Graphite and Graphene Fairy Circles:A Bottom-Up Approach for the Formation of Nanocorrals

A convenient covalent functionalization approach and nanopatterning method of graphite and graphene is developed. In contrast to expectations, electrochemically activated dediazotization of a mixture of two aryl diazonium compounds in aqueous media leads to a spatially inhomogeneous functionalization of graphitic surfaces, creating covalently modified surfaces with quasi-uniform spaced islands of pristine graphite or graphene, coined nanocorrals. Cyclic voltammetry and chronoamperometry approaches are compared. The average diameter (45-130 nm) and surface density (20-125 corrals/μm 2 ) of these nanocorrals are tunable. These chemically modified nanostructured graphitic (CMNG) surfaces are characterized by atomic force microscopy, scanning tunneling microscopy, Raman spectroscopy and microscopy, and X-ray photoelectron spectroscopy. Mechanisms leading to the formation of these CMNG surfaces are discussed. The potential of these surfaces to investigate supramolecular self-assembly and on-surface reactions under nanoconfinement conditions is demonstrated. © 2019 American Chemical Society

Enzymatic synthesis of a series of alkyl esters using novozyme 435 in a packed-bed, miniaturized, continuous flow reactor

Using lipase catalysed, enzymatic esterification as a model reaction, we successfully demonstrate the use of miniaturized technology for biocatalytic reactions. Benchmarked against batch reactions, nine alkyl esters have been synthesized effectively, using Novozyme 435 in a pressure driven, packed-bed, miniaturized, continuous flow reactor. In some cases close to 100% ester conversions were obtained. The paper also demonstrates the ability to screen the enzyme for substrate specificity

Self-limiting covalent modification of carbon surfaces: diazonium chemistry with a twist

The chemistry of carbon surfaces has regained traction in recent years in view of its applicability towards covalent modification of a variety of (2D) materials. A general requisite is the formation of a dense and well-defined monolayer of aryl groups covalently bound to the surface. Given the use of reactive chemistries however, it is often not easy to achieve precise control over the monolayer growth while maintaining high grafting densities. Here we present a straightforward experimental protocol for the fabrication of well-defined covalent monolayers onto the surface of graphite. Using a combination of surface analytical tools, we demonstrate that the ascorbic acid mediated dediazoniation of aryldiazonium salts leads to self-limiting growth of monolayers with high grafting densities. The aryl radicals preferentially attach to the basal plane of the substrate and once the surface is covered with a covalent monolayer, the surface reaction does not proceed further to an appreciable extent. The layer thickness of the covalent films was measured using atomic force microscopy whereas the grafting efficiencies were assessed using Raman spectroscopy. The chemical composition of the grafted films was studied using X-ray photoelectron spectroscopy whereas scanning tunneling microscopy provided nanometer scale insight into the structure of the covalent films. Mechanistic aspects of the process are also discussed. The self-terminating chemistry described here is a new addition to the synthetic armory for covalent modification of materials and sets a strong foundation for achieving precise nanoscale control over the covalent functionalization process.status: publishe

Covalent Functionalization of Carbon Surfaces: Diaryliodonium versus Aryldiazonium Chemistry

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Iodide mediated reductive decomposition of diazonium salts: towards mild and efficient covalent functionalization of surface-supported graphene

Covalent functionalization of graphene is highly sought after, not only in view of the potential applications of the chemically modified material, but also because it brings fundamental insight into the chemistry of graphene. Thus, strategies that yield chemically modified graphene with densely grafted films of aryl groups via simple experimental protocols have been the focus of intense research. Here we report a mild, straightforward and efficient approach to graphene/graphite functionalization using iodide mediated reductive dediazoniation of aryldiazonium salts. The experimental protocol employs aqueous solutions of the reagents. The reaction proceeds rapidly at room temperature without the need of any environmental or electrochemical control. The covalently modified surfaces were characterized at the nanometer scale using a combination of complementary surface analytical techniques. The degree of covalent functionalization, and the morphology, as well as the thickness of the grafted films were studied at the molecular level using Raman spectroscopy and scanning probe microscopy, respectively. Furthermore, solution phase UV-Vis spectroscopy was employed to understand the mechanistic aspects. This work demonstrates a facile and scalable covalent modification method compatible for both bulk and monolayer functionalization of graphene.status: publishe