Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry (2015) 45, 173–176
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.819903
Template Synthesis and Characterization of Bi O -Based
2
3
Composite Nanoclusters Within Diblock Copolymer
1
2
2
CHUANYI PAN , XUEHUI LI , and LEFU WANG
1
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, P. R. China
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, P. R. China
2
Received 28 April 2013; accepted 11 June 2013
Diblock copolymer templates were synthesized using norbornene and 5-norbornene-2, 3-dicarboxylic acid by ring-opening metathe-
sis polymerization. By introducing bismuth salt into these prepared diblock copolymer template, the Bi O -based composite nano-
2
3
clusters were achieved. XRD, FTIR, and TEM were used severally to characterize the Bi O particles, the process of oxide
2
3
formation, and the size of nanoclusters.
Keywords: bismuth oxide, diblock copolymer, nanocluster, norbornene, template
Introduction
NBNCOOSiMe and norbornene at the ration of 400:50
3
[
6]
(
molecular ratio).
A Grubbs catalyst (Bis(tricyclohexylphosphine)[(phenyl-
Templating methods have been proved to be valid in control-
ling the material structure on a nanometer scale. The norbor- thio)methylene]ruthenium(II)dichloride) was purchased
nene diblock copolymer synthesized by ring-opening alternatively from Strem Chemicals. This catalyst has
metathesis polymerization is one of these kind templates. highly selective for the ring-opening metathesis polymeriza-
[
7]
Many nanoclusters such as Ag, Au, Fe O , Co O , and tion and high tolerance toward impurities. Hence, it has
2
3
3
4
CoFe O have been synthesized by using diblock copolymers been adopted in this finding without any further modifica-
2
4
[
1–4]
template recently.
This research first introduce the synthe- tion. 300.0 mg Grubbs catalyst was dissolved in 10.0 ml tet-
sis of the diblock copolymers template, then a Bi salt was rahydrofuran (THF) and CH Cl (1:1 volume ratio) mixed
2
2
–
1
introduced into the template, the Bi O -based composites solvent to get a 30 mg.mL stock solutions. 0.08 mol mono-
2
3
within the diblock copolymer template was achieved by mer norbornene was dissolved in 10 mL THF to get the solu-
NaOH soaking and water wash at room temperature, and, tion of NBN. The polymerization was initiated by adding
finally, the process of compounds formation was discussed by 5 mL of Grubbs catalyst solution. 1 h later, 0.01 mol
FTIR and the composite morphology of nanoclusters was NBNCOOSiMe was added into the polymer solution. The
3
investigated by TEM.
reaction was terminated after 24 h. A solution with water,
acetic acid, and methanol (1:5:5, volume ratio) was prepared
to precipitate this above polymer solution to get white
diblock copolymers.
Experimental
Synthesis and of Bi O -Based Nanoclusters Within
3
2
Synthesis of Diblock Copolymers Template
the Template
Norbornene (NBN) and 5-norbornene-2, 3-dicarboxylic
acid (NBNCOOH) were used as the starting monomer
materials. 5-norbornene-2, 3-dicarboxylic acid bis(trime-
The diblock copolymer was dissolved in THF, and then
BiCl were added into the copolymer solution according to
3
3+
2
5:1 molecular ratio (Bi :-COOH D 1:4, molecular ratio).
thylsilyl) ester (NBNCOOSiMe ) were synthesized accord-
3
[
5]
BiCl had a prior attach to the [NBNCOOH] block due to
3
ing to reported procedures. The copolymer template was
prepared by ring-opening metathesis polymerization with
3+
the firmer affinity of Bi toward the carboxylic group.
After the solvent had evaporated completely, the diblock
copolymers became the solid films after static casting over
7
2 h. The films were dipped into 2 mol/L NaOH solution
Address correspondence to Chuanyi Pan, School of Chemical Engi- for 48 h, and then washed with pure water until the pH
neering and Light Industry, Guangdong University of Technology, value of washed water reached 7.0. The films had turned
Guangzhou, P.R. China. E-mail: panchuanyi@gdut.edu.cn.
yellow and were dried under vacuum for further test. The