Anderson-type polyoxometalate (POM) with general formula of [Hy(XO6)M6O18]n- (y=0-6, n=2-8, M=addenda atom, X=heteroatom) represents one of the basic topological structures among POM-type family. Anderson-type POMs have a planar arrangement and two terminal oxygen atoms attached to each addenda metal atom unlike other type. Thus, the Anderson-type POMs have high reactivity and various coordination modes. The various multifunctional organic-inorganic hybrid materials can be synthesized using the Anderson-type POMs as an inorganic building block. Another important feature of the Anderson-type POMs is the incorporation of the heteroatoms with various sizes and oxidation states, which can lead to tune chemical properties. No Anderson-type POMs with early transition metal ions in the heteroatom site have been reported previously. Recently, we reported the synthesis of titanium-containing Anderson-type POM, Na2K6Ti0.92W6.08O24∙12H2O (Ti-POM), which consists of pure inorganic framework built from a central Ti atom surrounded by six WO6 inorganic scaffold. Herein, in-depth studies were conducted to find optimal synthesis conditions such as composition and pH. The success of synthesis was confirmed with Powder X-ray Diffraction that the Ti-POM has a rhombohedral structure with space group of R-3m (No. 166) when the TiOSO4·xH2SO4∙yH2O/ Na2WO4∙2H2O molar ratio is in the range of 0.07 to 0.33. But outside of this range, other unwanted phases coexist. In a basic condition (pH=12), a single-phase Ti-POM with good crystallinity can be obtained, while a Keggin-type POM, NaxK10-x(H2W12O42), was formed through the decomposition of Ti-POM at pH lower than 7.

• Hye Ran Noh(University of Science and Technology (UST), Korea Atomic Energy Research Institute (KAERI))
• Jong-Yun Kim(University of Science and Technology (UST), Korea Atomic Energy Research Institute (KAERI))
• Tae-Hyeong Kim(Korea Atomic Energy Research Institute (KAERI))
• Jeongmook Lee(University of Science and Technology (UST), Korea Atomic Energy Research Institute (KAERI))
• Jung Hwan Park(Korea Atomic Energy Research Institute (KAERI), Korea Advanced Institute of Science and Technology (KAIST))
• Sang Ho Lim(University of Science and Technology (UST), Korea Atomic Energy Research Institute (KAERI)) Corresponding author