RESUMEN

Efficient and sustainable energy storage remains a critical challenge in the advancement of energy technologies. This study presents the fabrication and electrochemical evaluation of a self-supporting electrode material composed of MnO2 nanorods grown directly on a carbon paper and carbon nanotube (CNT) substrate using a hydrothermal method. The resulting CNT/MnO2 electrodes exhibit a unique structural architecture with a high surface area and a three-dimensional hierarchical arrangement, contributing to a substantial electrochemical surface area. Electrochemical testing reveals remarkable performance characteristics, including a specific capacitance of up to 316.5 F/g, which is 11 times greater than that of conventional CP/MnO2 electrodes. Moreover, the CNT/MnO2 electrodes demonstrate outstanding retention capacity, exhibiting a remarkable 165% increase over 10,000 cycles. Symmetric supercapacitor devices utilizing CNT/MnO2 electrodes maintain a large voltage window of 3 V and a specific capacitance as high as 200 F/g. These results underscore the potential of free-standing CNT/MnO2 electrodes to advance the development of high-performance supercapacitors, which can be crucial for efficient and sustainable energy storage solutions in various industrial and manufacturing applications.

RESUMEN

Infiltration of the mesoporous structure of SBA-15 silica as a hard template with phenanthroline complexes of Fe3+ and Co2+ allowed the simultaneous dispersion of nitrogen, iron and cobalt species on the surface of the obtained carbonaceous CMK-3 silica replica, with potential as bifunctional heterogeneous catalysts for the cathodic oxygen reduction and evolution reactions (ORR and OER). The textural properties and mesopore structure depended on the composition of the material. The carbonaceous FeCoNCMK-3 (1/1), obtained with an Fe/Co molar ratio of 1/1, exhibited an ordered cylindrical mesoporous structure with a high mesopore volume, a rather homogeneous composition in terms of total and surface concentrations of iron and cobalt, and a balanced presence of pyridinic-, pyrrolic- and graphitic-N species. FeCoNCMK-3 (1/1) could improve the ORR kinetics by adsorption and reduction of O2 through the 4-electron mechanism with a current density of -17.37 mA cm-2, Eonset of 1.13 V vs. RHE and E1/2 of 0.75 V when compared to metal-free, monometallic or bimetallic electrocatalysts with a higher amount of cobalt than that of iron. In addition, FeCoNCMK-3 (1/1) exhibited activity for the OER, presenting lower values of Eonset (1.52 V), Ej10 (1.78 V) and the Tafel slope (76.3 mV dec-1) with respect to other catalysts. When evaluated as a cathode in a prototype of a Zn-air battery, FeCoNCMK-3 (1/1) exhibited a high open circuit voltage of 1.41 V, a peak power density of 66.84 mW cm-2, a large specific capacity of 818.88 mA h gZn-1, and cycling for 20 h but with deactivation upon cycling.

RESUMEN

It is now recognized that the development of self-supported and efficient bifunctional air cathodes via the direct growth of earth-abundant catalysts onto the surface of the conductive collector would be a cutting-edge strategy to reduce interfacial resistance, enhance the mechanical tenure, and reduce the final weight and cost of manufacturing of rechargeable Zn-air batteries (ZABs). This work reports an innovative self-supported precious metal-free electrode, comprising carbon sphere chains (CSCs) directly grown onto a carbon paper (CP) substrate, wherein the CSCs have a functionalized surface bearing carbon nanobud defects, oxygen functional groups, and high-density MnO2 hierarchical nanorods (NRs), uniformly coating the surface of CSCs. Not only is the metal-free functionalized CSC catalyst functional for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) but its combination with MnO2 NRs impressively enhances the ORR/OER activities. A homemade ZAB assembled with functionalized CSC/MnO2 air cathode can successfully power a timer for a period of 17 days with no voltage loss, whereas two series-connected ZABs can light up 39 red light-emitting diode (LED) bulbs. The self-supported and earth-abundant-based CSC/MnO2 materials open up an opportunity for lightweight and cost-effective ZABs and metal-air batteries in general.

RESUMEN

We report here the synthesis of binderless and template-less three-dimensional (3D) pinecone-shaped Pt/TiO2/Ti mesh structure. The TiO2 hydrothermally synthesized onto Ti mesh is composed of a mixture of flower-like nanorods and vertically aligned bar-shaped structures, whereas Pt film grown by pulsed laser deposition displays a smooth surface. XRD analyses reveal an average crystallite size of 41.4 nm and 68.5 nm of the TiO2 nanorods and Pt, respectively. In H2SO4 solution, the platinum oxide formation at the Pt/TiO2/Ti mesh electrode is 180 mV more negative than that at the Pt/Ti mesh electrode, indicating that TiO2 provides oxygeneous species at lower potentials, which will facilitate the removal of CO-like intermediates and accelerate an ethanol oxidation reaction (EOR). Indeed, the Pt/TiO2/Ti mesh catalyst exhibits current activity of 1.19 mA towards an EOR at a remarkably superior rate of 4.4 times that of the Pt/Ti mesh electrode (0.27 mA). Moreover, the presence of TiO2 as a support to Pt delivers a steady-state current of 2.1 mA, with an increment in durability of 6.6 times compared to Pt/Ti mesh (0.32 mA). Pt is chosen here as a benchmark catalyst and we believe that with catalysts that perform better than Pt, such 3D pinecone structures can be useful for a variety of catalytic or photoelectrochemical reactions.

RESUMEN

It is today advanced that the development of a free-standing (binderless) air cathode via direct growth of nonprecious metal electrocatalysts onto the surface of the conductive collector would be a cutting-edge strategy to reduce the interfacial resistance, improve the mechanical stability, and reduce the final weight and the cost of manufacturing. Here, for Zn-air batteries (ZABs), we propose an innovative binderless noble-metal-free hierarchical nanostructured bifunctional air cathode in which high-density MnOx nanorods (NRs) are directly grown on carbon nanotubes (CNTs) themselves synthesized on a microfibrous carbon paper (CP) substrate. All carbon/MnOx air cathodes achieved specific capacities very close to the theoretical value of 820 mAh gZn-1. A very stable voltage gap between the charge and discharge processes along hundred cycles was obtained, demonstrating the stability and good bifunctional electrocatalytic activities of these cathodes toward the oxygen reduction reaction/oxygen evolution reaction in a real ZAB device. As a proof-of-concept for handheld electronic applications, a ZAB assembled with CP/MnOx NRs as the air electrode and a Zn plate anode operated a timer for 14 days successfully, whereas two ZAB-based CNTs/MnOx cathodes connected in series powered a 2 V light-emitting diode (LED) bulb and a 3 V multimeter. The proposed strategy and results may pave the way for the rational design of hierarchical free-standing bifunctional electrocatalysts for ZABs, other metal-air batteries, and fuel cells.

RESUMEN

The rational design of durable materials is an important issue for improving the performance of electrocatalysts towards the ethanol oxidation reaction (EOR). In this work, binderless thin nanostructured layers of SnO2, Pt, Rh, bilayers of Pt/SnO2, Rh/Pt and tri-layers of Rh (ca. 10 nm thickness)/PtSnO2 are directly grown by pulsed laser deposition onto carbon nanotubes (CNTs). SEM analysis shows that CNTs are perfectly coated with the catalysts. The onset potentials of the CO stripping and EOR indicate that Rh/Pt/SnO2 is the most active for the CO and the EOR. The incorporation of the CNTs in the catalyst layer is outstandingly beneficial to both the catalytic current activity and the durability. Indeed Rh/Pt/SnO2/CNT delivers mass activity as high as 213.42 mA mg-1 Pt. Moreover, Rh/Pt/SnO2/CNT demonstrates not only the lowest poisoning rate (by intermediate species, such as adsorbed CO) but also the highest durability current of 132.17 mA mg-1 Pt far superior to CNT-free Rh/Pt/SnO2/CP (58.33 mA mg-1 Pt). XPS shows that SnO2, Pt and Rh are all present at the surface of Rh/Pt/SnO2/CNT, the presence of two oxophilic materials like SnO2 and Rh, implies an earlier source of OHads-species, which facilitates the oxidation of CO and assuming a second contribution from Rh is to enhance the cleavage of the C-C bond for the complete oxidation of ethanol. The 3D porous and binderless structure, the low amount of the noble catalyst, the excellent electroactivity and durability of the Rh5/PtSnO2/CNT/CP composite represents an important step in advancing its use as an anode in commercial applications in DEFC.

RESUMEN

In this work, we report for the first time the use of tungsten oxide (WOx) as catalyst support for Au toward the direct electrooxidation of glucose. The nanostructured WOx/Au electrodes were synthesized by means of laser-ablation technique. Both micro-Raman spectroscopy and transmission electron microscopy showed that the produced WOx thin film is amorphous and made of ultrafine particles of subnanometer size. X-ray diffraction and X-ray photoelectron spectroscopy revealed that only metallic Au was present at the surface of the WOx/Au composite, suggesting that the WOx support did not alter the electronic structure of Au. The direct electrocatalytic oxidation of glucose in neutral medium such as phosphate buffered saline (pH 7.2) solution has been investigated with cyclic voltammetry, chronoamperometry, and square-wave voltammetry. Sensitivity as high as 65.7 µA cm(-2) mM(-1) up to 10 mM of glucose and a low detection limit of 10 µM were obtained with square-wave voltammetry. This interesting analytical performance makes the laser-fabricated WOx/Au electrode potentially promising for implantable glucose fuel cells and biomedical analysis as the evaluation of glucose concentration in biological fluids. Finally, owing to its unique capabilities proven in this work, it is anticipated that the laser-ablation technique will develop as a fabrication tool for chip miniature-sized sensors in the near future.

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RESUMEN

We present a free-standing catalyst layer comprising current collector/CNTs (catalyst support)/CeO(2)/Pt (catalyst) nanostructured layers, each layer constructed upon the one below it. FESEM and TEM showed that a CeO(2) layer has a fluffy morphology recalling the texture of cotton, whereas Pt nanoparticles assemble into cauliflower or broccoli-like arrangement. New insights have been gained into the effect of CeO(2) on the structural properties of the beneath CNTs layer and on the above Pt layer. First, by means of Raman analysis, it was found that interaction of CeO(2) with CNTs induced a decrease in the crystallinity of the latter. Second, by TEM and XPS analyses, it was observed that the size of Pt nanoparticles in the CNT/CeO(2)/Pt structure was inferior to that in the CNT/Pt, implying that CeO(2) influenced the dispersion quality of Pt nanoparticles. For the first time, it is observed that CeO(2) supported CNTs undergo oxidation/reduction reactions at low potentials in the ethanol electrolyte. The electrochemical analysis showed that entities produced from those redox processes are surface adsorbed/desorbed species most likely hydroxides. This unexpected electroactivity is due to the beneath CNTs that boosted the conductivity of CeO(2). Such improved conductivity of CeO(2) has fostered the electron-transfer kinetics of ethanol at Pt as demonstrated by the decreased overpotential required to oxidize ethanol and by the specific mass activity, which was greater than that of CNT/Pt.

Asunto(s)

RESUMEN

Interesting architectures built with electrically conductive substrates of interest for microelectrochemical power sources were obtained by directly growing carbon nanotubes on each microfibre constituting a carbon paper. The carbon nanotubes were fabricated by the chemical vapour deposition technique. Results of electrochemical tests showed high-resolution responses in different chemical media, which indicate good electrical contact between the carbon nanotubes and the carbon paper substrate. These architectures hold great promise for incorporation into microelectrochemical power sources.