Application of micro-dried droplets for quantitative analysis of particulate inorganic samples with LA-ICP-MS demonstrated on surface-modified nanoparticle TiO2 catalyst materials

A quick, flexible and reliable method was developed, based on laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), for accurate assessment of nanomaterial composition with sample amounts in the picogram to nanogram range. We demonstrate its capabilities for the analysis of surface-modified TiO2 nanoparticulate (NP) catalyst materials. For sampling, suspensions of NP were deposited on a substrate material, ablated with a pulsed laser and then analysed using quadrupole ICP-MS. The calibration and quantification approach is based on the use of so-called micro-dried droplets (mu DD) as the standard material. To overcome some of the major drawbacks of conventional dried droplet approaches, self-aliquoting wells were used in this work. By mimicking the ablation conditions for the sample and standard, it was possible to create a pseudo-matrix-matched calibration, not only for this specific NP composition but also for a larger variety of samples. A commercially available reference material (AUROlite (TM), Strem Chemicals) was used to compare the method against established methods such as slurry analysis and microwave-assisted digestion in combination with subsequent liquid sample measurement. The results obtained with the proposed procedure (0.74%wt0.13%wt) are in good agreement to a certified value (0.8%wt) and added an additional layer of information. Due to the significantly reduced sampling size in comparison with the investigated liquid measurement approaches, it was possible to obtain information about the homogeneity of the catalyst material. The results indicate that the AUROlite (TM) reference material has a heterogeneous loading which requires more than 300 pg of material to be used to cancel out. This was not observed for the custom materials discussed in this work.