4.8 Article

Acceleration of Electrochemical CO2 Reduction to Formate at the Sn/Reduced Graphene Oxide Interface

Journal

ACS CATALYSIS
Volume 11, Issue 6, Pages 3310-3318

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.0c04887

Keywords

carbon dioxide; electrochemical reduction; reduced graphene oxide; tin; scanning electrochemical cell microscopy; formate

Funding

  1. JST-PRESTO [JPMJPR18T8]
  2. JSPS [JP20H04628, JP20H04639, JP17H06460]
  3. JSPS KAKENHI [JP15H05422, JP18K14174, JP18H01774, JP19K15505, JP19H00915]
  4. Futaba Research Grant Program of the Futaba Foundation
  5. Toyota Mobility Foundation (TMF)
  6. Asahi Glass Foundation
  7. Hokuriku Bank
  8. Murata Science Foundation
  9. World Premier International Research Center Initiative (WPI) of MEXT, Japan
  10. CRDAM-IMR, Tohoku University [20G0002]
  11. KONDO-ZAIDAN

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Reduced graphene oxide (rGO) plays a crucial role in enhancing the CO2 adsorption ability of Sn/rGO composites, leading to a 4-fold increase compared to bare Sn catalysts. The oxidized functional groups of rGO provide adsorption sites for CO2 towards the adjacent Sn surface, promoting the production of formate while suppressing the formation of CO* near the surface. Experimental results show that CO2 reduction is accelerated at the interface of Sn/rGO, improving the Faradaic efficiency by 1.8 times compared to bare Sn catalysts.
Electrochemical CO2 reduction is a key technology to recycle CO2 as a renewable resource, but adsorbing CO2 on the catalyst surface is challenging. We explored the effects of reduced graphene oxide (rGO) in Sn/rGO composites and found that the CO2 adsorption ability of Sn/rGO was almost 4-times higher than that of bare Sn catalysts. Density functional theory calculations revealed that the oxidized functional groups of rGO offered adsorption sites for CO2 toward the adjacent Sn surface and that CO2-rich conditions near the surface facilitated the production of formate via COOH* formation while suppressing CO* formation. Scanning electrochemical cell microscopy directly indicated that CO2 reduction was accelerated at the interface, together with the kinetic suppression of undesirable and competitive hydrogen evolution at the interface. Thus, the synergism of Sn/rGO ensures a substantial/rapid supply of CO2 from the functional groups to the Sn surface, thereby enhancing the Faradaic efficiency 1.8-times compared with that obtained with bare Sn catalysts.

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