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Title: Mechanism by which Tungsten Oxide Promotes the Activity of Supported V 2O 5/TiO 2 Catalysts for NO X Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy

Abstract

Growing concern for environmental pollutants coupled with an expansion of energy demand has promoted significant interest in technologies to abate contaminating species. Nitrogen oxides are particularly alarming due to their numerous detrimental impacts to the environment and public health, where selective catalytic reduction to inert N 2 is an industrially-relevant mitigation technology. Herein, we provide unique, molecular-level insight on the structure and reactivity of V 2O 5(-WO 3)/TiO 2 catalysts employed at stationary facilities for NO x removal. Detailed catalytic testing, spectroscopy (nuclear magnetic resonance, Raman, and electron paramagnetic resonance), and electronic structure-based predictions of 51V chemical shifts help clarify the promotional role of tungsten oxide and identify an active site requirement for SCR of NO x. We show that progressive addition of vanadia to the catalyst surface increases the catalytic SCR performance and promotes the formation of larger vanadium domains, demonstrating the proportional relationship of SCR reaction rate to [VO x loading]2 for supported V 2O 5/TiO 2 catalysts with increasing surface vanadia coverage. Tungsten oxide incorporation enhances catalyst reactivity which is shown to stem not from electronic effects, but from changes to the vanadium structure as observed spectroscopically. The progressive addition of tungsten oxide to the catalyst surfacemore » also increases the catalytic performance and promotes the formation of larger vanadium domains, which are beneficial for catalytic turnover in a two-site model. Further, unique monomeric species are confidently ascribed to distorted tetrahedral and square pyramidal structures, resolving a long-standing uncertainty in literature assignments for the signals. These findings provide strong support for both the dual-site requirement for the SCR reaction and the important structural promotional effect that tungsten offers for mitigation of these harmful pollutants.« less

Authors:
ORCiD logo [1];  [2];  [3];  [3];  [4];  [4];  [3];  [3];  [3];  [3];  [2];  [1]; ORCiD logo [3]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
  2. Lehigh Univ., Bethlehem, PA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. The Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1572978
Alternate Identifier(s):
OSTI ID: 1547078
Report Number(s):
PNNL-SA-141251
Journal ID: ISSN 1433-7851; ANIE
Grant/Contract Number:  
AC05-76RL01830; SC0012577; 66628
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 36; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; NMR spectroscopy; NOx; selective catalytic reduction (SCR); vanadium

Citation Formats

Jaegers, Nicholas R., Lai, Jun-Kun, He, Yang, Walter, Eric, Dixon, David A., Vasiliu, Monica, Chen, Ying, Wang, Chongmin, Hu, Mary Y., Mueller, Karl T., Wachs, Israel E., Wang, Yong, and Hu, Jian Zhi. Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy. United States: N. p., 2019. Web. doi:10.1002/anie.201904503.
Jaegers, Nicholas R., Lai, Jun-Kun, He, Yang, Walter, Eric, Dixon, David A., Vasiliu, Monica, Chen, Ying, Wang, Chongmin, Hu, Mary Y., Mueller, Karl T., Wachs, Israel E., Wang, Yong, & Hu, Jian Zhi. Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy. United States. doi:10.1002/anie.201904503.
Jaegers, Nicholas R., Lai, Jun-Kun, He, Yang, Walter, Eric, Dixon, David A., Vasiliu, Monica, Chen, Ying, Wang, Chongmin, Hu, Mary Y., Mueller, Karl T., Wachs, Israel E., Wang, Yong, and Hu, Jian Zhi. Mon . "Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy". United States. doi:10.1002/anie.201904503.
@article{osti_1572978,
title = {Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy},
author = {Jaegers, Nicholas R. and Lai, Jun-Kun and He, Yang and Walter, Eric and Dixon, David A. and Vasiliu, Monica and Chen, Ying and Wang, Chongmin and Hu, Mary Y. and Mueller, Karl T. and Wachs, Israel E. and Wang, Yong and Hu, Jian Zhi},
abstractNote = {Growing concern for environmental pollutants coupled with an expansion of energy demand has promoted significant interest in technologies to abate contaminating species. Nitrogen oxides are particularly alarming due to their numerous detrimental impacts to the environment and public health, where selective catalytic reduction to inert N2 is an industrially-relevant mitigation technology. Herein, we provide unique, molecular-level insight on the structure and reactivity of V2O5(-WO3)/TiO2 catalysts employed at stationary facilities for NOx removal. Detailed catalytic testing, spectroscopy (nuclear magnetic resonance, Raman, and electron paramagnetic resonance), and electronic structure-based predictions of 51V chemical shifts help clarify the promotional role of tungsten oxide and identify an active site requirement for SCR of NOx. We show that progressive addition of vanadia to the catalyst surface increases the catalytic SCR performance and promotes the formation of larger vanadium domains, demonstrating the proportional relationship of SCR reaction rate to [VOx loading]2 for supported V2O5/TiO2 catalysts with increasing surface vanadia coverage. Tungsten oxide incorporation enhances catalyst reactivity which is shown to stem not from electronic effects, but from changes to the vanadium structure as observed spectroscopically. The progressive addition of tungsten oxide to the catalyst surface also increases the catalytic performance and promotes the formation of larger vanadium domains, which are beneficial for catalytic turnover in a two-site model. Further, unique monomeric species are confidently ascribed to distorted tetrahedral and square pyramidal structures, resolving a long-standing uncertainty in literature assignments for the signals. These findings provide strong support for both the dual-site requirement for the SCR reaction and the important structural promotional effect that tungsten offers for mitigation of these harmful pollutants.},
doi = {10.1002/anie.201904503},
journal = {Angewandte Chemie (International Edition)},
number = 36,
volume = 58,
place = {United States},
year = {2019},
month = {7}
}

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