Heat-treated Fe/N/C catalysts for O2 electroreduction: are active sites hosted in micropores?

Limited availability of platinum is a potential threat to fuel cell commercialization. Since the 1970s, alternative catalysts to the electrochemical reduction of oxygen have been obtained from heat treatment at T > 600 degrees C of carbon with a non-noble metal and a source of nitrogen atoms. However, the process by which the heat treatment activates these materials remains an open question. Here, we report that the activation process of carbon black and iron acetate heat-treated in NH(3) comprises three consecutive steps: (i) incorporation of nitrogen atoms in the carbon, (ii) micropore formation through reaction between carbon and ammonia, and (iii) completion of active sites in the micropores by reaction of iron with ammonia. Step (ii) is the slowest. Moreover, the microporous surface per mass of catalyst controls the macroscopic activity when enough nitrogen atoms are incorporated in the structure of the carbon support. These facts should help in determining the structure of the active sites and in identifying methods to increase the site density of such catalysts.     

Does CO poison Fe-based catalysts for ORR?

Catalysts for the oxygen reduction reaction (ORR) were prepared on carbon black (C) using Fe^IIphthalocyanine (FePc) and Cl–Fe^IIItetramethoxyphenylporphyrin (ClFeTMPP), as Fe precursors with and without a pyrolysis step at 800 °C. CO poisoning of the ORR catalytic sites for all these Fe/N/C electrocatalysts was attempted at pH 1 and 13, but to no avail, even if an iron ion is known to occupy the center of the active sites in at least the unpyrolyzed FePc/C or ClFeTMPP/C. The exact nature of the active center of these Fe-based heat-treated catalysts may still be a subject of debate but, in light of the absence of CO poisoning for unpyrolyzed FePc/C and ClFeTMPP/C, resistance to CO poisoning by the heat-treated catalysts cannot be used as evidence that the active center of their catalytic site is devoid of iron.     

Non-PGM Electrocatalysts for PEM Fuel Cells: A DFT Study on the Effects of Fluorination of FeNx-Doped and N-Doped Carbon Catalysts

Fluorination is considered as a means of reducing the degradation of Fe/N/C, a highly active FeN_x-doped disorganized carbon catalyst for the oxygen reduction reaction (ORR) in PEM fuel cells. Our recent experiments have, however, revealed that fluorination poisons the FeN_x moiety of the Fe/N/C catalytic site, considerably reducing the activity of the resulting catalyst to that of carbon only doped with nitrogen. Using the density functional theory (DFT), we clarify in this work the mechanisms by which fluorine interacts with the catalyst. We studied 10 possible FeN_x site configurations as well as 2 metal-free sites in the absence or presence of fluorine molecules and atoms. When the FeN_x moiety is located on a single graphene layer accessible on both sides, we found that fluorine binds strongly to Fe but that two F atoms, one on each side of the FeN_x plane, are necessary to completely inhibit the catalytic activity of the FeN_x sites. When considering the more realistic model of a stack of graphene layers, only one F atom is needed to poison the FeN_x moiety on the top layer since ORR hardly takes place between carbon layers. We also found that metal-free catalytic N-sites are immune to poisoning by fluorination, in accordance with our experiments. Finally, we explain how most of the catalytic activity can be recovered by heating to 900 °C after fluorination. This research helps to clarify the role of metallic sites compared to non-metallic ones upon the fluorination of FeN_x-doped disorganized carbon catalysts.     

Structure of the catalytic sites in Fe/N/C-catalysts for O(2)-reduction in PEM fuel cells

Fe-based catalytic sites for the reduction of oxygen in acidic medium have been identified by (57)Fe M?ssbauer spectroscopy of Fe/N/C catalysts containing 0.03 to 1.55 wt% Fe, which were prepared by impregnation of iron acetate on carbon black followed by heat-treatment in NH(3) at 950 °C. Four different Fe-species were detected at all iron concentrations: three doublets assigned to molecular FeN(4)-like sites with their ferrous ions in a low (D1), intermediate (D2) or high (D3) spin state, and two other doublets assigned to a single Fe-species (D4 and D5) consisting of surface oxidized nitride nanoparticles (Fe(x)N, with x≤ 2.1). A fifth Fe-species appears only in those catalysts with Fe-contents ≥0.27 wt%. It is characterized by a very broad singlet, which has been assigned to incomplete FeN(4)-like sites that quickly dissolve in contact with an acid. Among the five Fe-species identified in these catalysts, only D1 and D3 display catalytic activity for the oxygen reduction reaction (ORR) in the acid medium, with D3 featuring a composite structure with a protonated neighbour basic nitrogen and being by far the most active species, with an estimated turn over frequency for the ORR of 11.4 e(-) per site per s at 0.8 V vs. RHE. Moreover, all D1 sites and between 1/2 and 2/3 of the D3 sites are acid-resistant. A scheme for the mechanism of site formation upon heat-treatment is also proposed. This identification of the ORR-active sites in these catalysts is of crucial importance to design strategies to improve the catalytic activity and stability of these materials.     

pH-effect on oxygen reduction activity of Fe-based electro-catalysts

Recently, our group reported on an innovative synthesis of Fe/N/C-catalysts that considerably increased their activity for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). This work investigates the ORR-activity in 0.1 M KOH and 0.1 M HClO₄ of one such new Fe/N/C-catalyst prepared by ball-milling and compares it to that of a former Fe/N/C-catalyst prepared by impregnation and to that of 46 wt% Pt/C.At pH 13, the volumetric activities at 0.9 V vs. RHE of the ball-milling Fe/N/C-catalyst, the impregnation Fe/N/C-catalyst and 46 wt% Pt/C are 3.2, 0.3 and 14.8 A cm⁻³, respectively. The ball-milling Fe/N/C-catalyst is promising for alkaline fuel cells.     

Identification and Capture of Phenolic Compounds from a Rapeseed Meal Protein Isolate Production Process By-Product by Macroporous Resin and Valorization Their Antioxidant Properties

In this study, phenolic compounds from an aqueous protein by-product from rapeseed meal (RSM) were identified by HPLC-DAD and HPLC-ESI-MS, including sinapine, sinapic acid, sinapoyl glucose, and 1,2-di-sinapoyl gentibiose. The main phenolic compound in this by-product was sinapine. We also performed acid hydrolysis to convert sinapine, and sinapic acid derivatives present in the permeate, to sinapic acid. The adsorption of phenolic compounds was investigated using five macroporous resins, including XAD4, XAD7, XAD16, XAD1180, and HP20. Among them, XAD16 showed the highest total phenolic contents adsorption capacities. The adsorption behavior of phenolic compounds was described by pseudo-second-order and Langmuir models. Moreover, thermodynamics tests demonstrated that the adsorption process of phenolic compounds was exothermic and spontaneous. The highest desorption ratio was obtained with 30% (v/v) and 70% (v/v) ethanol for sinapine and sinapic acid, respectively, with a desorption ratio of 63.19 ± 0.03% and 94.68 ± 0.013%. DPPH and ABTS tests revealed that the antioxidant activity of the hydrolyzed fraction was higher than the non-hydrolyzed fraction and higher than the one of vitamin C. Antioxidant tests demonstrated that these phenolic compounds could be used as natural antioxidants, which can be applied in the food industry.