Tuning Two-Dimensional Phthalocyanine Dual Site Metal–Organic Framework Catalysts for the Oxygen Reduction Reaction

Wei, Lingze; Hossain, Md Delowar; Chen, Gan; Kamat, Gaurav A.; Kreider, Melissa E.; Chen, Junjie; Yan, Katherine; Bao, Zhenan; Bajdich, Michal; Stevens, Michaela Burke; Jaramillo, Thomas F.

doi:10.1021/jacs.4c02229

Title: Tuning Two-Dimensional Phthalocyanine Dual Site Metal–Organic Framework Catalysts for the Oxygen Reduction Reaction

Journal Article · 06 May 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c02229 · OSTI ID:2447434

^[1]; Hossain, Md Delowar ^[2]; Chen, Gan ^[3];

^[2]; Kreider, Melissa E. ^[2];

^[2]; Yan, Katherine ^[2];

^[2];

^[4];

^[2]

Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; SLAC
Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
Stanford Univ., CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis

Metal-organic frameworks (MOFs) offer an interesting opportunity for catalysis, particularly for metal-nitrogen-carbon (M-N-C) motifs by providing an organized porous structural pattern and well-defined active sites for the oxygen reduction reaction (ORR), a key need for hydrogen fuel cells and related sustainable energy technologies. Here, in this work, we leverage electrochemical testing with computational models to study the electronic and structural properties in these systems and their relationship to ORR activity and stability based on dual transitional metal centers. These consists of two M1 metals with amine nodes coordinated to a single M2 metal with a phthalocyanine linker, where M1/M2 = Co, Ni, or Cu. Co-based metal centers, in particular Ni-Co, demonstrate the highest overall activity of all nine tested MOFs. Computationally, we identify the dominance of Co-sites, relative higher importance of the M2 site, and the role of layer M1 interactions on the ORR activity. Selectivity measurements indicate that M1 sites of MOFs, particularly Co, exhibits lowest (< 4%), and Ni demonstrates highest (>46%) two-electron selectivity, in good agreement with computational studies. Direct in-situ stability characterization, measuring dissolved metal ions, and calculations, using an alkaline stability metric, confirm that Co is the most stable metal in the MOF, while Cu exhibits notable instability at the M1. Overall, this study reveals how atomistic coupling of electronic and structural properties affects the ORR performance of dual site MOF catalysts and opens new avenues for tunable design and future development of these systems for practical electrochemical applications.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: AC02-76SF00515; AC02-05CH11231

OSTI ID:: 2447434

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 19 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Tuning Two-Dimensional Phthalocyanine Dual Site Metal–Organic Framework Catalysts for the Oxygen Reduction Reaction

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