Covalent Porphyrin Framework-Derived Fe₂P@Fe₄N-Coupled Nanoparticles Embedded in N-Doped Carbons as Efficient Trifunctional Electrocatalysts

Abstract

A new porous covalent porphyrin framework (CPF) filled with triphenylphosphine was designed and synthesized using the rigid tetrakis(p-bromophenyl)porphyrin (TBPP) and 1,3,5-benzenetriboronic acid trivalent alcohol ester as building blocks. The carbonization of this special CPF has afforded coupled FeP and FeN nanoparticles embedded in N-doped carbons (FeP/FeN@N-doped carbons). This CPF serves as an "all in one" precursor of Fe, N, P, and C. The porous property and solid skeleton of the CPF endow FeP/FeN@N-doped carbons with porous structure and a high degree of graphitization. As a result, FeP/FeN@N-doped carbons exhibited highly efficient multifunctional electrocatalytic performance for water splitting and oxygen electroreduction. Typically, FeP/FeN@C-800, obtained at a heat-treatment temperature of 800 °C, showed an ORR half-wave potential of 0.80 V in alkaline media and 0.68 V in acidic media, close to that of commercial Pt/C catalysts. FeP/FeN@C-800 also displayed efficient OER and HER activities, comparable to other phosphide and nitride electrocatalysts. The coupled FeN and FeP nanoparticles embedded in carbons exert unique catalytic efficiency for water splitting and fuel cells.

Metal Silicide Nanosphere Decorated Carbon‐Rich Polymer‐Derived Ceramics: Bifunctional Electrocatalysts towards Oxygen and their Application in Anion Exchange Membrane Fuel Cells

“…The satellite peaks at 788 eV and 804.4 correspond to Co2P 1/2 and Co2P 3/ 2. The deconvoluted spectra of N1s show the three peaks at 398.2 eV, 400.1 eV and 401.7 eV corresponding to pyridinic, pyrrolic and graphitic type nitrogen functionalities in the Co/SiOC ceramic matrix (Figure f) . Further, the nitrogen spectra show relatively higher content of pyridinic and graphitic nitrogen, which are beneficial for better ORR reaction kinetics.…”

“…[5] The deconvoluted spectra of N1s show the three peaks at 398.2 eV, 400.1 eV and 401.7 eV corresponding to pyridinic, pyrrolic and graphitic type nitrogen functionalities in the Co/SiOC ceramic matrix (Figure 3 f). [47,48] Further, the nitrogen spectra show relatively higher content of pyridinic and graphitic nitrogen, which are beneficial for better ORR reaction kinetics. The amount of oxygen, silicon, and cobalt in Co/SiOC were found to be 20.9 wt %, 14.25 wt %, 5.22 wt % through XPS elemental composition analysis data.…”

Robust Synthesis of High‐Performance N‐Graphite Hollow Nanocatalysts Based on the Ostwald Ripening Mechanism for Oxygen Reduction Reaction Electrocatalysis

“…In good agreement with the HRTEM result, the characteristic G (1580 cm −1 ) and D (1352 cm −1 ) bands of graphite carbon were observed in the Raman spectroscopy of the N‐graphite hollow nanoparticles (Figure S4, Supporting Information). The degree of graphitization could be estimated from the ratio between the relevant intensities of D and G bands . The I D / I G value of the N‐graphite hollow nanoparticles was 0.89, suggesting their high degree of graphitization.…”

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.…”