Thermal vapor sulfurization of molybdenum layers

Sulfurization of molybdenum layers is a promising route for obtaining large-scale and high-quality transition metal dichalcogenides. Here we describe the synthesis of continuous and homogeneous MoS2 in the centimeter scale by the thermal vapor sulfurization of pre-deposited molybdenum precursors on SiO2. Metallic molybdenum as well as MoO3 were used as precursors while the sulfurization was performed by chemical vapor deposition. A multi-technique characterization was employed to fully describe the deposition of molybdenum as well as its sulfurization. Thus, Raman spectroscopy, X-ray and ultra-violet photoelectron spectroscopies as well as scanning electron and atomic force microscopies indicated that the molybdenum layers were completely transformed in MoS2. The samples were homogeneous in the centimeter scale and quite flat with a root mean square roughness of 1.4 Å. Furthermore, its work function was 4.1 eV.publishe

X-ray photoelectron spectroscopy: a surface characterization technique

During the last years, an increasing number of students have visited the XPS laboratory for characterizing their samples with this experimental technique. Their background span over a wide range of fields such as physics, material science, chemistry and biology, among others. For most of them, both XPS and ultra-high vacuum technology were something new and they needed help to deal with the data of their samples. This book tries to concentrate the key information that a young researcher needs for a first approach to XPS. We hope the students will understand its working principle and will obtain the basic tools for analysing their data.publishe

Graphene Based Sensors for Air Quality Monitoring - Preliminary Development Evaluation

Indoor air pollution can induce adverse health effects on building occupants and pose a significant role in health worldwide. To avoid such effects, it is extremely important to monitor and control common indoor pollutants such as CO2, VOCs and relative humidity. Therefore, this work focuses on recent advances in the field of graphene-based gas sensors, emphasizing the use of modified graphene that broadly expands the range of nanomaterials sensors. Graphene films were grown on copper by chemical vapor deposition (CVD) and transferred to arbitrary substrates. After synthesis, the samples were functionalized with Al2O3 by ALD and characterized by a large set of experimental techniques such as XPS, Raman and SEM. The results demonstrated that graphene was successfully synthesized and transferred to SiO2, glass and polymer. As a proof-of-concept, ALD of Al2O3 was performed on the graphene surface to produce a graphene/metal oxide nanostructure towards the development of nanocomposites for gas sensing. From this perspective, a laboratory prototype device based in measuring the electrical properties of the graphene sample as a function of the gas absorption is under development

Reductive nanometric patterning of graphene oxide paper using electron beam lithography

Electron beam lithography (EBL) was used for preparing nanostructured reduced patterns on the GO paper surface, while preserving its mechanical resistance and flexibility. Different EBL parameters, like dose and time of exposure for patterning were tested. SEM analysis showed the consequent increase of contrast of the reduced stripes on the patterned regions due to the increase of electron beam doses. Moreover, surface potential microscopy experiments also exhibited a clear contrast between the patterned and non-patterned regions. Structural analysis of the patterned paper through X-ray diffraction and nanoindentation showed that the interlayer distance between GO sheets decreases after reduction allowing the increase of the Hardness and Young modulus that makes this material able to be manipulated and integrated on different devices. Furthermore, we also observe that exposed areas to electron beam reduction process show an increase in the electrical conductivity up to 3 × 104 times. The developed flexible GO films can have interesting applications such as biosensors or templates for inducing tissue regeneration, by providing a surface with differently patterned cues with contrasting electron mobility. Preliminary in vitro studies with L929 fibroblasts support the cytocompatible nature of this patterned GO paper.Gil Gonçalves thanks the Fundação para a Ciência e a Tecnologia for the PostDoc grant (SFRH/BDP/84419/2012). P.A.A.P.M. acknowledge the FCT/MCTES for a research contract under the Program Investigator 2013 (IF/00917/2013/CP1162/CT0016) and TEMA – Centre for Mechanical Technology and Automation (UID/EMS/00481/2013), financed by national funds through the FCT/MEC. I.B. wish to acknowledge the Portuguese Foundation for Science and Technology for the financial support (grant IF/00582/2015). H·I·S.N. acknowledges CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. The biological studies of this work have been funded by the Ministerio de Economía y Competitividad and the Fondo Europeo de Desarrollo Regional (MAT2016-78857-R, MINECO/FEDER, UE). AGM and MCS acknowledge ISCIII-MINECO-FEDER for respective contracts. Authors would like to thank Dr M. Teresa Portolés from the Biochemistry and Molecular Biology Department at Universidad Complutense de Madrid for the generous supply of L929 fibroblasts. Dr José Ángel Rodríguez and Dr Javier Mazarío from the Service of Microscopy and Image Analysis at the Hospital Nacional de Parapléjicos are acknowledged for assistance with CLSM studies and Dr Enrique Rodríguez from the Servicio Interdepartamental de Investigación at the Universidad Autónoma de Madrid for SEM studies.info:eu-repo/semantics/acceptedVersio

Solid-gas phase photo-catalytic behaviour of rutile and TiOn (1<n<2) sub-oxide phases for self-cleaning applications

The solid-gas phase photo-catalytic activities of rutile TiO2 and TiOn (1 < n < 2) sub-oxide phases have been evaluated. Varying concentrations of Ti3+ defects were introduced into the rutile polymorph of titanium dioxide through carbo-thermal reduction at temperatures ranging from 350 °C to 1300 °C. The resulting sub-oxides formed were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, impedance spectroscopy and UV-visible diffuse reflectance spectroscopy. The presence of Ti3+ in rutile exposed to high reduction temperatures was confirmed by X-ray diffraction. In addition, a Ti3+-Ti4+ system was demonstrated to enhance the photo-catalytic properties of rutile for the degradation of the air pollutants NO2 and CO2 under UV irradiation of wavelengths (λ) 376–387 nm and 381–392 nm. The optimum reduction temperature for photo-catalytic activity was within the range 350–400 °C and attributed to improved charge-separation. The materials that were subject to carbo-thermal reduction at temperatures of 350 °C and 400 °C exhibited electrical conductivities over one hundred times higher compared to the non-reduced rutile. The results highlight that sub-oxide phases form an important alternative approach to doping with other elements to improve the photo-catalytic performance of TiO2. Such materials are important for applications such as self-cleaning where particles can be incorporated into surface coatings

On-surface self-organization of a robust metal-organic cluster based on copper(i) with chloride and organosulphur ligands

Direct sublimation of a Cu4Cl4 metal-organic cluster on Cu(110) under ultra-high vacuum allows the formation of ultra-large well-organized metal-organic supramolecular wires. Our results show that the large monomers assemble with each other by π-π interactions connecting dipyrimidine units and are stabilized by the surfaceWe thank Spanish MINECO (Grants: MAT2013-46753-C2-1-P, MAT2013-47878-C2-1-R and MAT2011-26534) for financial support. JIM acknowledges a CSIC-JaeDoc fellowship, cofunded by ES

Chemistry below graphene: Decoupling epitaxial graphene from metals by potential-controlled electrochemical oxidation

While high-quality defect-free epitaxial graphene can be efficiently grown on metal substrates, strong interaction with the supporting metal quenches its outstanding properties. Thus, protocols to transfer graphene to insulating substrates are obligatory, and these often severely impair graphene properties by the introduction of structural or chemical defects. Here we describe a simple and easily scalable general methodology to structurally and electronically decouple epitaxial graphene from Pt(111) and Ir(111) metal surfaces. A multi-technique characterization combined with ab-initio calculations was employed to fully explain the different steps involved in the process. It was shown that, after a controlled electrochemical oxidation process, a single-atom thick metal-hydroxide layer intercalates below graphene, decoupling it from the metal substrate. This decoupling process occurs without disrupting the morphology and electronic properties of graphene. The results suggest that suitably optimized electrochemical treatments may provide effective alternatives to current transfer protocols for graphene and other 2D materials on diverse metal surfacesWe acknowledge funding from the Spanish MINECO (Grants MAT2014-54231-C4-1-P, MAT2014-54231-C4-4-P, MAT2013- 47898-C2-2-R and MAT2017-85089-C2-1-R), the EU via the ERCSynergy Program (Grant ERC-2013-SYG-610256 NANOCOSMOS), the innovation program under grant agreement No. 696656 (GrapheneCore1- Graphene-based disruptive technologies), the Comunidad Aut_onoma de Madrid (CAM) MAD2D-CM Program (S2013/ MIT-3007) and computing resources from CTI-CSIC. GOI acknowledges financial support from FCT, Ministry of Science and Technology, Portugal (Grant No. PTDC/CTM-NAN/121108/2010 and IF/ 01054/2015). EL acknowledges funding from Spanish “Consolider” project CSD2010-00024. JIM acknowledges the financial support by the “Ramón y Cajal” Program of MINECO (Grant RYC-2015-17730) and NANOCOSMO

4th International Conference on Nanomaterials Science and Mechanical Engineering: conference proceedings

Sem resumo disponível.publishe

Chemical Changes of Graphene Oxide Thin Films Induced by Thermal Treatment under Vacuum Conditions

Reduction of graphene oxide is one of the most promising strategies for obtaining bulk quantities of graphene-like materials. In this study, graphene oxide was deposited on SiO2 and reduced by annealing at 500 K under vacuum conditions (5 × 10−1 Pa). Here, graphene oxide films as well as their chemical changes upon heating were characterized in depth by X-ray photoelectron spectroscopy, Raman spectroscopy, and scanning electron and atomic force microscopies. From the chemical point of view, the as prepared graphene oxide films presented a large quantity of oxidized functional groups that were reduced to a large extent upon heating. Moreover, residual oxidized sulfur species that originated during the synthesis of graphene oxide (GO) were almost completely removed by heating while nitrogen traces were integrated into the carbon framework. On the other hand, regarding structural considerations, reduced graphene oxide films showed more homogeneity and lower roughness than graphene oxide films

Graphene oxide/polyethyleneimine aerogel for high-performance mercury sorption from natural waters

The development of effective sorbent materials to remove mercury (Hg) from real waters is a challenge. Here, we report the simple preparation of high-performance GOPEI aerogel for Hg remediation by self-assembly of high branched polyethyleneimine (PEI) with elevated molecular weight (Mw = 750 k) and graphene oxide (GO) under acidic conditions (pH < 3). Our studies revealed that the improved dimensional stability of GOPEI aerogels, critical for their use as sorbent materials, was obtained for a ratio GO:PEI 3:1. A small amount (10 mg L−1) of GOPEI proved a highly efficiency for Hg removal from natural waters (tap (91%), river (90%) and sea (81%)) under realistic environmental concentrations (50 μg L−1), where the existence of co-ions and different Hg-speciation are usually inhibitory factors of a good removal efficiency. This excellent performance was attributed to the synergistic effect resultant from the interactions between GO and PEI, giving a high content of N-rich groups and negative zeta potential over a wide pH range (from 2 to 12). Kinetic modelling pointed to differences on the main mechanisms behind the Hg removal by GOPEI in ultrapure vs natural waters. In ultrapure water pseudo-first order, usually associated with physical sorption, showed to be the best fit according to Akaike's Information Criterion (99.8% of probability), while in natural waters pseudo-second order model performed better (51.5% to 99.9% of probability), suggesting that the sorption is likely to rely on chemical interactions between Hg ions and the functional groups of GOPEI. Furthermore, GOPEI showed to be easily regenerated, keeping its high removal performance after 3 successive sorption-desorption cycles.publishe