Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO reduction in water
Wang, Jia-Wei (Barcelona Institute of Science and Technology (BIST))
Zhao, Fengyi (Emory University. Department of Chemistry)
Velasco, Lucia (Instituto de Ciencia de Materiales de Madrid)
Sauvan, Maxime (Instituto de Ciencia de Materiales de Madrid)
Moonshiram, Dooshaye (Instituto de Ciencia de Materiales de Madrid)
Salati, Martina (Barcelona Institute of Science and Technology (BIST))
Luo, Zhi-Mei (Barcelona Institute of Science and Technology (BIST))
He, Sheng (Emory University. Department of Chemistry)
Jin, Tao (Emory University. Department of Chemistry)
Mu, Yan-Fei (Tianjin University of Technology)
Ertem, Mehmed Z. (Brookhaven National Laboratory)
Lian, Tianquan (Emory University. Department of Chemistry)
Llobet Dalmases, Antoni (Universitat Autònoma de Barcelona. Departament de Química)

Data:	2024
Resum:	The selective photoreduction of CO2 in aqueous media based on earth-abundant elements only, is today a challenging topic. Here we present the anchoring of discrete molecular catalysts on organic polymeric semiconductors via covalent bonding, generating molecular hybrid materials with well-defined active sites for CO2 photoreduction, exclusively to CO in purely aqueous media. The molecular catalysts are based on aryl substituted Co phthalocyanines that can be coordinated by dangling pyridyl attached to a polymeric covalent triazine framework that acts as a light absorber. This generates a molecular hybrid material that efficiently and selectively achieves the photoreduction of CO2 to CO in KHCO3 aqueous buffer, giving high yields in the range of 22 mmol g-1 (458 μmol g-1 h-1) and turnover numbers above 550 in 48 h, with no deactivation and no detectable H2. The electron transfer mechanism for the activation of the catalyst is proposed based on the combined results from time-resolved fluorescence spectroscopy, in situ spectroscopies and quantum chemical calculations.
Ajuts:	European Commission 101006839 Agencia Estatal de Investigación PID2019-111086RA-I00 Agencia Estatal de Investigación PID2022-143013OB-I00 Agencia Estatal de Investigación CNS2023-145046 Agencia Estatal de Investigación TED2021-132757B-I00 Agencia Estatal de Investigación RYC2020-029863-I Agencia Estatal de Investigación PID2019-111617RB-I00 Agencia Estatal de Investigación PRE2020-093789 Agencia Estatal de Investigación PID2022-140143OB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1631 Agencia Estatal de Investigación CEX2019-000925-S
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, i la comunicació pública de l'obra, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original. No es permet la creació d'obres derivades.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Publicat a:	Nature communications, Vol. 15 (November 2024) , art. 9779, ISSN 2041-1723

DOI: 10.1038/s41467-024-54026-2
PMID: 39532887

14 p, 5.0 MB

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