Covalent stabilization of copper porphyrin into carbon nitride for the catalytic reduction of CO2

• DOI: 10.1016/j.jcat.2024.115597
• Publication Date: 2024-06-06T23:57:45Z
• Authors: Claudio Cometto; Giulia Marafon; Verónica Celorrio; Gonzalo García; Steffi Y. Woo; Enrico Paron; Alberto Zobelli; Gregorio Bottaro; Lidia Armelao; Elena Pastor; Alessandro Moretto; Laura Calvillo
• Keywords: Methyl formate; Carbon nitride

The development of active, selective, and durable (photo)electrocatalytic hybrid systems by combining molecular catalysts semiconductor substrates is crucial for efficiently converting solar light into high-value products. Herein, a one-step synthesis method to obtain carbon nitride (CN) nanosheets, which allows the direct covalent polymerization with catalysts, was developed. Copper-porphyrin (CuPor) units were embedded in CN structure as case-study. single materials fully characterized microscopic spectroscopic techniques tested (photo)electrocatalysts CO2 reduction reaction (CO2RR) aqueous solution. Experimental evidence confirmed an effective boost photoelectrocatalytic activity introducing CuPor units. Formate identified only CO2RR product on both CuPor-CN, simultaneously hydrogen from competitive evolution reaction. However, formate/hydrogen ratio higher when material used catalyst, suggesting synergetic effect between CN, that favors hinders HER. In addition, stability matrix under catalytic conditions studied situ X-ray absorption. No changes Cu porphyrin or formation copper clusters/nanoparticles observed function applied potential nor after accelerated ageing treatment, able stabilize sites avoiding their agglomeration.