Impact of SO2 on NiFe Nanoparticle Exsolution and Dissolution from LaFe0.9Ni0.1O3 Perovskite Oxides

Najimu, Musa; Hurlock, Matthew J.; Parvin, Sahanaz; Brea, Courtney; Kumar, Neelesh; Cho, Yoon Jin; Wu, Yiqing; Hu, Guoxiang; Wu, Zili; Nikolla, Eranda; Baltrusaitis, Jonas; Nenoff, Tina M.; Wachs, Israel E.; Gilliard-AbdulAziz, Kandis Leslie

doi:10.1021/acs.chemmater.4c03439

Title: Impact of SO₂ on NiFe Nanoparticle Exsolution and Dissolution from LaFe_0.9Ni_0.1O₃ Perovskite Oxides

Journal Article · Wed Mar 05 00:00:00 UTC 2025 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.4c03439 · OSTI ID:2587226

Najimu, Musa ^[1];

^[2]; Parvin, Sahanaz ^[3]; Brea, Courtney ^[4]; Kumar, Neelesh ^[3];

^[5]; Wu, Yiqing ^[6]; Hu, Guoxiang ^[4];

^[6];

^[5];

^[3];

^[7];

^[3];

^[8]

Univ. of Southern California, Los Angeles, CA (United States); Univ. of California, Riverside, CA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Lehigh Univ., Bethlehem, PA (United States)
Georgia Institute of Technology, Atlanta, GA (United States)
Univ. of Michigan, Ann Arbor, MI (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Univ. of Southern California, Los Angeles, CA (United States); Univ. of California, Riverside, CA (United States)

Ni-doped LaFeO₃ perovskite oxide is a promising cathode material for solid oxide electrolysis cells (SOECs) designed for CO₂/H₂O coelectrolysis. Here, the performance of LaFe_0.9Ni_0.1O₃ is being investigated under real-world conditions that include exposure to acid gases, such as SO₂, relevant to SOEC operation. Experiments show that LaFe_0.9Ni_0.1O₃ exsolves NiFe nanoparticles, along with the formation of surface SO₄^2– and SO₃^2– after being exposed to 200 ppm of SO₂. This suggests that the ionic diffusion of Ni³⁺ and Fe³⁺ between the bulk and the surface remains unaffected throughout the exsolution–dissolution–exsolution cycle. Thermochemical water splitting has been employed as a probe reaction to evaluate the catalytic properties of the exsolved NiFe nanoparticles. These nanoparticles demonstrated improved hydrogen production compared to bare perovskite oxide substrates. However, after exposure to SO₂, the formation of Fe-rich NiFe nanoparticles led to poor thermocatalytic performance and rapid deactivation of the perovskite at elevated temperatures. Density functional theory (DFT) analysis was utilized to validate the experimental findings, indicating a significantly negative reaction energy for water splitting over exsolved Fe, as well as stronger binding of SO₂ to Fe than to Ni. Computational analysis further suggests that the presence of surface sulfate promotes the formation of Fe-rich NiFe nanoparticles, aligning with the experimental results. Overall, this study clarifies how SO₂ affects the structure of SOEC perovskite oxide candidate materials. Future engineering efforts should focus on enhancing nanoparticle exsolution and sulfur resistance, which is crucial for improving the hydrogen production capacity of La-based perovskite oxides for electro- and thermocatalytic water splitting in real environments containing acid gases.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

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

Grant/Contract Number:: AC05-76RL01830; NA0003525; SC0012577

OSTI ID:: 2587226

Report Number(s):: PNNL-SA--208515

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 6 Vol. 37; ISSN 1520-5002; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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