A Metal-Free Covalent Organic Polymer for Electrocatalytic Hydrogen Evolution

Abstract

Metal-free catalysis for electrocatalytic hydrogen evolution from water is very demanding for the production of sustainable and clean fuel. Herein, we report the synthesis of a porphyrin-based metal-free covalent organic polymer (TpPAM) through a simple condensation between triformyl phloroglucinol (Tp) and 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin (PAM). The as-prepared porous TpPAM exhibited superior activity for the hydrogen evolution reaction (HER) current density of 10 mA cm −2 at a low overpotential of 250 mV and a small Tafel slope of 106 mV decade −1 , which are better than those of related metal-free electrocatalysts. The high HER activity of TpPAM was investigated in-depth via theoretical density functional theory (DFT) calculations. The theoretical findings were correlated with the experimental results, and these were in good agreement for high HER catalytic efficiency of the porous TpPAM polymer. The Faradaic efficiency of the TpPAMbased electrode was found to be 98%, which is very close to the ideal value of 100%, reflecting its potential for practical implementation. Moreover, the as-synthesized catalyst showed good stability by retaining 91% of the initial current density after 1000 cycles.

Pore Surface Engineering of Covalent Triazine Frameworks@MoS2 Electrocatalyst for the Hydrogen Evolution Reaction

“…Carbon materials with large surfacearea and rapid electron migration can effectively reduce HER overpotential of MoS 2 by forming ac arbon@MoS 2 combined system,w hen two materials are mutualistic symbiosis in one bulk material. At present,anumber of specially carbon analogue porousm aterials for electrocatalyst have been under the limelight of research, such as metal-organic frameworks (MOFs), [13] conjugated microporous polymers (CMPs), [14,15] and other porousm aterials. [16,17] Most of those pore materials were adopted as carriers for loading of active nanoparticles to furtheri mprove catalytic activity.…”

IrO2 and Pt Doped Mesoporous SnO2 Nanospheres as Efficient Electrocatalysts for the Facile OER and HER

“…The performance of these nanocomposites could be attributed to the increase in the number of active sites, synergistic interactions, crystal phase and surface properties . In the case of IrO 2 supported over SnO 2 , latter would not only promote the dispersion of nanoparticles but also efficiently remove the adsorbed hydroxy groups from the active sites …”

Two‐Dimensional MOF and COF Nanosheets: Synthesis and Applications in Electrochemistry

“…Therefore, it is necessary to develop new catalysts with low cost. Patra et al. reported 2D COFs (TpPAM) as metal‐free catalysts for HER by using triformyl phloroglucinol (Tp) and 5,10,15,20‐tetra(4‐aminophenyl)‐21 H,23H‐porphyrin (PAM) (Figure d).…”