Insights into Copper Sulfide Formation from Cu and S K edge XAS and DFT studies
Abstract
An understanding of the fundamentals of the reaction between CuO with trace amounts of H2S to form CuS products is critical for the optimal utilization of this process in sulfur removal applications. Unfortunately, CuS is a complex material, featuring various Cu2-xS compounds (with 0 ≤ x ≤ 1), distorted crystal phases, and varying electronic structures and coordination environments of Cu and S ions. In this work, we combine ex situ and in situ X-ray absorption spectroscopy (XAS) at S and Cu K edges, fixed bed sorption experiments, DFT simulations, and other characterization techniques to speciate the CuS products formed at different temperatures (298–383 K) and from CuO sorbents with different crystallite sizes (2.8–40 nm). The results of our analysis identify the formation of a distorted CuS layer at the surface of CuO crystals with disulfide groups with shorter Cu–S bonds and higher delocalization of the positive charge of the Cu center into (S1–)2. This distorted CuS layer dominates the XAS signal at lower temperatures (298–323 K) and at the initial stages of sulfidation at higher temperatures (353 and 383 K) where conversion is low (<40%). First-principles atomistic simulations confirm the thermodynamic favorability of the formation of surface (S1–)2 on both CuO (111) and ($$\bar{1}11$$) surfaces, providing further support for our experimental observations. Furthermore, these simulations reveal that the presence of disulfide bonds stabilized surface hydroxyl groups, leading to lower Gibbs Free Energies of their surface migration.
- Authors:
-
- Univ. of California, Los Angeles, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Karlsruhe Inst. of Technology (KIT) (Germany)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Univ. of New Mexico, Albuquerque, NM (United States)
- Univ. of California, Los Angeles, CA (United States); Institute for Carbon Management (ICM), Los Angeles, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1769621
- Grant/Contract Number:
- AC02-76SF00515; EEC-1647722; 56978-DNI5
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 20; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray absorption near edge spectroscopy; Extended X-ray absorption fine structure; Chemical reactions; Sorbents; Materials
Citation Formats
Azzam, Sara A., Boubnov, Alexey, Hoffman, Adam S., López-Ausens, Tirso, Chiang, Nicole, Canning, Griffin, Sautet, Philippe, Bare, Simon R., and Simonetti, Dante A. Insights into Copper Sulfide Formation from Cu and S K edge XAS and DFT studies. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.0c02232.
Azzam, Sara A., Boubnov, Alexey, Hoffman, Adam S., López-Ausens, Tirso, Chiang, Nicole, Canning, Griffin, Sautet, Philippe, Bare, Simon R., & Simonetti, Dante A. Insights into Copper Sulfide Formation from Cu and S K edge XAS and DFT studies. United States. https://doi.org/10.1021/acs.inorgchem.0c02232
Azzam, Sara A., Boubnov, Alexey, Hoffman, Adam S., López-Ausens, Tirso, Chiang, Nicole, Canning, Griffin, Sautet, Philippe, Bare, Simon R., and Simonetti, Dante A. Thu .
"Insights into Copper Sulfide Formation from Cu and S K edge XAS and DFT studies". United States. https://doi.org/10.1021/acs.inorgchem.0c02232. https://www.osti.gov/servlets/purl/1769621.
@article{osti_1769621,
title = {Insights into Copper Sulfide Formation from Cu and S K edge XAS and DFT studies},
author = {Azzam, Sara A. and Boubnov, Alexey and Hoffman, Adam S. and López-Ausens, Tirso and Chiang, Nicole and Canning, Griffin and Sautet, Philippe and Bare, Simon R. and Simonetti, Dante A.},
abstractNote = {An understanding of the fundamentals of the reaction between CuO with trace amounts of H2S to form CuS products is critical for the optimal utilization of this process in sulfur removal applications. Unfortunately, CuS is a complex material, featuring various Cu2-xS compounds (with 0 ≤ x ≤ 1), distorted crystal phases, and varying electronic structures and coordination environments of Cu and S ions. In this work, we combine ex situ and in situ X-ray absorption spectroscopy (XAS) at S and Cu K edges, fixed bed sorption experiments, DFT simulations, and other characterization techniques to speciate the CuS products formed at different temperatures (298–383 K) and from CuO sorbents with different crystallite sizes (2.8–40 nm). The results of our analysis identify the formation of a distorted CuS layer at the surface of CuO crystals with disulfide groups with shorter Cu–S bonds and higher delocalization of the positive charge of the Cu center into (S1–)2. This distorted CuS layer dominates the XAS signal at lower temperatures (298–323 K) and at the initial stages of sulfidation at higher temperatures (353 and 383 K) where conversion is low (<40%). First-principles atomistic simulations confirm the thermodynamic favorability of the formation of surface (S1–)2 on both CuO (111) and ($\bar{1}11$) surfaces, providing further support for our experimental observations. Furthermore, these simulations reveal that the presence of disulfide bonds stabilized surface hydroxyl groups, leading to lower Gibbs Free Energies of their surface migration.},
doi = {10.1021/acs.inorgchem.0c02232},
journal = {Inorganic Chemistry},
number = 20,
volume = 59,
place = {United States},
year = {Thu Oct 01 00:00:00 EDT 2020},
month = {Thu Oct 01 00:00:00 EDT 2020}
}
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