Microstructure effect of carbon nanofibers on Pt/CNFs electrocatalyst for oxygen reduction

Pt nanoparticles supported on microstructure controllable carbon nanofibers (CNFs), i.e. platelet CNFs (p-CNFs), fish-bone CNFs (f-CNFs) and tubular CNFs (t-CNFs), are synthesized, and CNF microstructure effect on physio-chemical and oxygen reduction reaction (ORR) properties of Pt/CNFs is investigated. The physio-chemical properties of different Pt/CNFs electrocatalysts are characterized by high resolution transmission electron microscope (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). HRTEM results exhibit Pt nanoparticles are uniformly dispersed on CNF surface, and Pt/p-CNFs shows a smaller particle size compared with those other catalysts. XPS results reveal that CNF microstructure can influence the metal–support interaction, and Pt/p-CNFs have a higher binding energy compared with Pt/t-CNFs. From cyclic voltammetric studies, it is found that Pt/p-CNFs performed a higher ORR activity than Pt/f-CNFs and Pt/t-CNFs, which may be resulted from the smaller Pt particle size and the stronger metal–support interaction of Pt/p-CNFs. Furthermore, CNF microstructure can influence the reaction process. ORR on Pt/p-CNFs or Pt/f-CNFs is controlled by diffusion process, while on Pt/t-CNFs is surface reaction controlled.     

Pt nanodendrites anchored on bamboo-shaped carbon nanofiber arrays as highly efficient electrocatalyst for oxygen reduction reaction

In order to improve the Pt utilization and enhance their catalytic performance in fuel cells, a novel composite electrode composed of single-crystalline Pt nanodendrites and support constructed by bamboo-shaped carbon nanofiber arrays (CNFAs) on carbon paper, is reported. This electrode is designed by growing vertically CNFAs on carbon paper via plasma enhanced chemical vapor deposition, followed by the direct synthesis of Pt nanodendrites using a simple surfactant-free aqueous solution method. Electron microscopy studies reveal that the Pt nanodendrites are uniformly high dispersed and anchored on the surface of CNFAs. Electrochemical measurements demonstrate that the resultant electrode exhibits higher electrocatalytic activity and stability for oxygen reduction reaction than commercial Pt/C catalyst, suggesting its potential application in fuel cells.     

Ultrasonic synthesis of nitrogen-doped carbon nanofibers as platinum catalyst support for oxygen reduction

Oxygen- and nitrogen-containing groups are successfully introduced onto the carbon nanofiber (CNF) surfaces by sonochemical treatment in mixed acids (concentrated sulfuric acid and nitric acid) and ammonia, respectively. Pt electrocatalysts supported on the acid-treated CNF (CNF-O) and ammonia-treated CNF (CNF-ON) are prepared and the effect of CNF surface functional groups on the electrocatalytic activities of supported catalysts for oxygen reduction reaction (ORR) is investigated. High resolution transmission electron microscopy reveals that Pt particles are uniformly dispersed on the two CNF supports and the CNF-ON supported Pt nanoparticles have a smaller average particle size and a more uniform particle size distribution. Cyclic voltammetric analysis shows the Pt/CNF-ON has a larger electrochemically active surface area than Pt/CNF-O. Rotating disk electrode measurements show that the Pt/CNF-ON exhibits a considerably higher electrocatalytic activity toward ORR as compared with Pt/CNF-O. It is believed that the good electrocatalytic activity of Pt/CNF-ON can be attributed to the smaller Pt particle size and more uniform particle size distribution, to the synergistic effect and the enhanced Pt-CNF-ON interaction, and to the unique structural and electronic properties of CNF-ON.     

PtCo incorporated porous carbon nanofiber as a promising oxygen reduction electrocatalyst

Designing oxygen reduction reaction (ORR) catalysts with high activity and long durability is significant for the development of proton exchange membrane fuel cells. Herein, the optimized platinum nanowires are used as templates for inducing growth of cobalt-containing metal-organic framework, deriving uniform nanofibers. After the calcination, the metal ions are transferred into the nitrogen-rich porous carbon, and wrapped by the carbon skeleton to form the PtCo bimetal incorporated nanofibers as high-performance ORR electrocatalyst. The Pt₄Co@NC-900 catalyst yields high specific activity (1.37 mA cm⁻²) in comparison to Pt/C (0.38 mA cm⁻²). The mass activity (MA) of Pt₄Co@NC-900 catalyst is approximately 3.8-fold higher than that of the commercial Pt/C under acidic conditions. After the accelerated durability tests, the Pt₄Co@NC-900 catalyst presents only 16% loss in MA, while Pt/C catalyst retains 73.0% of the initial MA. The improved ORR performance can be ascribed to the synergistic interaction between Co and Pt.     

Three-dimensional nitrogen-doped carbon nanotubes/carbon nanofragments complexes for efficient metal-free electrocatalyst towards oxygen reduction reaction

Heteroatom-doped carbon materials as one of the most promising oxygen reduction reaction (ORR) catalysts have attracted much attention. Rational design and exploration of suitable heteroatom-doped carbon materials greatly affects their ORR performance. Herein, we successfully prepared nitrogen-doped carbon nanotubes/carbon nanofragments (NCNT/CNF) complexes by a pyrolysis process using oxidized open-ended carbon nanotubes (OCNT)/oxidized carbon nanofragments (OCNF) hybrids as carbon precursors. The effect of carbon precursors on the synthesis of the corresponding nitrogen-doped carbon products was systematically investigated. The result showed the OCNT retained good conductivity, while the OCNF offered adequate structure defects for efficient post-doping. Benefiting from the co-merits of sole constitute, the obtained NCNT/CNF_1-15 (1–15 refers to the mass ratio) complexes possessed a typical three-dimensional architecture and much increased specific surface area, which facilitated reactant/electrolyte infiltration and ion/electron transfer. More importantly, they built the most optimized balance on ORR catalytic sites and conductivity. Thus, the NCNT/CNF_1-15 complexes showed much enhanced ORR performance. Clearly, our work provides a good guidance on the design of advanced heteroatom-doped carbon-based ORR catalysts.     

Waste wine mash-derived doped carbon materials as an efficient electrocatalyst for oxygen reduction reaction

Oxygen reduction reaction (ORR) is a core reaction of fuel cell and metal-air cell. In recent years, it has been a hot topic to study non-precious metal catalysts for ORR. Herein, we have used waste wine mash-derived carbon, melamine and ferric chloride to prepare a Fe- and N- co-doped carbon catalyst. The specific surface area of the catalyst is up to 1066.6 m² g⁻¹. And its wave potential is 15 mV higher than that of commercial Pt/C catalyst. The ORR on our catalyst followed a four-electron pathway; and it has high stability and high impressive immunity to methanol. After continuous oxygen reduction of 30,000s, the retention rate is 90%.     

Oxidized carbon/nano-SiC supported platinum nanoparticles as highly stable electrocatalyst for oxygen reduction reaction

Nano-SiC particles with derived carbon shells were prepared by an acid-etching method at room temperature. The mixture solutions of concentrated HF and HNO₃ were chosen to etch the nano-SiC particles, and an amorphous carbon shell absorbed by oxygen functional groups was formed on the SiC surface. The oxidized carbon/SiC (O-C/SiC) particles were used as supports for preparation of Pt electrocatalysts. The O-C/SiC supported Pt electrocatalysts showed a high catalytic activity and an excellent stability for oxygen reduction reaction. The improved stability can be ascribed to the anchoring effect of the carbon shell to Pt NPs and the high stability of nano-SiC core.     

ZIF-8/PEDOT @ flexible carbon cloth electrode as highly efficient electrocatalyst for oxygen reduction reaction

Design and fabrication of highly efficient and low-cost oxygen reduction reaction (ORR) electrocatalysts is of paramount importance for practical applications. Herein, we proposed a cost-effective, metal-free catalyst based on ZIF-8 metal-organic framework nanoparticles/electro-polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) film on the surface of flexible carbon cloth (CC) electrode (ZIF-8/PEDOT/CC) via a two-step procedure. For this purpose, worm-like PEDOT nanostructures were deposited on the surface of carbon fibers using a pulse electro-polymerization technique followed by facile growth of ZIF-8 polyhedra nanoparticles via a chemical bath deposition method. The ORR measurements in O₂-saturated KOH electrolyte solution using the modified CC electrode demonstrated that the prepared electrode exhibits remarkable electrocatalytic activity towards ORR with 8 times increase in the cathodic current density compared to bare CC (J = 0.13–1.1 mA/cm²) along with lower overpotential due to the synergetic effects between ZIF-8 nanoparticles as particularly porous nanostructure act as electrolyte reservoirs and highly conductive PEDOT film. The Kouteckey-Levich analysis for the ZIF-8/PEDOT-modified CC electrode revealed that the oxygen reduction reaction proceeds via a nearly four-electron pathway along with superior tolerance to methanol crossover as well as enhanced stability in alkaline solution compared to the gold standard commercial Pt catalyst.     

Heteroatom-doped carbon nanospheres derived from cuttlefish ink: A bifunctional electrocatalyst for oxygen reduction and evolution

The development of efficient bifunctional catalysts for both oxygen reduction and oxygen evolution reactions is highly desirable but challenging in energy conversion and storage systems. Here, a simple yet cost-effective strategy is developed to produce heteroatom-doped carbon nanospheres using natural cuttlefish ink as the precursor. For the oxygen reduction reaction, the catalyst exhibits more positive onset-potential and larger diffusion limiting current density compared with benchmark platinum catalyst in alkaline medium. Moreover, the as synthesized catalyst shows low onset-potential for oxygen evolution reaction, indicating its outstanding catalytic activity. The catalyst shows a potential gap of 0.75 V between the oxygen evolution reaction potential at a current density of 10 mA cm^?2 and the oxygen reduction reaction potential at the half-wave potential, outperforming most of other noble metal-free carbon catalysts in the current state of research. The remarkable catalytic performance can be assigned to heteroatoms doping, full exposure of the active sites, large surface area and enrichment of pores for sufficient contact and rapid transportation of the reactants. This study offers a new approach for the synthesis of metal-free carbon nanomaterials from natural resources, and broadens the design for the fabrication of bifunctional oxygen reduction and oxygen evolution catalysts.     

Encapsulation of metal precursor within ZIFs for bimetallic N-doped carbon electrocatalyst with enhanced oxygen reduction

High-performance non-precious metal-doped carbon catalysts for oxygen reduction reactions (ORR) are viable candidates in lieu of platinum-based catalysts. It has been universally reported that active Co–N sites combined with Fe–N sites embedded in carbon matrix represent the most promising active sites for ORR process. Benefiting from the cage-encapsulated-precursor pyrolysis strategy, herein, we fabricated a Fe–N and Co–N homogeneously doped carbon framework by one step. TEM demonstrated the ultimate product had well-defined morphology with Fe (0.54 at%), Co (0.31 at%) and N (2.94 at%) uniformly distributed into the carbon skeleton. The N₂ absorption-desorption isotherms indicated the MOF-derived catalyst had a high specific surface area of 647.6 m² g^?1 and inherit hierarchical porosity. Significantly, such FeCo–NC catalyst outperformed a current density (5.6 mA cm^?2) at 0.70 V (vs reversible hydrogen electrode) 1.18 times higher than that of a commercial 20 wt% Pt/C (5 mA cm^?2) catalyst in alkaline medium, and more positive peak potential of 0.63 V than its counterparts. Its high cycling stability and immunity towards methanol crossover in a wide range pH value showed good potential to be used as cathodes in proton exchange membrane fuel cells (PEMFCs) for long term operation. This simple synthesis strategy would to some degree leverage a cage-encapsulated-precursor for tailored utility of active sites for ORR in a porous carbon framework.     

Supercapacitors using carbon nanotubes films by electrophoretic deposition

Multi-walled carbon nanotube (MWNT) thin films have been fabricated by electrophoretic deposition technique in this study. The supercapacitors built from such thin film electrodes have exhibited near-ideal rectangular cyclic voltammograms even at a scan rate as high as 1000 mV s⁻¹ and a high specific power density over 20 kW kg⁻¹. More importantly, the supercapacitors showed superior frequency response, with a frequency ‘knee’ at about 7560 Hz, which is more than 70 times higher than the highest ‘knee’ frequency (100 Hz) so far reported for such supercapacitors. Our study also demonstrated that these carbon nanotube thin films can serve as a coating layer over ordinary current collectors to drastically enhance the electrode performance, indicating the huge potential in supercapacitor and battery manufacturing. Finally, it is clear that electrophoretic deposition is a promising technique for massive fabrication of carbon nanotube electrodes for various electronic devices.     

Mn3O4 nanosheets coated on carbon nanotubes as efficient electrocatalysts for oxygen reduction reaction

MnO-MnC_x coated carbon nanotubes (MnO/MnC_x/CNTs) nanocomposites were prepared by a one-pot deposition method. The coating consisted of MnO, Mn₅C₂, Mn₁₅C₄ and Mn₂₃C₆ was formed on the surface of CNTs by heating a mixture of Mn particles and CNTs at 600 °C for 40 min under vacuum. Then after heated MnO/MnC_x/CNTs in air at 350 °C for 2 h, MnO nanoparticles were partially converted to Mn₃O₄ nanosheets. Then Mn₃O₄-MnC_x coated carbon nanotubes (Mn₃O₄/MnC_x/CNTs) composed of interconnected nanosheets structure were successfully synthesized by a two-step method of one-pot deposition and heat post-treatment. The Mn₃O₄/MnC_x/CNTs showed better oxygen reduction reaction performance in alkaline condition than MnO/MnC_x/CNTs and pristine CNTs. Besides, the formed MnC_x (Mn₅C₂ and Mn₂₃C₆) by one-pot deposition method provided a strong interface bonding between Mn₃O₄ and CNTs, leading to improved stability of Mn₃O₄/MnC_x/CNTs as an electrode material.     

Nitrogen doped amorphous carbon as metal free electrocatalyst for oxygen reduction reaction

A non metal catalyst for the oxygen reduction reaction is prepared by simply pyrolyzing ion exchange resin D113 in NH₃. The product is nitrogen doped amorphous carbon. The pyrolysis of D113 exchanged with iron ion results in nitrogen doped graphitic carbon. The amorphous carbon is easier to be doped by NH₃ with higher nitrogen content. The nitrogen doped amorphous carbon is more active than graphitized carbon, together with much improved stability. The higher activity is explained by the higher total nitrogen content and higher pyridinic/graphitic nitrogen percentage. The higher stability is because there is no loss or dissolution of the active sites. The results of this work prove metal element and graphitization of carbon are not necessary factors for nitrogen doped carbon as non noble metal catalyst for the oxygen reduction reaction.     

Electrosynthesis of Mn-Fe oxide nanopetals on carbon paper as bi-functional electrocatalyst for oxygen reduction and oxygen evolution reaction

A layered binary Mn-Fe oxide as bi-functional electro-catalyst with nanopetals morphology is grown on porous carbon paper for the first time via one-step electrodeposition process. The electrocatalyst is characterized by X-ray diffraction, scanning electron microscopy (SEM) and energy dispersive spectroscopy analysis. SEM analysis demonstrates notable morphology viz. nanopetals of the Mn-Fe oxide grown on carbon paper. The electrocatalytic activity is checked for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline medium. Rotating disk electrode (RDE) voltammetry is carried out to study the ORR kinetics, which proves that ORR process follows four-electron pathway in alkaline medium. Oxygen evolution reaction study reveals that it has higher activity for OER with a lower onset potential of 1.6 V vs RHE and higher current density of 11.5 mA/cm² at 2.0 V vs RHE reference electrode.     

Melamine-assisted synthesis of paper mill sludge-based carbon nanotube/nanoporous carbon nanocomposite for enhanced electrocatalytic oxygen reduction activity

Developing efficient and cheap electrocatalysts as substitutes for commercial Pt/C in the oxygen reduction reaction(ORR)is extremely necessary. Herein, paper mill sludge (PMS) was utilized to produce iron, nitrogen and sulfur co-doped carbon nanotube/nanoporous carbon nanocomposite (PMS-CNT/C) by pyrolysis. PMS-CNT/C-b, one of as-prepared PMS-CNT/C exhibited excellent oxygen reduction reaction activity with an onset potential of 0.99 V vs. RHE and half-wave potential of 0.77 V vs. RHE, which was similar to the commercial Pt/C catalyst (onset potential of 0.99 V vs. RHE and half-wave potential of 0.76 V vs. RHE). It had longer-term stability and higher methanol tolerance in alkaline medium than Pt/C. Moreover, the new catalyst also exhibited excellent catalytic performance in neutral solution. The energy output of microbial fuel cells loaded with PMS-CNT/C-b catalyst was also higher than that of commercial Pt/C under neutral condition. The excellent ORR performance of PMS-CNT/C-b was due to the carbon nanotube/nanoporous structure and the synergistic effect of abundant N groups, iron nitrides and thiophene-S. The formation of CNTs in the carbon nanotube/nanoporous carbon nanocomposite was mainly attributed to melamine, which was added into PMS and was at first just considered as a nitrogen source to develop N-doped PMS-based catalysis in this work. The synthesis of paper mill sludge-based carbon nanotube/nanoporous nanocomposite and its excellent ORR activity will make the new catalyst a promising cathodic electrocatalyst alternative for fuel cells.     

Spindle-shaped CeO2/biochar carbon with oxygen-vacancy as an effective and highly durable electrocatalyst for oxygen reduction reaction

Highly durable and active CeO₂ on biochar carbon (CeO₂/BC) derived from Spirulina platensis microalgae and synthesized by simple one-pot hydrothermal treatment and further activated through pyrolysis approach. A spindle-shaped morphology of CeO₂ with predominant (111) facet was evidently observed from X-ray diffraction patterns and electron microscopy images. The structural features such as high specific surface area, defect-rich carbon with N & P atoms, increased oxygen vacancy and π-electron transfer play an important role for the improved oxygen reduction reaction (ORR). The considerable amount of Ce³⁺ and higher proportion of pyridinic N and graphitic N species are substantially contributed to the superior ORR performance of CeO₂/BC700, which surpasses other similar catalysts and competing with Pt/C. Hence, the significant kinetic ORR parameters and extended stability (no loss after 5000 potential cycles) of the CeO₂/BC700 catalysts provides the promising insight to develop the rare-earth metal oxide nanostructures as a possible candidate for ORR in alkaline medium.     

Celery-like nitrogen and phosphorous co-doped carbon nanofiber frameworks supporting oxygen reduction and methanol oxidation electrocatalysis

Doped materials with well-defined morphologies have attracted substantial research interest due to their excellent activity and stability in fuel cells. Herein, celery-like nitrogen and phosphorous co-doped carbon nanofibers frameworks (PNCNF) have been successfully fabricated via a novel in-situ doping and self-assembly strategy, serving as superior supports for uniform Pt nanoparticles. The resulting Pt/PNCNF composite possesses a porous architecture and high-surface area, which exhibits remarkable mass activity, durability, and anti-poisoning ability towards oxygen reduction and methanol oxidation reactions, compared to the commercial Pt/C electrocatalyst. In addition, the high CO tolerance of Pt/PNCNF could be ascribed to a strong interaction between the Pt nanocrystals and PNCNF, which facilitates OH^? adsorption to remove CO intermediate. The improved electrocatalytic properties benefit from the morphological and compositional advantages of the N and P co-doped carbon nanofiber frameworks. Specifically, the orientation of celery-like carbon nanofibers layers in Pt/PNCNF optimizes its mechanical properties. This synthetic strategy for the preparation of N and P co-doped carbon is envisaged as a new and general pathway for the rational engineering of heteroatom doped carbon composites for renewable energy conversion applications.     

Flame synthesis of nitrogen,boron co-doped carbon as efficient electrocatalyst for oxygen reduction reaction

The flame synthesis provides a simple low-cost method to produce novel carbon materials. In this study, N, B co-doped carbon (NBC) materials have been prepared by flame synthesis. Among many as-prepared samples, the NBC catalyst which prepared under carbonization temperature of 1000 °C for 3 h with acetonitrile/acetone precursor of 1:1 exhibits the best catalytic activity and stability, as well as good resistance to methanol interference for oxygen reduction reaction (ORR), with half-wave potential being almost nearly to Pt/C, and a quasi-four-electron transfer process. This study would provide an economic, environmental feasible and scalable approach for fabricating novel heteroatom co-doped carbon materials for ORR applications.     

Trace sulfur promoted Fe,N-codoped carbon black as electrocatalyst for oxygen reduction reaction

Doping carbon materials with Fe and N attracts great attention due to its promising application in preparing ORR electrode with high performance and low cost. Previously, Fe, N-codoped catalyst (Fe/N/C) had been synthesized via a simple one-pot method using carbon materials, dopamine and FeCl₃ by our group. However, the unstable activity and low selectivity (electron transfer number of ∼3.5) are key problems that should be solved. Herein, trace sulfur has been introduced into Fe, N-codoped carbon black by using 2-mercaptoethanol as an adhesive sulfur precursor. By the doping of trace S atoms (∼0.25 at%) into Fe, N-codoped carbon frameworks, the ORR performance has been obviously improved simply without any re-treatment process, such as acid-etching or nitrogen supplement. The mechanism of this process has been systematically investigated by changing the amount of initial sulfur precursor. A moderate amount of trace sulfur can effectively enhance the ORR performance of Fe, N-codoped carbon black due to suitable interactions among Fe, N, S and C elements. Both the content and the state of Fe and N species on the surface of carbon black can be changed and controlled by trace sulfur. The as-synthesized 1.0 SFe/N/C catalyst exhibits a good ORR activity (E_1/2 = 0.749 V, J_k = 54.56 mA cm⁻²) and a total 4-electron selectivity. 1.0 SFe/N/C also shows better catalytic stability and methanol tolerance than 20 wt% Pt/C.     

Stability of hemin/C electrocatalyst for oxygen reduction reaction

Hemin has been reported to be an effective electrocatalyst for mediating the oxygen reduction reaction. In this work, the stability of hemin/C is extensively investigated in both acid and alkaline media by the electrochemical methods. It is found that the pristine hemin/C yields significant change in the composition and the electrochemical features when it undergoes the potential cycling in acid media. In comparison, the catalyst shows superior stability in alkaline media. The pyrolysis can improve the stability of the hemin/C catalyst by removing the organic groups in hemin; however, the heat treatment cannot prevent the metal ion loss in acid media. Finally, the acid-leaching experiment reveals that the active center for the 4-electron reaction tends to get lost in acid, indicating that the iron metal ion should be involved in catalyzing the 4-electron reduction reaction. Furthermore, the XPS result indicates that the element N is also involved in the active center. Therefore, it can be concluded that the Fe–N contributes to the active center for the complete reduction of oxygen in alkaline media.