期刊
ACS APPLIED MATERIALS & INTERFACES
卷 13, 期 17, 页码 19927-19937出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c00243
关键词
in situ electrochemical liquid TEM; X-ray absorption spectroscopy; water oxidation; copper complexes; oxygen evolution reaction
资金
- University of Zurich Research Priority Program (URPP) for Solar Light to Chemical Energy Conversion (LightChEC)
- Swiss National Science Foundation (Sinergia grant) [CRSII2_160801]
- Institute for Advanced Studies in Basic Sciences
- National Elite Foundation
- Swiss National Science Foundation (SNF) [CRSII2_160801] Funding Source: Swiss National Science Foundation (SNF)
The research investigates the role of nanosized Cu oxide particles, ions, or clusters in the electrochemical OER with a mononuclear copper(II) complex with TMC. It is found that Cu oxide-based nanoparticles, rather than a molecular structure, serve as the true OER catalysts. This approach provides a roadmap for informed molecular catalyst design in the field of sustainable catalysis.
The design of molecular oxygen-evolution reaction (OER) catalysts requires fundamental mechanistic studies on their widely unknown mechanisms of action. To this end, copper complexes keep attracting interest as good catalysts for the OER, and metal complexes with TMC (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) stand out as active OER catalysts. A mononuclear copper complex, [Cu(TMC)(H2O)](NO3)(2) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), combined both key features and was previously reported to be one of the most active copper-complex-based catalysts for electrocatalytic OER in neutral aqueous solutions. However, the functionalities and mechanisms of the catalyst are still not fully understood and need to be clarified with advanced analytical studies to enable further informed molecular catalyst design on a larger scale. Herein, the role of nanosized Cu oxide particles, ions, or clusters in the electrochemical OER with a mononuclear copper(II) complex with TMC was investigated by operando methods, including in situ vis-spectroelectrochemistry, in situ electrochemical liquid transmission electron microscopy (EC-LTEM), and extended X-ray absorption fine structure (EXAFS) analysis. These combined experiments showed that Cu oxide-based nanoparticles, rather than a molecular structure, are formed at a significantly lower potential than required for OER and are candidates for being the true OER catalysts. Our results indicate that for the OER in the presence of a homogeneous metal complex-based (pre)catalyst, careful analyses and new in situ protocols for ruling out the participation of metal oxides or clusters are critical for catalyst development. This approach could be a roadmap for progress in the field of sustainable catalysis via informed molecular catalyst design. Our combined approach of in situ TEM monitoring and a wide range of complementary spectroscopic techniques will open up new perspectives to track the transformation pathways and true active species for a wide range of molecular catalysts.
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