The water-soluble polypyridine copper complex [Cu(F3TPA)(ClO4)2] [1; F3TPA=tris(2-fluoro-6-pyridylmethyl)amine] catalyzes water oxidation in a pH 8.5 borate buffer at a relatively low overpotential of 610 mV. Assisted by photosensitizer and an electron acceptor, 1 also exhibits activity as a homogeneous catalyst for photo-induced O2 evolution with a maximum turnover frequency (TOF) of (1.58 ± 0.03) × 10(-1) s(-1) and a maximum turnover number (TON) of 11.61 ± 0.23. In comparison, the reference [Cu(TPA)(ClO4)2] [TPA=tris(2-pyridylmethyl)amine] displayed almost no activity under either set of conditions, implying the crucial role of the ligand in determining the behavior of the catalyst. Experimental evidence indicate the molecular catalytic nature of 1, leading to a potentially practical strategy to apply the copper complex in a photoelectrochemical device for water oxidation.
Here, we report a water-soluble copper(II) complex acting as a hydrogen evolution catalyst in a neutral aqueous solution, which could be further developed to form water reduction material through electrodeposition. The material with extremely low loading of 33 μg Cu cm −2 showed impressive TON value of 5876 and TOF of 734 h −1 in 8 h CPE experiment in a neutral phosphate buffer solution. In X-ray photoelectron spectroscopy (XPS), the high-resolution C 1s peak is corresponding to a CC bond at 284.8 eV, C−N bond at 285.6 eV, C−O bond at 286.4 eV, and two different types of nitrogen configurations at around 398.5 and 399.9 eV are ascribed to pyridinic CN and tertiary amine C−N bonds, respectively, which implies that the ligand might be incorporated into the copper active material. It is assumed that the presence of the ligand has an influence on the activity and stability of the deposit.
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