Dimethyl methylphosphonate adsorption and decomposition on MoO2 as studied by ambient pressure x-ray photoelectron spectroscopy and DFT calculations

Head, Ashley R.; Tsyshevsky, Roman; Trotochaud, Lena; Yu, Yi; Karslıoǧlu, Osman; Eichhorn, Bryan; Kuklja, Maija M.; Bluhm, Hendrik

doi:10.1088/1361-648X/aab192

Title: Dimethyl methylphosphonate adsorption and decomposition on MoO₂ as studied by ambient pressure x-ray photoelectron spectroscopy and DFT calculations

Journal Article · Fri Mar 09 00:00:00 EST 2018 · Journal of Physics. Condensed Matter

DOI:https://doi.org/10.1088/1361-648X/aab192· OSTI ID:1465445

^[1]; Tsyshevsky, Roman ^[2]; Trotochaud, Lena ^[1]; Yu, Yi ^[3];

^[1]; Eichhorn, Bryan ^[2];

^[2]; Bluhm, Hendrik ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of Maryland, College Park, MD (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Maryland, College Park, MD (United States)

Organophosphonates range in their toxicity and are used as pesticides, herbicides, and chemical warfare agents (CWAs). Few laboratories are equipped to handle the most toxic molecules, thus simulants such as dimethyl methylphosphonate (DMMP), are used as a first step in studying adsorption and reactivity on materials. Benchmarked by combined experimental and theoretical studies of simulants, calculations offer an opportunity to understand how molecular interactions with a surface changes upon using a CWA. However, most calculations of DMMP and CWAs on surfaces are limited to adsorption studies on clusters of atoms, which may differ markedly from the behavior on bulk solid-state materials with extended surfaces. We have benchmarked our solid-state periodic calculations of DMMP adsorption and reactivity on MoO₂ with ambient pressure x-ray photoelectron spectroscopy studies (APXPS). Furthermore, DMMP is found to interact strongly with a MoO₂ film, a model system for the MoOxcomponent in the ASZM-TEDA.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1465445

Journal Information:: Journal of Physics. Condensed Matter, Vol. 30, Issue 13; Related Information: © 2018 IOP Publishing Ltd.; ISSN 0953-8984

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 21 works

Citation information provided by
Web of Science

References (42)

Update 1 of: Destruction and Detection of Chemical Warfare Agents Jang, Yoon Jeong; Kim, Kibong; Tsay, Olga G. Chemical Reviews, Vol. 115, Issue 24 https://doi.org/10.1021/acs.chemrev.5b00402	journal	December 2015
Adsorption and Decomposition of Dimethyl Methylphosphonate on Metal Oxides Mitchell, Mark B.; Sheinker, V. N.; Mintz, Eric A. The Journal of Physical Chemistry B, Vol. 101, Issue 51 https://doi.org/10.1021/jp972724b	journal	December 1997
Adsorption and Decomposition of Dimethyl Methylphosphonate on TiO ₂ Rusu, Camelia N.; Yates, John T. The Journal of Physical Chemistry B, Vol. 104, Issue 51 https://doi.org/10.1021/jp002560q	journal	December 2000
The Room Temperature Decomposition Mechanism of Dimethyl Methylphosphonate (DMMP) on Alumina-Supported Cerium Oxide − Participation of Nano-Sized Cerium Oxide Domains Mitchell, Mark B.; Sheinker, Viktor N.; Cox, Woodrow W. The Journal of Physical Chemistry B, Vol. 108, Issue 5 https://doi.org/10.1021/jp035590c	journal	February 2004
Uptake of a Chemical Warfare Agent Simulant (DMMP) on TiO ₂ : Reactive Adsorption and Active Site Poisoning Panayotov, Dimitar A.; Morris, John R. Langmuir, Vol. 25, Issue 6 https://doi.org/10.1021/la804018b	journal	March 2009
Interaction of dimethyl methylphosphonate with metal oxides Aurian-Blajeni, B.; Boucher, M. M. Langmuir, Vol. 5, Issue 1 https://doi.org/10.1021/la00085a032	journal	January 1989
Fourier transform infrared photoacoustic spectroscopy study of the adsorption of organophosphorus compounds on heat-treated magnesium oxide Li, Yong Xi.; Schlup, John R.; Klabunde, Kenneth J. Langmuir, Vol. 7, Issue 7 https://doi.org/10.1021/la00055a018	journal	July 1991
Adsorption and Decomposition of Dimethyl Methylphosphonate on Y 2 O 3 Nanoparticles Gordon, Wesley O.; Tissue, Brian M.; Morris, John R. The Journal of Physical Chemistry C, Vol. 111, Issue 8 https://doi.org/10.1021/jp0650376	journal	January 2007
Hydrolysis of Dimethyl Methylphosphonate by the Cyclic Tetramer of Zirconium Hydroxide Schweigert, Igor V.; Gunlycke, Daniel The Journal of Physical Chemistry A, Vol. 121, Issue 40 https://doi.org/10.1021/acs.jpca.7b06403	journal	October 2017
Mechanism and Kinetics for Reaction of the Chemical Warfare Agent Simulant, DMMP( g ), with Zirconium(IV) MOFs: An Ultrahigh-Vacuum and DFT Study Wang, G.; Sharp, C.; Plonka, A. M. The Journal of Physical Chemistry C, Vol. 121, Issue 21 https://doi.org/10.1021/acs.jpcc.7b00070	journal	May 2017
Spectroscopic and Computational Investigation of Room-Temperature Decomposition of a Chemical Warfare Agent Simulant on Polycrystalline Cupric Oxide Trotochaud, Lena; Tsyshevsky, Roman; Holdren, Scott Chemistry of Materials, Vol. 29, Issue 17 https://doi.org/10.1021/acs.chemmater.7b02489	journal	August 2017
Photoelectron spectroscopy under ambient pressure and temperature conditions Frank Ogletree, D.; Bluhm, Hendrik; Hebenstreit, Eleonore D. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 601, Issue 1-2 https://doi.org/10.1016/j.nima.2008.12.155	journal	March 2009
Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source Bluhm, H.; Andersson, K.; Araki, T. Journal of Electron Spectroscopy and Related Phenomena, Vol. 150, Issue 2-3 https://doi.org/10.1016/j.elspec.2005.07.005	journal	February 2006
A differentially pumped electrostatic lens system for photoemission studies in the millibar range Ogletree, D. Frank; Bluhm, Hendrik; Lebedev, Gennadi Review of Scientific Instruments, Vol. 73, Issue 11 https://doi.org/10.1063/1.1512336	journal	November 2002
Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate Head, Ashley R.; Tsyshevsky, Roman; Trotochaud, Lena The Journal of Physical Chemistry A, Vol. 120, Issue 12 https://doi.org/10.1021/acs.jpca.6b01098	journal	March 2016
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ultrafine MoO2 nanoparticles grown on graphene sheets as anode materials for lithium-ion batteries Yang, Qian; Liang, Qiang; Liu, Jun Materials Letters, Vol. 127 https://doi.org/10.1016/j.matlet.2014.03.055	journal	July 2014
MoO ₂ /Mo ₂ C Heteronanotubes Function as High-Performance Li-Ion Battery Electrode Zhang, Hao-Jie; Wang, Kai-Xue; Wu, Xue-Yan Advanced Functional Materials, Vol. 24, Issue 22 https://doi.org/10.1002/adfm.201303856	journal	February 2014
MoO2/Mo2C/C spheres as anode materials for lithium ion batteries Ihsan, Mohammad; Wang, Hongqiang; Majid, Siti R. Carbon, Vol. 96 https://doi.org/10.1016/j.carbon.2015.10.076	journal	January 2016
Porous MoO ₂ Nanosheets as Non-noble Bifunctional Electrocatalysts for Overall Water Splitting Jin, Yanshuo; Wang, Haotian; Li, Junjie Advanced Materials, Vol. 28, Issue 19 https://doi.org/10.1002/adma.201506314	journal	March 2016
A Refinement of the Crystal Structure of Molybdenum Dioxide. Brandt, Björn G.; Skapski, A. C.; Thom, Erling Acta Chemica Scandinavica, Vol. 21 https://doi.org/10.3891/acta.chem.scand.21-0661	journal	January 1967
Electronic structure and relaxed geometry of the TiO 2 rutile (110) surface Vogtenhuber, D.; Podloucky, R.; Neckel, A. Physical Review B, Vol. 49, Issue 3 https://doi.org/10.1103/PhysRevB.49.2099	journal	January 1994
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Theoretical and Experimental Study of the Electronic Structures of MoO ₃ and MoO ₂ Scanlon, David O.; Watson, Graeme W.; Payne, D. J. The Journal of Physical Chemistry C, Vol. 114, Issue 10 https://doi.org/10.1021/jp9093172	journal	March 2010
The Nature of Water Nucleation Sites on TiO ₂ (110) Surfaces Revealed by Ambient Pressure X-ray Photoelectron Spectroscopy Ketteler, Guido; Yamamoto, Susumu; Bluhm, Hendrik The Journal of Physical Chemistry C, Vol. 111, Issue 23 https://doi.org/10.1021/jp068606i	journal	June 2007
Natural widths of atomic K and L levels, K α X‐ray lines and several K L L Auger lines Krause, M. O.; Oliver, J. H. Journal of Physical and Chemical Reference Data, Vol. 8, Issue 2 https://doi.org/10.1063/1.555595	journal	April 1979
Adsorption of Dimethyl Methylphosphonate on MoO ₃ : The Role of Oxygen Vacancies Head, Ashley R.; Tsyshevsky, Roman; Trotochaud, Lena The Journal of Physical Chemistry C, Vol. 120, Issue 51 https://doi.org/10.1021/acs.jpcc.6b07340	journal	December 2016
Dimethyl methylphosphonate decomposition on fully oxidized and partially reduced ceria thin films Chen, Donna A.; Ratliff, Jay S.; Hu, Xiaofeng Surface Science, Vol. 604, Issue 5-6 https://doi.org/10.1016/j.susc.2009.12.028	journal	March 2010
Quantum-Chemical Study of the Adsorption of DMMP and Sarin on γ-Al ₂ O ₃ Bermudez, V. M. The Journal of Physical Chemistry C, Vol. 111, Issue 9 https://doi.org/10.1021/jp066439g	journal	February 2007
Thermal desorption of dimethyl methylphosphonate from MoO ₃ Head, Ashley R.; Tang, Xin; Hicks, Zachary Catalysis, Structure & Reactivity, Vol. 3, Issue 1-2 https://doi.org/10.1080/2055074X.2017.1278891	journal	February 2017
Charge transfer in transition metal carbides and related compounds studied by ESCA Ramqvist, Lars; Hamrin, Kjell; Johansson, Gunilla Journal of Physics and Chemistry of Solids, Vol. 30, Issue 7 https://doi.org/10.1016/0022-3697(69)90252-2	journal	July 1969
Adsorption of boron on molybdenum(100) and its effect on chemisorption of carbon monoxide, ethene, propene, and 3,3,3-trifluoropropene Fryberger, T. B.; Grant, J. L.; Stair, P. C. Langmuir, Vol. 3, Issue 6 https://doi.org/10.1021/la00078a024	journal	November 1987
Decomposition of dimethyl methylphosphonate on TiO2(110): principal component analysis applied to X-ray photoelectron spectroscopy Zhou, J.; Varazo, K.; Reddic, J. E. Analytica Chimica Acta, Vol. 496, Issue 1-2 https://doi.org/10.1016/S0003-2670(03)01008-0	journal	October 2003
Dimethyl Methylphosphonate Decomposition on Titania-Supported Ni Clusters and Films: A Comparison of Chemical Activity on Different Ni Surfaces Zhou, J.; Ma, S.; Kang, Y. C. The Journal of Physical Chemistry B, Vol. 108, Issue 31 https://doi.org/10.1021/jp040185m	journal	August 2004
Adsorption and Photodegradation of Dimethyl Methylphosphonate Vapor at TiO ₂ Surfaces Moss, John A.; Szczepankiewicz, Steven H.; Park, Eleanor The Journal of Physical Chemistry B, Vol. 109, Issue 42 https://doi.org/10.1021/jp052057j	journal	October 2005
Thermal Decomposition of a Chemical Warfare Agent Simulant (DMMP) on TiO 2 : Adsorbate Reactions with Lattice Oxygen as Studied by Infrared Spectroscopy Panayotov, Dimitar A.; Morris, John R. The Journal of Physical Chemistry C, Vol. 113, Issue 35 https://doi.org/10.1021/jp9036233	journal	August 2009

Similar Records

Thermal desorption of dimethyl methylphosphonate from MoO ₃

Journal Article · Fri Mar 03 00:00:00 EST 2017 · Catalysis, Structure & Reactivity · OSTI ID:1465445

Head, Ashley R.; Tang, Xin; Hicks, Zachary; +12 more

Room temperature decomposition of dimethyl methylphosphonate on cuprous oxide yields atomic phosphorus

Journal Article · Thu Oct 11 00:00:00 EDT 2018 · Surface Science · OSTI ID:1465445

Trotochaud, Lena; Head, Ashley R.; Büchner, Christin; +7 more

Adsorption of Dimethyl Methylphosphonate on MoO₃: The Role of Oxygen Vacancies

Journal Article · Wed Dec 07 00:00:00 EST 2016 · Journal of Physical Chemistry. C · OSTI ID:1465445

Head, Ashley R.; Tsyshevsky, Roman; Trotochaud, Lena; +5 more

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
chemical warfare agent simulant
solid-state periodic calculations
DMMP
organophosphonate
metal oxide
surface reaction
surface modelling

Title: Dimethyl methylphosphonate adsorption and decomposition on MoO2 as studied by ambient pressure x-ray photoelectron spectroscopy and DFT calculations

Citation Formats

References (42)

Similar Records

Related Subjects

Title: Dimethyl methylphosphonate adsorption and decomposition on MoO₂ as studied by ambient pressure x-ray photoelectron spectroscopy and DFT calculations