Support-based transfer and contacting of individual nanomaterials for in-situ nanoscale investigations

Although in-situ transmission electron microscopy (TEM) of nanomaterials has been gaining importance in recent years, difficulties in sample preparation have limited the number of studies on electrical properties. Here, a support-based preparation method of individual 1D and 2D materials is presented, which yields a reproducible sample transfer for electrical investigation by in-situ TEM. Using a mechanically rigid support grid allows the reproducible transfer and contacting to in-situ chips by focused ion beam with minimum damage and contamination. The transfer quality is assessed by exemplary studies of different nanomaterials, including a monolayer of WS2. Preliminary results from in-situ test experiments give an overview of possible studies, which concern the interplay between structural properties and electrical characteristics on the individual nanomaterial level as well as failure analysis under electrical current or studies of electromigration, Joule heating and related effects. The TEM measurements can be enriched by additional correlative microscopy techniques, which allow the study with a spatial resolution in the range of a few microns. Although developed for in-situ TEM, the present transfer method is also applicable to transferring nanomaterials to similar chips for performing further studies or even for using them in potential electrical/optoelectronic/sensing devices.Comment: 23 pages, 15 figure

Gap and Van Hove Measurements via Low-loss Electron Energy Loss Spectroscopy on Atomically thin MoxW(1-x)S2 Nanoflakes

Band gap tailoring of 2D materials has been of interest for the past years. Using low-loss electron energy loss spectroscopy (EELS), in a scanning transmission electron microscope (STEM), it has been confirmed, following previous experimental (photoluminescence) and theoretical (DFT) studies, that the band gap of atomically thin nanoflakes of MoxW(1-x)S2 does shift with the alloying degree of the sampl

Generation of gold nanoclusters encapsulated in an MCM-22 zeolite for the aerobic oxidation of cyclohexane

[EN] In this work, we will report the generation of Au clusters in a purely siliceous MCM-22 zeolite. The catalytic properties of these Au clusters have been tested for the selective oxidation of cyclohexane to cyclohexanol and cyclohexanone (KA-oil). The Au clusters encapsulated in the MCM-22 zeolite are highly active and selective for the oxidation of cyclohexane to KA-oil, which is superior to Au nanoparticles on the same support. These results suggest that Au clusters are highly active for the activation of oxygen to produce radical species.This work has been supported by the European Union through the European Research Council (grant ERC-AdG-2014-671093, SynCatMatch) and the Spanish government through the "Severo Ochoa Program" (SEV-2016-0683). The authors also thank the Microscopy Service of UPV for kind help with TEM and STEM measurements. Mr J. A. Gaona is greatly acknowledged for his very helpful assistance on the catalytic studies. The XAS data were acquired at European Synchrotron Radiation Facility. The HAADF-HRSTEM studies were conducted in the Laboratorio de Microscopias Avanzadas (LMA) at the Instituto de Nanociencia de Aragon (INA)-Universidad de Zaragoza (Spain), Spanish ICTS National facility. R. A. gratefully acknowledges the support from the Spanish Ministry of Economy and Competitiveness (MINECO) through project grant MAT2016-79776-P (AEI/FEDER, UE).Liu, L.; Arenal, R.; Meira, DM.; Corma Canós, A. (2019). Generation of gold nanoclusters encapsulated in an MCM-22 zeolite for the aerobic oxidation of cyclohexane. Chemical Communications. 55(11):1607-1610. https://doi.org/10.1039/c8cc07185cS160716105511Claus, P. (2005). Heterogeneously catalysed hydrogenation using gold catalysts. Applied Catalysis A: General, 291(1-2), 222-229. doi:10.1016/j.apcata.2004.12.048Hashmi, A. S. K., & Hutchings, G. J. (2006). Gold Catalysis. 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J., Navas, J., Yacaman, M. J., … Mayoral, A. (2013). Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity. Nature Chemistry, 5(9), 775-781. doi:10.1038/nchem.1721Boronat, M., Leyva-Pérez, A., & Corma, A. (2013). Theoretical and Experimental Insights into the Origin of the Catalytic Activity of Subnanometric Gold Clusters: Attempts to Predict Reactivity with Clusters and Nanoparticles of Gold. Accounts of Chemical Research, 47(3), 834-844. doi:10.1021/ar400068wYamazoe, S., Koyasu, K., & Tsukuda, T. (2013). Nonscalable Oxidation Catalysis of Gold Clusters. Accounts of Chemical Research, 47(3), 816-824. doi:10.1021/ar400209aBore, M. T., Pham, H. N., Switzer, E. E., Ward, T. L., Fukuoka, A., & Datye, A. K. (2005). The Role of Pore Size and Structure on the Thermal Stability of Gold Nanoparticles within Mesoporous Silica. The Journal of Physical Chemistry B, 109(7), 2873-2880. doi:10.1021/jp045917pOtto, T., Zones, S. I., & Iglesia, E. (2016). Challenges and strategies in the encapsulation and stabilization of monodisperse Au clusters within zeolites. Journal of Catalysis, 339, 195-208. doi:10.1016/j.jcat.2016.04.015Liu, L., Díaz, U., Arenal, R., Agostini, G., Concepción, P., & Corma, A. (2016). Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Materials, 16(1), 132-138. doi:10.1038/nmat4757Liu, L., Zakharov, D. N., Arenal, R., Concepcion, P., Stach, E. A., & Corma, A. (2018). Evolution and stabilization of subnanometric metal species in confined space by in situ TEM. Nature Communications, 9(1). doi:10.1038/s41467-018-03012-6Xue, Y., Li, X., Li, H., & Zhang, W. (2014). Quantifying thiol–gold interactions towards the efficient strength control. Nature Communications, 5(1). doi:10.1038/ncomms5348Pensa, E., Cortés, E., Corthey, G., Carro, P., Vericat, C., Fonticelli, M. H., … Salvarezza, R. C. (2012). The Chemistry of the Sulfur–Gold Interface: In Search of a Unified Model. Accounts of Chemical Research, 45(8), 1183-1192. doi:10.1021/ar200260pShivhare, A., Chevrier, D. M., Purves, R. W., & Scott, R. W. J. (2013). Following the Thermal Activation of Au25(SR)18 Clusters for Catalysis by X-ray Absorption Spectroscopy. The Journal of Physical Chemistry C, 117(39), 20007-20016. doi:10.1021/jp4063687Miller, J. T., Kropf, A. J., Zha, Y., Regalbuto, J. R., Delannoy, L., Louis, C., … van Bokhoven, J. A. (2006). The effect of gold particle size on AuAu bond length and reactivity toward oxygen in supported catalysts. Journal of Catalysis, 240(2), 222-234. doi:10.1016/j.jcat.2006.04.004Zhu, M., Aikens, C. M., Hollander, F. J., Schatz, G. C., & Jin, R. (2008). Correlating the Crystal Structure of A Thiol-Protected Au25Cluster and Optical Properties. Journal of the American Chemical Society, 130(18), 5883-5885. doi:10.1021/ja801173rI. 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Nature Communications, 8(1). doi:10.1038/ncomms1488

Stable CoO2_2 Nanoscrolls With Outstanding Electrical Properties

Layered CoO$_2$ is of great interest for its promising properties but is meta-stable in its bulk form. CoO$_2$ was synthesized in a long-term stable nanotubular or scrolled form by converting the quasi-one-dimensional crystal structure of bulk Ca$_3$Co$_2$O$_6$ via a hydrothermal treatment. The resulting one-dimensional nanostructures with very thin walls are investigated in detail. The CoO_$2$ is found to crystallize in monoclinic form, similar to the related CaCoO$_2$-CoO$_2$ misfit structure. Individual nanoscrolls are characterized electrically and show a p-type semiconducting nature with a high current-carrying capacity of $7.6 \times 10^6$ A/cm$^2$ and an extremely high breakdown voltage of 27 kV/cm. The results demonstrate the possibility to stabilize meta-stable materials in low-dimensional forms and a promising application of the nanoscrolls as interconnect in high-voltage electronic circuitry

One-step covalent hydrophobic/hydrophilic functionalization of chemically exfoliated molybdenum disulfide nanosheets with RAFT derived polymers

The covalent functionalization of chemically exfoliated molybdenum disulfide (ce-MoS2) with hydrophobic poly(methyl methacrylate) and hydrophilic poly(acrylic acid) polymers, in a single-step without additives, is presented. The nature of chemical modification and the impact on the structure of ce-MoS2 were spectroscopically investigated. Complexation of Eu3+ was accomplished on grafted polycarboxylate chains on MoS2

In-situ preparation of ultra-small Pt nanoparticles within rod-shaped mesoporous silica particles: 3-D tomography and catalytic oxidation of n-hexane

The shape and porous configuration of supports are key parameters to design outstanding catalysts. However, the selection of a proper mesoporous support, such as SBA-15, by itself does not guarantee accessibility to catalytic sites. The distribution of the active phase and its stability are strongly related to the procedure used to deposit it on the catalytic substrate. Herein, we have prepared rod-shaped SBA-15 silica supports functionalized with amine groups to facilitate the electrostatic attraction and a good distribution of the resulting Pt-based catalytic nanoparticles along the pore walls. Additionally, the use of tetrakis-(hydroxymethyl)-phosphonium chloride (THPC) as both reductant and stabilizer is presented as a novel alternative for Pt nanoparticle synthesis. The behaviour of this catalyst in the total oxidation of n-hexane demonstrates high activity and excellent stability after 70 h on reaction stream. STEM-HAADF and 3-D tomography were used to confirm the presence of the metallic nanoparticles within the mesochannels and to corroborate their reduced sintering after reaction

Asymmetrical Plasmon Distribution in Hybrid AuAg Hollow/Solid Coded Nanotubes

Metal nanotubes; Nanotubes; NanowiresNanotubos metálicos; Nanotubos; NanocablesNanotubs metàl·lics; Nanotubs; NanofilsMorphological control at the nanoscale paves the way to fabricate nanostructures with desired plasmonic properties. In this study, we discuss the nanoengineering of plasmon resonances in 1D hollow nanostructures of two different AuAg nanotubes, including completely hollow nanotubes and hybrid nanotubes with solid Ag and hollow AuAg segments. Spatially resolved plasmon mapping by electron energy loss spectroscopy (EELS) revealed the presence of high order resonator-like modes and localized surface plasmon resonance (LSPR) modes in both nanotubes. The experimental findings accurately correlated with the boundary element method (BEM) simulations. Both experiments and simulations revealed that the plasmon resonances are intensely present inside the nanotubes due to plasmon hybridization. Based on the experimental and simulated results, we show that the novel hybrid AuAg nanotubes possess two significant coexisting features: (i) LSPRs are distinctively generated from the hollow and solid parts of the hybrid AuAg nanotube, which creates a way to control a broad range of plasmon resonances with one single nanostructure, and (ii) the periodicity of the high-order modes are disrupted due to the plasmon hybridization by the interaction of solid and hollow parts, resulting in an asymmetrical plasmon distribution in 1D nanostructures. The asymmetry could be modulated/engineered to control the coded plasmonic nanotubes.ICN2 acknowledges funding from the Generalitat de Catalunya 2021SGR00457. This study was supported by MCIN with funding from the European Union NextGenerationEU (PRTR-C17.I1) and the Generalitat de Catalunya. This research is part of the CSIC program for the Spanish Recovery, Transformation and Resilience Plan which is funded by the Recovery and Resilience Facility of the European Union and was established by Regulation (EU) 2020/2094. The authors are thankful for the support from the project NANOGEN (PID2020-116093RB-C43) which was funded by MCIN/AEI/10.13039/501100011033/, “ERDF A way of making Europe”, and the European Union. ICN2 is supported by the Severo Ochoa program at the Spanish MCIN/AEI (grant no. CEX2021-001214-S) and is funded by the CERCA Programme/Generalitat de Catalunya. R.A. acknowledges support from the Spanish MCIN (PID2019-104739GB-100/AEI/10.13039/501100011033), the Government of Aragon (project DGA E13-20R (FEDER, EU)), and the EU H2020 “ESTEEM3” (grant no. 823717). NGB and VP acknowledge financial support from the Spanish Ministerio de Ciencia, Innovación y Universidades (MCIU) (RTI2018-099965-B-I00, AEI/FEDER, UE)

On-chip monitoring of toxic gases: capture and label-free SERS detection with plasmonic mesoporous sorbents

AThe detection of the spread of toxic gas molecules in the air at low concentration in the field requires a robust miniaturized system combined with an analytical technique that is portable and able to detect and identify the molecules, as is the case with surface enhanced Raman scattering (SERS). This work aims to address capability gaps faced by first responders in real-time detection, identification and monitoring of neurotoxic gases by developing robust, reliable and reusable SERS microfluidic chips. Thus, the key performance attributes of a portable SERS detection system that must be addressed in detail are its limit of detection, response time and reusability. To this purpose, we integrate a 3D plasmonic architecture based on closely packed mesoporous silica (MCM48) nanospheres decorated with Au nanoparticle arrays, denoted as MCM48@Au, into a Si microfluidic chip designed and used for preconcentration and label-free detection of gases at a trace concentration level. The SERS performance of the plasmonic platform is thoroughly analyzed using DMMP as a model neurotoxic simulant over a 1 cm2 SERS active area and over a range of concentrations from 100 ppbV to 2.5 ppmV. The preconcentration-based SERS signal amplification by the mesoporous silica moieties is evaluated against dense silica counterparts, denoted as Stöber@Au. To assess the potential for applications in the field, the microfluidic SERS chip has been interrogated with a portable Raman spectrometer, evaluated with temporal and spatial resolution and subjected to several gas detection/regeneration cycles. The reusable SERS chip shows exceptional performance for the label-free monitoring of 2.5 ppmV gaseous DMMP

Oxidation-assisted graphene heteroepitaxy on copper foil

We propose an innovative, easy-to-implement approach to synthesize large-area singlecrystalline graphene sheets by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.Comment: Main text (18 pages, 6 figures) + supplementary information (26 pages, 15 figures