Search Results (8)

Following the core theme of a circular economy, a novel strategy to upcycle cigarette butt waste into platinum group metal (PGM)-free metal nitrogen carbon (M-N-C) electrocatalysts for oxygen reduction reaction (ORR) is presented. The experimental route was composed of (i) the transformation of the powdered cigarette butts into carbonaceous char via pyrolysis at 450 °C, 600 °C, 750 °C and 900 °C, (ii) the porosity activation with KOH and (iii) the functionalization of the activated chars with iron (II) phthalocyanine (FePc). The electrochemical outcomes obtained by the rotating disk electrode (RRDE) technique revealed that the sample pyrolyzed at 450 °C (i.e., cig_450) outperformed the other counterparts with its highest onset (E_on) and half-wave potentials (E_1/2) and demonstrated nearly tetra-electronic ORR in acidic, neutral and alkaline electrolytes, all resulting from the optimal surface chemistry and textural properties. Full article

The development of low-cost, highly active, and stable oxygen reduction reaction (ORR) catalysts is of great importance for practical applications in numerous energy conversion devices. Herein, iron/nitrogen/phosphorus co-doped carbon electrocatalysts (NPFe-C) with multistage porous structure were synthesized by the self-template method using melamine, phytic acid and ferric trichloride as precursors. In an alkaline system, the ORR half-wave potential is 0.867 V (vs. RHE), comparable to that of platinum-based catalysts. It is noteworthy that NPFe-C performs better than the commercial Pt/C catalyst in terms of power density and specific capacity. Its unique structure and the feature of heteroatom doping endow the catalyst with higher mass transfer ability and abundant available active sites, and the improved performance can be attributed to the following aspects: (1) Fe-, N-, and P triple doping created abundant active sites, contributing to the higher intrinsic activity of catalysts. (2) Phytic acid was crosslinked with melamine to form hydrogel, and its carbonized products have high specific surface area, which is beneficial for a large number of active sites to be exposed at the reaction interface. (3) The porous three-dimensional carbon network facilitates the transfer of reactants/intermediates/products and electric charge. Therefore, Fe/N/P Co-doped 3D porous carbon materials prepared by a facile and scalable pyrolysis route exhibit potential in the field of energy conversion/storage. Full article

The development of electrocatalysts for energy conversion and storage devices is of paramount importance to promote sustainable development. Among the different families of materials, catalysts based on transition metals supported on a nitrogen-containing carbon matrix have been found to be effective catalysts toward oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) with high potential to replace conventional precious metal-based catalysts. In this work, we developed a facile synthesis strategy to obtain a Fe-N-C bifunctional ORR/HER catalysts, involving wet impregnation and pyrolysis steps. Iron (II) acetate and imidazole were used as iron and nitrogen sources, respectively, and functionalized carbon black pearls were used as conductive support. The bifunctional performance of the Fe-N-C catalyst toward ORR and HER was investigated by cyclic voltammetry, rotating ring disk electrode experiments, and electrochemical impedance spectroscopy in alkaline environment. ORR onset potential and half-wave potential were 0.95 V and 0.86 V, respectively, indicating a competitive performance in comparison with the commercial platinum-based catalyst. In addition, Fe-N-C had also a good HER activity, with an overpotential of 478 mV @10 mAcm⁻² and Tafel slope of 133 mVdec⁻¹, demonstrating its activity as bifunctional catalyst in energy conversion and storage devices, such as alkaline microbial fuel cell and microbial electrolysis cells. Full article

Searching for high-efficient, good long-term stability, and low-cost electrocatalysts toward oxygen reduction reaction (ORR) is highly desirable for the development of sustainable energy conversion devices. Iron–nitrogen doped carbon (Fe–N/C) catalysts have been recognized as the most promising candidates for traditional Pt-based catalysts that benefit from their high activity, excellent anti-poisoning ability, and inexpensiveness. Here, a super-dispersed and high-performance Fe–N/C catalyst was derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. It produced a series of catalysts, whose sizes could be tuned in the range from 62 to over 473 nm in diameter. After rationally regulating the component and heating treatment, the best ORR activity was measured for the catalyst with a size of 105 nm, which was obtained when the Fe³⁺/Zn²⁺ molar ratio was 0.05 and carbonization temperature was 900 °C. It exhibited a high onset potential (E_onset = 0.99 V) and half-wave potential (E_1/2 = 0.885 V) compared with a commercial 20% Pt/C catalyst (E_onset = 0.10 V, E_1/2 = 0.861 V) as well as much better durability and methanol resistance in an alkaline electrolyte. Full article

The development of platinum group metal-free (PGM-free) electrocatalysts derived from cheap and environmentally friendly biomasses for oxygen reduction reaction (ORR) is a topic of relevant interest, particularly from the point of view of sustainability. Fe-nitrogen-doped carbon materials (Fe-N-C) have attracted particular interest as alternative to Pt-based materials, due to the high activity and selectivity of Fe-N_x active sites, the high availability and good tolerance to poisoning. Recently, many studies focused on developing synthetic strategies, which could transform N-containing biomasses into N-doped carbons. In this paper, chitosan was employed as a suitable N-containing biomass for preparing Fe-N-C catalyst in virtue of its high N content (7.1%) and unique chemical structure. Moreover, the major application of chitosan is based on its ability to strongly coordinate metal ions, a precondition for the formation of Fe-N_x active sites. The synthesis of Fe-N-C consists in a double step thermochemical conversion of a dried chitosan hydrogel. In acidic aqueous solution, the preparation of physical cross-linked hydrogel allows to obtain sophisticated organization, which assure an optimal mesoporosity before and after the pyrolysis. After the second thermal treatment at 900 °C, a highly graphitized material was obtained, which has been fully characterized in terms of textural, morphological and chemical properties. RRDE technique was used for understanding the activity and the selectivity of the material versus the ORR in 0.5 M H₂SO₄ electrolyte. Special attention was put in the determination of the active site density according to nitrite electrochemical reduction measurements. It was clearly established that the catalytic activity expressed as half wave potential linearly scales with the number of Fe-N_x sites. It was also established that the addition of the iron precursor after the first pyrolysis step leads to an increased activity due to both an increased number of active sites and of a hierarchical structure, which improves the access to active sites. At the same time, the increased graphitization degree, and a reduced density of pyrrolic nitrogen groups are helpful to increase the selectivity toward the 4e^- ORR pathway. Full article

Platinum group metal-free (PGM-free) catalysts based on transition metal-nitrogen-carbon nanomaterials have been studied by a combination of ex situ and in situ synchrotron X-ray spectroscopy techniques; high-resolution Transmission Electron Microscope (TEM); Mößbauer spectroscopy combined with electrochemical methods and Density Functional Theory (DFT) modeling/theoretical approaches. The main objective of this study was to correlate the HO₂⁻ generation with the chemical nature and surface availability of active sites in iron-nitrogen-carbon (Fe-N-C) catalysts derived by sacrificial support method (SSM). These nanomaterials present a carbonaceous matrix with nitrogen-doped sites and atomically dispersed and; in some cases; iron and nanoparticles embedded in the carbonaceous matrix. Fe-N-C oxygen reduction reaction electrocatalysts were synthesized by varying several synthetic parameters to obtain nanomaterials with different composition and morphology. Combining spectroscopy, microscopy and electrochemical reactivity allowed the building of structure-to-properties correlations which demonstrate the contributions of these moieties to the catalyst activity, and mechanistically assign the active sites to individual reaction steps. Associated with Fe-N_x motive and the presence of Fe metallic particles in the electrocatalysts showed the clear differences in the variation of composition; processing and treatment conditions of SSM. From the results of material characterization; catalytic activity and theoretical studies; Fe metallic particles (coated with carbon) are main contributors into the HO₂⁻ generation. Full article

The development of direct formate fuel cells encounters important obstacles related to the sluggish oxygen reduction reaction (ORR) and low tolerance to formate ions in Pt-based cathodes. In this study, electrocatalysts formed by earth-abundant elements were synthesized, and their activity and selectivity for the ORR were tested in alkaline electrolyte. The results showed that carbon-encapsulated iron-cobalt alloy nanoparticles and carbon-supported metal nitrides, characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD), do not present significant activity for the ORR, showing the same half-wave potential of Vulcan carbon. Contrarily, nitrogen-doped carbon, synthesized using imidazole as the nitrogen source, showed an increase in the half-wave potential, evidencing an influential role of nitrogen in the ORR electrocatalysis. The synthesis with the combination of Vulcan, imidazole, and iron or cobalt precursors resulted in the formation of nitrogen-coordinated iron (or cobalt) moieties, inserted in a carbon matrix, as revealed by X-ray absorption spectroscopy (XAS). Steady-state polarization curves for the ORR evidenced a synergistic effect between Fe and Co when these two metals were included in the synthesis (FeCo-N-C material), showing higher activity and higher limiting current density than the materials prepared only with Fe or Co. The FeCo-N-C material presented not only the highest activity for the ORR (approaching that of the state-of-the-art Pt/C) but also high tolerance to the presence of formate ions in the electrolyte. In addition, measurements with FeCo-N-C in the cathode of an passive air-breathing direct formate fuel cells, (natural diffusion of formate), showed peak power densities of 15.5 and 10.5 mW cm⁻² using hydroxide and carbonate-based electrolytes, respectively, and high stability over 120 h of operation. Full article

The great challenge of boosting the oxygen reduction reaction (ORR) activity of non-noble-metal electrocatalysts is how to achieve effective exposure and full utilization of nitrogen-rich active sites. To realize the goals of high utilization of active sites and fast electron transport, here we report a new strategy for synthesis of an iron and nitrogen co-doped carbon nanolayers-wrapped multi-walled carbon nanotubes as ORR electrocatalyst (N-C@CNT-Fe) via using partially carbonized hemoglobin as a single-source precursor. The onset and half-wave potentials for ORR of N-C@CNT-Fe are only 45 and 54 mV lower than those on a commercial Pt/C (20 wt.% Pt) catalyst, respectively. Besides, this catalyst prepared in this work has been confirmed to follow a four-electron reaction mechanism in ORR process, and also displays ultra-high electrochemical cycling stability in both acidic and alkaline electrolytes. The enhancement of ORR activity can be not only attributed to full exposure and utilization of active site structures, but also can be resulted from the improvement of electrical conductivity owing to the introduction of CNT support. The analysis of X-ray photoelectric spectroscopy shows that both Fe–N and graphitic-N species may be the ORR active site structures of the prepared catalyst. Our study can provide a valuable idea for effective improvement of the electrocatalytic activity of non-noble-metal ORR catalysts. Full article