Achieving High Selectivity for Alkyne Hydrogenation at High Conversions with Compositionally Optimized PdAu Nanoparticle Catalysts in Raspberry Colloid-Templated SiO2

Luneau, Mathilde; Shirman, Tanya; Foucher, Alexandre C.; Duanmu, Kaining; Verbart, David M. A.; Sautet, Philippe; Stach, Eric A.; Aizenberg, Joanna; Madix, Robert J.; Friend, Cynthia M.

doi:10.1021/acscatal.9b04243

Achieving High Selectivity for Alkyne Hydrogenation at High Conversions with Compositionally Optimized PdAu Nanoparticle Catalysts in Raspberry Colloid-Templated SiO₂

Journal Article · Wed Nov 06 23:00:00 EST 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b04243· OSTI ID:1595073

Luneau, Mathilde ^[1]; Shirman, Tanya ^[2]; ^[3]; Duanmu, Kaining ^[4]; Verbart, David M. A. ^[5]; ^[4]; ^[3]; Aizenberg, Joanna ^[2]; ^[2]; ^[2]

Harvard Univ., Cambridge, MA (United States); Harvard University
Harvard Univ., Cambridge, MA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)
Univ. of California, Los Angeles, CA (United States)
Harvard Univ., Cambridge, MA (United States); Utrecht Univ. (The Netherlands)

Improving the selectivity for catalytic hydrogenation of alkynes is a key step in upgrading feedstocks for olefin polymerization. Herein, dilute Pd_xAu_1-x alloy nanoparticles embedded in raspberry colloidtemplated silica (x = 0.02, 0.04, and 0.09) are demonstrated to be highly active and selective for the gas-phase hydrogenation of 1-hexyne, exhibiting higher selectivity than pure Pd at high conversion. The conversion of 1-hexyne remains high even for the very low amounts of Pd in Pd_0.02Au_0.98. These catalysts are highly resistant to sintering—addressing a long-standing challenge in the use of Au-based catalysts. Clear evidence is presented that the addition of the second hydrogen to the halfhydrogenated intermediate is the rate-limiting step, and that the stability of the half-hydrogenated intermediate of the alkyne is higher than the half-hydrogenated alkene which explains the high selectivity even at high conversions. Moreover, of the three compositions investigated, optimum selectivity and activity is observed for the nanoparticles containing 4% Pd. The apparent activation energy for production of 1-hexene from 1-hexyne is measured to be 38 kJ mol^-1 for the Pd_0.04Au_0.96 catalysts, which is ~14 kJ mol^-1 lower than for pure Pd. The hydrogenation is completely, but reversibly, suppressed by adding CO to the reactant mixture, indicating that the Pd centers are the active sites for reaction. The method of templating used in preparation of the catalysts is highly customizable and versatile. As a result, this study demonstrates that the composition of the nanoparticles as defined by the dilution ratio of Pd in Au and by the method used to make the supported catalyst are important tunable parameters that can be used to optimize activity and selectivity of bimetallic systems.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012573

OSTI ID:: 1595073

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 1 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Achieving High Selectivity for Alkyne Hydrogenation at High Conversions with Compositionally Optimized PdAu Nanoparticle Catalysts in Raspberry Colloid-Templated SiO2

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References (49)

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