Sensing pH of individual microdroplet by combining SERS and indicator paper

Microdroplets present unique physiochemical properties, which can influence chemical reactions and atmospheric aerosol processes. The microdroplets’ pH is one of the most important factors that dictate chemical processes, such as heterogeneous and condensed reactions. However, currently, there is no well-established method for directly measuring the pH in microdroplets. Herein, we develop a straightforward method, for the first time, to directly measure the pH of size-resolved, micron-sized single droplets with Surface Enhanced Raman Scattering (SERS)-activated pH-indicator paper; realized by embedded Au nanoparticles (20, 40 and 60 nm). We establish the key parameters for optimizing the method, and demonstrate its accuracy by benchmarking various acids and solutions with different ionic strength. With the established method, we report the pH dependence on the size of microdroplets. Microdroplets of sizes down to 230 nm can be analyzed by our method. We also showcase our method's applicability to ambient samples, establishing its promising potential beyond the laboratory environment.