Fabrication of Low Loading Ag Electrodes for CO2 Reduction Reaction in Zero-Gap Electrolyzer
Authors: Alihosseinzadeh Amir , Unnikrishnan Anusree , Karan Kunal , Ponnurangam Sathish 
Published: July 2022

In recent years, there has been intense effort directed towards catalyst development and electrode design for electrochemical carbon dioxide reduction reaction (CO2RR) with an objective of achieving high production rate (current density) of desirable products including CO, CH3OH, CH4 and C2+ hydrocarbons. Silver electrocatalyst is reported to exhibit remarkable CO selectivity and high current density, both of which are requisite parameters for CO2RR electrolyzer scale up. Silver is still moderately priced and reduction of Ag loading in CO2RR electrode is one of the technological goals for electrolyzer development.
Most of the prior studies on Ag electrodes for CO2RR have utilized Ag nanoparticles, which are typically spray coated on a substrate from Ag or Ag-ionomer suspension resulting in high-Ag loading (> 1 mg/cm2 loading) and hence low mass specific activity (MSA) < 150 mA.mg-1
Ag. In this work, we developed a combined approach for Ag deposition using pulse electrodeposition (PE) and spray coating (SC) with an aim of decreasing Ag loading and increasing MSA. Such electrodes were found to exhibit high current densities and CO selectivity even with low Ag loading (< 0.5 mg/cm2).
Specifically, several different gas diffusion electrodes (GDE) prepared by pulse electrodeposition of silver, spray coating of Ag nanoparticles, and combination of the two were prepared by coating of Sigracet gas diffusion layer (GDL). Commercial IrO2 electrode and the fabricated silver electrode were utilized as the anode and cathode, respectively. The anode and the cathode were separated by a polymer electrolyte membrane, which was Sustainion® X37-50 Grade 60- an anion exchange membrane. 10 mM KHCO3 electrolyte was re-circulated at the anode using a pump while humidified CO2 gas was flowed through the cathode. CO2RR tests are performed in a zero-gap electrolyzer setup, at a temperature of 25 °C.
The main findings are summarized in the Figure below. The electrode prepared by pulse electrodeposition (PE) exhibits a low areal current density (~30 mA/cm2) but high mass-specific activity of 302 mA.mg-1
Ag. However, the selectivity for CO is low. On the other hand, spray coated (SC) electrodes yield higher CO selectivity and higher areal current density but mass specific activity is lower. By depositing silver sequentially, either pulse electrodeposition (PE) followed by spray coating (SC), i.e. the SC+PE electrode, or SC followed by PE (PE+SC electrode), both the mass-specific and areal current density increased drastically while CO selectivity remained high (99%). In particular, the current densities of the PE and SC electrodes are improved by 2 and 4.5 times, respectively, from 31 and 70 mA.cm-2 up to 136 mA.cm-2 on the SP+PE electrode, at the cell voltage of -3 V. Also, the CO selectivity of the electrodes is improved from 25 % (PE sample) and 81 % (SC sample) up to 99 % on the SC+PE electrode. The optimized electrode provided a catalyst layer with high surface coverage of silver on the GDL substrate at low Ag loadings (<0.5 mg/cm2). Further optimization of electrode is underway including modification of silver deposition and incorporation of ionomer to increase current density while maintaining the CO selectivity and durability of GDE. Details of the electrode fabrication and characterization as well as performance evaluation will be presented at the meeting.

Figure 1