Rapid Polyolefin Hydrogenolysis by a Single‐Site Organo‐Tantalum Catalyst on a Super‐Acidic Support: Structure and Mechanism

Lai, Qingheng; Mason, Alexander H.; Agarwal, Amol; Edenfield, Wilson C.; Zhang, Xinrui; Kobayashi, Takeshi; Kratish, Yosi; Marks, Tobin J.

doi:10.1002/ange.202312546

Title: Rapid Polyolefin Hydrogenolysis by a Single‐Site Organo‐Tantalum Catalyst on a Super‐Acidic Support: Structure and Mechanism

Journal Article · 10 November 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202312546 · OSTI ID:2229179

Lai, Qingheng ^[1]; Mason, Alexander H. ^[1]; Agarwal, Amol ^[2]; Edenfield, Wilson C. ^[1]; Zhang, Xinrui ^[2];

^[3];

^[1];

^[1]

Department of Chemistry Northwestern University 2145 Sheridan Road Evanston IL-60208-3113 USA
Department of Materials Science &, Engineering Northwestern University 2220 Campus Drive Evanston IL-60208-3113 USA
U.S. DOE Ames National Laboratory IOWA State University Ames IA50011-3020 USA

Abstract The novel electrophilic organo‐tantalum catalyst AlS/TaNp _x ( 1 ) (Np=neopentyl) is prepared by chemisorption of the alkylidene Np ₃ Ta=CH ^t Bu onto highly Brønsted acidic sulfated alumina (AlS). The proposed catalyst structure is supported by EXAFS, XANES, ICP, DRIFTS, elemental analysis, and SSNMR measurements and is in good agreement with DFT analysis. Catalyst 1 is highly effective for the hydrogenolysis of diverse linear and branched hydrocarbons, ranging from C2 to polyolefins. To the best of our knowledge, 1 exhibits one of the highest polyolefin hydrogenolysis activities (9,800 (CH ₂ units) ⋅ mol(Ta) ⁻¹ ⋅ h ⁻¹ at 200 °C/17 atm H ₂ ) reported to date in the peer‐reviewed literature. Unlike the AlS/ZrNp ₂ analog, the Ta catalyst is more thermally stable and offers multiple potential C−C bond activation pathways. For hydrogenolysis, AlS/TaNp _x is effective for a wide variety of pre‐ and post‐consumer polyolefin plastics and is not significantly deactivated by standard polyolefin additives at typical industrial concentrations.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001329; AC02-06CH11357; AC02-07CH11358

OSTI ID:: 2229179

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 135 Journal Issue: 50; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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