Beatriz Martín-García

Graphene-based technologies for energy applications, challenges and perspectives

Here we report on technology developments implemented into the Graphene Flagship European project for the integration of graphene and graphene-related materials (GRMs) into energy application devices. Many of the technologies investigated so far aim at producing composite materials associating graphene or GRMs with either metal or semiconducting nanocrystals or other carbon nanostructures (e.g., CNT, graphite). These composites can be used favourably as hydrogen storage materials or solar cell absorbers. They can also provide better performing electrodes for fuel cells, batteries, or supercapacitors. For photovoltaic (PV) electrodes, where thin layers and interface engineering are required, surface technologies are preferred. We are using conventional vacuum processes to integrate graphene as well as radically new approaches based on laser irradiation strategies. For each application, the potential of implemented technologies is then presented on the basis of selected experimental and modelling results. It is shown in particular how some of these technologies can maximize the benefit taken from GRM integration. The technical challenges still to be addressed are highlighted and perspectives derived from the running works emphasized.

Functionalization of Reduced Graphite Oxide Sheets with a Zwitterionic Surfactant

Films of a few layers in thickness of reduced graphite oxide (RGO) sheets functionalized by the zwitterionic surfactant N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDPS) are obtained by using the Langmuir-Blodgett method. The quality of the RGO sheets is checked by analyzing the degrees of reduction and defect repair by means of X-ray photoelectron spectroscopy, atomic force microscopy (AFM), field-emission scanning electron microscopy (SEM), micro-Raman spectroscopy, and electrical conductivity measurements. A modified Hummers method is used to obtain highly oxidized graphite oxide (GO) together with a centrifugation-based method to improve the quality of GO. The GO samples are reduced by hydrazine or vitamin C. Functionalization of RGO with the zwitterionic surfactant improves the degrees of reduction and defect repair of the two reducing agents and significantly increases the electrical conductivity of paperlike films compared with those prepared from unfunctionalized RGO.

Langmuir and Langmuir−Blodgett Films of a Maleic Anhydride Derivative: Effect of Subphase Divalent Cations

We report the study of the equilibrium and dynamic properties of Langmuir monolayers of poly(styrene-co-maleic anhydride) partial 2-buthoxyethyl ester cumene terminated polymer and the effect of the Mg(NO(3))(2) addition in the water subphase on the film properties. Results show that the polymer monolayer becomes more expanded when the electrolyte concentration in the subphase increases. Dense polymer films aggregate at the interface. The aggregates are transferred onto silicon wafers using the Langmuir-Blodgett methodology and the morphology is observed by AFM. The structure of aggregates depends on the subphase composition of the Langmuir film transferred onto the silicon wafer.

Efficient charge transfer in solution-processed PbS quantum dot–reduced graphene oxide hybrid materials

Quantum dot–graphene hybrid materials have attracted significant interest due to the unique synergy of the optical properties of colloidal quantum dots (QDs) and the transport properties of graphene. This stimulated the development of low-cost and up-scalable solution-processed strategies for hybrid materials with potential applications in light harvesting and optoelectronic devices. Herein, we report a versatile covalent linking-based approach for the functionalization of reduced graphene oxide (rGO), to prepare a variety of QD–rGO hybrid dispersions with QDs of different sizes and compositions (PbS, PbS–CdS and CdSe QDs), and shapes (CdSe–CdS dot-in-rods). We achieved a well-controlled QD coverage of the rGO sheets by functionalizing the rGO surface with mercapto-silane linkers. A further spectroscopic investigation of near-infrared PbS QD–rGO materials demonstrates efficient electronic coupling between both materials. The QD photoluminescence emission quenching and exciton lifetime shortening of up to 95%, together with subtle graphene Raman G-band shifts upon QD linking, support electron transfer as the dominant relaxation pathway from the QD to the rGO. The use of core–shell PbS–CdS QDs allows tuning of the transfer efficiency from 94% for a 0.2 nm thin CdS shell, down to 30% for a 1.1 nm thick shell.

Nanoparticle self-assembly assisted by polymers: the role of shear stress in the nanoparticle arrangement of Langmuir and Langmuir-Blodgett films.

We propose to use the self-assembly ability of a block copolymer combined with compression-expansion cycles to obtain CdSe quantum dots (QDs) structures of different morphology. The methodology proposed consists in transferring onto mica mixed Langmuir monolayers of QDs and the polymer poly(styrene-co-maleic anhydride) partial 2-butoxyethyl ester cumene terminated, PS-MA-BEE, previously sheared by 50 compression-expansion cycles. Results indicate that the shear stress takes out nanoparticles at the air-water interface from metastable states and promotes a new equilibrium state of the Langmuir monolayer. This new state was transferred onto mica by the Langmuir-Blodgett (LB) methodology, and the morphology of the LB films was analyzed by atomic force microscopy and transmission electron microscopy measurements. Our results show that when the amplitude strain increases, the QDs domain size decreases and the QDs LB film arrangement becomes more ordered. The dynamics of the monolayer relaxation after cycling involves at least three time scales which are related to the damping of surface fluctuation, raft rearrangement, and component movements inside each raft. Brewster angle microscopy allowed visualizing in situ the raft rearrangement at the air-water interface.

Solution-Processed Hybrid Graphene Flake/2H-MoS2 Quantum Dot Heterostructures for Efficient Electrochemical Hydrogen Evolution

We designed solution-processed, flexible hybrid graphene flake/2H-MoS2 quantum dot (QD) heterostructures, showing enhanced electrocatalytic activity for the hydrogen evolution reaction (HER) with respect to their native individual components. The 2H-MoS2 QDs are produced through a scalable, environmentally friendly, one-step solvothermal approach from two-dimensional (2D) 2H-MoS2 flakes obtained by liquid phase exfoliation (LPE) of their bulk counterpart in 2-Propanol. This QDs synthesis avoids the use of high boiling point and/or toxic solvents. Graphene flakes are produced by LPE of graphite in N-Methyl-2-pyrrolidone. The electrochemical properties of 2H-MoS2 QDs and their HER-favorable chemical and electronic coupling with graphene enable to reach current density of 10 mA/cm² at an overpotential of 136 mV, surpassing the performances of graphene flake/2H-MoS2 (1T-MoS2) flake heterostructures. Our approach provides a shortcut, viable and cost-effective method for enhancing the 2D materials electrocataly...

Graphene-Based Hole-Selective Layers for High-Efficiency, Solution-Processed, Large-Area, Flexible, Hydrogen-Evolving Organic Photocathodes

Regio-regular poly(3-hexylthiophene-2,5-diyl) (rr-P3HT), the work-horse of organic photovoltaics, has been recently exploited in bulk heterojunction (BHJ) configuration with phenyl-C61-butyric acid methyl ester (PCBM) for solution-processed hydrogen-evolving photocathodes, reaching cathodic photocurrents at 0 V vs. RHE (J0V vs RHE) of up to 8 mA cm-2. The photoelectrochemical performance of these photocathodes strongly depends on the presence of the electron (ESL) and hole (HSL) selective layer. While TiO2 and its sub-stoichiometric phases are consolidated ESL materials, the currently used HSLs (e.g., MoO3, CuI, PEDOTT:PSS, WO3) suffer electrochemical degradation under hydrogen evolution reaction (HER)-working conditions. In this work, we use solution-processed graphene derivatives as HSL to boost efficiency and durability of rr-P3HT:PCBM-based photocathodes, demonstrating record-high performance. In fact, our devices show cathodic J0V vs RHE of 6.01 mA cm-2, onset potential (Vo) of 0.6 V vs. RHE, ratiome...

Chloride-Induced Thickness Control in CdSe Nanoplatelets

Current colloidal synthesis methods for CdSe nanoplatelets (NPLs) routinely yield samples that emit, in discrete steps, from 460 to 550 nm. A significant challenge lies with obtaining thicker NPLs, to further widen the emission range. This is at present typically achieved via colloidal atomic layer deposition onto CdSe cores, or by synthesizing NPL core/shell structures. Here, we demonstrate a novel reaction scheme, where we start from 4.5 monolayer (ML) NPLs and increase the thickness in a two-step reaction that switches from 2D to 3D growth. The key feature is the enhancement of the growth rate of basal facets by the addition of CdCl2, resulting in a series of nearly monodisperse CdSe NPLs with thicknesses between 5.5 and 8.5 ML. Optical characterization yielded emission peaks from 554 nm up to 625 nm with a line width (fwhm) of 9–13 nm, making them one of the narrowest colloidal nanocrystal emitters currently available in this spectral range. The NPLs maintained a short emission lifetime of 5–11 ns. Finally, due to the increased red shift of the NPL band edge photoluminescence excitation spectra revealed several high-energy peaks. Calculation of the NPL band structure allowed us to identify these excited-state transitions, and spectral shifts are consistent with a significant mixing of light and split-off hole states. Clearly, chloride ions can add a new degree of freedom to the growth of 2D colloidal nanocrystals, yielding new insights into both the NPL synthesis as well as their optoelectronic properties.

Solution-processed silver sulphide nanocrystal film for resistive switching memories

Resistive switching memories allow electrical control of the conductivity of a material, by inducing a high resistance (OFF) or a low resistance (ON) state, using electrochemical and ion transport processes. As alternative to high temperature and vacuum-based physical sulphurization methods of silver (Ag), here we propose, as resistive switching medium, a layer built from colloidal Ag

Langmuir‐Blodgett Methodology: A Versatile Technique to Build 2D Material Films

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