Abstract
Numerous experiments have demonstrated that the metal atom is the active center of monoatomic catalysts for hydrogen evolution reaction (HER), while the active sites of nonmetal doped atoms are often neglected. By combining theoretical prediction and experimental verification, we designed a unique ternary Ru-N4-P coordination structure constructed by monodispersed Ru atoms supported on N,P dual-doped graphene for highly efficient hydrogen evolution in acid solution. The density functional theory calculations indicate that the charge polarization will lead to the most charge accumulation at P atoms, which results in a distinct nonmetallic P active sites with the moderate H∗ adsorption energy. Notably, these P atoms mainly supply highly efficient catalytic sites with ultrasmall absorption energy of 0.007 eV. Correspondingly, the Ru-N4-P demonstrated outstanding HER performance not only in an acidic condition but also in alkaline environment. Notably, the performance of Ru-NPC catalyst at high current is even superior to the commercial Pt/C catalysts, whether in acidic or alkaline medium. Our in situ synchrotron radiation infrared spectra demonstrate that a P-Hads intermediate is continually emerging on the Ru-NPC catalyst, actively proving the nonmetallic P catalytically active site in HER that is very different with previously reported metallic sites.
Highlights
Single-atom catalysts (SACs) are synthesized by doping active atoms onto the surface of a catalyst
Ruthenium monoatomic catalysts anchored by nitrogen atoms (Ru-N4 structure) were considered a better choice for monoatomic catalysts
We found that if the P atom locates on the farther position from the Ru-N4 structure, the system will become more unstable with higher total energy
Summary
Single-atom catalysts (SACs) are synthesized by doping active atoms onto the surface of a catalyst. Metal-Nx coordinated carbon nanostructures have been extensively demonstrated as the catalytically active sites to enhance the catalytic performance for various reactions rather than the presence of nanoparticles [24,25,26,27,28,29,30] In this way, the nonmetallic atoms change the electronic structure of the bonded metals to improve their catalytic performance. Due to the synergistic effect between P and Ru, the as-prepared Ru-NPC catalysts exhibited superior HER performance than the control Ru-NC or commercial Pt/C catalysts at acid or alkaline environment This unique engineering and the coordination environment of well-dispersed monoatomic structures with metal and nonmetal bonding provide a better understanding of synergistic effect in SACs, opening a new way for the future rational design of highly efficient HER catalytic materials with multiple active sites
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