Synergistic Solvent-Surface Interactions Enable Alkyne Semihydrogenation at Palladium

Rahmani, Azina [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000190291857); Kim, Yu Lim [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0009000981385849); Israel, Deborah [University of Central Florida, Orlando, FL (United States)]; Currie, Taylor M. [University of Central Florida, Orlando, FL (United States)] (ORCID:000900081256167X); Javier-Jiménez, Diego R. [University of Central Florida, Orlando, FL (United States)]; Butkus, Brian [University of Central Florida, Orlando, FL (United States)]; Kaminski, Dawid [University of Central Florida, Orlando, FL (United States)] (ORCID:0009000014014700); Beazley, Melanie J. [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000199737798); Banerjee, Parag [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000304018155); Zhai, Lei [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000238862154); Tetard, Laurene [University of Central Florida, Orlando, FL (United States); Centre National de la Recherche Scientifique (CNRS), Villeurbanne (France). Institut des Sciences Analytiques (ISA); Universite Claude Bernard Lyon 1 (UCBL), Villeurbanne (France)] (ORCID:000000031771466X); Kaden, William [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000308367109); Liu, Cong [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000221455034); Jurca, Titel [University of Central Florida, Orlando, FL (United States)] (ORCID:000000033656912X)

doi:10.1021/acsami.6c06421

DOE OSTI · 3375874

Synergistic Solvent-Surface Interactions Enable Alkyne Semihydrogenation at Palladium

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Abstract

Enabling higher yield and better selectivity for fine-chemical synthesis through heterogeneous catalysis is intricately linked to the interplay of active sites, reaction conditions, and mass transfer influence provided by the catalyst. Alkyne semihydrogenation is ubiquitous in the production of bulk chemicals in the pharmaceutical, polymer, or fine-chemical industries, but product selectivity remains a major challenge. Here, in this study, we demonstrate that the design of catalysts encompassing nickel (Ni) foams as contiguous monolith supports, decorated with ultralow loading of Pd/PdO x nanoparticles on a carbonized polydopamine interface and tuned with a thin layer of Al 2 O 3 , in conjunction with an optimized reaction environment leads to highly selective alkyne semihydrogenation. The reactions demonstrate good functional group tolerance and applicability to flow reactor systems. Combined computational and experimental studies are presented to describe the synergistic effect between the solvent-surface interaction and the degree of Pd surface reduction that are necessary to promote this selectivity. The system highlights the opportunity for catalyst-solvent codesign as a benign alternative to more complex reactants featuring extrinsic poisons or less-favored dopants.

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Rahmani, Azina [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000190291857), Kim, Yu Lim [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0009000981385849), Israel, Deborah [University of Central Florida, Orlando, FL (United States)], Currie, Taylor M. [University of Central Florida, Orlando, FL (United States)] (ORCID:000900081256167X), Javier-Jiménez, Diego R. [University of Central Florida, Orlando, FL (United States)], Butkus, Brian [University of Central Florida, Orlando, FL (United States)], Kaminski, Dawid [University of Central Florida, Orlando, FL (United States)] (ORCID:0009000014014700), Beazley, Melanie J. [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000199737798), Banerjee, Parag [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000304018155), Zhai, Lei [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000238862154), Tetard, Laurene [University of Central Florida, Orlando, FL (United States); Centre National de la Recherche Scientifique (CNRS), Villeurbanne (France). Institut des Sciences Analytiques (ISA); Universite Claude Bernard Lyon 1 (UCBL), Villeurbanne (France)] (ORCID:000000031771466X), Kaden, William [University of Central Florida, Orlando, FL (United States)] (ORCID:0000000308367109), Liu, Cong [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000221455034), Jurca, Titel [University of Central Florida, Orlando, FL (United States)] (ORCID:000000033656912X). 2026-06-23. Synergistic Solvent-Surface Interactions Enable Alkyne Semihydrogenation at Palladium. https://doi.org/10.1021/acsami.6c06421

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