Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Nitrate Radical Facilitates Indirect Benzyl Alcohol Oxidation on Bismuth(III) Vanadate Photoelectrodes

Abstract

Abstract Bismuth(III) vanadate (BiVO 4 ) films show activity for direct benzyl alcohol (PhCH 2 OH) oxidation to benzaldehyde (PhCHO) in acetonitrile solvent. Introducing tetrabutylammonium nitrate (Bu 4 NNO 3 ) drastically reduces the overpotential required to generate the PhCHO product while maintaining a high faradaic efficiency (FE) >90 %. BiVO 4 corrosion accompanies PhCH 2 OH oxidation. However, the presence of nitrate ions (NO 3 − ) results in significantly less bismuth‐ and vanadium‐ion leaching (determined by ICP‐MS analysis), as well as reduced surface roughening (determined by SEM imaging). In this reaction, it is proposed that rate‐determining NO 3 − oxidation generates a highly reactive nitrate radical (NO 3 ⋅) that reacts with PhCH 2 OH by hydrogen‐atom abstraction (HAT). NO 3 − is stoichiometrically consumed by the irreversible formation of electrochemically inert HNO 3 , characterized by an EC i mechanism, rather than a catalytic EC′ mechanism. In the presence of PhCH 2 OH, NO 3 − oxidation on BiVO 4 becomes more facile; every order of magnitude increase in PhCH 2 OH concentration shifts the NO 3 − / NO 3 ⋅ equilibrium potential negatively by 200 mV. The shift results from the introduction of a consumptionmore » pathway for the nitrate radical intermediate via a coupled chemical step with benzyl alcohol. This report is the first example of photoelectrochemical NO 3 ⋅ generation to initiate indirect PhCH 2 OH oxidation.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Michigan, Ann Arbor, MI (United States)
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1780868
Alternate Identifier(s):
OSTI ID: 1664555
Grant/Contract Number:  
SC0006587; DMR-0420785
Resource Type:
Accepted Manuscript
Journal Name:
ChemElectroChem
Additional Journal Information:
Journal Volume: 7; Journal Issue: 18; Journal ID: ISSN 2196-0216
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Terry, Bradley D., DiMeglio, John L., Cousineau, John P., and Bartlett, Bart M. Nitrate Radical Facilitates Indirect Benzyl Alcohol Oxidation on Bismuth(III) Vanadate Photoelectrodes. United States: N. p., 2020. Web. doi:10.1002/celc.202000911.
Copy to clipboard
Terry, Bradley D., DiMeglio, John L., Cousineau, John P., & Bartlett, Bart M. Nitrate Radical Facilitates Indirect Benzyl Alcohol Oxidation on Bismuth(III) Vanadate Photoelectrodes. United States. https://doi.org/10.1002/celc.202000911
Copy to clipboard
Terry, Bradley D., DiMeglio, John L., Cousineau, John P., and Bartlett, Bart M. Tue . "Nitrate Radical Facilitates Indirect Benzyl Alcohol Oxidation on Bismuth(III) Vanadate Photoelectrodes". United States. https://doi.org/10.1002/celc.202000911. https://www.osti.gov/servlets/purl/1780868.
Copy to clipboard
@article{osti_1780868,
title = {Nitrate Radical Facilitates Indirect Benzyl Alcohol Oxidation on Bismuth(III) Vanadate Photoelectrodes},
author = {Terry, Bradley D. and DiMeglio, John L. and Cousineau, John P. and Bartlett, Bart M.},
abstractNote = {Abstract Bismuth(III) vanadate (BiVO 4 ) films show activity for direct benzyl alcohol (PhCH 2 OH) oxidation to benzaldehyde (PhCHO) in acetonitrile solvent. Introducing tetrabutylammonium nitrate (Bu 4 NNO 3 ) drastically reduces the overpotential required to generate the PhCHO product while maintaining a high faradaic efficiency (FE) >90 %. BiVO 4 corrosion accompanies PhCH 2 OH oxidation. However, the presence of nitrate ions (NO 3 − ) results in significantly less bismuth‐ and vanadium‐ion leaching (determined by ICP‐MS analysis), as well as reduced surface roughening (determined by SEM imaging). In this reaction, it is proposed that rate‐determining NO 3 − oxidation generates a highly reactive nitrate radical (NO 3 ⋅) that reacts with PhCH 2 OH by hydrogen‐atom abstraction (HAT). NO 3 − is stoichiometrically consumed by the irreversible formation of electrochemically inert HNO 3 , characterized by an EC i mechanism, rather than a catalytic EC′ mechanism. In the presence of PhCH 2 OH, NO 3 − oxidation on BiVO 4 becomes more facile; every order of magnitude increase in PhCH 2 OH concentration shifts the NO 3 − / NO 3 ⋅ equilibrium potential negatively by 200 mV. The shift results from the introduction of a consumption pathway for the nitrate radical intermediate via a coupled chemical step with benzyl alcohol. This report is the first example of photoelectrochemical NO 3 ⋅ generation to initiate indirect PhCH 2 OH oxidation.},
doi = {10.1002/celc.202000911},
journal = {ChemElectroChem},
number = 18,
volume = 7,
place = {United States},
year = {Tue Sep 15 00:00:00 EDT 2020},
month = {Tue Sep 15 00:00:00 EDT 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/celc.202000911
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Efficient Aerobic Oxidation of Secondary Alcohols at Ambient Temperature with an ABNO/NO x Catalyst System
journal, October 2013

  • Lauber, Markus B.; Stahl, Shannon S.
  • ACS Catalysis, Vol. 3, Issue 11
  • DOI: 10.1021/cs400746m

Electrochemical oxidation of alcohols: Part II preparative anodic oxidation of secondary alkanols employing lithium nitrate
journal, January 1980

Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium-Sulfur Batteries
journal, October 2016

  • Peng, Hong-Jie; Zhang, Ge; Chen, Xiang
  • Angewandte Chemie International Edition, Vol. 55, Issue 42
  • DOI: 10.1002/anie.201605676

Enhanced Activity and Acid pH Stability of Prussian Blue-type Oxygen Evolution Electrocatalysts Processed by Chemical Etching
journal, December 2016

  • Han, Lijuan; Tang, Pengyi; Reyes-Carmona, Álvaro
  • Journal of the American Chemical Society, Vol. 138, Issue 49
  • DOI: 10.1021/jacs.6b09778

Nitrate-Mediated Alcohol Oxidation on Cadmium Sulfide Photocatalysts
journal, May 2019

Selective Activation of Benzyl Alcohol Coupled with Photoelectrochemical Water Oxidation via a Radical Relay Strategy
journal, April 2020

Combined biomass valorization and hydrogen production in a photoelectrochemical cell
journal, March 2015

  • Cha, Hyun Gil; Choi, Kyoung-Shin
  • Nature Chemistry, Vol. 7, Issue 4, p. 328-333
  • DOI: 10.1038/nchem.2194

Selective oxidation of benzyl alcohol by two phase electrolysis using nitrate as mediator
journal, January 2012

  • Christopher, C.; Lawrence, S.; Bosco, A. John
  • Catalysis Science & Technology, Vol. 2, Issue 4
  • DOI: 10.1039/c2cy00424k

Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans
journal, April 1995

New Reaction Pathway Induced by Plasmon for Selective Benzyl Alcohol Oxidation on BiOCl Possessing Oxygen Vacancies
journal, February 2017

  • Li, Hao; Qin, Feng; Yang, Zhiping
  • Journal of the American Chemical Society, Vol. 139, Issue 9
  • DOI: 10.1021/jacs.6b12850

Semiconducting materials for photoelectrochemical energy conversion
journal, January 2016

Photoelectrochemical Oxidation of Benzylic Alcohol Derivatives on BiVO 4 /WO 3 under Visible Light Irradiation
journal, September 2017

  • Tateno, Hiroyuki; Miseki, Yugo; Sayama, Kazuhiro
  • ChemElectroChem, Vol. 4, Issue 12
  • DOI: 10.1002/celc.201700710

Distinguishing ionic and radical mechanisms of hydroxylamine mediated electrocatalytic alcohol oxidation using NO–H bond dissociation energies
journal, January 2018

  • Dao, Rina; Zhao, Chenxuan; Yao, Jia
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 44
  • DOI: 10.1039/C8CP06134C

Impacts of the Regeneration Pathways of the Oxoammonium Cation on Electrochemical Nitroxyl Radical-Mediated Alcohol Oxidation
journal, November 2019

  • Taitt, Brandon J.; Bender, Michael T.; Choi, Kyoung-Shin
  • ACS Catalysis, Vol. 10, Issue 1
  • DOI: 10.1021/acscatal.9b03241

Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Kinetics and mechanism
journal, July 1995

Visible light photooxidation of nitrate: the dawn of a nocturnal radical
journal, January 2015

  • Hering, T.; Slanina, T.; Hancock, A.
  • Chemical Communications, Vol. 51, Issue 30
  • DOI: 10.1039/C5CC01580D

Nanoporous BiVO4 Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting
journal, February 2014

Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO‐Mediated Oxidation of 5‐Hydroxymethylfurfural
journal, July 2019

  • Chadderdon, David J.; Wu, Li‐Pin; McGraw, Zachary A.
  • ChemElectroChem, Vol. 6, Issue 13
  • DOI: 10.1002/celc.201900482

Electrochemical selective oxidation of aromatic alcohols with sodium nitrate mediator in biphasic medium at ambient temperature
journal, June 2012

Prediction of acidity in acetonitrile solution with COSMO-RS
journal, April 2009

  • Eckert, Frank; Leito, Ivo; Kaljurand, Ivari
  • Journal of Computational Chemistry, Vol. 30, Issue 5
  • DOI: 10.1002/jcc.21103

Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium-Sulfur Batteries
journal, October 2016

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin
journal, April 2013

  • Rahimi, Alireza; Azarpira, Ali; Kim, Hoon
  • Journal of the American Chemical Society, Vol. 135, Issue 17, p. 6415-6418
  • DOI: 10.1021/ja401793n

Mechanistic Studies of O 2 -Based Sulfoxidations Catalyzed by NO x /Br Systems
journal, September 2011

  • Luo, Zhen; Geletii, Yurii V.; Hillesheim, Daniel A.
  • ACS Catalysis, Vol. 1, Issue 10
  • DOI: 10.1021/cs2003643

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators
journal, June 2016

Electrochemical Azidooxygenation of Alkenes Mediated by a TEMPO–N 3 Charge-Transfer Complex
journal, August 2018

  • Siu, Juno C.; Sauer, Gregory S.; Saha, Ambarneil
  • Journal of the American Chemical Society, Vol. 140, Issue 39
  • DOI: 10.1021/jacs.8b06744

A Practical Beginner’s Guide to Cyclic Voltammetry
journal, November 2017

  • Elgrishi, Noémie; Rountree, Kelley J.; McCarthy, Brian D.
  • Journal of Chemical Education, Vol. 95, Issue 2
  • DOI: 10.1021/acs.jchemed.7b00361

Photoelectrochemical oxidation of organic substrates in organic media
journal, August 2017

Charging a Li–O2 battery using a redox mediator
journal, May 2013

  • Chen, Yuhui; Freunberger, Stefan A.; Peng, Zhangquan
  • Nature Chemistry, Vol. 5, Issue 6
  • DOI: 10.1038/nchem.1646
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: