This review (162 references) focuses on two-dimensional carbon materials, which include graphene as well as its allotropes varying in size, number of layers, and defects, for their application in electrochemical sensors. Many preparation methods are known to yield two-dimensional carbon materials which are often simply addressed as graphene, but which show huge variations in their physical and chemical properties and therefore on their sensing performance. The first section briefly reviews the most promising as well as the latest achievements in graphene synthesis based on growth and delamination techniques, such as chemical vapor deposition, liquid phase exfoliation via sonication or mechanical forces, as well as oxidative procedures ranging from chemical to electrochemical exfoliation. Two-dimensional carbon materials are highly attractive to be integrated in a wide field of sensing applications. Here, graphene is examined as recognition layer in electrochemical sensors like field-effect transistors, chemiresistors, impedance-based devices as well as voltammetric and amperometric sensors. The sensor performance is evaluated from the material’s perspective of view and revealed the impact of structure and defects of the 2D carbon materials in different transducing technologies. It is concluded that the performance of 2D carbon-based sensors is strongly related to the preparation method in combination with the electrical transduction technique. Future perspectives address challenges to transfer 2D carbon-based sensors from the lab to the market.
The label-free nature of surface plasmon resonance techniques (SPR) enables a fast, specific, and sensitive analysis of molecular interactions. However, detection of highly diluted concentrations and small molecules is still challenging. It is shown here that in contrast to continuous gold films, gold nanohole arrays can significantly improve the performance of SPR devices in angle-dependent measurement mode, as a signal amplification arises from localized surface plasmons at the nanostructures. This leads consequently to an increased sensing capability of molecules bound to the nanohole array surface. Furthermore, a reduced graphene oxide (rGO) sensor surface was layered over the nanohole array. Reduced graphene oxide is a 2D nanomaterial consisting of sp2-hybridized carbon atoms and is an attractive receptor surface for SPR as it omits any bulk phase and therefore allows fast response times. In fact, it was found that nanohole arrays demonstrated a higher shift in the resonance angle of 250–380% compared to a continuous gold film. At the same time the nanohole array structure as characterized by its diameter-to-periodicity ratio had minimal influence on the binding capacity of the sensor surface. As a simple and environmentally highly relevant model, binding of the plasticizer diethyl phthalate (DEP) via π-stacking was monitored on the rGO gold nanohole array realizing a limit of detection of as low as 20 nM. The concentration-dependent signal change was studied with the best performing rGO-modified nanohole arrays. Compared to continuous gold films a diameter-to-periodicity ratio (D/P) of 0.43 lead to a 12-fold signal enhancement. Finally, the effect of environmental waters on the sensor was evaluated using samples from sea, lake and river waters spiked with analytically relevant amounts of DEP during which significant changes in the SPR signal are observed. It is expected that this concept can be successfully transferred to enhance the sensitivity in SPR sensors.
Two-dimensional carbon nanomaterials are very popular in chemo-and biosensor development. The high surface area and the outstanding electrochemical and electronical properties make them attractive candidates as sensing material. To date, it is still challenging to prepare well-defined, defect-free 2D-nanomaterials in a reproducible way. Here, chemical and mechanical methods for the fabrication of colloidal stable graphene dispersions with focus on the flake-size distribution, the number of defects and the physicochemical properties are discussed. A method is proposed to transfer the graphene materials on electrodes and nanostructured gold surfaces for sensor development. As one example for a feasibility study, amperometric sensors were constructed with various types of graphene using glucose as the model analyte. Selectivity was introduced by electrochemical deposition of Nickel nanoparticles on top of the 2D-nanomaterial. For plasmonic sensing, graphene is shown to enhance surface plasmon resonance sensitivity, especially for small molecules such as plastisizers or purine-based biomarkers when combining nanostructured gold substrates with 2D-nanomaterials.
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