Synthesis and electrocatalytic reactivity for water oxidation of two cerium complexes
Two cerium complexes with and without manganese ion, [MnCe4(dipic)6(H2O)20][Ce(dipic)3]2·7H2O (dipic = dipicolinate) (1) and [Ce2(H2O)4(O2CMe)6][Ce(H2O)4(NO3)2(O2CMe)]2·2H2O·2MeOH
(2), have been prepared, and their electrocatalytic reactivity for water oxidation has been investigated. Compound 1 is a heterometallic 3d-4f compound which possesses four Ce(IV) ions, two Ce(III) ions, and one Mn(II). Compound 2 is composed of three neutral parts, one
of which is a dinuclear cerium molecule lying on an inversion center, and the other two are symmetric monomer units; the four cerium ions in 2 are all Ce(III). Electrochemical studies of 1 and 2 show that 1 can catalyze water oxidation at the potential ~1.5 V
with an overpotential of ca. 900 mV versus NHE. Control potential electrolysis (CPE) experiments at 1.50 V of 1 displayed a stable current density of 2.5 mA/cm2, and the calculated Faradaic efficiency is 60%. However, no electrocatalytic reactivity
was observed for 2. By comparison experiments, it was found that the electrocatalysis of 1 may result from the cooperative catalytic effect of the 4f cerium ion and 3d transition metal manganese ion.
Keywords: Heterometallic 3d-4f compound; cerium; electrocatalytic; manganese; water oxidation
Document Type: Research Article
Affiliations: 1: Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, PR China 2: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, China 3: School of Chemistry and Environmental Engineering, Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan, PR China
Publication date: 03 May 2018
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