New lithium tungstophosphate complex. synthesis, crystal structure. Catalytic properties of a tetranuclear cobalt complex with tungstenphosphate ligands and lithium countercation in the reaction of photochemical water oxidation in artificial photosynthesis

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Abstract

Polyoxotungstophosphate complex Li7[γ-PW10O36] · 7H2O was synthesized. Structure was studied by the X-ray method. Rhombic crystals, space group P21212, a = 12.401(3) b = 18.948(4), c = 9.636(2) Å, V = 2265 Å3, Z = 2 (the heteropolyanion sits on a crystallographic twofold axis), λ = 0.71069 Å. The complex is thermostable. The interaction of Li7W10PO36 with Co(NO3)2 forms a tetranuclear complex Co(II) Li7[Co4(H2O)2(γ-PW10O36)2] · 36H2O – an effective catalyst for the water oxidation to O2. The number of turns of the catalyst is TON = 330, the quantum yield of photogenerated oxygen is ФO₂ = 0.46.

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About the authors

Z. M. Dzhabieva

Federal Research Center for Problems of Chemical Physics and Medical Chemistry of the Russian Academy of Sciences

Email: dzhabiev@icp.ac.ru
Russian Federation, Chernogolovka

G. V. Shilov

Federal Research Center for Problems of Chemical Physics and Medical Chemistry of the Russian Academy of Sciences

Email: dzhabiev@icp.ac.ru
Russian Federation, Chernogolovka

L. V. Avdeeva

Federal Research Center for Problems of Chemical Physics and Medical Chemistry of the Russian Academy of Sciences

Email: dzhabiev@icp.ac.ru
Russian Federation, Chernogolovka

T. A. Savinykh

Federal Research Center for Problems of Chemical Physics and Medical Chemistry of the Russian Academy of Sciences

Email: dzhabiev@icp.ac.ru
Russian Federation, Chernogolovka

T. S. Dzhabiev

Federal Research Center for Problems of Chemical Physics and Medical Chemistry of the Russian Academy of Sciences

Author for correspondence.
Email: dzhabiev@icp.ac.ru
Russian Federation, Chernogolovka

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2. Fig. 1. Crystal structure of heteropolyanion Li7[γ-PW10O36] · 7H2O

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3. Fig. 2. 31P NMR spectrum of Li7PW10O36 (H2O/D2O, 400 MHz) in sodium phosphate buffer solution, pH 8, 25°C, the chemical shift (δ) with respect to the reference standard, 85% H3PO4, is -13.2 m.d

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4. Fig. 3. IR spectrum of the tetra-nuclear cobalt complex Li7[Co4(H2O)2 - (γ-PW10O36)2] - 36H2O

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5. Fig. 4. Electronic absorption spectrum of the complex Li7[Co4(H2O)2 - (γ-PW10O36)2] - 36H2O (500 μmol) at λ = 580 nm in 0.1 M sodium phosphate buffer solution, pH 8, cuvette thickness l = 1 cm

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6. Fig. 5. Thermogravimetric analysis curves of Li7[Co4(H2O)2 - (γ-PW10O36)2] - 36H2O complex in nitrogen atmosphere: 1 - TG; 2 - DTG. Heating rate 5 deg/min

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7. Fig. 6. Kinetics of oxygen formation in the photocatalytic system in the presence of catalysts: 1 - Li7[Co4(H2O)2(γ-PW9O34)2] - 36H2O (Li7Co4), 2 - Li10[{Ru4(μ-O)4(μ-OH)2(H2O)4} - (γ-SiW10O36)2] - 10H2O (Li10Ru4), 3 - Rb8K2[{Ru4(μ-O)4(μ-OH)2(H2O)4} - (γ-SiW10O36)2] - 25H2O (Rb8K2Ru4). Conditions: DRSH-1000 lamp, light filter λ = 450 nm, dquartz reactor = 4 cm, Vp = 48 mL, 1 mM [Ru(bpy)3]2+, 5 mM Na2S2O8, 5 μM catalyst. 1 - 80 mM sodium phosphate buffer; 2 - 80 mM sodium phosphate buffer; 3 - 3 M H2SO4

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