Adriano Ambrosi

Electrochemistry at Chemically Modified Graphenes

Electrochemical applications of graphene are of great interest to many researchers as they can potentially lead to crucial technological advancements in fabrication of electrochemical devices for energy production and storage, and highly sensitive sensors. There are many routes towards fabrication of bulk quantities of chemically modified graphenes (CMG) for applications such as electrode materials. Each of them yields different graphene materials with different functionalities and structural defects. Here, we compare the electrochemical properties of five different chemically modified graphenes: graphite oxide, graphene oxide, thermally reduced graphene oxide, chemically reduced graphene oxide, and electrochemically reduced graphene oxide. We characterized these materials using transmission electron microscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry, which allowed us to correlate the electrochemical properties with the structural and chemical features of the CMGs. We found that thermally reduced graphene oxide offers the most favorable electrochemical performance among the different materials studied. Our findings have a profound impact for the applications of chemically modified graphenes in electrochemical devices.

Layered transition metal dichalcogenides for electrochemical energy generation and storage

Layered transition metal dichalcogenides (TMDs) (MoS2, MoSe2, WS2, WSe2, etc.) are a chemically diverse class of compounds having band gaps from 0 to ∼2 eV and remarkable electrochemical properties. The band gaps and electrochemical properties of TMDs can be tuned by exchanging the transition metal or chalcogenide elements. After a brief description of the most commonly followed synthetic routes to prepare TMDs, we wish to highlight in this review the diverse electrochemical applications of MoS2, a representative and well-studied TMD, which range from its use as catalysts in hydrogen evolution reactions to its adoption in supercapacitors, batteries, solar cells, and hydrogen storage.

Enhanced Gold Nanoparticle Based ELISA for a Breast Cancer Biomarker

In this work, we developed an optical enzyme-linked immunosorbent assay (ELISA) immunoassay for the analysis of CA15-3 antigen, an important biomarker present in blood samples and useful for the follow-up of the medical treatment of breast cancer. Gold nanoparticles (AuNPs) were used as carriers of the signaling antibody anti-CA15-3-HRP (horseradish peroxidase) in order to achieve an amplification of the optical signal. In the range between 0 and 60 U/mL, the assay adopting AuNPs as an enhancer resulted in higher sensitivity and shorter assay time when compared to classical ELISA procedures. The application of AuNPs to the commercially available ELISA test can be useful to improve important immunoanalysis procedures where a more confident result is needed.

“Metal-Free” Catalytic Oxygen Reduction Reaction on Heteroatom-Doped Graphene is Caused by Trace Metal Impurities†

The oxygen reduction reaction (ORR) is of high industrial importance. There is a large body of literature showing that metal-based catalytic nanoparticles (e.g. Co, Mn, Fe or hybrid Mn/Co-based nanoparticles) supported on graphene act as efficient catalysts for the ORR. A significant research effort is also directed to the so-called “metal-free” oxygen reduction reaction on heteroatom-doped graphene surfaces. While such studies of the ORR on nonmetallic heteroatom-doped graphene are advertised as “metal-free” there is typically no sufficient effort to characterize the doped materials to verify that they are indeed free of any trace metal. Here we argue that the claimed “metal-free” electrocatalysis of the oxygen reduction reaction on heteroatom-doped graphene is caused by metallic impurities present within the graphene materials.

Graphenes prepared by Staudenmaier, Hofmann and Hummers methods with consequent thermal exfoliation exhibit very different electrochemical properties

Large-scale fabrication of graphene is highly important for industrial and academic applications of this material. The most common large-scale preparation method is the oxidation of graphite to graphite oxide using concentrated acids in the presence of strong oxidants and consequent thermal exfoliation and reduction by thermal shock to produce reduced graphene. These oxidation methods typically use concentrated sulfuric acid (a) in combination with fuming nitric acid and KClO(3) (Staudenmaier method), (b) in combination with concentrated nitric acid and KClO(3) (Hofmann method) or (c) in the absence of nitric acid but in the presence of NaNO(3) and KMnO(4) (Hummers method). The evaluation of quality and applicability of the graphenes produced by these various methods is of high importance and is attempted side-by-side for the first time in this paper. Full-scale characterization of thermally reduced graphenes prepared by these standard methods was performed with techniques such as transmission and scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Their applicability for electrochemical devices was further evaluated by means of cyclic voltammetry techniques. We showed that while Staudenmaier and Hofmann methods (methods that do not use potassium permanganate as oxidant) generated thermally reduced graphenes with comparable electrochemical properties, the graphene prepared by the Hummers method which uses permanganate as oxidant showed higher heterogeneous electron transfer rates and lower overpotentials as compared to graphenes prepared by the Staudenmaier or Hofmann methods. This clearly shows that the methods of preparations have dramatic influences on the materials properties and, thus, such findings are of eminent importance for practical applications as well as for academic research.

Electrochemistry of Transition Metal Dichalcogenides: Strong Dependence on the Metal-to-Chalcogen Composition and Exfoliation Method

Beyond MoS2 as the first transition metal dichalcogenide (TMD) to have gained recognition as an efficient catalyst for the hydrogen evolution reaction (HER), interest in other TMD nanomaterials is steadily beginning to proliferate. This is particularly true in the field of electrochemistry, with a myriad of emerging applications ranging from catalysis to supercapacitors and solar cells. Despite this rise, current understanding of their electrochemical characteristics is especially lacking. We therefore examine the inherent electroactivities of various chemically exfoliated TMDs (MoSe2, WS2, WSe2) and their implications for sensing and catalysis of the hydrogen evolution and oxygen reduction reactions (ORR). The TMDs studied are found to possess distinctive inherent electroactivities and together with their catalytic effects for the HER are revealed to strongly depend on the chemical exfoliation route and metal-to-chalcogen composition particularly in MoSe2. Despite its inherent activity exhibiting large variations depending on the exfoliation procedure, it is also the most efficient HER catalyst with a low overpotential of -0.36 V vs RHE (at 10 mA cm(-2) current density) and fairly low Tafel slope of ∼65 mV/dec after BuLi exfoliation. In addition, it demonstrates a fast heterogeneous electron transfer rate with a k0obs of 9.17×10(-4) cm s(-1) toward ferrocyanide, better than that seen for conventional glassy carbon electrodes. Knowledge of TMD electrochemistry is essential for the rational development of future applications; inherent TMD activity may potentially limit certain purposes, but intended objectives can nonetheless be achieved by careful selection of TMD compositions and exfoliation methods.

Lithium Intercalation Compound Dramatically Influences the Electrochemical Properties of Exfoliated MoS2

MoS2 and other transition metal dichalcogenides (TMDs) have recently gained a renewed interest due to the interesting electronic, catalytic, and mechanical properties which they possess when down-sized to single or few layer sheets. Exfoliation of the bulk multilayer structure can be achieved by a preliminary chemical Li intercalation followed by the exfoliation due to the reaction of Li with water. Organolithium compounds are generally adopted for the Li intercalation with n-butyllithium (n-Bu-Li) being the most common. Here, the use of three different organolithium compounds are investigated and compared, i.e., methyllithium (Me-Li), n-butyllithium (n-Bu-Li) and tert-butyllithium (t-Bu-Li), used for the exfoliation of bulk MoS2 . Scanning transmission electron microscopy (STEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) are adopted for a comprehensive characterization of all materials under investigation. In addition, catalytic properties towards the hydrogen evolution reaction (HER) and capacitive properties are also tested. Different organolithium compounds exhibit different extent of Li intercalation resulting in different degrees of exfoliation. The inherent electrochemical behavior of MoS2 consisting of significant anodic and cathodic peaks as well as its capacitive behavior and catalytic properties towards hydrogen evolution reaction are strongly connected to the exfoliation compound used. This research significantly contributes to the development of large-scale synthesis of electrocatalytic MoS2 -based materials.

Noble metal (Pd, Ru, Rh, Pt, Au, Ag) doped graphene hybrids for electrocatalysis

Metal decorated graphene materials are highly important for catalysis. In this work, noble metal doped-graphene hybrids were prepared by a simple and scalable method. The thermal reductions of metal doped-graphite oxide precursors were carried out in nitrogen and hydrogen atmospheres and the effects of these atmospheres as well as the metal components on the characteristics and catalytic capabilities of the hybrid materials were studied. The hybrids exfoliated in nitrogen atmosphere contained a higher amount of oxygen-containing groups and lower density of defects on their surfaces than hybrids exfoliated in hydrogen atmosphere. The metals significantly affected the electrochemical behavior and catalysis of compounds that are important in energy production and storage and in electrochemical sensing. Research in the field of energy storage and production, electrochemical sensing and biosensing as well as biomedical devices can take advantage of the properties and catalytic capabilities of the metal doped graphene hybrids.

Chemically reduced graphene contains inherent metallic impurities present in parent natural and synthetic graphite

Graphene-related materials are in the forefront of nanomaterial research. One of the most common ways to prepare graphenes is to oxidize graphite (natural or synthetic) to graphite oxide and exfoliate it to graphene oxide with consequent chemical reduction to chemically reduced graphene. Here, we show that both natural and synthetic graphite contain a large amount of metallic impurities that persist in the samples of graphite oxide after the oxidative treatment, and chemically reduced graphene after the chemical reduction. We demonstrate that, despite a substantial elimination during the oxidative treatment of graphite samples, a significant amount of impurities associated to the chemically reduced graphene materials still remain and alter their electrochemical properties dramatically. We propose a method for the purification of graphenes based on thermal treatment at 1,000 °C in chlorine atmosphere to reduce the effect of such impurities on the electrochemical properties. Our findings have important implications on the whole field of graphene research.

Metallic Impurities in Graphenes Prepared from Graphite Can Dramatically Influence Their Properties

All at C? Graphenes prepared by the top-down exfoliation of graphite are shown to contain metallic impurities (see scheme, metal impurities shown as black dots). These impurities may dominate their properties and can have a negative influence on their potential applications.