In Situ Monitoring of H2-Induced Nonstoichiometry in Cu2O

Wang, Jianyu; Li, Chaoran; Zhu, Yaguang; Boscoboinik, Jorge Anibal; Zhou, Guangwen

doi:10.1021/acs.jpclett.2c00988

In Situ Monitoring of H₂-Induced Nonstoichiometry in Cu₂O

Journal Article · 14 June 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c00988· OSTI ID:1898609

Wang, Jianyu ^[1]; Li, Chaoran ^[1]; Zhu, Yaguang ^[1]; ^[2]; ^[1]

State University of New York (SUNY), Binghamton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Nonstoichiometry plays a pivotal role in the functioning of oxide materials, but it is challenging to measure the non-stoichiometric formation and the resulting charge redistribution around the point defects. Using ambient-pressure X-ray photoelectron spectroscopy and Auger electron spectroscopy to monitor the reduction of Cu₂O in H₂, we identify the formation of an intermediate, oxygen-deficient Cu₂O phase and its progressive inward growth into the deeper region of the oxide. Complemented by DFT modeling, we show that the oxygen-deficient Cu₂O formation occurs via molecular H₂ adsorption at the Cu₂O surface, which results in the loss of lattice O from the formation of H₂O molecules that desorb spontaneously from the oxide surface. The resulting oxy-gen-deficient Cu₂O is a stable intermediate that persists before the Cu₂O is fully reduced to metallic Cu. The O vacancy induced charge redistribution of the coordinating Cu atoms results in a satellite feature in Cu LMM, which can be used a fingerprint to identify the nonstoichiometry and local charge transfer in non-stoichiometric oxides.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

DOE Contract Number:: SC0012704; SC0001135

OSTI ID:: 1898609

Report Number(s):: BNL-223691-2022-JAAM

Journal Information:: Journal of Physical Chemistry Letters, Vol. 13, Issue 24; ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

References (29)

Oxidation of Polycrystalline Copper Thin Films at Ambient Conditions Platzman, Ilia; Brener, Reuven; Haick, Hossam The Journal of Physical Chemistry C, Vol. 112, Issue 4 https://doi.org/10.1021/jp076981k	journal	January 2008
Water Adsorption and Dissociation on Polycrystalline Copper Oxides: Effects of Environmental Contamination and Experimental Protocol Trotochaud, Lena; Head, Ashley R.; Pletincx, Sven The Journal of Physical Chemistry B, Vol. 122, Issue 2 https://doi.org/10.1021/acs.jpcb.7b10732	journal	November 2017
α-Fe2O3 as a versatile and efficient oxygen atom transfer catalyst in combination with H2O as the oxygen source Zhao, Yukun; Deng, Chaoyuan; Tang, Daojian Nature Catalysis, Vol. 4, Issue 8 https://doi.org/10.1038/s41929-021-00659-1	journal	August 2021
Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation Wang, Xiao Xia; Swihart, Mark T.; Wu, Gang Nature Catalysis, Vol. 2, Issue 7 https://doi.org/10.1038/s41929-019-0304-9	journal	July 2019
XAS Study of Au Supported on TiO₂: Influence of Oxidation State and Particle Size on Catalytic Activity Schwartz, Viviane; Mullins, David R.; Yan, Wenfu The Journal of Physical Chemistry B, Vol. 108, Issue 40 https://doi.org/10.1021/jp048076v	journal	September 2004
Surface Oxidation and Reduction of CuO and Cu2O Studied Using XPS and XAES Poulston, S.; Parlett, P. M.; Stone, P. Surface and Interface Analysis, Vol. 24, Issue 12 https://doi.org/10.1002/(SICI)1096-9918(199611)24:12<811::AID-SIA191>3.0.CO;2-Z	journal	November 1996
Time-resolved Studies for the Mechanism of Reduction of Copper Oxides with Carbon Monoxide: Complex Behavior of Lattice Oxygen and the Formation of Suboxides Wang, Xianqin; Hanson, Jonathan C.; Frenkel, Anatoly I. The Journal of Physical Chemistry B, Vol. 108, Issue 36 https://doi.org/10.1021/jp040366o	journal	September 2004
In situ atomic-scale imaging of the metal/oxide interfacial transformation Zou, Lianfeng; Li, Jonathan; Zakharov, Dmitri Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00371-4	journal	August 2017
Oxygen-deficient metal oxides: Synthesis routes and applications in energy and environment Zu, Di; Wang, Haiyang; Lin, Sen Nano Research, Vol. 12, Issue 9 https://doi.org/10.1007/s12274-019-2377-9	journal	April 2019
Electronic structures of C u 2 O , C u 4 O 3 , and CuO: A joint experimental and theoretical study Wang, Y.; Lany, S.; Ghanbaja, J. Physical Review B, Vol. 94, Issue 24 https://doi.org/10.1103/PhysRevB.94.245418	journal	December 2016
Direct Evidence of Subsurface Oxygen Formation in Oxide‐Derived Cu by X‐ray Photoelectron Spectroscopy Wang, Hsin‐Yi; Soldemo, Markus; Degerman, David Angewandte Chemie International Edition, Vol. 61, Issue 3 https://doi.org/10.1002/anie.202111021	journal	December 2021
Effect of surface stresses on CuO nanowire growth in the thermal oxidation of copper Mema, Rediola; Yuan, Lu; Du, Qingtian Chemical Physics Letters, Vol. 512, Issue 1-3 https://doi.org/10.1016/j.cplett.2011.07.012	journal	August 2011
Copper oxide on alumina I. XRD studies of catalyst composition during air oxidation of carbon monoxide Pierron, E. Journal of Catalysis, Vol. 9, Issue 1 https://doi.org/10.1016/0021-9517(67)90177-7	journal	September 1967
Ambient-Pressure X-ray Photoelectron Spectroscopy (APXPS) Karslıoğlu, Osman; Bluhm, Hendrik Springer Series in Chemical Physics https://doi.org/10.1007/978-3-319-44439-0_2	book	December 2016
Ambient pressure photoelectron spectroscopy: A new tool for surface science and nanotechnology Salmeron, M.; Schlogl, R. Surface Science Reports, Vol. 63, Issue 4 https://doi.org/10.1016/j.surfrep.2008.01.001	journal	April 2008
Rapid oxygen exchange between hematite and water vapor Jakub, Zdenek; Meier, Matthias; Kraushofer, Florian Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26601-4	journal	November 2021
Measuring Charge Transfer between Adsorbate and Metal Surfaces Wang, Jianyu; Lu, Deyu; Li, Chaoran The Journal of Physical Chemistry Letters, Vol. 11, Issue 16 https://doi.org/10.1021/acs.jpclett.0c02002	journal	July 2020
Satellite structure in photoelectron and Auger spectra of copper dihalides van der Laan, G.; Westra, C.; Haas, C. Physical Review B, Vol. 23, Issue 9 https://doi.org/10.1103/PhysRevB.23.4369	journal	May 1981
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
Indirect Phase Transformation of CuO to Cu₂O on a Nanowire Surface Wu, Fei; Banerjee, Sriya; Li, Huafang Langmuir, Vol. 32, Issue 18 https://doi.org/10.1021/acs.langmuir.6b00915	journal	April 2016
Driving force and growth mechanism for spontaneous oxide nanowire formation during the thermal oxidation of metals Yuan, Lu; Wang, Yiqian; Mema, Rediola Acta Materialia, Vol. 59, Issue 6 https://doi.org/10.1016/j.actamat.2010.12.052	journal	April 2011
Synthesis and catalytic properties of metal nanoparticles: Size, shape, support, composition, and oxidation state effects Cuenya, Beatriz Roldan Thin Solid Films, Vol. 518, Issue 12 https://doi.org/10.1016/j.tsf.2010.01.018	journal	April 2010
Redox Properties of Cu ₂ O(100) and (111) Surfaces Wang, Chunlei; Tissot, Heloise; Escudero, Carlos The Journal of Physical Chemistry C, Vol. 122, Issue 50 https://doi.org/10.1021/acs.jpcc.8b08494	journal	November 2018
In Situ XRD, XPS, TEM, and TPR Study of Highly Active in CO Oxidation CuO Nanopowders Svintsitskiy, Dmitry A.; Kardash, Tatyana Yu.; Stonkus, Olga A. The Journal of Physical Chemistry C, Vol. 117, Issue 28 https://doi.org/10.1021/jp403339r	journal	July 2013
Insight into the Phase Transformation Pathways of Copper Oxidation: From Oxygen Chemisorption on the Clean Surface to Multilayer Bulk Oxide Growth Wang, Jianyu; Li, Chaoran; Zhu, Yaguang The Journal of Physical Chemistry C, Vol. 122, Issue 46 https://doi.org/10.1021/acs.jpcc.8b09145	journal	October 2018
Role of Defects in Surface Chemistry on Cu ₂ O(111) Önsten, Anneli; Weissenrieder, Jonas; Stoltz, Dunja The Journal of Physical Chemistry C, Vol. 117, Issue 38 https://doi.org/10.1021/jp3112217	journal	September 2013
The effect of metal precursor on copper phase dispersion and nanoparticle formation for the catalytic transformations of furfural Islam, Mohammed J.; Granollers Mesa, Marta; Osatiashtiani, Amin Applied Catalysis B: Environmental, Vol. 273 https://doi.org/10.1016/j.apcatb.2020.119062	journal	September 2020
Experimental and theoretical investigation of the electronic structure of Cu ₂ O and CuO thin films on Cu(110) using x-ray photoelectron and absorption spectroscopy Jiang, Peng; Prendergast, David; Borondics, Ferenc The Journal of Chemical Physics, Vol. 138, Issue 2 https://doi.org/10.1063/1.4773583	journal	January 2013
Reduction of CuO and Cu ₂ O with H ₂ : H Embedding and Kinetic Effects in the Formation of Suboxides Kim, Jae Y.; Rodriguez, José A.; Hanson, Jonathan C. Journal of the American Chemical Society, Vol. 125, Issue 35 https://doi.org/10.1021/ja0301673	journal	September 2003

Similar Records

Defect chemistry of La{sub 2-x}Sr{sub x}CuO{sub 4-{delta}}: Oxygen nonstoichiometry and thermodynamic stability

Journal Article · 1997 · Journal of Solid State Chemistry · OSTI ID:589042

Kanai, Hideki; Tagawa, Hiroaki; Mizusaki, Junichiro

Nonstoichiometry, point defects and magnetic properties in Sr{sub 2}FeMoO{sub 6-{delta}} double perovskites

Journal Article · 2012 · Journal of Solid State Chemistry · OSTI ID:21612853

Kircheisen, R; Toepfer, J

Local Structural Disorder in Metavanadates MV₂O₆ (M = Zn and Cu) Synthesized by the Deep Eutectic Solvent Route: Photoactive Oxides with Oxygen Vacancies

Journal Article · 2021 · Chemistry of Materials · OSTI ID:2000444

Hong, Sangki; Burkhow, Sadie J.; Doughty, Rachel M.; +8 more

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
adsorption
lattices
oxides
oxygen
redox actions

In Situ Monitoring of H2-Induced Nonstoichiometry in Cu2O

Citation Formats

References (29)

Similar Records

Related Subjects

In Situ Monitoring of H₂-Induced Nonstoichiometry in Cu₂O