Platinum Porphyrin-Based Conjugated Porous Polymer:Synthesis And Application For Electrocatalytic Hydrogen Evolution Reaction

With the advent of smart cities,people have an increasingly high demand for new energy,and traditional fossil energy sources,such as coal and petroleum,has been not able to meet the demand.In order to solve this urgent problem,new energy sources need to be effectively used.At present,new energy sources discovered by scientists have been greatly developed because of their clean and sustainable nature.Among them,hydrogen energy is an ideal alternative to traditional fossil energy,because of the clean hydrogen oxidation and high energy density.In recent years,conjugated porous polymers have significant applications in electrocatalysis and photocatalysis because of their planar morphology and adjustable layered porous structure.Besides,the performance of Platinum(Pt)cluster or Pt single atom in electrocatalytic hydrogen evolution is comparable to or even superior to that of commercial Pt/C.Therefore,this paper takes platinum porphyrin-based conjugated porous polymer as the research object and carries out the research work from the following two aspects:1.Two kinds of Pt porphyrin-based porous polymers(CMP-PtN4 and CMP-PtN3C)were synthesized by simple Yamamoto coupling reaction.Both have good thermal stability and Pt is evenly distributed in the material.The overpotentials of CMP-PtN3C at current density of 10 mA cm-2 and 20 mA cm-2 are 212 and 332 mV,and of CMP-PtN4 are 293 and 378 mV,respectively.This showed that CMP-PtN3C had better Hydrogen Evolution Reaction(HER)performance,which indicated that the co-coordinate metal active sites of C and N could reduce HER kinetic energy barrier,and thus promoting the electrocatalytic performance.In addition,the both all have high electrocatalytic stability,which provides a new idea for Pt based electrocatalytic electrode materials.2.Porous polymers are a good class of carbon precursors.A Pt atom/Pt cluster co-doped porous carbon material was prepared by high-temperature calcination CMP-PtN4.Due to the composition of atomically dispersed Pt and ultra-fine Pt nanoparticles(NPs)embedded in N-doped porous carbon,the prepared PC-PtN4-600 has an extremely low overpotential of 31 mV at current density of 10 mA cm-2.In addition,when the overpotential is 100 mV,its mass activity is as high as 1.3 A mgPt-1,which is twice that of commercial Pt/C(0.66 A mgPt-1).