Hydrogen Intercalation‐Induced Crystallization of Ternary PdNiP Alloy Nanoparticles For Direct Formic Acid Fuel Cells

Abstract

Direct formic acid fuel cells (DFAFCs) are among the promising energy sources in the future low‐carbon economy. A key challenge hindering their scale‐up and commercialization is the lack of efficient electrocatalysts for anodic formic acid oxidation (FAO). Very recently, the FAO performance of palladium hydrides (PdHx) has been found to be superior to the pristine Pd that is well known for its high intrinsic FAO activity. However, there is enormous space for the controlled synthesis and electrocatalytic behaviors of PdHx‐based nanomaterials awaiting to be explored. Herein, the hydrogen intercalation‐induced crystallization of PdNiP alloy nanoparticles is reported, and the obtained PdNiP‐H nanoparticles exhibit excellent FAO performance. Of particular note, the FAO stability of PdNiP‐H is much better than that of pristine Pd‐H. Furthermore, the PdNiP‐H nanoparticles are used as the anode catalyst in a prototype DFAFC, which demonstrate much higher power density than commercial Pd/C. Density functional theory calculations show that the synergistic effect of alloying Ni and P endows the PdNiP‐H with a higher preference toward FAO via the direct pathway and better anti‐CO* poisoning capability. This work shines new light on the development of PdHx‐based nanoalloys with good activity and stability for DFAFC applications.

Facile Synthesis of the TiO2-Supported Ultrathin Palladium Facet Composite Catalyst with Superior Metal Dispersion and Enhanced Catalytic Performance in Formic Acid Electro-Oxidation

“…Direct formic acid fuel cells (DFAFCs) are a well-known sustainable power source in transportation and portable electronic devices because of their efficient and clean energy supply. ,,− The development of an active anodic catalyst for formic acid electro-oxidation, which is the key reaction of DFAFCs, is an active research field. Supported Pd catalysts with high metal loadings have been verified to be preferred catalysts in formic acid oxidation since Pd is less vulnerable to being poisoned by strongly adsorbed CO ads reaction intermediates as compared to Pt because of the dominance of the direct formic acid oxidation path. ,, As compared to carbon support, which usually undergoes corrosion/oxidation in harsh fuel cell environments, the TiO 2 support is a more preferable candidate to use because of its high thermal and chemical stabilities in acidic and oxidative environments .…”

Recent advances of H-intercalated Pd-based nanocatalysts for electrocatalytic reactions

“…5a-e). 66 Mechanistic study uncovered that the alloying effect of Ni and P in the PdH x can lead to a higher preference for the direct pathway and stronger adsorption of OH*, thus reducing CO* poisoning and resulting in excellent electrochemical durability (Fig. 5f-i).…”

Recent progress of Ni-based nanomaterials for the electrocatalytic oxygen evolution reaction at large current density

“…The climate change and depleting petroleum supplies have stimulated the research and development of green and clean energy in recent decades. Various efficient energy technologies for clean conversion, such as metal–air batteries, 1,2 metal-ion batteries, 3 water electrolysis, 4–7 and fuel cells, 8–11 are the subject of fundamental research and utilitarian studies. Among them, producing hydrogen via water electrolysis has been widely investigated by academic and government organizations, with the goal of not only resolving the serious environmental issues but also alleviating the energy crisis.…”