the surface. This study reveals a new paradigm for effective enhancement of surface oxygen vacancy concentrations essential for a variety of technologies including advanced energy conversion applications such as electrochemical energy storage, catalysis, and low-temperature thermochemical water splitting |
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| Beschreibung: | Date Completed 10.09.2018 Date Revised 10.09.2018 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1520-5827 |
| DOI: | 10.1021/acs.langmuir.8b00539 |