• Koshy, David
• Bao, Zhenan
• Jaramillo, Thomas
• Higgins, Drew Christopher
• Abdellah, Ahmed
• Lee, Dong Un
• Chen, Shucheng
• Gallo, Allessandro
• Hahn, Christopher
• Nordlund, Dennis
• Chen, Gan
• Stevens, Michaela Burke
• Dull, Samuel

Abstract

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO 2 electroreduction (CO 2 R) to CO; this activity has been attributed to the presence of nitrogen-coordinated, single metal atom active sites. However, experimentally confirming Ni-N bonding and correlating CO 2 reduction (CO 2 R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni, N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO- 2 R to CO partial current density increased with increased Ni content before plateauing at 2 wt% which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft x-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.

Topics

• density
• pyrolysis
• Carbon
• Nitrogen
• current density
• X-ray spectroscopy