Rapid Polyolefin Hydrogenolysis by a Single‐Site Organo‐Tantalum Catalyst on a Super‐Acidic Support: Structure and Mechanism
Year: 2023
Type: article
Abstract: The novel electrophilic organo‐tantalum catalyst AlS/TaNpx (1) (Np=neopentyl) is prepared by chemisorption of the alkylidene Np3Ta=CHtBu 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 (CH2 units) ⋅ mol(Ta)−1 ⋅ h−1 at 200 °C/17 atm H2) reported to date in the peer‐reviewed literature. Unlike the AlS/ZrNp2 analog, the Ta catalyst is more thermally stable and offers multiple potential C−C bond activation pathways. For hydrogenolysis, AlS/TaNpx 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.
Authors: Qingheng Lai, Alexander H. Mason, Amol Agarwal, Wilson C. Edenfield, Xinrui Zhang, Takeshi Kobayashi, Yosi Kratish, Tobin J. Marks
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: bronze
Funders: National Science Foundation, U.S. Department of Energy, National Aeronautics and Space Administration, Dow Chemical Company, DuPont, Northwestern University, Iowa State University, Office of Science, Ames Research Center, Oak Ridge Institute for Science and Education, Quest High Performance Computing, Division of Electrical, Communications and Cyber Systems, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Argonne National Laboratory
Awards: G102163711, G107546177, G1166121473, NNCI: Soft Hybrid Nanotechnology Experimental (SHyNE) Resource, G1286251239, G1313983767, G1338583345, G1418315740, G1505794299, G1519358529, G1664757510, G1866217153, INSTITUTE FOR ENVIRONMENTAL CATALYSIS, G2001921306, NEW AWARD; TITLE: NORTHWESTERN UNIVERSITY FACILITY FOR CLEAN CATALYTIC PROCESS RESEARCH; PI: TOBIN J. MARKS, FOR CONSTRUCTION OF THE INSTITUTE FOR PROTEOMICS A ND NANOBIOTECHNOLOGY, G2101401529, G222768804, G2287611682, G2316606464, G2327333655, G2357880494, G249831736, G262962599, G285533474, G2887060908, G2917895714, G2980159964, G3010471893, G303010891, G3075337988, G316399430, G340565428, NEW AWARD; TITLE: NORTHWESTERN UNIVERSITY FACILITY FOR CLEAN CATALYTIC PROCESS RESEARCH; PI: TOBIN J. MARKS, G4120964173, G426311843, G473123490, G473396326, G4958141111, G498139845, G5106849484, G524707868, G5387317844, G5425137327, INSTITUTE FOR CATALYSIS IN ENERGY PROCESS, G5648016710, G5910536577, G5955693984, G5959670421, G601061201, G6017181652, G665223801, G6848031779, G6918803902, G7368700025, G7583137537, G7619220232, G8570346810, INSTITUTE FOR CATALYSIS IN ENERGY PROCESS, G9000239236, G969889393, G993149817
OpenAlex ID: W4388564120