Electrocatalytic Hydrogenation of Phenol over Platinum and Rhodium: Unexpected Temperature Effects Resolved

doi:10.1021/acscatal.6b02296

Title: Electrocatalytic Hydrogenation of Phenol over Platinum and Rhodium: Unexpected Temperature Effects Resolved

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Abstract

Both electrocatalytic hydrogenation (ECH) and thermal catalytic hydrogenation (TCH) of phenol by Pt and Rh show a roll-over in rate with increasing temperature without changing the principal reaction pathways. The negative effect of tempera-ture for aqueous-phase phenol TCH and ECH on Pt and Rh is deduced to be from dehydrogenated phenol adsorbates, which block active sites. ECH and TCH rates increase similarly with increasing hydrogen chemical potential whether in-duced by applied potential or H2 pressure, both via increasing H coverage, and indirectly by removing site blockers, a strong effect at high temperature. This enables unprecedented phenol TCH rates at 60-100 °C.

Authors:

Singh, Nirala ^[1]; Song, Yang ^[2]; Gutiérrez, Oliver Y. ^[2]; Camaioni, Donald M. ^[3]; Campbell, Charles T. ^[4]; Lercher, Johannes A. ^[5]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
Technische Univ. Munchen, Garching (Germany)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Washington, Seattle, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Technische Univ. Munchen, Garching (Germany)

Publication Date:: 2016-10-04

Research Org.:: Univ. of Washington, Seattle, WA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1597974

Grant/Contract Number:: [FG02-96ER14630]

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: [ Journal Volume: 6; Journal Issue: 11]; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrogenation; electrocatalysis; poisoning; phenol; platinum; rhodium

Citation Formats


                    Singh, Nirala, Song, Yang, Gutiérrez, Oliver Y., Camaioni, Donald M., Campbell, Charles T., and Lercher, Johannes A. Electrocatalytic Hydrogenation of Phenol over Platinum and Rhodium: Unexpected Temperature Effects Resolved.  United States: N. p., 2016. 
        Web.  doi:10.1021/acscatal.6b02296.

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                    Singh, Nirala, Song, Yang, Gutiérrez, Oliver Y., Camaioni, Donald M., Campbell, Charles T., & Lercher, Johannes A. Electrocatalytic Hydrogenation of Phenol over Platinum and Rhodium: Unexpected Temperature Effects Resolved.  United States.  doi:10.1021/acscatal.6b02296.

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                    Singh, Nirala, Song, Yang, Gutiérrez, Oliver Y., Camaioni, Donald M., Campbell, Charles T., and Lercher, Johannes A. Tue .  
        "Electrocatalytic Hydrogenation of Phenol over Platinum and Rhodium: Unexpected Temperature Effects Resolved".  United States.  doi:10.1021/acscatal.6b02296.  https://www.osti.gov/servlets/purl/1597974.

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@article{osti_1597974,

  title        = {Electrocatalytic Hydrogenation of Phenol over Platinum and Rhodium: Unexpected Temperature Effects Resolved},

  author       = {Singh, Nirala and Song, Yang and Gutiérrez, Oliver Y. and Camaioni, Donald M. and Campbell, Charles T. and Lercher, Johannes A.},

  abstractNote = {Both electrocatalytic hydrogenation (ECH) and thermal catalytic hydrogenation (TCH) of phenol by Pt and Rh show a roll-over in rate with increasing temperature without changing the principal reaction pathways. The negative effect of tempera-ture for aqueous-phase phenol TCH and ECH on Pt and Rh is deduced to be from dehydrogenated phenol adsorbates, which block active sites. ECH and TCH rates increase similarly with increasing hydrogen chemical potential whether in-duced by applied potential or H2 pressure, both via increasing H coverage, and indirectly by removing site blockers, a strong effect at high temperature. This enables unprecedented phenol TCH rates at 60-100 °C.},

  doi          = {10.1021/acscatal.6b02296},

  journal      = {ACS Catalysis},

  number       = [11],

  volume       = [6],

  place        = {United States},

  year         = {2016},

  month        = {10}

}

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DOI: 10.1021/acscatal.6b02296

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