Physisorption of Cyclic Poly(ethylene glycol) on Platinum Nanoparticles for Dispersion Stabilization and Catalytic Applications

Dispersion stabilization of nanoparticles for catalytic reactions is an important issue. However, dispersing agents should be carefully selected not to hinder catalytic performance. In the present study, physisorption of cyclic poly(ethylene glycol) (c-PEG) onto platinum nanoparticles (PtNPs) was investigated in comparison with unmodified PtNPs (PtNPs/No PEG), PtNPs mixed with linear PEG (PtNPs/HO-PEG-OH), and PtNPs chemisorbed with HS-PEG-OMe (PtNPs/HS-PEG-OMe). DLS showed a significant increase in the particle size for PtNPs/c-PEG and PtNPs/HS-PEG-OMe compared to PtNPs/No PEG and PtNPs/HO-PEG-OH. ζ-potential measurements revealed values around −30 mV for PtNPs/No PEG and PtNPs/HO-PEG-OH, whereas PtNPs/c-PEG and PtNPs/HS-PEG-OMe approached 0 mV, which indicated that c-PEG and HS-PEG-OMe adsorb onto PtNPs to form a shielding layer. Moreover, PtNPs/c-PEG and PtNPs/HS-PEG-OMe were stable in a phosphate-buffered saline (PBS) solution, but PtNPs/No PEG and PtNPs/HO-PEG-OH immediately aggregated. This suggests that high dispersion stability by c-PEG is comparable to ordinary surface modification using HS-PEG-OMe. Furthermore, the catalytic ability of PtNPs/c-PEG and PtNPs/HS-PEG-OMe was compared in various reactions. As a result, physisorbed PtNPs/c-PEG showed suitable catalytic activities, whereas chemisorbed PtNPs/HS-PEG-OMe was significantly hampered by the blocking of the catalytic sites with thiol in some reactions. Thus, physisorption of c-PEG endows PtNPs with dispersion stability and maintains the catalytic ability, leading to an alternative way of modifying metal nanoparticles.