Dehydrogenation of Propane and n-Butane Catalyzed by Isolated PtZn4 Sites Supported on Self-Pillared Zeolite Pentasil Nanosheets

Qi, Liang; Zhang, Yanfei; Babucci, Melike; Chen, Cailing; Lu, Peng; Li, Jingwei; Dun, Chaochao; Hoffman, Adam S.; Urban, Jeffrey J.; Tsapatsis, Michael; Bare, Simon R.; Han, Yu; Gates, Bruce C.; Bell, Alexis T.

doi:10.1021/acscatal.2c01631

Dehydrogenation of Propane and n-Butane Catalyzed by Isolated PtZn₄ Sites Supported on Self-Pillared Zeolite Pentasil Nanosheets

Journal Article · Wed Aug 31 00:00:00 EDT 2022 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.2c01631· OSTI ID:1908733

Qi, Liang ^[1]; Zhang, Yanfei ^[2]; ^[3]; ^[4]; Lu, Peng ^[5]; Li, Jingwei ^[6]; Dun, Chaochao ^[7]; ^[8]; ^[7]; ^[5]; ^[8]; ^[4]; ^[9]; ^[2]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Chinese Academy of Sciences (CAS), Dalian (China); SLAC
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
University of California, Davis, CA (United States); Uppsala University (Sweden)
King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia)
Johns Hopkins University, Baltimore, MD (United States)
Chongqing University (China)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Chinese Academy of Sciences (CAS), Dalian (China)

Propene and 1,3-butadiene are important building-block chemicals that can be produced by dehydrogenation of propane and butane over Pt catalysts. The challenge is to develop highly active and selective catalysts that are resistant to deactivation by Pt sintering and coke formation. We have recently shown that these objectives can be met for propane dehydrogenation using atomically dispersed Pt atoms anchored to neighboring ≡SiOZn-OH groups bonded to the framework dealuminated zeolite BEA. In the present study, we demonstrate that significantly superior performance can be achieved by using self-pillared pentasil (SPP) zeolite nanosheets. Following catalyst reduction in H₂, atomic-resolution, scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) indicate that Pt is stabilized in structures well approximated as (≡Si-O-Zn)_4-5Pt. These species are highly active, selective, and stable for propane dehydrogenation (PDH) to give propene and for n-butane dehydrogenation (BDH) to give 1,3-butadiene. No catalyst deactivation was observed after 12 days of time on stream, and the selectivity remained at nearly 100% for PDH conducted at 823 K and a weight hourly space velocity (WHSV) of 1,350 h^-1. The apparent rate coefficient for PDH over this catalyst is significantly higher than that reported previously for Pt-containing catalysts. For BDH at 823 K and a WHSV of 3560 h^-1, the selectivity to butene isomers and 1,3-butadiene is 98.9%, and the selectivity to 1,3-butadiene is 45%. Here, we propose that the high catalyst stability observed during PDH and BDH is a consequence of a large fraction of the Pt-containing centers being located on the external surface of the zeolite nanosheets, where nascent coke precursors can desorb before condensing to form coke.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Dalian Institute of Chemical Physics; Chinese Academy of Sciences

Grant/Contract Number:: AC02-76SF00515; AC02-05CH11231; SC0012702; SC0001004

OSTI ID:: 1908733

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 18 Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalytic dehydrogenation
isolated PtZn4
light alkane
zeolite nanosheet

Dehydrogenation of Propane and n-Butane Catalyzed by Isolated PtZn4 Sites Supported on Self-Pillared Zeolite Pentasil Nanosheets

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Dehydrogenation of Propane and n-Butane Catalyzed by Isolated PtZn₄ Sites Supported on Self-Pillared Zeolite Pentasil Nanosheets