Mechanistic insight into efficient H generation upon HCOONa hydrolysis.

Sodium formate (SF) is regarded as a technological additive to improve H generation upon HCOOH dehydrogenation. The development of SF as a hydrogen storage material is still a challenge. Herein, we report the design and synthesis of carbon nanosphere-stabilized Pd nanoparticles (Pd/CNS) for the direct H generation upon SF hydrolysis in the presence of Fe. The tandem reaction, isotopic mass spectrometry, and gas chromatograms result confirmed that SF hydrolysis generates H with one H atom provided by SF and other H by HO. The kinetic study and detailed mechanistic investigations have demonstrated that the concerted process between the cleavage of O-H bond in HO and -OC-H bond oxidative addition is the rate-controlling step in SF hydrolysis. This work offers a new chemical hydrogen storage material (HCOONa) for the high-efficiency generation, transport, and storage of H.