Block copolymer templating syntheses of ordered large-pore stable mesoporous aluminophosphates and Fe-aluminophosphate based on an "acid-base pair" route

Limin Wang, Bozhi Tian, Jie Fan, Xiaoying Liu, Haifeng Yang, Chengzhong Yu, Bo Tu, Dongyuan Zhao

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77 Scopus citations

Abstract

Ordered large-pore (up to 12 nm) and stable mesoporous aluminophosphates (AlPO) have been synthesized by using block copolymer (EO106PO70 EO106, Pluronic F127) as a structure-directing agent. The selection of inorganic precursors is based on an "acid-base pair" route. Three acid-base pair, including AlCl3/H3PO4, AlCl3/OP (OCH3)3 and Al(OC4H9)3/PCl3 are confirmed to be efficient for the assembly of periodic mesoporous frameworks. Ordered 2-D hexagonal mesoporous aluminophosphates can be obtained by using AlCl3/H3PO4 as precursors, while disordered mesoporous aluminophosphates are produced by using AlCl3/OP(OCH3)3 or Al(OC4H9)3/PCl3 as precursors. BET surface areas and pore sizes of the products vary from 261 to 115 m2/g and from 9.4 to 12 nm, respectively. The solution and solid state 27Al and31P MAS NMR were used to characterize the chemical environment of aluminium and phosphorus before and after the formation of mesostructured AlPO products, which simultaneously allows us to evaluate the efficiency of inorganic-inorganic (I-I) interactions (Al-O-P) of different acid-base pair. Both 27Al and 31P MAS NMR results show that among the three acid-base pair, AlCl3/H3PO4 pair interacts more readily with each other than the other two pairs [AlCl3/ OP(OCH3)3, Al(OC4H9 3/ PCl3], and tends to form rigid framework before calcination. The detailed structural characterizations reveal that strong I-I interactions (Al-O-P) between inorganic precursors will lead to a final mesoporous material with high structure regularity. This method can also be applied to synthesize iron-incorporated aluminophosphate (FeAlPO) with highly ordered 2-D hexagonal structure. BET surface are a and pore size of FeAlPO prepared with Fe/Al=0.1 (molar ratio) are 181 m2/g and 8.9 nm, respectively. Electron spin resonance (ESR) and UV-vis spectra were employed to characterize the chemical state of Fe3+ ion.

Original languageEnglish
Pages (from-to)123-133
Number of pages11
JournalMicroporous and Mesoporous Materials
Volume67
Issue number2-3
DOIs
StatePublished - 6 Feb 2004
Externally publishedYes

Keywords

  • Aluminophosphate
  • Block copolymer
  • Large pore
  • Mesoporous materials
  • Synthesis

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