Pd-Decorated PdO Hollow Shells: A H₂-Sensing System in Which Catalyst Nanoparticle and Semiconductor Support are Interconvertible

Developing a simple strategy to fabricate high-performance hydrogen sensors with long-term stability remains quite challenging. Here, we report the H2-sensing performance of Pd-decorated PdO hollow shells (Pd/PdO HSs). In this novel system, the catalyst nanoparticles (Pd NPs) and semiconductor support (PdO) are interconvertible, which is different from traditional hydrogen-sensing systems such as Pd/TiO2 and Pd/ZnO. This Pd/PdO system exhibits multiple unique properties. First, well-distributed Pd NPs with controllable density can be decorated on PdO support through a one-step NaBH4 treatment during which PdO is partially reduced into Pd. Second, the decorated Pd NPs are physically inlaid in the PdO support, which not only prevents the agglomeration or detachment of Pd NPs but also enhances the electron transfer between Pd NPs and PdO. Third, Pd/PdO HSs can be reoxidized into PdO HSs once their sensing performance degrades, which repeatedly manipulates Pd/PdO HSs under the initial reduction process, leading to the reactivation of the sensing performance. With all these advantages, Pd/PdO HSs demonstrate a detection limit lower than 1 ppm, a response/recovery time to 1% H2 of 5 s/32 s at room temperature, and a repeatable reactivation ability. The strategy presented here is convenient and time saving and has no need to prefunctionalize the PdO surface for the decoration of catalyst NPs. Moreover, the unique reactivation ability of Pd/PdO system opens a new strategy toward extending the lifetime of H2 sensors.