Charge Redistribution Caused by S,P Synergistically Active Ru Endows an Ultrahigh Hydrogen Evolution Activity of S‐Doped RuP Embedded in N,P,S‐Doped Carbon

Abstract

Water splitting for production of hydrogen as a clean energy alternative to fossil fuel has received much attention, but it is still a tough challenge to synthesize electrocatalysts with controllable bonding and charge distribution. In this work, ultrafine S‐doped RuP nanoparticles homogeneously embedded in a N, P, and S‐codoped carbon sheet (S‐RuP@NPSC) is synthesized by pyrolysis of poly(cyclotriphosphazene‐co‐4,4′‐sulfonyldiphenol) (PZS) as the source of C/N/S/P. The bondings between Ru and N, P, S in PZS are regulated to synthesize RuS2 (800 °C) and S‐RuP (900 °C) by different calcination temperatures. The S‐RuP@NPSC with low Ru loading of 0.8 wt% with abundant active catalytic sites possesses high utilization of Ru, the mass catalytic activity is 22.88 times than 20 wt% Pt/C with the overpotential of 250 mV. Density functional theory calculation confirms that the surface Ru (−0.18 eV) and P (0.05 eV) are catalytic active sites for the hydrogen evolution reaction (HER), and the according charge redistribution of Ru is regulated by S and P with reverse electronegativity and electron–donor property to induce a synergistically enhanced reactivity toward the HER. This work provides a rational method to regulate the bonding and charge distribution of Ru‐based electrocatalysts by reacting macromolecules with multielement of C/N/S/P with Ru.

Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO2 Photoreduction

“…A potential solution to the aforementioned challenge is homogeneous heteroatom doping, which is capable of concurrently modulating both the bulk electronic structures and geometric surface structures of catalysts. [ 29–33 ] However, strategies for homogeneous doping remain limited and are characterized by certain drawbacks. For instance, hydrothermal and solvothermal approaches are applicable only for homogeneous metal doping.…”

Engineering Ruthenium-Based Electrocatalysts for Effective Hydrogen Evolution Reaction

“…Doping with various non-metal elements can also improve the HER activity of Ru-based catalysts through the coordination effect. Zhou et al [ 36 ] reported ultrafine S-doped RuP nanoparticles being homogeneously embedded in an N-, P-, and S-codoped carbon sheet (S-RuP@NPSC) by pyrolysis. The mass activity was 22.88 times that of Pt/C at an ultra-low loading of 0.8 wt%.…”

Self‐Anti‐Stacking 2D Metal Phosphide Loop‐Sheet Heterostructures by Edge‐Topological Regulation for Highly Efficient Water Oxidation

“…[ 46 ] Also, a comparison of the Fourier transforms of EXAFS and fitting results at the Ni K‐edge of the different samples is applied to extract the structural parameters (Figure 3e). [ 47–48 ] The Ni−Ni(Fe) bond distance in NiFeP@NC/Ni 2 P is slightly shorter than that of Ni 2 P (Table S1, Supporting Information), meaning the Ni−Ni(Fe) bond strengthening and demonstrating an intimate interfacial contact of edge‐occupied Fe species with interconnected Ni 2 P nanoparticles. [ 43,44 ] The Fourier transforms of EXAFS and fitting results at the Fe K‐edge reveal a distinguished position difference of Fe−P and Fe−Fe(Ni) bond in NiFeP@NC/Ni 2 P as compared with those in Ni 2 P–FeP@NC (Figure 3h and Table S2, Supporting Information).…”