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Three Keggin-type heteropolyanions, namely H3PMo12O40·13H2O, (NH4)3PMo12O40·4H2O and H3PW12O40·13H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of the counter-cation (H+, NH4+) and the peripheral atoms (Mo, W) on the polymerization were investigated. It has been found that when the protons of H3PMo12O40·13H2O were replaced by the ammonium...