TY - JOUR
T1 - Preparation and optical properties of colloidal Ag0 nanoclusters from reduction of solution ionomer Ag-carboxylate ionic aggregates activated by swelling of covalently attached chain segments
AU - Li, Bofeng
AU - Hu, Tao
AU - Ma, Nian
AU - Hu, Zhen
AU - Gong, Xinghou
AU - Wu, Chonggang
AU - Hara, Masanori
N1 - Funding Information:
We acknowledge with gratitude that this work was supported by the Open Fund of the Hubei Provincial Key Laboratory of Green Materials for Light Industry, China (Contract no. [2013]2-key-3), as well as by the Overseas High-level Talents Scientific-research Starting Fund of Hubei University of Technology, China (Contract no. HBUT-science-[2005]2). We also very much thank Dr. Yan Xiong from MCE of HBUT for his helpful discussions.
Publisher Copyright:
© 2017, Springer-Verlag Berlin Heidelberg.
PY - 2017/4/1
Y1 - 2017/4/1
N2 - Small colloidal Ag0 nanoclusters successfully were prepared from solution reaction of CH3COOAg with a copolymer acid, poly(methyl methacrylate-ran-methacrylic acid) (MMA–MAA), in a methanol-containing solvent at room temperature in the dark in the absence of a typical chemical reductant. Tentatively mechanistically, slow PMMA-ionomerisation of the Ag+ ions produces intramolecular –COO−–Ag+ aggregate cross-links in the solution, which, upon swelling of the chain segments covalently bound to them, are activated by the resultant elastic forces to dissociate instantaneously at the O–Ag coordination bonds to give bare (i.e. uncoordinated), highly oxidative Ag+ ions, which are subject to reduction by the active α-H atoms of the solvent methanol to make Ag0 nanoclusters supported by the re-formed MMA–MAA; the MMA–MAA acid-copolymer, without itself undergoing any permanent chemical change, serves as a mechanical-activator or, say, catalyst for the mechanochemical reduction of CH3COOAg. This novel, facile approach may universally be extended to fabricate other transition-metal nanoclusters deposited in diverse polymeric matrices. [Figure not available: see fulltext.]
AB - Small colloidal Ag0 nanoclusters successfully were prepared from solution reaction of CH3COOAg with a copolymer acid, poly(methyl methacrylate-ran-methacrylic acid) (MMA–MAA), in a methanol-containing solvent at room temperature in the dark in the absence of a typical chemical reductant. Tentatively mechanistically, slow PMMA-ionomerisation of the Ag+ ions produces intramolecular –COO−–Ag+ aggregate cross-links in the solution, which, upon swelling of the chain segments covalently bound to them, are activated by the resultant elastic forces to dissociate instantaneously at the O–Ag coordination bonds to give bare (i.e. uncoordinated), highly oxidative Ag+ ions, which are subject to reduction by the active α-H atoms of the solvent methanol to make Ag0 nanoclusters supported by the re-formed MMA–MAA; the MMA–MAA acid-copolymer, without itself undergoing any permanent chemical change, serves as a mechanical-activator or, say, catalyst for the mechanochemical reduction of CH3COOAg. This novel, facile approach may universally be extended to fabricate other transition-metal nanoclusters deposited in diverse polymeric matrices. [Figure not available: see fulltext.]
KW - Ag
KW - Colloidal nanocluster
KW - Ionic aggregate
KW - Ionomer
KW - Reduction
UR - http://www.scopus.com/inward/record.url?scp=85013192525&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85013192525&partnerID=8YFLogxK
U2 - 10.1007/s00396-017-4033-9
DO - 10.1007/s00396-017-4033-9
M3 - Article
AN - SCOPUS:85013192525
VL - 295
SP - 583
EP - 599
JO - Colloid and Polymer Science
JF - Colloid and Polymer Science
SN - 0303-402X
IS - 4
ER -