RESUMEN
Bioinspired by the active sites of multicopper oxidases (MCOs), bi/multinuclear copper complexes have attracted great attention in promoting catalytic activity for the oxygen reduction reaction (ORR). Herein, we report the preparation of a Cu-N-C electrocatalyst Cu-BPOZ@CNB-400 for efficient ORR, which was obtained by low temperature pyrolysis of a dinuclear 2,5-bis(2-pyridyl)-1,3,4-oxadiazole (BPOZ) copper complex loaded on a N-doped carbon support at 400 °C. Cu-BPOZ@CNB-400 exhibited a half-wave potential (E1/2) of 0.86 V vs. RHE for the ORR in 0.1 M KOH solution, which was significantly higher than that of the Cu-BPOZ@CNB-800 (E1/2 = 0.83 V) catalyst treated under high temperature (at 800 °C) and the control catalyst Cu-Phen@CNB-400 (E1/2 = 0.82 V) derived from low-temperature-treatment (at 400 °C) of a mononuclear phenanthroline-coordinated-Cu complex loaded on a N-doped carbon support. When Cu-BPOZ@CNB-400 was applied as the cathode catalyst in zinc-air batteries a maximum power density (Pmax) of 127 mW cm-2 could be achieved, demonstrating comparable catalyst performance to the commercial 20 wt% Pt/C (Pmax = 122 mW cm-2) and the control Cu-Phen@CNB-400 catalyst (Pmax = 105 mW cm-2) under similar experimental conditions. Low-temperature pyrolysis of dinuclear copper complexes on a carbon support improved the charge transfer efficiency, inhibited metal aggregation, and could produce highly dispersed Cu-N-C catalysts with dinuclear copper sites for promoting the 4e--reduction selectivity of the ORR. It thus provides a cost-effective approach for the controllable fabrication of efficient ORR catalysts to be applied for energy conversion devices.
RESUMEN
Developing high performance noble-metal-free electrocatalysts as an alternative to Pt-based catalysts for the oxygen reduction reaction (ORR) in energy conversion devices is highly desirable. We report herein the preparation of a coordination-polymer (CP)-derived Fe/CP/C composite as an electrocatalyst for the ORR with excellent activity and stability both in solution and in Zn-air batteries. The Fe/CP/C catalyst was obtained from the pyrolysis of an iron porphyrin Fe(TPP)Cl (5,10,15,20-tetraphenyl-21H,23H-porphyrin iron(III) chloride) grafted Zn-coordination polymer with dangling functional groups 4,4'-oxybisbenzoic acid and 4,4'-bipyridine ligands. The Fe/CP/C catalyst showed much higher ORR activity with a half-wave potential (E1/2) of 0.90 V (vs. RHE) than the Fe/C catalyst (E1/2 = 0.85 V) derived from the carbon-black-supported Fe porphyrins in 0.1 M KOH solution. When Fe/CP/C was used as the cathode electrocatalyst in Zn-air batteries (ZABs), the ZABs achieved a significantly higher open circuit voltage (OCV = 1.43 V) and maximum power density (Pmax = 142.8 mW cm-2) compared with Fe/C (OCV = 1.38 V, Pmax = 104.5 mW cm-2) and commercial 20 wt% Pt/C (OCV = 1.41 V, Pmax = 117.6 mW cm-2). Using dangling functional groups in CP to increase the loading efficiency of iron porphyrins offered a facile method to prepare high-performance noble-metal-free electrocatalysts for the ORR, which may provide promising applications to energy conversion devices.
RESUMEN
Promoting the catalyst performance for oxygen reduction reaction (ORR) in energy conversion devices through controlled manipulation of the structure of catalytic active sites has been a major challenge. In this work, we prepared Fe-N-C single-atom catalysts (SACs) with Fe-N5 active sites and found that the catalytic activity of the catalyst with shrinkable Fe-N5-C11 sites for ORR was significantly improved compared with the catalyst bearing normal Fe-N5-C12 sites. The catalyst C@PVI-(TPC)Fe-800, prepared by pyrolyzing an axial-imidazole-coordinated iron corrole precursor, exhibited positive shifted half-wave potential (E1/2 = 0.89 V vs RHE) and higher peak power density (Pmax = 129 mW/cm2) than the iron porphyrin-derived counterpart C@PVI-(TPP)Fe-800 (E1/2 = 0.81 V, Pmax = 110 mW/cm2) in 0.1 M KOH electrolyte and Zn-air batteries, respectively. X-ray absorption spectroscopy (XAS) analysis of C@PVI-(TPC)Fe-800 revealed a contracted Fe-N5-C11 structure with iron in a higher oxidation state than the porphyrin-derived Fe-N5-C12 counterpart. Density functional theory (DFT) calculations demonstrated that C@PVI-(TPC)Fe-800 possesses a higher HOMO energy level than C@PVI-(TPP)Fe-800, which can increase its electron-donating ability and thus help achieve enhanced O2 adsorption as well as O-O bond activation. This work provides a new approach to tune the active site structure of SACs with unique contracted Fe-N5-C11 sites that remarkably promote the catalyst performance, suggesting significant implications for catalyst design in energy conversion devices.
RESUMEN
A P-doped PtNi alloy loaded on N,C-doped TiO2 nanosheets (P-PtNi@N,C-TiO2) exhibited excellent activity and durability for the oxygen reduction reaction (ORR) in 0.1 M HClO4 solution with mass (4×) and specific (6×) activity several times higher than those of commercial 20 wt% Pt/C, respectively. The P dopant mitigated the dissolution of Ni and strong interactions between the catalyst and the N,C-TiO2 support inhibited catalyst migration. This provides a new approach for the design of high-performance non-carbon-supported low-Pt catalysts to be used in harsh acidic environments.
