Exploring nanoparticle porosity using nano-impacts: platinum nanoparticle aggregates.

The porosity of platinum nanoparticles (PtNPs) is explored for the first time using tag-redox coulometry (TRC). This is achieved by monitoring the reduction of the 4-nitrobenzenethiol (NTP)-tagged PtNPs on carbon electrodes via both immobilisation and nanoimpacts. The average charge per impact is measured and attributed to the reduction of NTP adsorbed on individual PtNPs. The number of NTP molecules and thus the "active surface area" of the PtNPs is calculated and compared with two models: fully solid and porous nanoparticles, and the extent of the particle porosity is revealed. This allows a fuller understanding of the (electro-)catalytic behaviour of nanoparticles by providing insight into their porosity and "true/active surface areas".