Graphene-Mercury-Graphene Sandwich Electrode for Electroanalysis

We present a new class of hybrid 2D electrodes, where mercury is incorporated between two graphene monolayers, prepared by bottom-up assembly. First, the bottom graphene layer is electrochemically modified leading to the creation of fine mercury nanodroplets of variable size on the graphene surface. Although such electrodes show good sensitivity to heavy metal ions, their stability is limited due to the outgassing of mercury over time. After coverage with a top monolayer, the graphene surface is rendered with the favorable properties of mercury such as the high overpotential for hydrogen evolution, the ability to work at a broader cathodic potential range and higher sensitivity towards heavy metal ions such as Cd2+ and Pb2+. Most importantly, the outgassing of mercury is completely hindered by the top layer, which yields a stable mercury-like electrode but with a carbonaceous non-toxic interface. We attribute the favorable properties of the sandwich electrode to the subsurface mercury present below the top graphene sheet, which renders it with new electrochemical properties.German Science Foundation (DFG)Graduate School of Analytical Sciences AdlershofMPI StuttgartHZB http://dx.doi.org/10.13039/100013110HU BerlinPeer Reviewe

A highly durable graphene monolayer electrode under long-term hydrogen evolution cycling

Achieving long term stability of single graphene sheets towards repeated electrochemical hydrogen evolution reaction (HER) cycling has been challenging. Here, we show through appropriate electrode preparation that it is possible to obtain highly durable isolated graphene electrodes, which can survive several hundreds of HER cycles with virtually no damage to the sp2-carbon framework and persistently good electron transfer characteristics.Peer Reviewe

Investigations of Electron Transfer at Graphene and Graphene Sandwiches

Mit der Entdeckung von Graphen begann ein neuer Zeitabschnitt für die Entwicklung von Elektronik und Sensoren aufgrund der einzigartigen elektronischen Struktur Graphens. Graphen ist breit vertreten, beispielsweise in Anwendungsbereichen von Sensorik, Energiespeicherung und Katalyse. Elektronentransferprozesse sind fundamentale Prozesse für eben solche Anwendungen. Die Eigenschaften des heterogenen Elektronentransfers von Graphen sind sehr umstritten und es gibt immer noch kein einheitliches Bild, um eben jenen zu verstehen, da oft voneinander abweichende Eigenschaften in der Literatur dargestellt werden. Diese Arbeit präsentiert systematische Untersuchungen der Elektronentransfereigenschaften von einlagigen Graphenelektroden. Als weiterer Teil dieser Arbeit werden die Elektronentransfereigenschaften durch den Entwurf einer neuen Graphen-Hybridelektrode gezielt verändert. Der erste Teil ist auf die Verbesserung der Herstellungsschritte und der anschließenden Untersuchung des Einflusses von Kupferrückständen auf die Kinetik des Elektronentransfers von einlagigen Graphenelektroden fokussiert. Die Kupferrückstände kommen von der Herstellung und dem Transfer von Graphen. Die Elektronentransferkinetik von klassischen Redoxmediatoren mit inner-sphere Elektronentransfermechanismus nimmt nach erfolgreichen Entfernen von Kupferrückständen ab. Im Gegensatz dazu bleibt die Kinetik von outer-sphere Redoxmediatoren unberührt. Hier wird gezeigt, dass die Elektronentransferkinetik von solchen Redoxmediatoren vom pH-Wert der Lösung abhängig ist, obwohl bei dem Elektronentransfer Protonen nicht involviert sind. Weiterhin wird hier festgestellt, dass der Elektronentransfer von Kationen an Graphen am schnellsten in neutralem pH stattfindet, während der Elektronentransfer von Anionen am schnellsten in saurem Millieu abläuft. Diese pH-Abhängigkeit wird den elektrostatischen Wechselwirkungen zwischen den dissoziierten Redoxmediatoren und der Ladung der Graphen-Flüssigkeit-Grenzschicht zugeschrieben. Dieses Verhalten wird auch für Graphenelektroden auf anderen isolierenden Substraten und sogar mit einer unter dem Graphen liegenden Schicht von hexagonalem Bornitrid (hBN) gefunden. Basierend darauf ist die Schlussfolgerung, dass diese pH-Abhängigkeit für den Elektronentransfer von geladenen Redoxmediatoren an Graphenelektroden intrinsisch und spezifisch für Graphen ist. Mit Metallsubstraten unter dem Graphen kann dieser pH-Effekt unterdrückt werden, was für einen verstärkten elektrokatalytischen Effekt vom darunterliegenden Metall spricht, welcher dem vorher diskutierten elektrostatischen Effekt, vermutlich durch die Zunahme der gesamten Elektronendichte, überwiegt. Basierend darauf wurde eine neue Art von Graphenelektrode entwickelt: die Graphen-Sandwichelektrode. Diese Elektrode besteht aus zwei aufeinanderliegenden Graphenschichten mit dazwischenliegenden Metallpartikeln. Diese Sandwichelektrode nutzt die elektrochemischen Eigenschaften der in der Mitte liegenden Metallpartikeln aus, obwohl das Metall durch eine Graphenschicht bedeckt ist und nicht in Kontakt mit der Lösung kommt. Bei der Verwendung von Platinpartikeln wird die obere Graphenschicht mit elektrokatalytischen Eigenschaften versehen. Als Ergebnis wird die Bildung von Wasserstoff (HER) und die Reduktion von Sauerstoff (ORR) an dieser Elektrode katalysiert. Des Weiteren wird dieser Effekt hier dafür genutzt um Wasserstoffperoxid zu messen, auch wenn eine solche Reaktion an einer „normalen“ Graphenelektrode nicht beobachtet werden kann. Hierdurch wird eine neue Klasse von optimierten Elektroden mit maßgeschneiderten elektrokatalytischen Eigenschaften realisiert. Diese Ergebnisse heben den Einfluss eines unter Graphen liegenden Metalls auf die Elektrochemie von Graphen hervor. Der zweite Teil dieser Arbeit konzentriert sich auf die Untersuchungen von Ladungen an der Graphen-Flüssigkeit-Grenzschicht auf einem lokalen und räumlich aufgelösten Niveau mit Hilfe von Rasterionenleitfähigkeitsmikroskopie (Scanning Ion Conductance Microscope - SICM). Dafür sind weiche Trägerflächen benötigt, die die Spitzen von Glaskapillaren nicht beschädigen. Diesbezüglich werden drei Protokolle für den Transfer von Graphen auf ein weiches Polymersubstrat, dem Polydimetyhlsiloxan (PDMS), entwickelt. Die dadurch erhaltenen Graphenproben werden mit Hilfe von optischer und Rasterkraftmikroskopie charakterisiert. Anhand von Annäherungskurven aus der SICM kann die Oberflächenladung qualitativ charakterisiert werden. Die Oberflächenladung einer Graphenoberfläche kann als negativ geladen in einem pH-Wert von 7 entschlüsselt werden. Zusätzlich werden Herausforderungen und Hindernisse beim Arbeiten mit SICM zu Grenzflächenuntersuchungen von einlagigem Graphen diskutiert. Diese Ausarbeitung zeigt die Bedeutung von Grenzflächenladungen und den Einfluss von unter dem Graphen liegenden Metall auf Graphen und graphenverwandte Elektroden auf. Dieses Wissen kann genutzt werden, um neue graphenbasierte Sensoren und auch hybride Elektroden für Elektrokatalyse zu entwickeln.The discovery of graphene initiated a new era of electronic and sensor development due to graphene's unique electronic structure. Graphene covers a wide range of applications including sensing, energy storage and catalysis. The heterogeneous electron transfer (ET) is the most fundamental and most important process happening at devices in such applications. However, the ET properties of graphene are highly debated and still no coherent picture can be drawn to understand them since differing ET rates are presented in literature. This work presents systematic investigations of the ET characteristics of graphene monolayer electrodes. Furthermore, the ET properties are engineered by the fabrication of a novel graphene-based hybrid electrode. The first part focusses on the improvement of the fabrication steps and subsequent investigation of the influence of Cu trace residues on the ET kinetics of graphene monolayer electrodes. The residual Cu traces come from the fabrication process of graphene as well as from the transfer process of graphene monolayer electrodes. The ET kinetics of a classical inner-sphere redox probe decreases after a successful removal of Cu particles. In contrast to this, the ET kinetics for outer-sphere redox probes stay unaffected. Most importantly, the ET kinetics of both kinds of redox probes are found to be dependent on the solution pH, although these reactions are proton independent. ET at graphene with cations is found to be fastest in neutral pH, while the ET kinetics of anions are fastest in acidic media. This pH dependency is attributed to electrostatic interactions between the dissociated redox probes and the interfacial charge at the graphene-liquid interface (GLI). This behavior is further observed for graphene monolayer electrodes on other insulating substrates. Even with an underlying hexagonal boron nitride (hBN) layer that shields the graphene monolayer from the substrate, the same pH effect can be observed. Based on this, it can be concluded that the pH dependency of ET at graphene for charged redox species is intrinsic to graphene. By using a subsurface metal substrate, the pH effect is suppressed, indicating an enhanced electrocatalytic effect from the metal underneath that dominates the afore discovered electrostatic effect, most likely due to an increase of the overall electron density. By exploiting this effect, a new kind of graphene electrode is designed: the graphene sandwich electrode. This electrode consists of two graphene monolayers, with electrodeposited metal particles between both layers. This sandwich electrode exploits electrochemical properties of the metal in between, even though the metal is covered by a graphene monolayer and hence not exposed to the liquid. By using Pt particles, the upper graphene layer gets rendered with electrocatalytic properties. As a result, the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR) are found to be clearly catalyzed at this electrode. Furthermore, this effect is exploited for hydrogen peroxide sensing, while this reaction is not observable on pristine graphene. Thus, a new kind of engineered electrode with rendered novel electrocatalytic properties was designed. These findings highlight the influence of a subsurface metal on to the electrochemistry of graphene. The second part of this work focusses on using scanning ion conductance microscopy (SICM) to investigate interfacial charges at the GLI at a local and spatially resolved level. First, for investigations using an SICM, soft samples are needed for avoiding damage of SICM tips. For this, three different protocols are developed and discussed for transferring a graphene monolayer on a soft poly(dimethylsiloxane) (PDMS) substrate. The obtained graphene samples are characterized using optical and atomic force microscopy. By utilizing approach curves in SICM, the surface charge can be characterized qualitatively. At a graphene surface in pH 7, an overall negative surface charge can be deciphered. In addition, challenges and obstacles are discussed when using SICM for interfacial investigations of graphene monolayers. Taken together, this work presents systematic investigations of the ET of graphene monolayer and graphene sandwich electrodes. These findings improve the understanding of graphene electrochemistry and highlights the importance of interfacial charge and the influence of a subsurface metal on graphene and graphene-related electrodes. This knowledge can be used to design new graphene-based sensors and hybrid electrodes for electrocatalysis

Femtosecond-Pulsed Laser Written and Etched Fiber Bragg Gratings for Fiber-Optical Biosensing

We present the development of a label-free, highly sensitive fiber-optical biosensor for online detection and quantification of biomolecules. Here, the advantages of etched fiber Bragg gratings (eFBG) were used, since they induce a narrowband Bragg wavelength peak in the reflection operation mode. The gratings were fabricated point-by-point via a nonlinear absorption process of a highly focused femtosecond-pulsed laser, without the need of prior coating removal or specific fiber doping. The sensitivity of the Bragg wavelength peak to the surrounding refractive index (SRI), as needed for biochemical sensing, was realized by fiber cladding removal using hydrofluoric acid etching. For evaluation of biosensing capabilities, eFBG fibers were biofunctionalized with a single-stranded DNA aptamer specific for binding the C-reactive protein (CRP). Thus, the CRP-sensitive eFBG fiber-optical biosensor showed a very low limit of detection of 0.82 pg/L, with a dynamic range of CRP detection from approximately 0.8 pg/L to 1.2 µg/L. The biosensor showed a high specificity to CRP even in the presence of interfering substances. These results suggest that the proposed biosensor is capable for quantification of CRP from trace amounts of clinical samples. In addition, the adaption of this eFBG fiber-optical biosensor for detection of other relevant analytes can be easily realized

Highly Durable Graphene Monolayer Electrode on Insulating Substrate under Long-term Hydrogen Evolution Cycling

Electrochemical hydrogen evolution reaction (HER) at single graphene sheets has been investigated widely either in its pristine form or after chemical modification. One important challenge is the long-term stability of single graphene sheets on Si/SiO2 substrates under HER. Previous reports have found that due to stress developing under gas evolution, the sheets tend to break apart, with a very low lifetime limited to just a few cycles of HER. Here, we show through appropriate electrode preparation that it is possible to achieve highly durable single graphene electrodes on insulating substrates, which can survive several hundreds of HER cycles with virtually no damage to the sp2-carbon framework. Through systematic investigations including atomic force microscopy, Raman spectroscopy and electroanalysis, we show that even after so many cycles, the sheet is physically intact and the electron transfer capability of the electrodes remain unaffected. This extremely high stability of a single atomic sheet of carbon, when combined with appropriate chemical modification strategies, will pave way for the realization of novel 2D electrocatalysts

Faradaic effects in electrochemically gated graphene sensors in the presence of redox active molecules

Field-effect transistors (FETs) based on graphene are promising devices for the direct sensing of a range of analytes in solution. We show here that the presence of redox active molecules in the analyte solution leads to the occurrence of heterogeneous electron transfer with graphene generating a Faradaic current (electron transfer) in a FET configuration resulting in shifts of the Dirac point. Such a shift occurs if the Faradaic current is significantly high, e.g. due to a large graphene area. Furthermore, the redox shift based on the Faradaic current, reminiscent of a doping-like effect, is found to be non-Nernstian and dependent on parameters known from electrode kinetics in potentiodynamic methods, such as the electrode area, the standard potential of the redox probes and the scan rate of the gate voltage modulation. This behavior clearly differentiates this effect from other transduction mechanisms based on electrostatic interactions or molecular charge transfer doping effects, which are usually behind a shift of the Dirac point. These observations suggest that large-area unmodified/pristine graphene in field-effect sensors behaves as a non-polarized electrode in liquid. Strategies for ensuring a polarized interface are discussed.Deutsche Forschungsgemeinschafthttp://dx.doi.org/10.13039/501100001659Peer Reviewe

Binding Kinetics of Methylene Blue on Monolayer Graphene Investigated by Multiparameter Surface Plasmon Resonance

In this paper, we study the interaction of a small dye molecule, namely, methylene blue (MB) with graphene surfaces using surface plasmon resonance (SPR). We show that by utilizing all of the parameters of the SPR angular dip and exploiting the fact that MB absorbs light at the operating wavelength, it is possible to detect the binding of small molecules that would otherwise not give a significant signal. The binding of MB to unmodified graphene is found to be stronger than that for gold. By studying the interaction at modified surfaces, we demonstrate that electrostatic effects play a dominant role in the binding of MB on to graphene. Furthermore, following the binding kinetics at various concentrations allows us to estimate apparent equilibrium binding and rate constants for the interaction of MB with graphene