Novel Co3O4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction (OER).
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ABSTRACT:
SUBMITTER: Yang X
PROVIDER: S-EPMC6199064 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:We investigate kinetic barriers for the oxygen evolution reaction (OER) on singly and doubly nitrogen-doped single-walled carbon nanotubes (NCNTs) using the climbing image nudged elastic band method with solvent effects represented by a 45-water-molecule droplet. The studied sites were chosen based on a previous study of the same systems utilizing a thermodynamic model which ignored both solvent effects and kinetic barriers. According to that model, the two studied sites, one on a singly nitrogen-doped CNT and the other on a doubly doped CNT, were approximately equally suitable for OER. For the four-step OER process, however, our reaction barrier calculations showed a clear difference in the rate-determining *OOH formation step between the two systems, with barrier heights differing by more than 0.4 eV. Thus, the simple thermodynamic model may alone be insufficient for identifying optimal OER sites. Of the remaining three reaction steps, the two H2O forming ones were found to be barrierless in all cases. We also performed solvent-free barrier calculations on NCNTs and undoped CNTs. Substantial differences were observed in the energies of the intermediates when the solvent was present. In general, the observed low activation energy barriers for these reactions corroborate both experimental and theoretical findings of the utility of NCNTs for OER catalysis.
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Project description:The realization of a hydrogen economy would be facilitated by the discovery of a water-splitting electrocatalyst that is efficient, stable under operating conditions, and composed of earth-abundant elements. Density functional theory simulations within a simple thermodynamic model of the more difficult half-reaction, the anodic oxygen evolution reaction (OER), with a single-walled carbon nanotube as a model catalyst, show that the presence of 0.3-1% nitrogen reduces the required OER overpotential significantly compared to the pristine nanotube. We performed an extensive exploration of systems and active sites with various nitrogen functionalities (graphitic, pyridinic, or pyrrolic) obtained by introducing nitrogen and simple lattice defects (atomic substitutions, vacancies, or Stone-Wales rotations). A number of nitrogen functionalities (graphitic, oxidized pyridinic, and Stone-Wales pyrrolic nitrogen systems) yielded similar low overpotentials near the top of the OER volcano predicted by the scaling relation, which was seen to be closely observed by these systems. The OER mechanism considered was the four-step single-site water nucleophilic attack mechanism. In the active systems, the second or third step, the formation of attached oxo or peroxo moieties, was the potential-determining step of the reaction. The nanotube radius and chirality effects were examined by considering OER in the limit of large radius by studying the analogous graphene-based model systems. They exhibited trends similar to those of the nanotube-based systems but often with reduced reactivity due to weaker attachment of the OER intermediate moieties.
| S-EPMC6240890 | biostudies-literature
Project description:Developing a highly active and cost-effective cathode electrocatalyst with strong stability for oxygen reduction reaction (ORR) is extremely necessary. In this work, we reported a facile synthetic path to prepare a hybrid nanostructure formed of nitrogen-doped Ketjenblack carbon (N-KC) supported Co3O4 nanoparticles (Co3O4/N-KC), which could be used as a promising and stable electrocatalyst for ORR. Compared with the physical mixture of Co3O4 and N-KC and pure N-KC samples, the resulting Co3O4/N-KC nanohybrid afforded remarkably superb ORR activity with a half-wave potential of 0.82 V (vs. reversible hydrogen electrode, RHE) and a limiting current density of 5.70 mA cm-2 in KOH solution (0.1 M). Surprisingly, the Co3O4/N-KC sample possessed a similar electrocatalytic activity but better durability to the 20 wt% Pt/C catalyst. The remarkable ORR activity of the Co3O4/N-KC nanohybrid was mainly due to the strong coupling effect between Co3O4 and N-KC, the N species dopant, high electroconductivity, and the large BET surface area. Our work enlightens the exploitation of advanced Co3O4/carbon hybrid material alternative to the Pt-based electrocatalysts.
| S-EPMC6904301 | biostudies-literature
Project description:2D nitrogen-doped mesoporous carbon (NMC) is synthesized by using a mesoporous silica film as hard template, which is then investigated as a non-precious metal catalyst for the oxygen reduction reaction (ORR). The effect of the synthesis conditions on the silica template and carbon is extensively investigated. In this work, we employ dual templates-viz. graphene oxide and triblock copolymer F127-to control the textural features of a 2D silica film. The silica is then used as a template to direct the synthesis of a 2D nitrogen-doped mesoporous carbon. The resultant nitrogen-doped mesoporous carbon is characterized by transmission electron microscopy (TEM), nitrogen ad/desorption isotherms, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and rotating disk electrode measurements (RDE). The electrochemical test reveals that the obtained 2D-film carbon catalyst yields a highly electrochemically active surface area and superior electrocatalytic activity for the ORR compared to the 3D-particle. The superior activity can be firstly attributed to the difference in the specific surface area of the two catalysts. More importantly, the 2D-film morphology makes more active sites accessible to the reactive species, resulting in a much higher utilization efficiency and consequently better activity. Finally, it is noted that all the carbon catalysts exhibit a higher ORR activity than a commercial Pt catalyst, and are promising for use in fuel cells.
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Project description:To improve the power generation of a microbial fuel cell (MFC), a porous nitrogen-doped graphene/carbon black (NG/CB) composite as efficient oxygen reduction reaction (ORR) electrocatalyst was successfully synthesized by pyrolyzing graphene oxide (GO) encapsulated CB with cetyltrimethyl ammonium bromide as a bridge. This concept-to-proof synthesis can be considered as a template-like method. Based on this method, one composite named as NG/CB-10 was acquired using the optimized GO-to-CB mass ratio of 10:1. Electrochemical tests demonstrate that NG/CB-10 can catalyze ORR in neutral-pH medium through a four-electron pathway with positively shifted the onset potential, the enhanced current density and reduced charge transfer resistance. CB addition also prolongs the stability of NG/CB-10. The enhancement in electrochemical performance of NG/CB-10 was attributed to the enlarged surface area, abundant mesopores and high content of pyridinic nitrogen. The maximum power density of MFC equipping NG/CB-10 as cathode electrocatalyst reached 936 mW·m-2, which was 26% higher than that of NG and equal to that of platinum/carbon. The cost of NG/CB-10 was reduced by 25% compared with that of NG. This work provides a novel method to synthesize promising ORR electrocatalyst for MFC in the future.
| S-EPMC6631044 | biostudies-literature
Project description:The purpose of this study is to develop an active, low cost, non-precious, stable, and high-performance catalyst for oxygen reduction reaction (ORR). In this regard, Mn2O3-decorated nitrogen-doped carbon nanosheets (Mn2O3/NC) are fabricated by a two-step strategy involving a hydrothermal method and a solid-state method. In the resultant structures, very fine Mn2O3 nanoparticles with an average size of about 5 nm are strongly attached to nitrogen-doped carbon nanosheets. The role of the Mn2O3 nanoparticles is to provide active sites for ORR, while the presence of the nitrogen-doped carbon not only enhances the conductivity of the overall structure but is also helpful for overall stability. The Mn2O3/NC shows good onset potential (0.80 V@-1 mA/cm2), methanol crossover effect, and stability (90%).
| S-EPMC6856643 | biostudies-literature
Project description:Juncus is a perennial herb aquatic plant found worldwide, with high reproductive ability in warm regions. It has three-dimensional hierarchical porous triangular networks structures composited of tubular fibers. Here, juncus derived nitrogen-doped porous carbon (NDPC) was prepared by mixing juncus and ZnCl2 through one-step pyrolysis and activation which is a low-cost, simple, and environmentally friendly method. The NDPC had hierarchical porous structures and a high specific surface area and was applied for supercapacitor and oxygen reduction reaction (ORR). The resulted NDPC-3-800 was prepared by mixing juncus with ZnCl2 at a mass ratio of 1:3 and then carbonized at 800°C, it was used as electrode material of a supercapacitor. The supercapacitor exhibited excellent specific capacitance of 290.5 F g-1 and 175.0 F g-1 in alkaline electrolyte at the current densities of 0.5 A g-1 and 50 A g-1, respectively. The supercapacitor showed good cycle stability, and the capacitance was maintained at 94.5% after 10,000 cycles. The NDPC-5-800 was prepared by mixing juncus with ZnCl2 at a mass ratio of 1:5 and then carbonized at 800°C. It exhibited outstanding ORR catalytic activity and stability attributing to their high specific surface area and abundant actives sites. The juncus can derive various materials for application in different fields.
| S-EPMC7174754 | biostudies-literature
Project description:Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN4C12, CoN3C10,porp and CoN2C5. The O2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0?V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O2-adsorption strength, we conclude that cobalt-based moieties bind O2 too weakly for efficient O2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.
| S-EPMC5715157 | biostudies-literature
Project description:In order to reduce fuel cell material cost and promote its application, it is urgent to develop non-noble metal materials to replace platinum as the cathode catalysts in fuel cells. The cobalt sulfide and nitrogen co-doped carbon (S-Co-N/C) materials with metal-organic frameworks as precursors have shown good oxygen reduction reaction (ORR) catalytic activity. Benefiting from the protection of catalytic active sites by sulfur atoms, the stability and alcohol-tolerance of the S-Co-N/C catalyst can be significantly improved. In order to fully understand the effect of the sulfurization process on the properties of the material, zeolite imidazole frameworks (ZIF)-8, and ZIF-67 are used as precursors to prepare a novel material of S-Co-N/C by using a sulfurization-pyrolysis method. Another S-Co-N/C material by using a pyrolysis- sulfurization method is prepared for comparison. The effects of the sulfurization process in the preparation on the morphology, chemical structure, specific surface area, and ORR catalytic activity of the final material are investigated. The experimental results show that the surface of the S-Co-N/C material tends to be rough due to the sulfurization reaction of the metal elements. The porosity of the material is reduced to some extent due to the remaining Zn elements in the final product. Interestingly, some carbon nanotubes are found to be generated on the surface of the S-Co-N/C material because of the synergistic effect of Zn and Co on the carbon material during the pyrolysis process, which is beneficial to accelerate the adsorption of oxygen on the S-Co-N/C surface and the electron transportation during the oxygen reduction reaction. In addition, the generated CoS during the sulfurization process can further protect the Co elements from agglomeration, which can effectively increase the ORR catalytic active sites in the final material. The S-Co-N/C material prepared by the sulfurization-pyrolysis method performs a superior ORR catalytic activity to the one synthesized by the pyrolysis-sulfurization method.
| S-EPMC7199712 | biostudies-literature
Project description:A massive amount of animal biomass is generated daily from livestock farms, agriculture, and food industries, causing environmental and ecological problems. The conversion of animal biomass into value-added products has recently gained considerable interest in materials science research. Herein, horse manure (HM) was utilized as a precursor for synthesizing nitrogen-doped carbons (NCs) via hydrothermal ammonia treatment and the post pyrolysis process. The ammonia concentration varied between 0.5, 1.0, and 1.5 M in the hydrothermal process. From the comprehensive characterization results, horse manure-derived nitrogen-doped carbons (HMNCs) exhibited an amorphous phase and a hierarchical nanoporous structure. The specific surface area decreased from 170.1 to 66.6 m2 g-1 as the ammonia concentration increased due to micropore deterioration. The nitrogen content was 0.90 atom% even with no ammonia treatment, indicating self-nitrogen doping. With hydrothermal ammonia treatment, the nitrogen content slightly enhanced up to 1.54 atom%. The electrocatalytic activity for the oxygen reduction reaction (ORR) of HMNCs in an alkaline solution was found to be related to nitrogen doping content and porous structure. The ORR activity of HMNCs mainly proceeded via a combination of two- and four-electron pathways. Although the ORR activity of HMNCs was still not satisfactory and comparable to that of a commercial Pt/carbon catalyst, it showed better long-term durability. The results obtained in this work provide the potential utilization of HM as a precursor for ORR catalysts and other related applications.
| S-EPMC9194922 | biostudies-literature