Dynamical Change of Valence States and Structure in NiCu3 Nanoparticles during Redox Cycling

Foucher, Alexandre C.; Marcella, Nicholas; Lee, Jennifer D.; Tappero, Ryan; Murray, Christopher B.; Frenkel, Anatoly I.; Stach, Eric A.

doi:10.1021/acs.jpcc.1c10824

Title: Dynamical Change of Valence States and Structure in NiCu₃ Nanoparticles during Redox Cycling

Journal Article · 20 January 2022 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.1c10824 · OSTI ID:1844590

^[1];

^[2]; Lee, Jennifer D. ^[3]; Tappero, Ryan ^[4]; Murray, Christopher B. ^[1];

^[5];

^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Stony Brook Univ., NY (United States)
Harvard Univ., Cambridge, MA (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Alloyed materials are promising candidates to improve catalytic processes. Ni–Cu nanoparticles are used for various reactions, including processes with biomass-derived components. However, dynamical restructuring effects alter the catalytic properties and can deactivate the sample. To understand these structural modifications, a multimodal investigation of NiCu₃/C was performed to determine compositional and morphological changes during a redox cycle to simulate reduction and oxidation of the catalyst during reaction. We exploit a novel correlative, multimodal approach that combines in situ X-ray absorption spectroscopy (XAS) and in situ scanning transmission electron microscopy and electron energy-loss spectroscopy (STEM-EELS) to describe changes that occur in the sample in realistic conditions. In the fresh sample, there are two morphologies present: core–shell and hollow. Segregation of Cu was observed in both types of particles after synthesis, with Cu being more oxidized in the hollow structures. Upon reduction for 2 h under H₂ at 400 °C, the Cu was reduced, although segregation of Cu and Ni was still observed. Subsequent exposure to O₂ at 400 °C led to a strong reoxidation of Cu with the formation of hollow particles with compositional heterogeneities. The oxidation of metals and segregation phenomena can be related to known catalytic properties of NiCu₃/C particles, especially regarding the hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; SC0012573

OSTI ID:: 1844590

Report Number(s):: BNL--222719-2022-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 4 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electron energy loss spectroscopy
Hollow structures
Nanoparticles
Oxides
Redox reactions

Title: Dynamical Change of Valence States and Structure in NiCu3 Nanoparticles during Redox Cycling

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References (48)

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Related Subjects

Title: Dynamical Change of Valence States and Structure in NiCu₃ Nanoparticles during Redox Cycling