Polyoxometalate-Promoted Electrocatalytic CO2 Reduction at Nanostructured Silver in Dimethylformamide

SiXuan Guo, Fengwang Li, Lu Chen, Douglas R Macfarlane, Jie Zhang

Research output: Contribution to journalArticleResearchpeer-review

14 Citations (Scopus)

Abstract

Electrochemical reduction of CO2 is a promising method to convert CO2 into fuels or useful chemicals, such as carbon monoxide (CO), hydrocarbons, and alcohols. In this study, nanostructured Ag was obtained by electrodeposition of Ag in the presence of a Keggin type polyoxometalate, [PMo12O40]3- (PMo). Metallic Ag is formed upon reduction of Ag+. Adsorption of PMo on the surface of the newly formed Ag lowers its surface energy thus stabilizes the nanostructure. The electrocatalytic performance of this Ag-PMo nanocomposite for CO2 reduction was evaluated in a CO2 saturated dimethylformamide medium containing 0.1 M [n-Bu4N]PF6 and 0.5% (v/v) added H2O. The results show that this Ag-PMo nanocomposite can catalyze the reduction of CO2 to CO with an onset potential of -1.70 V versus Fc0/+, which is only 0.29 V more negative than the estimated reversible potential (-1.41 V) for this process and 0.70 V more positive than that on bulk Ag metal. High faradaic efficiencies of about 90% were obtained over a wide range of applied potentials. A Tafel slope of 60 mV dec-1 suggests that rapid formation of CO2 •- is followed by the rate-determining protonation step. This is consistent with the voltammetric data which suggest that the reduced PMo interacts strongly with CO2 (and presumably CO2 •-) and hence promotes the formation of CO2 •-.

Original languageEnglish
Pages (from-to)12690-12697
Number of pages8
JournalACS Applied Materials and Interfaces
Volume10
Issue number15
DOIs
Publication statusPublished - 18 Apr 2018

Keywords

  • COreduction
  • dimethylformamide
  • electrocatalysis
  • polyoxometalate
  • silver

Cite this

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title = "Polyoxometalate-Promoted Electrocatalytic CO2 Reduction at Nanostructured Silver in Dimethylformamide",
abstract = "Electrochemical reduction of CO2 is a promising method to convert CO2 into fuels or useful chemicals, such as carbon monoxide (CO), hydrocarbons, and alcohols. In this study, nanostructured Ag was obtained by electrodeposition of Ag in the presence of a Keggin type polyoxometalate, [PMo12O40]3- (PMo). Metallic Ag is formed upon reduction of Ag+. Adsorption of PMo on the surface of the newly formed Ag lowers its surface energy thus stabilizes the nanostructure. The electrocatalytic performance of this Ag-PMo nanocomposite for CO2 reduction was evaluated in a CO2 saturated dimethylformamide medium containing 0.1 M [n-Bu4N]PF6 and 0.5{\%} (v/v) added H2O. The results show that this Ag-PMo nanocomposite can catalyze the reduction of CO2 to CO with an onset potential of -1.70 V versus Fc0/+, which is only 0.29 V more negative than the estimated reversible potential (-1.41 V) for this process and 0.70 V more positive than that on bulk Ag metal. High faradaic efficiencies of about 90{\%} were obtained over a wide range of applied potentials. A Tafel slope of 60 mV dec-1 suggests that rapid formation of CO2 •- is followed by the rate-determining protonation step. This is consistent with the voltammetric data which suggest that the reduced PMo interacts strongly with CO2 (and presumably CO2 •-) and hence promotes the formation of CO2 •-.",
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author = "SiXuan Guo and Fengwang Li and Lu Chen and Macfarlane, {Douglas R} and Jie Zhang",
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Polyoxometalate-Promoted Electrocatalytic CO2 Reduction at Nanostructured Silver in Dimethylformamide. / Guo, SiXuan; Li, Fengwang; Chen, Lu; Macfarlane, Douglas R; Zhang, Jie.

In: ACS Applied Materials and Interfaces, Vol. 10, No. 15, 18.04.2018, p. 12690-12697.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Polyoxometalate-Promoted Electrocatalytic CO2 Reduction at Nanostructured Silver in Dimethylformamide

AU - Guo, SiXuan

AU - Li, Fengwang

AU - Chen, Lu

AU - Macfarlane, Douglas R

AU - Zhang, Jie

PY - 2018/4/18

Y1 - 2018/4/18

N2 - Electrochemical reduction of CO2 is a promising method to convert CO2 into fuels or useful chemicals, such as carbon monoxide (CO), hydrocarbons, and alcohols. In this study, nanostructured Ag was obtained by electrodeposition of Ag in the presence of a Keggin type polyoxometalate, [PMo12O40]3- (PMo). Metallic Ag is formed upon reduction of Ag+. Adsorption of PMo on the surface of the newly formed Ag lowers its surface energy thus stabilizes the nanostructure. The electrocatalytic performance of this Ag-PMo nanocomposite for CO2 reduction was evaluated in a CO2 saturated dimethylformamide medium containing 0.1 M [n-Bu4N]PF6 and 0.5% (v/v) added H2O. The results show that this Ag-PMo nanocomposite can catalyze the reduction of CO2 to CO with an onset potential of -1.70 V versus Fc0/+, which is only 0.29 V more negative than the estimated reversible potential (-1.41 V) for this process and 0.70 V more positive than that on bulk Ag metal. High faradaic efficiencies of about 90% were obtained over a wide range of applied potentials. A Tafel slope of 60 mV dec-1 suggests that rapid formation of CO2 •- is followed by the rate-determining protonation step. This is consistent with the voltammetric data which suggest that the reduced PMo interacts strongly with CO2 (and presumably CO2 •-) and hence promotes the formation of CO2 •-.

AB - Electrochemical reduction of CO2 is a promising method to convert CO2 into fuels or useful chemicals, such as carbon monoxide (CO), hydrocarbons, and alcohols. In this study, nanostructured Ag was obtained by electrodeposition of Ag in the presence of a Keggin type polyoxometalate, [PMo12O40]3- (PMo). Metallic Ag is formed upon reduction of Ag+. Adsorption of PMo on the surface of the newly formed Ag lowers its surface energy thus stabilizes the nanostructure. The electrocatalytic performance of this Ag-PMo nanocomposite for CO2 reduction was evaluated in a CO2 saturated dimethylformamide medium containing 0.1 M [n-Bu4N]PF6 and 0.5% (v/v) added H2O. The results show that this Ag-PMo nanocomposite can catalyze the reduction of CO2 to CO with an onset potential of -1.70 V versus Fc0/+, which is only 0.29 V more negative than the estimated reversible potential (-1.41 V) for this process and 0.70 V more positive than that on bulk Ag metal. High faradaic efficiencies of about 90% were obtained over a wide range of applied potentials. A Tafel slope of 60 mV dec-1 suggests that rapid formation of CO2 •- is followed by the rate-determining protonation step. This is consistent with the voltammetric data which suggest that the reduced PMo interacts strongly with CO2 (and presumably CO2 •-) and hence promotes the formation of CO2 •-.

KW - COreduction

KW - dimethylformamide

KW - electrocatalysis

KW - polyoxometalate

KW - silver

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U2 - 10.1021/acsami.8b01042

DO - 10.1021/acsami.8b01042

M3 - Article

VL - 10

SP - 12690

EP - 12697

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

SN - 1944-8244

IS - 15

ER -