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

doi:10.1016/j.micromeso.2003.11.007

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

^*Corresponding author for this work

Fudan University

Research output: Contribution to journal › Article › peer-review

78 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 language	English
Pages (from-to)	123-133
Number of pages	11
Journal	Microporous and Mesoporous Materials
Volume	67
Issue number	2-3
DOIs	https://doi.org/10.1016/j.micromeso.2003.11.007
State	Published - 6 Feb 2004
Externally published	Yes

Keywords

Aluminophosphate
Block copolymer
Large pore
Mesoporous materials
Synthesis

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10.1016/j.micromeso.2003.11.007

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@article{3e472e48628249f2a527fda1b66a588b,

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

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.",

keywords = "Aluminophosphate, Block copolymer, Large pore, Mesoporous materials, Synthesis",

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

year = "2004",

month = feb,

day = "6",

doi = "10.1016/j.micromeso.2003.11.007",

language = "英语",

volume = "67",

pages = "123--133",

journal = "Microporous and Mesoporous Materials",

issn = "1387-1811",

publisher = "Elsevier B.V.",

number = "2-3",

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TY - JOUR

T1 - Block copolymer templating syntheses of ordered large-pore stable mesoporous aluminophosphates and Fe-aluminophosphate based on an "acid-base pair" route

AU - Wang, Limin

AU - Tian, Bozhi

AU - Fan, Jie

AU - Liu, Xiaoying

AU - Yang, Haifeng

AU - Yu, Chengzhong

AU - Tu, Bo

AU - Zhao, Dongyuan

PY - 2004/2/6

Y1 - 2004/2/6

N2 - 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.

AB - 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.

KW - Aluminophosphate

KW - Block copolymer

KW - Large pore

KW - Mesoporous materials

KW - Synthesis

UR - https://www.scopus.com/pages/publications/0742302299

U2 - 10.1016/j.micromeso.2003.11.007

DO - 10.1016/j.micromeso.2003.11.007

M3 - 文章

AN - SCOPUS:0742302299

SN - 1387-1811

VL - 67

SP - 123

EP - 133

JO - Microporous and Mesoporous Materials

JF - Microporous and Mesoporous Materials

IS - 2-3

ER -

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

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Keywords

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