Stabilization of Super Electrophilic Pd+2 Cations in Small-Pore SSZ-13 Zeolite
Abstract
We offer the first observation and characterization of super electrophilic metal cations on a solid support. For Pd/SSZ-13, the results of our combined experimental (Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, high-angle annular dark-field scanning transmission electron microscopy) and density functional theory study reveal that Pd ions in zeolites, previously identified as Pd+3 and Pd+4, are, in fact, present as super electrophilic Pd+2 species (charge-transfer complex/ion pair with the negatively charged framework oxygens). In this contribution, we reassign the spectroscopic signatures of these species, discuss the unusual coordination environment of “naked” (ligand-free) super electrophilic Pd+2 in SSZ-13, and their complexes with CO and NO. With CO, nonclassical, highly positive [Pd(CO)2]2+ ions are formed with the zeolite framework acting as a weakly coordinating anion (ion pairs). Nonclassical carbonyl complexes also form with Pt+2 and Ag+ in SSZ-13. The Pd+2(CO)2 complex is remarkably stable in zeolite cages even in the presence of water. Dicarbonyl and nitrosyl Pd+2 complexes, in turn, serve as precursors to the synthesis of previously inaccessible Pd+2–carbonyl–olefin [Pd(CO)(C2H4)] and Pd+2–nitrosyl–olefin [Pd(NO)(C2H4)] complexes. In general, we show that the zeolite framework can stabilize super electrophilic metal (Pd) cations and show the new chemistry of the Pd/SSZ-13 system with implications formore »
- Authors:
-
[1];
[2];
[3];
[1];
[1];
[1];
[2];
[1]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
- Univ. of 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), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1617560
- Report Number(s):
- PNNL-SA-148282
Journal ID: ISSN 1932-7447
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 124; Journal Issue: 1; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Khivantsev, Konstantin, Jaegers, Nicholas R., Koleva, Iskra Z., Aleksandrov, Hristiyan A., Kovarik, Libor, Engelhard, Mark, Gao, Feng, Wang, Yong, Vayssilov, Georgi N., and Szanyi, Janos. Stabilization of Super Electrophilic Pd+2 Cations in Small-Pore SSZ-13 Zeolite. United States: N. p., 2019.
Web. doi:10.1021/acs.jpcc.9b06760.
Khivantsev, Konstantin, Jaegers, Nicholas R., Koleva, Iskra Z., Aleksandrov, Hristiyan A., Kovarik, Libor, Engelhard, Mark, Gao, Feng, Wang, Yong, Vayssilov, Georgi N., & Szanyi, Janos. Stabilization of Super Electrophilic Pd+2 Cations in Small-Pore SSZ-13 Zeolite. United States. https://doi.org/10.1021/acs.jpcc.9b06760
Khivantsev, Konstantin, Jaegers, Nicholas R., Koleva, Iskra Z., Aleksandrov, Hristiyan A., Kovarik, Libor, Engelhard, Mark, Gao, Feng, Wang, Yong, Vayssilov, Georgi N., and Szanyi, Janos. Wed .
"Stabilization of Super Electrophilic Pd+2 Cations in Small-Pore SSZ-13 Zeolite". United States. https://doi.org/10.1021/acs.jpcc.9b06760. https://www.osti.gov/servlets/purl/1617560.
@article{osti_1617560,
title = {Stabilization of Super Electrophilic Pd+2 Cations in Small-Pore SSZ-13 Zeolite},
author = {Khivantsev, Konstantin and Jaegers, Nicholas R. and Koleva, Iskra Z. and Aleksandrov, Hristiyan A. and Kovarik, Libor and Engelhard, Mark and Gao, Feng and Wang, Yong and Vayssilov, Georgi N. and Szanyi, Janos},
abstractNote = {We offer the first observation and characterization of super electrophilic metal cations on a solid support. For Pd/SSZ-13, the results of our combined experimental (Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, high-angle annular dark-field scanning transmission electron microscopy) and density functional theory study reveal that Pd ions in zeolites, previously identified as Pd+3 and Pd+4, are, in fact, present as super electrophilic Pd+2 species (charge-transfer complex/ion pair with the negatively charged framework oxygens). In this contribution, we reassign the spectroscopic signatures of these species, discuss the unusual coordination environment of “naked” (ligand-free) super electrophilic Pd+2 in SSZ-13, and their complexes with CO and NO. With CO, nonclassical, highly positive [Pd(CO)2]2+ ions are formed with the zeolite framework acting as a weakly coordinating anion (ion pairs). Nonclassical carbonyl complexes also form with Pt+2 and Ag+ in SSZ-13. The Pd+2(CO)2 complex is remarkably stable in zeolite cages even in the presence of water. Dicarbonyl and nitrosyl Pd+2 complexes, in turn, serve as precursors to the synthesis of previously inaccessible Pd+2–carbonyl–olefin [Pd(CO)(C2H4)] and Pd+2–nitrosyl–olefin [Pd(NO)(C2H4)] complexes. In general, we show that the zeolite framework can stabilize super electrophilic metal (Pd) cations and show the new chemistry of the Pd/SSZ-13 system with implications for adsorption and catalysis.},
doi = {10.1021/acs.jpcc.9b06760},
journal = {Journal of Physical Chemistry. C},
number = 1,
volume = 124,
place = {United States},
year = {2019},
month = {12}
}
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Works referencing / citing this record:
Palladium/Zeolite Low Temperature Passive NOx Adsorbers (PNA): Structure-Adsorption Property Relationships for Hydrothermally Aged PNA Materials
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- Khivantsev, Konstantin; Jaegers, Nicholas R.; Kovarik, Libor
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