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Title: 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 » adsorption and catalysis.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
  3. 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. 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., & 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 referenced in this record:

Zeolite-supported transition metal catalysts by design
journal, October 1992


Transition-metal ions in zeolites: the perfect surface sites
journal, January 1988


Activation of Hydrogen and Hexane over Pt,H-Mordenite Hydroisomerization Catalysts
journal, May 2009

  • Lónyi, Ferenc; Kovács, Anita; Szegedi, Ágnes
  • The Journal of Physical Chemistry C, Vol. 113, Issue 24
  • DOI: 10.1021/jp810716f

Crossing the Borders Between Homogeneous and Heterogeneous Catalysis: Developing Recoverable and Reusable Catalytic Systems
journal, April 2008


When Gold Is Not Noble: Catalysis by Nanoparticles
journal, April 2003


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
journal, November 2018

  • Khivantsev, Konstantin; Jaegers, Nicholas R.; Kovarik, Libor
  • Angewandte Chemie International Edition, Vol. 57, Issue 51
  • DOI: 10.1002/anie.201809343

Molecular Level Understanding of How Oxygen and Carbon Monoxide Improve NO x Storage in Palladium/SSZ-13 Passive NO x Adsorbers: The Role of NO + and Pd(II)(CO)(NO) Species
journal, April 2018

  • Khivantsev, Konstantin; Gao, Feng; Kovarik, Libor
  • The Journal of Physical Chemistry C, Vol. 122, Issue 20
  • DOI: 10.1021/acs.jpcc.8b01007

Palladium/Beta zeolite passive NOx adsorbers (PNA): Clarification of PNA chemistry and the effects of CO and zeolite crystallite size on PNA performance
journal, January 2019


Investigations of the Dispersion of Pd in H-ZSM-5
journal, December 1997

  • Aylor, Adam W.; Lobree, Lisa J.; Reimer, Jeffrey A.
  • Journal of Catalysis, Vol. 172, Issue 2
  • DOI: 10.1006/jcat.1997.1893

Co-ordination chemistry of palladium cations in Pd-H-ZSM-5 as revealed by FTIR spectra of adsorbed and co-adsorbed probe molecules (CO and NO)
journal, January 2004

  • Chakarova, K.; Ivanova, E.; Hadjiivanov, K.
  • Phys. Chem. Chem. Phys., Vol. 006, Issue 13
  • DOI: 10.1039/B401934B

Reversible Transformation of Pt Nanoparticles into Single Atoms inside High-Silica Chabazite Zeolite
journal, November 2016

  • Moliner, Manuel; Gabay, Jadeene E.; Kliewer, Chris E.
  • Journal of the American Chemical Society, Vol. 138, Issue 48
  • DOI: 10.1021/jacs.6b10169

X-Ray absorption spectroscopic study on LaPdO3
journal, February 2002

  • Kim, Seung-Joo; Lemaux, Sylvain; Demazeau, Gérard
  • Journal of Materials Chemistry, Vol. 12, Issue 4
  • DOI: 10.1039/b106795h

Can the state of platinum species be unambiguously determined by the stretching frequency of an adsorbed CO probe molecule?
journal, January 2016

  • Aleksandrov, Hristiyan A.; Neyman, Konstantin M.; Hadjiivanov, Konstantin I.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 32
  • DOI: 10.1039/C6CP03988J

The structure and stability of reduced and oxidized mononuclear platinum species on nanostructured ceria from density functional modeling
journal, January 2015

  • Aleksandrov, Hristiyan A.; Neyman, Konstantin M.; Vayssilov, Georgi N.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 22
  • DOI: 10.1039/C5CP01685A

Platinum Sintering on H-ZSM-5 Followed by Chemometrics of CO Adsorption and 2D Pressure-Jump IR Spectroscopy of Adsorbed Species
journal, December 2009

  • Rivallan, Mickaël; Seguin, Etienne; Thomas, Sébastien
  • Angewandte Chemie International Edition, Vol. 49, Issue 4
  • DOI: 10.1002/anie.200905181

Effect of Si/Al Ratio and Rh Precursor Used on the Synthesis of HY Zeolite-Supported Rhodium Carbonyl Hydride Complexes
journal, July 2015

  • Khivantsev, Konstantin; Vityuk, Artem; Aleksandrov, Hristiyan A.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 30
  • DOI: 10.1021/acs.jpcc.5b03969

Formation of cis-Bis(carbonyl)palladium(II) Fluorosulfate, cis-Pd(CO)2(SO3F)2, and Its Crystal and Molecular Structure
journal, August 1994

  • Wang, Changqing; Willner, Helge; Bodenbinder, Matthias
  • Inorganic Chemistry, Vol. 33, Issue 16
  • DOI: 10.1021/ic00094a014

Low-Temperature Pd/Zeolite Passive NO x Adsorbers: Structure, Performance, and Adsorption Chemistry
journal, July 2017

  • Zheng, Yang; Kovarik, Libor; Engelhard, Mark H.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 29
  • DOI: 10.1021/acs.jpcc.7b04312

Ag(CO)B(OTeF5)4: the first isolable silver carbonyl
journal, July 1991

  • Hurlburt, Paul K.; Anderson, Oren P.; Strauss, Steven H.
  • Journal of the American Chemical Society, Vol. 113, Issue 16
  • DOI: 10.1021/ja00016a058

Bis(carbonyl)silver tetrakis(pentafluorooxotellurato)borate: the first structurally characterized M(CO)2 complex
journal, February 1993

  • Hurlburt, Paul K.; Rack, Jeffrey J.; Dec, Steve F.
  • Inorganic Chemistry, Vol. 32, Issue 4
  • DOI: 10.1021/ic00056a003

The Effect of Si/Al Ratio for Pd/BEA and Pd/SSZ-13 Used as Passive NOx Adsorbers
journal, July 2018

  • Mihai, Oana; Trandafilović, Lidija; Wentworth, Travis
  • Topics in Catalysis, Vol. 61, Issue 18-19
  • DOI: 10.1007/s11244-018-1017-z

X-ray photoelectron spectroscopic studies of palladium oxides and the palladium-oxygen electrode
journal, February 1974

  • Kim, K. S.; Gossmann, A. F.; Winograd, Nicholas.
  • Analytical Chemistry, Vol. 46, Issue 2
  • DOI: 10.1021/ac60338a037

Mechanistic Studies of the Palladium(II)-Catalyzed Copolymerization of Ethylene with Carbon Monoxide
journal, January 1996

  • Rix, Francis C.; Brookhart, Maurice; White, Peter S.
  • Journal of the American Chemical Society, Vol. 118, Issue 20
  • DOI: 10.1021/ja953276t

Ethyne Adsorbed on CuNaY Zeolite:  FTIR Spectra and Quantum Chemical Calculations
journal, August 2003

  • Hübner, Georg; Rauhut, Guntram; Stoll, Hermann
  • The Journal of Physical Chemistry B, Vol. 107, Issue 33
  • DOI: 10.1021/jp034304u

Infrared Spectra and Normal Coordinate Analysis of Metal-Olefin Complexes. I. Zeise's Salt Potassium Trichloro(ethylene)platinate(II) Monohydrate 1
journal, December 1966

  • Grogan, Michael J.; Nakamoto, Kazuo
  • Journal of the American Chemical Society, Vol. 88, Issue 23
  • DOI: 10.1021/ja00975a016

Synthesis, Modeling, and Catalytic Properties of HY Zeolite-Supported Rhodium Dinitrosyl Complexes
journal, August 2017

  • Khivantsev, Konstantin; Vityuk, Artem; Aleksandrov, Hristiyan A.
  • ACS Catalysis, Vol. 7, Issue 9
  • DOI: 10.1021/acscatal.7b00864

Vibrational spectra of buta-1,3-diene iron tricarbonyl: comparison to surface species
journal, March 2017


An IR Study on Selective Hydrogenation of 1,3-Butadiene on Transition Metal Nitrides:  1,3-Butadiene and 1-Butene Adsorption on Mo 2 N/γ-Al 2 O 3 Catalyst
journal, December 2000

  • Wu, Zili; Hao, Zhixian; Ying, Pinliang
  • The Journal of Physical Chemistry B, Vol. 104, Issue 51
  • DOI: 10.1021/jp002488w

Infrared spectra of 1,3-butadiene matrices containing some atomic metals
journal, January 1984


Combined UHV and ambient pressure studies of 1,3-butadiene adsorption and reaction on Pd(1 1 1) by GC, IRAS and XPS
journal, March 2007

  • Silvestre-Albero, Joaquin; Borasio, Marta; Rupprechter, Günther
  • Catalysis Communications, Vol. 8, Issue 3
  • DOI: 10.1016/j.catcom.2006.06.030

An in situ diffuse reflectance FTIR study of the cyclodimerization of 1,3-butadiene over Cu-exchanged zeolites
journal, October 1998

  • Voskoboinikov, Timur V.; Coq, Bernard; Fajula, François
  • Microporous and Mesoporous Materials, Vol. 24, Issue 1-3
  • DOI: 10.1016/S1387-1811(98)00140-1

Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts
journal, September 2015


Superelectrophilic Solvation
journal, February 2004

  • Olah, George A.; Klumpp, Douglas A.
  • Accounts of Chemical Research, Vol. 37, Issue 4
  • DOI: 10.1021/ar020102p

Infrared and manometric evidence for the formation of the [Ag(CO)3]+ complex ion at high PCO
journal, January 1994

  • Rack, Jeffrey J.; Moasser, Bahram; Gargulak, Jerry D.
  • Journal of the Chemical Society, Chemical Communications, Issue 6
  • DOI: 10.1039/c39940000685

Oxidation of Methane to Methanol over Single Site Palladium Oxide Species on Silica: A Mechanistic view from DFT
journal, July 2017

  • Gannouni, Anis; Delbecq, Françoise; Saïd Zina, Mongia
  • The Journal of Physical Chemistry A, Vol. 121, Issue 29
  • DOI: 10.1021/acs.jpca.7b01509

Theoretical and experimental investigations on site occupancy for palladium oxidation states in mesoporous Al-MCM-41 materials
journal, May 2012


Nucleation and growth of Pd clusters in mordenite
journal, March 1998


Surface Sites of Pd/CeO 2 /Al 2 O 3 Catalysts in the Partial Oxidation of Propane
journal, May 2003

  • Guimarães, A. L.; Dieguez, L. C.; Schmal, M.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 18
  • DOI: 10.1021/jp0270194

Identification of active sites for CO and CH4 oxidation over PdO/Ce1−xPdxO2−δ catalysts
journal, May 2012


Structure and Bonding of a Site-Isolated Transition Metal Complex:  Rhodium Dicarbonyl in Highly Dealuminated Zeolite Y
journal, August 2000

  • Goellner, Jesse F.; Gates, Bruce C.; Vayssilov, Georgi N.
  • Journal of the American Chemical Society, Vol. 122, Issue 33
  • DOI: 10.1021/ja001209f

Characterisation of Porous Materials by FTIR Spectroscopy of Isotopically Labelled Probe Molecules
journal, April 2012

  • Hadjiivanov, Konstantin; Chakarova, Kristina; Drenchev, Nikola
  • Current Physical Chemistry, Vol. 2, Issue 2
  • DOI: 10.2174/1877946811202020151

A New Interpretation of the IR Bands of Supported Rh(I) Monocarbonyl Complexes
journal, April 2002

  • Vayssilov, Georgi N.; Rösch, Notker
  • Journal of the American Chemical Society, Vol. 124, Issue 14
  • DOI: 10.1021/ja011688y

FTIR spectroscopic study of CO adsorption on Pt–H–ZSM-5
journal, June 2005

  • Chakarova, Kristina; Mihaylov, Mihail; Hadjiivanov, Konstantin
  • Microporous and Mesoporous Materials, Vol. 81, Issue 1-3
  • DOI: 10.1016/j.micromeso.2005.01.033

Effect of preparation technique on the properties of platinum in NaY zeolite: A study by FTIR spectroscopy of adsorbed CO
journal, March 2007

  • Chakarova, Kristina; Hadjiivanov, Konstantin; Atanasova, Genoveva
  • Journal of Molecular Catalysis A: Chemical, Vol. 264, Issue 1-2
  • DOI: 10.1016/j.molcata.2006.09.040

Effect of various activation conditions on the low temperature NO adsorption performance of Pd/SSZ-13 passive NOx adsorber
journal, January 2019


The nature of “A,B,C”-type infrared spectra of strongly hydrogen-bonded systems; pseudo-maxima in vibrational spectra
journal, January 1969


Palladium/Zeolite Low Temperature Passive NOx Adsorbers (PNA): Structure-Adsorption Property Relationships for Hydrothermally Aged PNA Materials
journal, September 2019

  • Khivantsev, Konstantin; Jaegers, Nicholas R.; Kovarik, Libor
  • Emission Control Science and Technology, Vol. 6, Issue 2
  • DOI: 10.1007/s40825-019-00139-w

Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3
journal, October 2010


Two different cationic positions in Cu-SSZ-13?
journal, January 2012

  • Hun Kwak, Ja; Zhu, Haiyang; Lee, Jong H.
  • Chemical Communications, Vol. 48, Issue 39
  • DOI: 10.1039/c2cc31184d

Can Dynamics Be Responsible for the Complex Multipeak Infrared Spectra of NO Adsorbed to Copper(II) Sites in Zeolites?
journal, May 2015

  • Göltl, Florian; Sautet, Philippe; Hermans, Ive
  • Angewandte Chemie International Edition, Vol. 54, Issue 27
  • DOI: 10.1002/anie.201501942

Catalytic activation of ethylene C–H bonds on uniform d 8 Ir( i ) and Ni( ii ) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts
journal, January 2019

  • Jaegers, Nicholas R.; Khivantsev, Konstantin; Kovarik, Libor
  • Catalysis Science & Technology, Vol. 9, Issue 23
  • DOI: 10.1039/C9CY01442J

A Common Intermediate for N 2 Formation in Enzymes and Zeolites: Side-On Cu-Nitrosyl Complexes
journal, August 2013

  • Kwak, Ja Hun; Lee, Jong H.; Burton, Sarah D.
  • Angewandte Chemie International Edition, Vol. 52, Issue 38
  • DOI: 10.1002/anie.201303498

    Works referencing / citing this record:

    Palladium/Zeolite Low Temperature Passive NOx Adsorbers (PNA): Structure-Adsorption Property Relationships for Hydrothermally Aged PNA Materials
    journal, September 2019

    • Khivantsev, Konstantin; Jaegers, Nicholas R.; Kovarik, Libor
    • Emission Control Science and Technology, Vol. 6, Issue 2
    • DOI: 10.1007/s40825-019-00139-w

    Catalytic activation of ethylene C–H bonds on uniform d 8 Ir( i ) and Ni( ii ) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts
    journal, January 2019

    • Jaegers, Nicholas R.; Khivantsev, Konstantin; Kovarik, Libor
    • Catalysis Science & Technology, Vol. 9, Issue 23
    • DOI: 10.1039/c9cy01442j