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

DOI: 10.1016/j.jcat.2024.115597 DOI Help

Authors: Claudio Cometto (Università di Padova) , Giulia Marafon (Università di Padova and INSTM Research Unit) , Veronica Celorrio (Diamond Light Source) , Gonzalo Garcia (Universidad de La Laguna) , Steffi Y. Woo (Université Paris-Saclay, CNRS) , Enrico Paron (Università di Padova and INSTM Research Unit) , Alberto Zobelli (Université Paris-Saclay, CNRS) , Gregorio Bottaro (CNR-ICMATE and INSTM, Università di Padova) , Lidia Armelao (Università di Padova and INSTM Research Unit; Consiglio Nazionale delle Ricerche) , Elena Pastor (Universidad de La Laguna) , Alessandro Moretto (Università di Padova and INSTM Research Unit) , Laura Calvillo (Università di Padova and INSTM Research Unit)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of Catalysis , VOL 19

State: Published (Approved)
Published: August 2024
Diamond Proposal Number(s): 19850

Open Access Open Access

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

Journal Keywords: Co-polymerization synthesis; CO2 reduction; Heterogeneous molecular catalyst; DEMS; in situ XAS

Subject Areas: Chemistry, Materials, Energy

Instruments: B18-Core EXAFS

Added On: 12/06/2024 09:01


Discipline Tags:

Earth Sciences & Environment Sustainable Energy Systems Energy Climate Change Physical Chemistry Catalysis Chemistry Materials Science Nanoscience/Nanotechnology

Technical Tags:

Spectroscopy X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS)