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Title: Achieving Atomic Dispersion of Highly Loaded Transition Metals in Small-Pore Zeolite SSZ-13: High-Capacity and High-Efficiency Low-Temperature CO and Passive NO x Adsorbers

Abstract

Synthesis of small-pore zeolitic materials with realistic loadings of transition metals atomically dispersed in the micropores has been a formidable challenge. Herein, we demonstrate a new simple and scalable route to high Pd and Pt loadings (>1 wt%) atomically dispersed in the micropores of a small-pore zeolite, SSZ-13. Unlike all previous methods that require addition of expensive transition metal precursor complexes into the synthesis gel and produce low loading of atomically dispersed species, this method does not require any complicated synthetic proce-dures. We determine the factors that govern the stabilization of M(II) species in the micropores of SSZ-13. Using a combined spectroscopic and DFT approach, we offer a unifying explana-tion for the discrepancies existing in available M-zeolite litera-ture. Moreover, we highlight the difference between the behavior of Pt and Pd during synthesis, and demonstrate that ionically dispersed Pd/SSZ-13 shows superior performance as a new class of environmentally important passive NOx Adsorber (PNA) material under practically relevant conditions. It thus represents the 2nd known metal-small pore zeolite material that has immediate industrial application, and the only known met-al-small pore zeolite material in which metal is close to 100 % utilized. In addition to NO x, the material performs remarkably for COmore » removal during cold start as well due to the formation of a mixed carbonyl-nitrosyl complex Pd(II)(CO)(NO).« less

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [4];  [4];  [4];  [5];  [5];  [5];  [2];  [1]; ORCiD logo [1]
  1. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland WA 99352 USA
  2. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland WA 99352 USA; Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman WA 99163 USA
  3. Chemistry Department, Brookhaven National Laboratory, Uptown NY 11973 USA
  4. Department of Chemical and Petroleum Engineering and Center for Environmentally Beneficial Catalysis, University of Kansas, Lawrence KS 66045 USA
  5. Faculty of Chemistry and Pharmacy, University of Sofia, 1126 Sofia Bulgaria
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1490338
Report Number(s):
PNNL-SA-136340
Journal ID: ISSN 1433-7851
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 57; Journal Issue: 51; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English

Citation Formats

Khivantsev, Konstantin, Jaegers, Nicholas R., Kovarik, Libor, Hanson, Jonathan C., Tao, Franklin Feng, Tang, Yu, Zhang, Xiaoyan, Koleva, Iskra Z., Aleksandrov, Hristiyan A., Vayssilov, Georgi N., Wang, Yong, Gao, Feng, and Szanyi, János. Achieving Atomic Dispersion of Highly Loaded Transition Metals in Small-Pore Zeolite SSZ-13: High-Capacity and High-Efficiency Low-Temperature CO and Passive NOx Adsorbers. United States: N. p., 2018. Web. doi:10.1002/anie.201809343.
Khivantsev, Konstantin, Jaegers, Nicholas R., Kovarik, Libor, Hanson, Jonathan C., Tao, Franklin Feng, Tang, Yu, Zhang, Xiaoyan, Koleva, Iskra Z., Aleksandrov, Hristiyan A., Vayssilov, Georgi N., Wang, Yong, Gao, Feng, & Szanyi, János. Achieving Atomic Dispersion of Highly Loaded Transition Metals in Small-Pore Zeolite SSZ-13: High-Capacity and High-Efficiency Low-Temperature CO and Passive NOx Adsorbers. United States. doi:10.1002/anie.201809343.
Khivantsev, Konstantin, Jaegers, Nicholas R., Kovarik, Libor, Hanson, Jonathan C., Tao, Franklin Feng, Tang, Yu, Zhang, Xiaoyan, Koleva, Iskra Z., Aleksandrov, Hristiyan A., Vayssilov, Georgi N., Wang, Yong, Gao, Feng, and Szanyi, János. Mon . "Achieving Atomic Dispersion of Highly Loaded Transition Metals in Small-Pore Zeolite SSZ-13: High-Capacity and High-Efficiency Low-Temperature CO and Passive NOx Adsorbers". United States. doi:10.1002/anie.201809343.
@article{osti_1490338,
title = {Achieving Atomic Dispersion of Highly Loaded Transition Metals in Small-Pore Zeolite SSZ-13: High-Capacity and High-Efficiency Low-Temperature CO and Passive NOx Adsorbers},
author = {Khivantsev, Konstantin and Jaegers, Nicholas R. and Kovarik, Libor and Hanson, Jonathan C. and Tao, Franklin Feng and Tang, Yu and Zhang, Xiaoyan and Koleva, Iskra Z. and Aleksandrov, Hristiyan A. and Vayssilov, Georgi N. and Wang, Yong and Gao, Feng and Szanyi, János},
abstractNote = {Synthesis of small-pore zeolitic materials with realistic loadings of transition metals atomically dispersed in the micropores has been a formidable challenge. Herein, we demonstrate a new simple and scalable route to high Pd and Pt loadings (>1 wt%) atomically dispersed in the micropores of a small-pore zeolite, SSZ-13. Unlike all previous methods that require addition of expensive transition metal precursor complexes into the synthesis gel and produce low loading of atomically dispersed species, this method does not require any complicated synthetic proce-dures. We determine the factors that govern the stabilization of M(II) species in the micropores of SSZ-13. Using a combined spectroscopic and DFT approach, we offer a unifying explana-tion for the discrepancies existing in available M-zeolite litera-ture. Moreover, we highlight the difference between the behavior of Pt and Pd during synthesis, and demonstrate that ionically dispersed Pd/SSZ-13 shows superior performance as a new class of environmentally important passive NOx Adsorber (PNA) material under practically relevant conditions. It thus represents the 2nd known metal-small pore zeolite material that has immediate industrial application, and the only known met-al-small pore zeolite material in which metal is close to 100 % utilized. In addition to NOx, the material performs remarkably for CO removal during cold start as well due to the formation of a mixed carbonyl-nitrosyl complex Pd(II)(CO)(NO).},
doi = {10.1002/anie.201809343},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 51,
volume = 57,
place = {United States},
year = {2018},
month = {11}
}

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