Revealing Facet Effects of Palladium Nanocrystals on Electrochemical Biosensing

Noble-metal nanocrystals (NCs) are functional segments of biosensing platforms, but their sensitivity and facet effects are still challenging. Conventional synthesis using surfactants to direct crystal growth unfortunately causes adsorbate-surface hindrance, which not only reduces sensing responses but also leads to misunderstanding on facet-dependence. Herein, we utilize electrochemical CO displacement to remove residual surfactants from facet-engineered Pd NCs, and further investigate the structure-activity relationship on specific facets, for example, {100} in cubes, {111} in octahedrons, and {110} in rhombic dodecahedrons. Along with the remarkably boosted response, facet dependence is obvious for H₂O₂ sensing after surface cleaning. The Pd{100} shows high sensitivity, low detection limit, and wide applicable concentration range, superior to the {110} and {111}. This can be theoretically interpreted by the befitting *OH binding on {100} and thereby the facilitated H₂O₂ reduction kinetics. The outstanding selectivity to H₂O₂ ensures the high efficiency of Pd NCs to measure intracellular H₂O₂ and recognize different types of cancer cells. Moreover, facet effects are also evidenced in glucose detection, highlighting that this work can provide guidelines to design efficient sensing platforms.