Controlling the Activity and Stability of Electrochemical Interfaces Using Atom-by-Atom Metal Substitution of Redox Species

Prabhakaran, Venkateshkumar; Lang, Zhongling; Clotet, Anna; Poblet, Josep M.; Johnson, Grant E.; Laskin, Julia

doi:10.1021/acsnano.8b06813

Title: Controlling the Activity and Stability of Electrochemical Interfaces Using Atom-by-Atom Metal Substitution of Redox Species

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Abstract

Understanding the molecular-level properties of electrochemically active ions at operating electrode–electrolyte interfaces (EEI) is key to the rational development of high-performance nanostructured surfaces for applications in energy technology. An electrochemical cell coupled with ion soft landing is employed to examine the effect of “atom-by-atom” metal substitution on the activity and stability of well-defined redox-active anions, PMo_xW_12–xO₄₀^3– (x = 0, 1, 2, 3, 6, 9, or 12) at nanostructured ionic liquid EEI. A striking observation made by in situ electrochemical measurements and further supported by theoretical calculations is that the substitution of only one to three tungsten atoms by molybdenum atoms in the PW₁₂O₄₀^3– anions results in a substantial spike in their first reduction potential. Specifically, PMo₃W₉O₄₀^3– showed the highest redox activity in both in situ electrochemical measurements and as part of a functional redox supercapacitor device, making it a “super-active redox anion” compared with all other PMo_xW_12–xO₄₀^3– species. Electronic structure calculations showed that metal substitution in PMo_xW_12–xO₄₀^3– causes the lowest unoccupied molecular orbital (LUMO) to protrude locally, making it the “active site” for reduction of the anion. Several critical factors contribute to the observed trend in redox activity including (i) multiple isomeric structures populated at room temperature, which affect themore »« less

Authors:

^[1];

^[2]; Clotet, Anna ^[2];

^[2]; Johnson, Grant E. ^[1];

^[3]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
Rovira i Virgili Univ., Tarragona (Spain). Dept. of Inorganic Physical Chemistry
Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry

Publication Date:: Thu Dec 06 00:00:00 EST 2018

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Rovira i Virgili Univ., Tarragona (Spain)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); Ministry of Science and Innovation (Spain); Generalitat de Catalunya

OSTI Identifier:: 1507752

Report Number(s):: PNNL-SA-132145
Journal ID: ISSN 1936-0851

Grant/Contract Number:: AC05-76RL01830; CTQ2017-87269-P; 2014SGR199; XRQTC

Resource Type:: Accepted Manuscript

Journal Name:: ACS Nano

Additional Journal Information:: Journal Volume: 13; Journal Issue: 1; Journal ID: ISSN 1936-0851

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrode−electrolyte interface; in situ electrochemistry; ion soft landing; Keggin polyoxometalate; mixed-addenda; redox supercapacitor

Citation Formats


                    Prabhakaran, Venkateshkumar, Lang, Zhongling, Clotet, Anna, Poblet, Josep M., Johnson, Grant E., and Laskin, Julia. Controlling the Activity and Stability of Electrochemical Interfaces Using Atom-by-Atom Metal Substitution of Redox Species.  United States: N. p., 2018. 
Web.  doi:10.1021/acsnano.8b06813.

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                    Prabhakaran, Venkateshkumar, Lang, Zhongling, Clotet, Anna, Poblet, Josep M., Johnson, Grant E., & Laskin, Julia. Controlling the Activity and Stability of Electrochemical Interfaces Using Atom-by-Atom Metal Substitution of Redox Species.  United States.  https://doi.org/10.1021/acsnano.8b06813

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                    Prabhakaran, Venkateshkumar, Lang, Zhongling, Clotet, Anna, Poblet, Josep M., Johnson, Grant E., and Laskin, Julia. Thu .  
"Controlling the Activity and Stability of Electrochemical Interfaces Using Atom-by-Atom Metal Substitution of Redox Species".  United States.  https://doi.org/10.1021/acsnano.8b06813.  https://www.osti.gov/servlets/purl/1507752.

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@article{osti_1507752,

  title        = {Controlling the Activity and Stability of Electrochemical Interfaces Using Atom-by-Atom Metal Substitution of Redox Species},

  author       = {Prabhakaran, Venkateshkumar and Lang, Zhongling and Clotet, Anna and Poblet, Josep M. and Johnson, Grant E. and Laskin, Julia},

  abstractNote = {Understanding the molecular-level properties of electrochemically active ions at operating electrode–electrolyte interfaces (EEI) is key to the rational development of high-performance nanostructured surfaces for applications in energy technology. An electrochemical cell coupled with ion soft landing is employed to examine the effect of “atom-by-atom” metal substitution on the activity and stability of well-defined redox-active anions, PMoxW12–xO403– (x = 0, 1, 2, 3, 6, 9, or 12) at nanostructured ionic liquid EEI. A striking observation made by in situ electrochemical measurements and further supported by theoretical calculations is that the substitution of only one to three tungsten atoms by molybdenum atoms in the PW12O403– anions results in a substantial spike in their first reduction potential. Specifically, PMo3W9O403– showed the highest redox activity in both in situ electrochemical measurements and as part of a functional redox supercapacitor device, making it a “super-active redox anion” compared with all other PMoxW12–xO403– species. Electronic structure calculations showed that metal substitution in PMoxW12–xO403– causes the lowest unoccupied molecular orbital (LUMO) to protrude locally, making it the “active site” for reduction of the anion. Several critical factors contribute to the observed trend in redox activity including (i) multiple isomeric structures populated at room temperature, which affect the experimentally determined reduction potential; (ii) substantial decrease of the LUMO energy upon replacement of W atoms with more-electronegative Mo atoms; and (iii) structural relaxation of the reduced species produced after the first reduction step. Our results illustrate a path to achieving superior performance of technologically relevant EEIs in functional nanoscale devices through understanding of the molecular-level electronic properties of specific electroactive species with “atom-by-atom” precision.},

  doi          = {10.1021/acsnano.8b06813},

  journal      = {ACS Nano},

  number       = 1,

  volume       = 13,

  place        = {United States},

  year         = {Thu Dec 06 00:00:00 EST 2018},

  month        = {Thu Dec 06 00:00:00 EST 2018}

}

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