TY - JOUR
T1 - Influence of Pd speciation and support interactions for Suzuki reactions
AU - Moore, Samuel C.
AU - Carrasquillo-Flores, Ronald
AU - Yang, Rachel A.
AU - Trettin, James L.
AU - Becwar, Shona
AU - Huo, Jiajie
AU - Wood, Sharla
AU - Nye, Jeffrey
AU - Sarazen, Michele L.
N1 - Publisher Copyright:
© 2025 Elsevier B.V.
PY - 2025/6/25
Y1 - 2025/6/25
N2 - The carbon-carbon bond-formation via the Suzuki reaction is widely used in the pharmaceutical and chemical industries, typically catalyzed by homogeneous palladium (Pd)-ligand complexes. Despite their effectiveness, these catalysts face challenges such as difficult Pd separation and limited reusability. This study targets heterogeneous single atom catalysts (SACs) on varied supports, where Pd-UiO-66-NH2 metal-organic framework (MOF), synthesized via a ball milling method, was evaluated against Pd/TiO2 and Pd/C in Suzuki coupling reactions. Characterization data (TEM, XRD, DRIFTS, EDX, chemisorption) revealed that Pd-UiO-66-NH2 predominantly features isolated Pd atoms, while Pd/TiO2 contains both single atoms and nanoparticles and Pd/C has predominately nanoparticles. Turnover frequencies for varied substrates trended as Pd-UiO-66-NH2>Pd/TiO2>Pd/C, consistent with fitted kinetic parameters. Hot filtration experiments indicated reactivity from each catalyst stemmed from leached Pd. These results highlight the potential of SACs and the importance of support choice for achieving high catalytic efficiency with minimal metal loading, aligning with green chemistry principles and demonstrating the promising role of MOFs as efficient platforms for SACs.
AB - The carbon-carbon bond-formation via the Suzuki reaction is widely used in the pharmaceutical and chemical industries, typically catalyzed by homogeneous palladium (Pd)-ligand complexes. Despite their effectiveness, these catalysts face challenges such as difficult Pd separation and limited reusability. This study targets heterogeneous single atom catalysts (SACs) on varied supports, where Pd-UiO-66-NH2 metal-organic framework (MOF), synthesized via a ball milling method, was evaluated against Pd/TiO2 and Pd/C in Suzuki coupling reactions. Characterization data (TEM, XRD, DRIFTS, EDX, chemisorption) revealed that Pd-UiO-66-NH2 predominantly features isolated Pd atoms, while Pd/TiO2 contains both single atoms and nanoparticles and Pd/C has predominately nanoparticles. Turnover frequencies for varied substrates trended as Pd-UiO-66-NH2>Pd/TiO2>Pd/C, consistent with fitted kinetic parameters. Hot filtration experiments indicated reactivity from each catalyst stemmed from leached Pd. These results highlight the potential of SACs and the importance of support choice for achieving high catalytic efficiency with minimal metal loading, aligning with green chemistry principles and demonstrating the promising role of MOFs as efficient platforms for SACs.
KW - MOF
KW - Pd catalysts
KW - Suzuki
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U2 - 10.1016/j.apcata.2025.120279
DO - 10.1016/j.apcata.2025.120279
M3 - Article
AN - SCOPUS:105002656254
SN - 0926-860X
VL - 700
JO - Applied Catalysis A: General
JF - Applied Catalysis A: General
M1 - 120279
ER -