Connecting cation site location to alkane dehydrogenation activity in Ni/BEA catalysts

Farberow, Carrie A; Wegener, Evan C.; Kumar, Anurag; Miller, Jacob H; Dupuis, Daniel; Kim, Seonah; Ruddy, Daniel A.

doi:10.1016/j.jcat.2022.06.023

Connecting cation site location to alkane dehydrogenation activity in Ni/BEA catalysts

Journal Article · 01 September 2022 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2022.06.023· OSTI ID:1923317

Farberow, Carrie A; Wegener, Evan C.; Kumar, Anurag; Miller, Jacob H; Dupuis, Daniel; Kim, Seonah; Ruddy, Daniel A.

Ni-modified beta zeolite (Ni/BEA) catalysts activate carbon-hydrogen bonds in light alkanes, as demonstrated through isobutane reaction testing. Controlled synthesis of Ni/BEA allows for efficient introduction of ion-exchanged Ni sites at varying Ni loadings (0.43% - 1.8%). These catalysts exhibit site time yields (STY) for H2 production that increase with increasing Ni loading. A detailed analysis of secondary reactions and carbon deposition based on the relative molar flowrates of product C and H indicates that the observed increase in H2 STY with increasing Ni loading is likely attributed to both increasing alkane activation activity and increasing formation of hydrogen-deficient aromatic products retained within the catalyst pores. In situ diffuse-reflectance UV-visible-NIR absorbance and X-ray absorption spectroscopies indicate isolated, 4-coordinate Ni(2+) species for all loadings. Quantum mechanics/molecular mechanics modeling identifies two distinct Ni(2+) sites consistent with the structural characterization, but with differing relative stabilities due to their coordination environment. Computed reaction energetics for isobutane dehydrogenation demonstrate that the more stable Ni(2+) species at a six-membered 4Si-2Al ring, Ni-6MR, is less active for isobutane dehydrogenation than the less stable Ni(2+) at the five-membered 3Si-2Al ring, Ni-5MR. The differing local structure of the isolated cationic Ni sites in Ni/BEA offers a possible rationalization for the increased H2 STY observed at greater Ni loadings.

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Bioenergy Technologies Office (BETO)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1923317

Journal Information:: Journal of Catalysis, Vol. 413

Country of Publication:: United States

Language:: English

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