RT journal article
T1 Engineering single-atom Fe-N active sites on hollow carbon spheres for oxygen reduction reaction
A1 Ribeiro, Rui S.
A1 Vieira, Ana Luisa S.
A1 Biernacki, Krzysztof
A1 Magalhaes, Alexandre L.
A1 Delgado Jaén, Juan José
A1 Morais, Rafael G.
A1 Rey Raap, Natalia
A1 Rocha, Raquel P.
A1 Pereira, Manuel Fernando R.
A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
K1 oxygen reduction reaction (ORR)
K1 Single-atomic catalysts
K1 Electrocatalysis
K1 Density-functional theory (DFT)
K1 Fuel cells
AB Seeking alternatives to noble metals-based electrocatalysts for oxygen reduction reaction (ORR), hollow carbon spheres (CSs) were finely tuned with stable single-atom Fe-N species through a synthesis methodology requiring only earth-abundant metal precursors. CSs with different sizes were synthesized by sol-gel polycondensation of resorcinol with formaldehyde over silica nanoparticles, followed by thermal annealing and silica etching. A catalyst screening revealed the positive impact of both the hollow core and structural defects of the CSs for ORR. Single-atom Fe-N active sites were introduced on the best performing CSs through simultaneous incorporation of iron and nitrogen precursors, and glucose. A significant enhancement in ORR activity was observed despite the small iron load introduced (0.12 wt%). ORR performance indicators, advanced characterization, and molecular simulation studies revealed nitrogen's crucial role in anchoring individual iron atoms and modulating the charge density nearby the active sites (increase of 80 mV in the half-wave potential). Adding glucose as a chelating agent enhances the metal-heteroatom coordination and subsequent dispersion of iron, accounting for an increase of 20 mV in the half-wave potential, an average of electrons transferred as high as 3.9 (at 0.4 V vs. RHE), and higher stability (99%) than that of a platinum-based (20 wt%) electrocatalyst (92%).
PB Elsevier
SN 0008-6223
YR 2023
FD 2023-06-08
LK http://hdl.handle.net/10498/29418
UL http://hdl.handle.net/10498/29418
LA eng
DS Repositorio Institucional de la Universidad de Cádiz
RD 22-sep-2026