Organometallic Polymer Electrolyte Membrane Fuel Cell Bis‐Ligand Nickel(Ii) Complex of 1,5‐Di‐P‐Tolyl‐3,7‐Dipyridine‐1,5,3,7‐Diazadiphosphacyclo‐Octane Catalyst

Abstract

A 1,4‐Diaza‐3.7‐diphosphacyclo‐otane organometallic bis‐ligand nickel(II) complex [Ni(PPy2Np‐Tol2)2]2+2.[BF4]− on Vulcan XC‐72 (C) functions as both the cathode and anode catalysts in polymer electrolyte membrane fuel cell (PEMFC). In a PEMFC using Ni(Py‐p‐Tol)/C at the anode and Pt/C at the cathode the power density is shown to reach 14.66 mW cm−2, which is the highest power density of the none‐noble organometallic analogs. Based on the data produced using independent physico‐chemical methods, the mechanisms of the hydrogen oxidation and oxygen reduction reactions (HOR and ORR) on the anode and cathode sides of PEMFC, respectively, are reported.

A Nickel‐Based Pectin Metal‐Organic Framework as a Hydrogen Oxidation Reaction Catalyst for Proton‐Exchange‐Membrane Fuel Cells

“…In a PEMFC using Pt/C at the cathode this Ni‐based PEMFC reaches maximum power density of 14 mW cm −2 , a little more an order of magnitude less as compared to full‐Pt conventional PEMFC. In a PEMFC using bis‐Ligand nickel (ii) complex of 1,5‐di‐ p ‐tolyl‐3,7‐dipyridine‐ 1,5,3,7‐diazadiphospha‐cyclooctane catalyst at the anode and Pt/C at the cathode the maximum power density reaches 14.66 mW cm −2 , that is the highest power density of the none‐noble organometallic analogs …”

1,5‐Diaza‐3,7‐Diphosphacyclooctane Bis‐Ligand Nickel(II) Complexes as Oxygen Reduction Catalysts for Proton‐Exchange Membrane Fuel Cells

“…A new efficient bis ‐diphosphine catalyst for PEMFC—1,5‐diaza‐3,7‐diphosphacyclo‐octane organometallic bis ‐ligand complex of nickel [Ni(P Py 2 N p ‐Tol 2 ) 2 ] 2+ 2[BF 4 ] − —on carbon Vulcan XC‐72 substrate has been developed. The use of the aforementioned catalyst as an anode and Pt/C as a cathode makes it possible to achieve a power density of 14.66 mW cm −2 , which is superior to analogs without precious metals.…”

“…Despite the announced and reasoned possibility of using bis ‐diphosphine complexes as ORR catalysts for PEMFC, the first works on their use in this direction appeared relatively recently . This made it possible to develop and create PEMFC on nonplatinum catalysts, where, for the first time, the same organometallic complex serves both as the anodic and as the cathodic catalyst …”

“…[7][8][9] PEMFC using the anode catalyst of bis-diphosphine nickel complex, including the amino acid arginine in the second coordination sphere, immobilized on modified carbon nanotubes (CNTs) by electrostatic interactions, reaches a power density of 14 mW cm À2 . [9] A new [10] efficient bis-diphosphine catalyst for PEMFC-1,5-diaza-3,7-diphosphacyclo-octane organometallic bis-ligand complex of nickel [Ni(P Py 2 N p-Tol 2 ) 2 ] 2þ 2[BF 4 ] À -on carbon Vulcan XC-72 substrate has been developed. The use of the aforementioned catalyst as an anode and Pt/C as a cathode makes it possible to achieve a power density of 14.66 mW cm À2 , which is superior to analogs without precious metals.…”

“…Despite the announced and reasoned possibility of using bis-diphosphine complexes as ORR catalysts for PEMFC, [11] the first works on their use in this direction appeared relatively recently. [10,12] This made it possible to develop and create PEMFC on nonplatinum catalysts, where, for the first time, the same organometallic complex serves both as the anodic and as the cathodic catalyst. [11] This study reports the morphological, electron spin resonance (ESR), electrochemical, thermoanalytical, and ORR FC catalysts test results obtained with the bis-ligand nickel(II) 1,5-diaza-3, 7-diphosphacyclooctane complexes ( Figure 1).…”