Practical Guidelines for Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy of Heterogeneous Catalysts.

Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) has proven to be a useful characterization tool for heterogeneous catalysis research. The advantage of SHINERS lies in studying surface reactions on solid catalysts, including the detection of reactants, intermediates and products, in real time. However, due to the extremely strong local electric fields, minor amounts of contaminants can already have a big impact on the quality and interpretation of the spectroscopic data obtained. Often, a large part of the organic fingerprint region (1100-1700 cm ) is omitted from SHINER spectra as this is not the main region of interest. However, we show that bands in this region are an important indication of the cleanliness of the substrate. In this work, we propose robust synthesis and measurement protocols to obtain clean SHINERS substrates amenable for catalysis research. By cleaning the substrates with various heat and oxidation treatments, featureless Raman spectra can be obtained. Furthermore, very pure gas feeds are required and must be obtained by flushing the gas lines and the reaction chamber beforehand and installing a filter for further cleaning the gas feed. Controlling the laser power to limit substrate and sample degradation is also a crucial aspect of proper measurement protocols.