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Selective Activation of Propane Using Intermediates Generated during Water Oxidation

Zhang, Haochen and Li, Chunsong and Lu, Qi and Cheng, Mu-Jeng and Goddard, William A., III (2021) Selective Activation of Propane Using Intermediates Generated during Water Oxidation. Journal of the American Chemical Society, 143 (10). pp. 3967-3974. ISSN 0002-7863.

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Electrochemical conversion of light alkanes to high-value oxygenates provides an attractive avenue for eco-friendly utilization of these hydrocarbons. However, such conversion under ambient conditions remains exceptionally challenging due to the high energy barrier of C–H bond cleavage. Herein, we investigated theoretically the partial oxidation of propane on a series of single atom alloys by using active intermediates generated during water oxidation as the oxidant. We show that by controlling the potential and pH, stable surface oxygen atoms can be maintained under water oxidation conditions. The free energy barrier for C–H bond cleavage by the surface oxygen can be as small as 0.54 eV, which can be surmounted easily at room temperature. Our calculations identified three promising surfaces as effective propane oxidation catalysts. Our complementary experiments demonstrated the partial oxidation of propane to acetone on Ni-doped Au surfaces. We also investigated computationally the steps leading to acetone formation. These studies show that the concept of exploiting intermediates generated in water oxidation as oxidants provides a fruitful strategy for electrocatalyst design to efficiently convert hydrocarbons into value-added chemicals.

Item Type:Article
Related URLs:
URLURL TypeDescription
Zhang, Haochen0000-0002-2774-5868
Li, Chunsong0000-0002-8016-1896
Lu, Qi0000-0002-0380-2629
Cheng, Mu-Jeng0000-0002-8121-0485
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2021 American Chemical Society. Received: January 12, 2021; Published: March 5, 2021. H.Z., C.L., and Q.L. acknowledge the financial support from the National Natural Science Foundation of China (Grant 21872079). M.J.C. acknowledges financial support from the Ministry of Science and Technology of the Republic of China under Grant MOST 109-2113-M-006-009. W.A.G. thanks the US NSF (CBET-2005250) for support. The authors thank Prof. Zhiqiang Niu for advice on underpotential deposition of Ni on Au. All NMR experiments were performed at BioNMR facility, Tsinghua University Branch of China National Center for Protein Sciences (Beijing). The authors thank Dr. Ning Xu for assistance in NMR data collection. Our calculations were supported by Center of High Performance Computing, Tsinghua University. The authors declare no competing financial interest.
Funding AgencyGrant Number
National Natural Science Foundation of China21872079
Ministry of Science and Technology (Taipei)MOST 109-2113-M-006-009
Subject Keywords:Free energy, Gold, Ketones, Bond cleavage, Water oxidation
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Issue or Number:10
Record Number:CaltechAUTHORS:20210308-132156702
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Official Citation:Selective Activation of Propane Using Intermediates Generated during Water Oxidation. Haochen Zhang, Chunsong Li, Qi Lu, Mu-Jeng Cheng, and William A. Goddard. Journal of the American Chemical Society 2021 143 (10), 3967-3974; DOI: 10.1021/jacs.1c00377
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108345
Deposited By: Tony Diaz
Deposited On:08 Mar 2021 23:32
Last Modified:06 Jun 2021 00:52

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