Environmental TEM study of electron beam induced electro-chemistry of Pr₀̣₆₄Ca₀̣₃₆MnO₃ catalysts for oxygen evolution

Mildner, Stephanie; Beleggia, Marco; Mierwaldt, Daniel; Hansen, Thoma Willum; Wagner, Jakob Birkedal; Yazdi, Sadegh; Kasama, Takeshi; Ciston, Jim; Zhu, Yimei; Jooss, Christian

doi:10.1021/jp511628c

Title: Environmental TEM study of electron beam induced electro-chemistry of Pr₀̣₆₄Ca₀̣₃₆MnO₃ catalysts for oxygen evolution

Journal Article · Thu Mar 12 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp511628c· OSTI ID:1193217

Mildner, Stephanie ^[1]; Beleggia, Marco ^[2]; Mierwaldt, Daniel ^[1]; Hansen, Thoma Willum ^[3]; Wagner, Jakob Birkedal ^[3]; Yazdi, Sadegh ^[3]; Kasama, Takeshi ^[3]; Ciston, Jim ^[4]; Zhu, Yimei ^[5]; Jooss, Christian ^[1]

Univ. of Goettingen, Goettingen (Germany). Inst. of Materials Physics
Technical Univ. of Denmark, Lyngby (Denmark). Center for Electron Nanoscopy; Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy
Technical Univ. of Denmark, Lyngby (Denmark). Center for Electron Nanoscopy
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center for Electron Microscopy
Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics, Materials Science Dept., and Center for Functional Nanomaterials

Environmental Transmission Electron Microscopy (ETEM) studies offer great potential for gathering atomic scale information on the electronic state of electrodes in contact with reactants but also pose big challenges due to the impact of the high energy electron beam. In this article, we present an ETEM study of a Pr₀̣₆₄Ca₀̣₃₆MnO₃ (PCMO) thin film electro-catalyst for water splitting and oxygen evolution in contact with water vapor. We show by means of off-axis electron holography and electrostatic modeling that the electron beam gives rise to a positive electric sample potential due to secondary electron emission. The value of the electric potential depends on the primary electron flux, the sample -conductivity and grounding, and gas properties. We present evidence that two observed electro-chemical reactions are driven by a beam induced electrostatic potential of the order of a volt. The first reaction is an anodic electrochemical oxidation reaction of oxygen depleted amorphous PCMO which results in recrystallization of the perovskite structure. The second reaction is oxygen evolution which can be detected by the oxidation of a silane additive and formation of SiO_2–x at catalytically active surfaces. Recently published in-situ XANES observation of subsurface oxygen vacancy formation during oxygen evolution at a positive potential [³²] is confirmed in this work. The quantification of beam induced potentials is an important step for future controlled electro-chemical experiments in an ETEM.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC00112704

OSTI ID:: 1193217

Report Number(s):: BNL-108035-2015-JA; R&D Project: MA015MACA; KC0201010

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 10; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 34 works

Citation information provided by
Web of Science

References (40)

Atomic-scale imaging of carbon nanofibre growth Helveg, Stig; López-Cartes, Carlos; Sehested, Jens Nature, Vol. 427, Issue 6973 https://doi.org/10.1038/nature02278	journal	January 2004
In Situ XANES/XPS Investigation of Doped Manganese Perovskite Catalysts Mierwaldt, Daniel; Mildner, Stephanie; Arrigo, Rosa Catalysts, Vol. 4, Issue 2 https://doi.org/10.3390/catal4020129	journal	April 2014
Extraction of EELS white-line intensities of manganese compounds: Methods, accuracy, and valence sensitivity Riedl, T.; Gemming, T.; Wetzig, K. Ultramicroscopy, Vol. 106, Issue 4-5 https://doi.org/10.1016/j.ultramic.2005.09.002	journal	March 2006
Optimizing Perovskites for the Water-Splitting Reaction Vojvodic, A.; Norskov, J. K. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1215081	journal	December 2011
Solar Driven Water Oxidation by a Bioinspired Manganese Molecular Catalyst Brimblecombe, Robin; Koo, Annette; Dismukes, G. Charles Journal of the American Chemical Society, Vol. 132, Issue 9 https://doi.org/10.1021/ja910055a	journal	March 2010
The Electrocatalysis of Oxygen Evolution on Perovskites Bockris, John O'M. Journal of The Electrochemical Society, Vol. 131, Issue 2 https://doi.org/10.1149/1.2115565	journal	January 1984
Atomic-Resolution in Situ Transmission Electron Microscopy of a Promoter of a Heterogeneous Catalyst Hansen, T. W. Science, Vol. 294, Issue 5546 https://doi.org/10.1126/science.1064399	journal	November 2001
Electrical conductivity of magnesium oxide single crystal below 1200 K Kathrein, Hendrik; Freund, Friedemann Journal of Physics and Chemistry of Solids, Vol. 44, Issue 3 https://doi.org/10.1016/0022-3697(83)90052-5	journal	January 1983
Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals Hansen, P. L. Science, Vol. 295, Issue 5562 https://doi.org/10.1126/science.1069325	journal	March 2002
The use of environmental scanning electron microscopy for imaging wet and insulating materials Donald, Athene M. Nature Materials, Vol. 2, Issue 8 https://doi.org/10.1038/nmat898	journal	August 2003
Plasmons and Related Excitations Schattschneider, Peter; Jouffrey, Bernard Energy-Filtering Transmission Electron Microscopy, 151–224 https://doi.org/10.1007/978-3-540-48995-5_3	book	January 1995
In Situ Electrochemical Electron Microscopy Study of Oxygen Evolution Activity of Doped Manganite Perovskites Raabe, Stephanie; Mierwaldt, Daniel; Ciston, Jim Advanced Functional Materials, Vol. 22, Issue 16 https://doi.org/10.1002/adfm.201103173	journal	May 2012
A manganese oxyiodide cathode for rechargeable lithium batteries Kim, Jaekook; Manthiram, Arumugam Nature, Vol. 390, Issue 6657 https://doi.org/10.1038/36812	journal	November 1997
Aberration corrected and monochromated environmental transmission electron microscopy: challenges and prospects for materials science Hansen, T. W.; Wagner, J. B.; Dunin-Borkowski, R. E. Materials Science and Technology, Vol. 26, Issue 11 https://doi.org/10.1179/026708310X12756557336355	journal	November 2010
Simple calculation of energy distribution of low‐energy secondary electrons emitted from metals under electron bombardment Chung, M. S.; Everhart, T. E. Journal of Applied Physics, Vol. 45, Issue 2 https://doi.org/10.1063/1.1663306	journal	February 1974
In-situ X-ray Absorption Study of Evolution of Oxidation States and Structure of Cobalt in Co and CoPt Bimetallic Nanoparticles (4 nm) under Reducing (H ₂ ) and Oxidizing (O ₂ ) Environments Zheng, Fan; Alayoglu, Selim; Guo, Jinghua Nano Letters, Vol. 11, Issue 2 https://doi.org/10.1021/nl104209c	journal	February 2011
Calcium Manganese(III) Oxides (CaMn ₂ O ₄ ⋅ x H ₂ O) as Biomimetic Oxygen-Evolving Catalysts Najafpour, Mohammad Mahdi; Ehrenberg, Till; Wiechen, Mathias Angewandte Chemie International Edition, Vol. 49, Issue 12 https://doi.org/10.1002/anie.200906745	journal	March 2010
In Situ X-ray Absorption Spectroscopy Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction Gorlin, Yelena; Lassalle-Kaiser, Benedikt; Benck, Jesse D. Journal of the American Chemical Society, Vol. 135, Issue 23 https://doi.org/10.1021/ja3104632	journal	June 2013
Atomic-resolution imaging of oxidation states in manganites Varela, M.; Oxley, M. P.; Luo, W. Physical Review B, Vol. 79, Issue 8 https://doi.org/10.1103/PhysRevB.79.085117	journal	February 2009
Environmental high resolution electron microscopy and applications to chemical science Boyes, E. D.; Gai, P. L. Ultramicroscopy, Vol. 67, Issue 1-4 https://doi.org/10.1016/S0304-3991(96)00099-X	journal	June 1997
In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co²⁺ Kanan, M. W.; Nocera, D. G. Science, Vol. 321, Issue 5892, p. 1072-1075 https://doi.org/10.1126/science.1162018	journal	August 2008
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles Suntivich, J.; May, K. J.; Gasteiger, H. A. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1212858	journal	October 2011
Resolving the Structure of Active Sites on Platinum Catalytic Nanoparticles Chang, Lan Yun; Barnard, Amanda S.; Gontard, Lionel Cervera Nano Letters, Vol. 10, Issue 8 https://doi.org/10.1021/nl101642f	journal	August 2010
Precise oxygen evolution catalysts: Status and opportunities Trotochaud, Lena; Boettcher, Shannon W. Scripta Materialia, Vol. 74 https://doi.org/10.1016/j.scriptamat.2013.07.019	journal	March 2014
EELS study of interfaces in magnetoresistive LSMO/STO/LSMO tunnel junctions Samet, L.; Imhoff, D.; Maurice, J. -L. The European Physical Journal B - Condensed Matter, Vol. 34, Issue 2 https://doi.org/10.1140/epjb/e2003-00210-8	journal	July 2003
Experimental Characterization and Mitigation of Specimen Charging on Thin Films with One Conducting Layer Downing, Kenneth H.; McCartney, M. R.; Glaeser, Robert M. Microscopy and Microanalysis, Vol. 10, Issue 6 https://doi.org/10.1017/S143192760404067X	journal	December 2004
In Situ Study of the Gas-Phase Electrolysis of Water on Platinum by NAP-XPS Arrigo, Rosa; Hävecker, Michael; Schuster, Manfred E. Angewandte Chemie International Edition, Vol. 52, Issue 44 https://doi.org/10.1002/anie.201304765	journal	September 2013
Synthetic manganese–calcium oxides mimic the water-oxidizing complex of photosynthesis functionally and structurally Zaharieva, Ivelina; Najafpour, M. Mahdi; Wiechen, Mathias Energy & Environmental Science, Vol. 4, Issue 7 https://doi.org/10.1039/c0ee00815j	journal	January 2011
Thermodynamic and kinetic assessments of strontium-doped lanthanum manganite perovskites for two-step thermochemical water splitting Yang, Chih-Kai; Yamazaki, Yoshihiro; Aydin, Aykut J. Mater. Chem. A, Vol. 2, Issue 33 https://doi.org/10.1039/C4TA02694B	journal	January 2014
Soft-x-ray-induced secondary-electron emission from semiconductors and insulators: Models and measurements Henke, Burton L.; Liesegang, John; Smith, Steven D. Physical Review B, Vol. 19, Issue 6 https://doi.org/10.1103/PhysRevB.19.3004	journal	March 1979
Radiation damage in the TEM and SEM Egerton, R. F.; Li, P.; Malac, M. Micron, Vol. 35, Issue 6 https://doi.org/10.1016/j.micron.2004.02.003	journal	August 2004
Material contrast in SEM: Fermi energy and work function effects Cazaux, Jacques Ultramicroscopy, Vol. 110, Issue 3 https://doi.org/10.1016/j.ultramic.2009.12.002	journal	February 2010
Role of the product in the transformation of a catalyst to its active state Hutchings, Graham J.; Desmartin-Chomel, Arnold; Olier, René Nature, Vol. 368, Issue 6466 https://doi.org/10.1038/368041a0	journal	March 1994
Electric fields produced by electron irradiation of insulators in a low vacuum environment Toth, M.; Phillips, M. R.; Craven, J. P. Journal of Applied Physics, Vol. 91, Issue 7 https://doi.org/10.1063/1.1448876	journal	April 2002
Determination of manganese valency in La1−xSrxMnO3 using ELNES in the (S)TEM Riedl, T.; Gemming, T.; Gruner, W. Micron, Vol. 38, Issue 3 https://doi.org/10.1016/j.micron.2006.06.017	journal	April 2007
Electrocatalytic properties of transition metal oxides for oxygen evolution reaction Matsumoto, Y.; Sato, E. Materials Chemistry and Physics, Vol. 14, Issue 5, p. 397-426 https://doi.org/10.1016/0254-0584(86)90045-3	journal	May 1986
Experimental data and model simulations of beam spread in the environmental scanning electron microscope Wight, Scott A. Scanning, Vol. 23, Issue 5 https://doi.org/10.1002/sca.4950230505	journal	September 2001
Electrochemical synthesis: oxygen intercalation Grenier, Jean-Claude; Pouchard, Michel; Wattiaux, Alain Current Opinion in Solid State and Materials Science, Vol. 1, Issue 2 https://doi.org/10.1016/S1359-0286(96)80090-8	journal	April 1996
Reductive dissolution of microparticulate manganese oxides Bakardjieva, Snejana; Bezdička, Petr; Grygar, Tomáš Journal of Solid State Electrochemistry, Vol. 4, Issue 6 https://doi.org/10.1007/s100089900104	journal	July 2000
Topotactic Electrochemical Redox Reactions of the Defect Perovskite SrCoO_2.5+x Nemudry, A.; Rudolf, P.; Schollhorn, R. Chemistry of Materials, Vol. 8, Issue 9, p. 2232-2238 https://doi.org/10.1021/cm950504+		September 1996

Cited By (10)

ETEM Studies of Electrodes and Electro-catalysts Jooss, Christian; Mildner, Stephanie; Beleggia, Marco Controlled Atmosphere Transmission Electron Microscopy https://doi.org/10.1007/978-3-319-22988-1_11	book	January 2016
Local charge measurement using off-axis electron holography Beleggia, M.; Gontard, L. C.; Dunin-Borkowski, R. E. Journal of Physics D: Applied Physics, Vol. 49, Issue 29 https://doi.org/10.1088/0022-3727/49/29/294003	journal	July 2016
Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions Yang, Chunzhen; Grimaud, Alexis Catalysts, Vol. 7, Issue 5 https://doi.org/10.3390/catal7050149	journal	May 2017
Frontiers of water oxidation: the quest for true catalysts Li, J.; Güttinger, R.; Moré, R. Chemical Society Reviews, Vol. 46, Issue 20 https://doi.org/10.1039/c7cs00306d	journal	January 2017
Anomalous Resistance Hysteresis in Oxide ReRAM: Oxygen Evolution and Reincorporation Revealed by In Situ TEM Cooper, David; Baeumer, Christoph; Bernier, Nicolas Advanced Materials, Vol. 29, Issue 23 https://doi.org/10.1002/adma.201700212	journal	April 2017
Mastering Surface Reconstruction of Metastable Spinel Oxides for Better Water Oxidation Duan, Yan; Sun, Shengnan; Sun, Yuanmiao Advanced Materials, Vol. 31, Issue 12 https://doi.org/10.1002/adma.201807898	journal	January 2019
On the role of the gas environment, electron-dose-rate, and sample on the image resolution in transmission electron microscopy Ek, Martin; Jespersen, Sebastian P. F.; Damsgaard, Christian D. Advanced Structural and Chemical Imaging, Vol. 2, Issue 1 https://doi.org/10.1186/s40679-016-0018-x	journal	May 2016
Oxygen Evolution at Manganite Perovskite Ruddlesden-Popper Type Particles: Trends of Activity on Structure, Valence and Covalence Ebrahimizadeh Abrishami, Majid; Risch, Marcel; Scholz, Julius Materials, Vol. 9, Issue 11 https://doi.org/10.3390/ma9110921	journal	November 2016
Nanoscale structural oscillations in perovskite oxides induced by oxygen evolution Han, Binghong; Stoerzinger, Kelsey A.; Tileli, Vasiliki Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4764	journal	October 2016
Electrochemical Behavior of Carbon Electrodes for In Situ Redox Studies in a Transmission Electron Microscope Girod, Robin; Nianias, Nikolaos; Tileli, Vasiliki Microscopy and Microanalysis, Vol. 25, Issue 6 https://doi.org/10.1017/s1431927619015034	journal	October 2019

Similar Records

Colossal Electroresistive Properties Of CSD Grown Pr{sub 0.7}Ca{sub 0.3}MnO{sub 3} Films For Nonvolatile Memory Applications

Journal Article · Wed Dec 01 00:00:00 EST 2010 · AIP Conference Proceedings · OSTI ID:1193217

Bhavsar, K H; Joshi, U S

The observation of valence band change on resistive switching of epitaxial Pr{sub 0.7}Ca{sub 0.3}MnO{sub 3} film using removable liquid electrode

Journal Article · Mon Dec 07 00:00:00 EST 2015 · Applied Physics Letters · OSTI ID:1193217

Lee, Hong-Sub; Park, Hyung-Ho

Determination of effective work function of Pr{sub 0.7}Ca{sub 0.3}MnO{sub 3} and Pt films on ZrO{sub x} using terraced-oxide method

Journal Article · Mon Jul 15 00:00:00 EDT 2013 · Applied Physics Letters · OSTI ID:1193217

Lei, Bi; Pandey, Sumeet C.; Ramaswamy, Nirmal

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
Environmental Transmission Electron Microscopy (ETEM)
thin film electro-catalyst
perovskite structure

Title: Environmental TEM study of electron beam induced electro-chemistry of Pr₀̣₆₄Ca₀̣₃₆MnO₃ catalysts for oxygen evolution

Citation Formats

References (40)

Cited By (10)

Similar Records

Related Subjects