Artículos > Grupo de Nanoestructuras de Carbono y Nanotecnología (G-CNN)

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Controlling the surface chemistry of graphene oxide: Key towards efficient ZnO-GO photocatalysts

Catalysis Today 2020

Graphene oxide (GO) and related materials are widely reported to enhance the photocatalytic activity of zinc oxide. However, the origin of the observed performance improvements remains elusive and studies contributing to a deeper understanding of this critical issue are largely missing. In this work, we have prepared a set of benchmark ZnO-GO hybrid materials in order to systematically put under closer scrutiny the influence of the surface chemistry of GO on the photocatalytic degradation of methylene blue. The set of ZnO-GO hybrids has been synthesized in an ultrasonication process involving ZnO nanoparticles obtained in a microwave synthesis process and GO with three distinct oxidation degrees, employed in three different loading fractions. Structural and physical-chemical characterization by XRD, FTIR, Raman, UV–vis, photoluminescence and spectroscopy and XPS, consistently demonstrate the importance of the surface chemistry of GO for establishing photo-induced charge-transfer interface interactions with ZnO, facilitating the enhancement of the catalytic activity of the ZnO-GO catalyst. Optimized interface interactions thus enabled the design of a ZnO-GO catalyst exhibiting a conversion rate of 80% obtained in a time of 70 min and at a catalyst concentration of only 0.045 mg/mL.

Towards high-efficient microsupercapacitors based on reduced graphene oxide with optimized reduction degree


Reduced graphene oxide aerogels synthetized using different times of hydrothermal treatment have been tested as raw material to prepare electrochemical supercapacitors. The gravimetric electrochemical capacitance measured using 1M Na2SO4 as electrolyte was maximized for aerogels that underwent 45 min of hydrothermal treatment. The aerogels synthetized for longer durations of hydrothermal treatment exhibited higher electrical conductivity but the gravimetric capacitance drops dramatically due to an increasing resistance to diffusion of the electrolyte ions. The impeded diffusion is boosted by the intensified crosslinking between graphene sheets, which narrows the pores between them in the prepared electrode. The rGO aerogel attained for 45 min of hydrothermal treatment provided a high gravimetric capacitance of 400 F g-1 and 100 F g-1 at 50 A g-1 for three-electrode and two electrodes configuration, respectively, as well as good cyclic stability, competing with other similar carbon materials. Activation pretreatments or adding a second component (glucose, dopamine, Mn, Fe, CNT) did not provide significant change of capacitance respect to pristine rGO aerogel.

Ru supported on N-doped reduced graphene oxide aerogels with different N-type for alcohol selective oxidation

MOLECULAR CATALYSIS. 2020, 484, 110737

Reduced graphene oxide aerogels doped with nitrogen have been prepared via two different strategies, namely, direct doping of rGO nanosheets with NH3 (GANH3) and coating the rGO nanosheets with an N-containing amorphous carbon derived from polydopamine (GADA). Both methods lead to comparable N/C ratios (3.4–4.7 %) but the relative contribution of quaternary nitrogen is 30 % for GADA while only 15 % for GANH3. Moreover, the N is incorporated within graphene lattice for GANH3 while it is within an amorphous carbon layer on top of graphene nanosheets for GADA. The Ru catalyst supported on the aerogels exhibited very distinct performance in the selective oxidation of benzyl alcohol depending on the support material despite having similar Ru particle size. The best performance for 5 wt% Ru on GADA can be explained by the larger reduction extent of Ru and the more hydrophobic surface. The open macroporosity of the aerogel makes it an excellent platform for using as structured catalyst in a continuous flow process.

Differential properties and effects of fluorescent carbon nanoparticles towards intestinal theranostics.

COLLOIDS AND SURFACES B: Biointerfaces 2020, 185, 110612

Given the potential applications of fluorescent carbon nanoparticles in biomedicine, the relationship between their chemical structure, optical properties and biocompatibility has to be investigated in detail. In this work, different types of fluorescent carbon nanoparticles are synthesized by acid treatment, sonochemical treatment, electrochemical cleavage and polycondensation. The particle size ranges from 1 to 6 nm, depending on the synthesis method. Nanoparticles that were prepared by acid or sonochemical treatments from graphite keep a crystalline core and can be classified as graphene quantum dots. The electrochemically produced nanoparticles do not clearly show the graphene core, but it is made of heterogeneous aromatic structures with limited size. The polycondensation nanoparticles do not have CC double bonds. The type of functional groups on the carbon backbone and the optical properties, both absorbance and photoluminescence, strongly depend on the nanoparticle origin. The selected types of nanoparticles are compatible with human intestinal cells, while three of them also show activity against colon cancer cells. The widely different properties of the nanoparticle types need to be considered for their use as diagnosis markers and therapeutic vehicles, specifically in the digestive system.

In-situ growth and immobilization of CdS nanoparticles onto functionalized MoS2 for managing charge-transfer processes.

CHEMISTRY- An Asian Journal 2020.

A facile strategy for the controllable growth of CdS nanoparticles at the periphery of MoS2 en route the preparation of electron donor‐acceptor nanoensembles is developed. Precisely, the carboxylic group of α‐lipoic acid, as addend of the modified MoS2 obtained upon 1,2‐dithiolane functionalization, was employed as anchor site for the in situ preparation and immobilization of the CdS nanoparticles in an one‐pot two‐step process. The newly prepared MoS2/CdS hybrid material was characterized by complementary spectroscopic, thermal and microscopy imaging means. Absorption spectroscopy was employed to register the formation of MoS2/CdS, by observing a broad shoulder centered at 420 nm due to CdS nanoparticles, while the excitonic bands of MoS2 were also evident. Moreover, based on the efficient quenching of the characteristic fluorescence emission of CdS at 725 nm by the presence of MoS2, strong electronic interactions at the excited state between the two species within the ensemble were identified. Photoelectrochemical assays of MoS2/CdS thin‐film electrodes revealed a prompt, steady and reproducible anodic photoresponse during repeated on‐off cycles of illumination. A significant zero‐current photopotential of −540 mV and an anodic photocurrent of 1 μA were observed, underlining improved charge‐separation and electron transport from CdS to MoS2. The superior performance of the charge‐transfer processes in MoS2/CdS is of direct interest for the fabrication of photoelectrochemical and optoelectronic devices.

Laser-Deposited Carbon Aerogel Derived from Graphene Oxide Enables NO2-Selective Parts-Per-Billion Gas Sensing

ACS APPL MAT & INTERFACES. 2020, 12, 35, 39541-39548

Laser-deposited carbon aerogel is a low-density porous network of carbon clusters synthesized using a laser process. A one-step synthesis, involving deposition and annealing, results in the formation of a thin porous conductive film which can be applied as a chemiresistor. This material is sensitive to NO2 compared to ammonia and other volatile organic compounds and is able to detect ultra-low concentrations down to at least 10 parts-per-billion. The sensing mechanism, based on the solubility of NO2 in the water layer adsorbed on the aerogel, increases the usability of the sensor in practically relevant ambient environments. A heating step, achieved in tandem with a microheater, allows the recovery to the baseline, making it operable in real world environments. This, in combination with its low cost and scalable production, makes it promising for Internet-of-Things air quality monitoring.

Cobalt-Doped ZnO Nanorods Coated with Nanoscale Metal-Organic Framework Shells for Water-Splitting Photoanodes

ACS APPL NANO MATER 2020,3,8, 7781-7788.

Developing highly efficient and stable photoelectrochemical (PEC) water-splitting electrodes via inexpensive, liquid phase processing is one of the key challenges for the conversion of solar energy into hydrogen for sustainable energy production. ZnO represents one the most suitable semiconductor metal oxide alternatives because of its high electron mobility, abundance, and low cost, although its performance is limited by its lack of absorption in the visible spectrum and reduced charge separation and charge transfer efficiency. Here, we present a solution-processed water-splitting photoanode based on Co-doped ZnO nanorods (NRs) coated with a transparent functionalizing metal–organic framework (MOF). The light absorption of the ZnO NRs is engineered toward the visible region by Co-doping, while the MOF significantly improves the stability and charge separation and transfer properties of the NRs. This …

Functionalized carbon dots on TiO2 for perovskite photovoltaics and stable photoanodes for water splitting


Various types of fluorescent carbon nanoparticles, often called carbon dots (CDs), are synthesized by different polycondensation methods: microwave irradiation, hydrothermal conditions or solution chemistry at ambient temperature with subsequent chemical functionalization. The CDs are deposited on TiO2 films to be probed as electron transport layers in perovskite photovoltaics and the anode for photoelectrochemical water splitting. Nitrogen CDs, which do not contain oxygen, lead to an increase of around 50 mV in the open circuit voltage of perovskite solar cells. All the CD types produce an improved photocurrent in water splitting, particularly CDs that are functionalized with thiol groups and butyl chains. It is demonstrated that the modified electrode is stable under continuous operation. Other electrochemical characteristics of the electrode, such as the voltammogram shape, onset potentials and open circuit potentials, remain nearly unchanged upon the deposition of CDs. Only the incident photon to current conversion efficiency improves clearly, extending the absorption range by around 20 nm towards longer wavelengths. This study provides new data about mechanisms and electrode arrangements for improving the performance of n-type semiconductors in photovoltaic cells and photoelectrochemical hydrogen production.

Bottom-up synthesized MoS2 interfacing polymer carbon nanodots with electrocatalytic activity for hydrogen evolution


The preparation of an MoS2–polymer carbon nanodot (MoS2‐PCND) hybrid material was accomplished by employing an easy and fast bottom‐up synthetic approach. Specifically, MoS2‐PCND was realized by the thermal decomposition of ammonium tetrathiomolybdate and the in situ complexation of Mo with carboxylic acid units present on the surface of PCNDs. The newly prepared hybrid material was comprehensively characterized by spectroscopy, thermal means, and electron microscopy. The electrocatalytic activity of MoS2‐PCND was examined in the hydrogen evolution reaction (HER) and compared with that of the corresponding hybrid material prepared by a top‐down approach, namely MoS2‐PCND(exf‐fun), in which MoS2 was firstly exfoliated and then covalently functionalized with PCNDs. The MoS2‐PCND hybrid material showed superior electrocatalytic activity toward the HER with low Tafel slope, excellent electrocatalytic stability, and an onset potential of −0.16 V versus RHE. The superior catalytic performance of MoS2‐PCND was rationalized by considering the catalytically active sites of MoS2, the effective charge/energy‐transfer phenomena from PCNDs to MoS2, and the synergetic effect between MoS2 and PCNDs in the hybrid material.

The effect of graphene oxide reduction temperature on the kinetics of low-temperature sorption of hydrogen
The effect of thermal reduction of graphene oxide on the hydrogen sorption and desorption kinetics was studied by temperature-programmed desorption in the 7–120 K temperature range. The heat treatment of graphene oxide samples resulted in a decrease in the activation energy for hydrogen diffusion by more than an order of magnitude (by a factor of 12–13) compared with the initial graphite oxide. This change in the activation energy is, most likely, caused by exfoliation (loosening) of the graphite oxide carbon sheets upon the thermal removal of intercalated water, which changes the sorption character by decreasing the influence of the opposite walls in the interlayer spaces.