Eduardo Gracia-Espino

Formation of nitrogen-doped graphene nanoscrolls by adsorption of magnetic γ-Fe2O3 nanoparticles

Graphene nanoscrolls are Archimedean-type spirals formed by rolling single-layer graphene sheets. Their unique structure makes them conceptually interesting and understanding their formation gives important information on the manipulation and characteristics of various carbon nanostructures. Here we report a 100% efficient process to transform nitrogen-doped reduced graphene oxide sheets into homogeneous nanoscrolls by decoration with magnetic γ-Fe2O3 nanoparticles. Through a large number of control experiments, magnetic characterization of the decorated nanoparticles, and ab initio calculations, we conclude that the rolling is initiated by the strong adsorption of maghemite nanoparticles at nitrogen defects in the graphene lattice and their mutual magnetic interaction. The nanoscroll formation is fully reversible and upon removal of the maghemite nanoparticles, the nanoscrolls return to open sheets. Besides supplying information on the rolling mechanism of graphene nanoscrolls, our results also provide important information on the stabilization of iron oxide nanoparticles.

Effects of 45-nm silver nanoparticles on coronary endothelial cells and isolated rat aortic rings

This study was undertaken to determine whether silver nanoparticles (Ag-45 nm NPs) induce selective and specific biological effects, such as induction of proliferation and nitric oxide (NO) production, and cytotoxicity in coronary endothelial cells (CECs), and regulation of vascular tone in isolated rat aortic rings. Physical characterization of Ag-45 nm NPs by transmission electron microscopy (TEM) demonstrated that nanoparticles ranging in size from 10 to 90 nm had biological effects on CECs. Increasing concentrations of Ag-45 nm NPs exerted a dual effect on cell proliferation whereby proliferation was inhibited at low concentrations of NPs and stimulated at high concentrations. The effects of high, but not low, concentrations of Ag-45 nm NPs were dependent on NO because the effects were partially blocked by N(G)-nitro-L-arginine methyl ester (L-NAME). We have also shown that high, but not low, concentrations of Ag-45 nm NPs induce NO-dependent proliferation through activation of endothelial nitric oxide synthase (eNOS) by phosphorylation of Serine 1177. Moreover, the antiproliferative and proliferative effects of Ag-45 nm NPs were concentration-dependent and inversely correlated with cellular toxicity. In isolated rat aortic rings, a low concentration of NPs induced vasoconstriction and a high concentration stimulated vasodilation. The physiologic effects induced by a low concentration of Ag-45 nm NPs inhibited acetylcholine- (ACh-) induced NO-mediated relaxation. Vasodilation induced by a high concentration of NPs was partially abolished by L-NAME pretreatment. When the endothelium was removed from the rings, all physiologic responses were blocked. These results clearly demonstrate that the NPs have selective and specific effects on the vascular endothelium in a concentration-dependent manner and suggest that opposite effects could be associated with NPs of different sizes.

Electrical Transport and Field-Effect Transistors Using Inkjet-Printed SWCNT Films Having Different Functional Side Groups

The electrical properties of random networks of single-wall carbon nanotubes (SWNTs) obtained by inkjet printing are studied. Water-based stable inks of functionalized SWNTs (carboxylic acid, amide, poly(ethylene glycol), and polyaminobenzene sulfonic acid) were prepared and applied to inkjet deposit microscopic patterns of nanotube films on lithographically defined silicon chips with a back-side gate arrangement. Source-drain transfer characteristics and gate-effect measurements confirm the important role of the chemical functional groups in the electrical behavior of carbon nanotube networks. Considerable nonlinear transport in conjunction with a high channel current on/off ratio of approximately 70 was observed with poly(ethylene glycol)-functionalized nanotubes. The positive temperature coefficient of channel resistance shows the nonmetallic behavior of the inkjet-printed films. Other inkjet-printed field-effect transistors using carboxyl-functionalized nanotubes as source, drain, and gate electrodes, poly(ethylene glycol)-functionalized nanotubes as the channel, and poly(ethylene glycol) as the gate dielectric were also tested and characterized.

Hydroxyl-functionalized and N-doped multiwalled carbon nanotubes decorated with silver nanoparticles preserve cellular function.

The present study aims to investigate biocompatibility of silver nanoparticles (Ag-NPs) anchored to different types of multiwalled carbon nanotubes (MWNTs). The MWNTs were decorated with Ag-NPs via a novel chemical route without using any sulfur containing reagent. Three different MWNTs were used as substrate materials for anchoring Ag-NPs: MWNTs-Ag (pure carbon), COx-MWNTs-Ag (carboxyl functionalized), and CNx-MWNTs-Ag (nitrogen-doped). The Ag-NPs, synthesized without thiol capping groups, and which were strongly anchored to the nanotubes surfaces, exhibit an average size of 7 ± 1, 10 ± 1, and 12 ± 1 nm in MWNTs, COx-MWNTs, and CNx-MWNTs, respectively. To determine biocompatibility of these three types of novel hybrid Ag-nanotube materials, cellular function and immune response were evaluated in the human keratinocyte cell line (HaCaT). Cellular assays revealed marginal toxicity after 24 h, and full cellular recovery was observed at 48 h based on an MTS assay for cellular viability. Therefore, Ag-nanotube systems appear to be very different from isolated dispersed Ag-NPs, and due to the strong interactions between the Ag-NPs and the doped nanotube surfaces, they make the Ag particles less toxic because they are not released easily to the cells. Pure carbon MWNTs appear to start releasing Ag-NPs at periods longer than 1 week by an observed decrease in cell proliferation. However, the use of N- and COx-doped MWNTs do not appear to release Ag-NPs to the cells due to the strong binding to the tube surfaces caused by the doped sites. We envisage the use of COx-MWNTs, and CNx-MWNTs anchored with Ag-NP as efficient drug delivery carriers and biosensors.

Small palladium islands embedded in palladium–tungsten bimetallic nanoparticles form catalytic hotspots for oxygen reduction

The sluggish kinetics of the oxygen reduction reaction at the cathode side of proton exchange membrane fuel cells is one major technical challenge for realizing sustainable solutions for the transportation sector. Finding efficient yet cheap electrocatalysts to speed up this reaction therefore motivates researchers all over the world. Here we demonstrate an efficient synthesis of palladium-tungsten bimetallic nanoparticles supported on ordered mesoporous carbon. Despite a very low percentage of noble metal (palladium:tungsten=1:8), the hybrid catalyst material exhibits a performance equal to commercial 60% platinum/Vulcan for the oxygen reduction process. The high catalytic efficiency is explained by the formation of small palladium islands embedded at the surface of the palladium-tungsten bimetallic nanoparticles, generating catalytic hotspots. The palladium islands are ~1 nm in diameter, and contain 10-20 palladium atoms that are segregated at the surface. Our results may provide insight into the formation, stabilization and performance of bimetallic nanoparticles for catalytic reactions.

Understanding the Interface of Six-Shell Cuboctahedral and Icosahedral Palladium Clusters on Reduced Graphene Oxide: Experimental and Theoretical Study

Studies on noble-metal-decorated carbon nanostructures are reported almost on a daily basis, but detailed studies on the nanoscale interactions for well-defined systems are very rare. Here we report a study of reduced graphene oxide (rGOx) homogeneously decorated with palladium (Pd) nanoclusters with well-defined shape and size (2.3 ± 0.3 nm). The rGOx was modified with benzyl mercaptan (BnSH) to improve the interaction with Pd clusters, and N,N-dimethylformamide was used as solvent and capping agent during the decoration process. The resulting Pd nanoparticles anchored to the rGOx-surface exhibit high crystallinity and are fully consistent with six-shell cuboctahedral and icosahedral clusters containing ~600 Pd atoms, where 45% of these are located at the surface. According to X-ray photoelectron spectroscopy analysis, the Pd clusters exhibit an oxidized surface forming a PdO(x) shell. Given the well-defined experimental system, as verified by electron microscopy data and theoretical simulations, we performed ab initio simulations using 10 functionalized graphenes (with vacancies or pyridine, amine, hydroxyl, carboxyl, or epoxy groups) to understand the adsorption process of BnSH, their further role in the Pd cluster formation, and the electronic properties of the graphene-nanoparticle hybrid system. Both the experimental and theoretical results suggest that Pd clusters interact with functionalized graphene by a sulfur bridge while the remaining Pd surface is oxidized. Our study is of significant importance for all work related to anchoring of nanoparticles on nanocarbon-based supports, which are used in a variety of applications.

Synergistic Effects between Atomically Dispersed Fe−N−C and C−S−C for the Oxygen Reduction Reaction in Acidic Media

Various advanced catalysts based on sulfur-doped Fe/N/C materials have recently been designed for the oxygen reduction reaction (ORR); however, the enhanced activity is still controversial and usually attributed to differences in the surface area, improved conductivity, or uncertain synergistic effects. Herein, a sulfur-doped Fe/N/C catalyst (denoted as Fe/SNC) was obtained by a template-sacrificing method. The incorporated sulfur gives a thiophene-like structure (C-S-C), reduces the electron localization around the Fe centers, improves the interaction with oxygenated species, and therefore facilitates the complete 4 e- ORR in acidic solution. Owing to these synergistic effects, the Fe/SNC catalyst exhibits much better ORR activity than the sulfur-free variant (Fe/NC) in 0.5 m H2 SO4 .

Reduction free room temperature synthesis of a durable and efficient Pd/ordered mesoporous carbon composite electrocatalyst for alkaline direct alcohols fuel cell

The development of easy and environmentally benign synthesis methods of efficient electrocatalysts for use in energy conversion applications motivates researchers all over the world. Here we report a novel and versatile method to synthesize well-dispersed palladium-functionalized ordered mesoporous carbons (Pd–OMCs) at room temperature without any reducing agent by one-pot mixing of tri(dibenzylideneacetone)palladium(0) (Pd2DBA3) and OMCs together in a common N,N-dimethylformamide (DMF) solution. The formation of Pd nanoparticles and their crystallization on the OMC is catalyzed by protons in the solution and can thus be controlled by the solution pH. The complete process and the as-prepared nanocomposite was characterized by UV-spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrum (XPS), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The electrocatalytic property of the decorated material was examined with cyclic voltammetry (CV). The Pd–OMC composite shows up to two times higher electrocatalytic ability with a significantly better durability towards ethanol and methanol oxidation in alkaline media compared to commercial high surface area conductive carbon black Vulcan XC-72 decorated with equivalent Pd nanoparticles. Our described method provides new insight for the development of highly efficient carbon based nanocatalysts by simple and environmentally sound methods.

Comprehensive Study of an Earth-Abundant Bifunctional 3D Electrode for Efficient Water Electrolysis in Alkaline Medium

We report efficient electrolysis of both water-splitting half reactions in the same medium by a bifunctional 3D electrode comprising Co3O4 nanospheres nucleated on the surface of nitrogen-doped carbon nanotubes (NCNTs) that in turn are grown on conductive carbon paper (CP). The resulting electrode exhibits high stability and large electrochemical activity for both oxygen and hydrogen evolution reactions (OER and HER). We obtain a current density of 10 mA/cm(2) in 0.1 M KOH solution at overpotentials of only 0.47 and 0.38 V for OER and HER, respectively. Additionally, the experimental observations are understood and supported by analyzing the Co3O4:NCNT and NCNT:CP interfaces by ab initio calculations. Both the experimental and the theoretical studies indicate that firm and well-established interfaces along the electrode play a crucial role on the stability and electrochemical activity for both OER and HER.

Sn/Be Sequentially co-doped Hematite Photoanodes for Enhanced Photoelectrochemical Water Oxidation : Effect of Be2+ as co-dopant

For ex-situ co-doping methods, sintering at high temperatures enables rapid diffusion of Sn4+ and Be2+ dopants into hematite (α–Fe2O3) lattices, without altering the nanorod morphology or damaging their crystallinity. Sn/Be co-doping results in a remarkable enhancement in photocurrent (1.7 mA/cm2) compared to pristine α–Fe2O3 (0.7 mA/cm2), and Sn4+ mono-doped α-Fe2O3 photoanodes (1.0 mA/cm2). From first-principles calculations, we found that Sn4+ doping induced a shallow donor level below the conduction band minimum, which does not contribute to increase electrical conductivity and photocurrent because of its localized nature. Additionally, Sn4+-doping induce local micro-strain and a decreased Fe-O bond ordering. When Be2+ was co-doped with Sn4+-doped α–Fe2O3 photoanodes, the conduction band recovered its original state, without localized impurities peaks, also a reduction in micro-strain and increased Fe-O bond ordering is observed. Also the sequence in which the ex-situ co-doping is carried out is very crucial, as Be/Sn co-doping sequence induces many under-coordinated O atoms resulting in a higher micro-strain and lower charge separation efficiency resulting undesired electron recombination. Here, we perform a detailed systematic characterization using XRD, FESEM, XPS and comprehensive electrochemical and photoelectrochemical studies, along with sophisticated synchrotron diffraction studies and extended X-ray absorption fine structure.