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Aminopolysiloxane as Cu 2 O Photocathode Overlayer: Photocorrosion Inhibitor and Low Overpotential CO 2 ‐to‐formate Selectivity Promoter
Author(s) -
Galante Miguel T.,
Santiago Patrícia V. B.,
Yukuhiro Victor Y.,
Silva Leonardo A.,
Dos Reis Natália A.,
Pires Cléo T. G. V. M. T.,
Macedo Nadia G.,
Costa Luelc S.,
Fernandez Pablo S.,
Longo Claudia
Publication year - 2021
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202001638
Subject(s) - overpotential , overlayer , formate , chemistry , photochemistry , electrochemistry , selectivity , inorganic chemistry , faraday efficiency , amine gas treating , organic chemistry , catalysis , electrode
Cu 2 O, a photoactive p‐type semiconductor based on earth‐abundant elements, shows promising features for photoelectrochemical CO 2 reduction reaction (PEC CO2RR). However, despite the broad light absorption and appropriate conduction band edge energy, it promptly undergoes photocorrosion in PEC CO2RR conditions. Herein, we evaluate an amine‐functionalized polysiloxane (AF−PSi) as both protective layer and PEC CO2RR promoter via amine‐CO 2 adduct formation. Electrochemistry experiments and X‐ray diffraction showed that photostability is significantly enhanced with AF−PSi overlayer. Electrolyses experiments under visible light irradiation indicated selective production of formate with faradaic efficiency of 61 % at low overpotential. Detailed in situ FTIR studies revealed that amine groups bind to CO 2 to form carbamate species and that this process is favoured by cathodic polarization, confirming the dual role of AF−PSi layer.