Revealing the Catalytic Activities of Single-Dispersed Pd Clusters Embedded on Hollow Nanoparticles toward the...

Hydrogen evolution reaction (HER) is one of the revolutionary aspects that grab lots of attention for the production of clean energy sources, increasing the demands of revealing the intrinsic activities of HER catalysts for designing efficient candidates. Based on using only surface active sites on solid nanoparticles (SNPs), catalysts with high atom dispersion are immensely desirable to magnify their efficiency through maximum atom utilization. Herein, we employed hollow mesoporous silica nanoparticles (HMSNPs) as an insulating nanoplatform for engineering single-dispersed Pd clusters on their surface, assuring high dispersion of the Pd clusters. We then tracked their intrinsic activities using stochastic nanocollision electrochemistry (SNCEC). The insulating silica nanoplatform helped investigate the single-dispersed Pd clusters per contact point of Pd@HMSNP at the electrode surface, revealing exceptional HER performance with high maximum turnover numbers and low onset potential for initiating the HER compared to those of SNPs. Using insulating silica allowed electron transfer only from the single-dispersed Pd cluster at the contact point of Pd@HMSNP to the electrode. Moreover, the high-temporal measurement of SNCEC revealed the diversity of spike shapes based on the heterogeneity of the contact point of Pd@HMSNP, ensuring the capability of the single-entity measurements to distinguish the structure relationship behaviors of the single-dispersed Pd cluster at the electrode/solution interface and clearly clarifying the electron transfer process with complementary information. This work provides sufficient evidence for the importance of atom dispersions in designing highly efficient HER Pd catalysts.