Highly Efficient and Selective CO₂ Electro-Reduction to HCOOH on Sn Particle-Decorated Polymeric Carbon Nitride

Electrochemical conversion of CO₂ into liquid fuels by efficient and earth-abundant catalysts is of broad interest but remains a great challenge in renewable energy production and environmental remediation. Herein, a Sn particle-decorated polymeric carbon nitride (CN) electrocatalyst was successfully developed for efficient, durable, and highly selective CO₂ reduction to formic acid. High-resolution X-ray photoelectron spectroscopy confirmed that the metallic Sn particles and CN matrix are bound by strong chemical interaction, rendering the composite catalyst a stable structure. More notably, the electronic structure of Sn was well tuned to be highly electron-rich due to the electron transfer from N atoms of CN to Sn atoms via metal-support interactions, which favored the adsorption and activation of CO₂ molecules, promoted charge transport, and thus enhanced the electrochemical conversion of CO₂. The composite electrocatalyst demonstrated an excellent Faradaic efficiency of formic acid (FE_HCOOH) up to 96±2 % at the potential of −0.9 V vs. reversible hydrogen electrode, which remained at above 92 % during the electrochemical reaction of 10 h, indicating that the present Sn particle-decorated polymeric carbon nitride electrocatalyst is among the best in comparison with reported Sn-based electrocatalysts.