Laser-induced graphene electrodes for electrochemical ion sensing, pesticide monitoring, and water splitting.

Laser-induced graphene (LIG) has shown to be a scalable manufacturing route to create graphene electrodes that overcome the expense associated with conventional graphene electrode fabrication. Herein, we expand upon initial LIG reports by functionalizing the LIG with metallic nanoparticles for ion sensing, pesticide monitoring, and water splitting. The LIG electrodes were converted into ion-selective sensors by functionalization with poly(vinyl chloride)-based membranes containing K+ and H+ ionophores. These ion-selective sensors exhibited a rapid response time (10-15 s), near-Nernstian sensitivity (53.0 mV/dec for the K+ sensor and - 56.6 mV/pH for the pH sensor), and long storage stability for 40 days, and were capable of ion monitoring in artificial urine. The pesticide biosensors were created by functionalizing the LIG electrodes with the enzyme horseradish peroxidase and displayed a high sensitivity to atrazine (28.9 nA/µM) with negligible inference from other common herbicides (glyphosate, dicamba, and 2,4-dichlorophenoxyacetic acid). Finally, the LIG electrodes also exhibited a small overpotential for hydrogen evolution reaction and oxygen evolution reaction. The oxygen evolution reaction tests yielded overpotentials of 448 mV and 995 mV for 10 mA/cm2 and 100 mA/cm2, respectively. The hydrogen evolution reaction tests yielded 35 mV and 281 mV for the corresponding current densities. Such a versatile LIG platform paves the way for simple, efficient electrochemical sensing and energy harvesting applications.

Protein-assisted scalable mechanochemical exfoliation of few-layer biocompatible graphene nanosheets.

A facile method to produce few-layer graphene (FLG) nanosheets is developed using protein-assisted mechanical exfoliation. The predominant shear forces that are generated in a planetary ball mill facilitate the exfoliation of graphene layers from graphite flakes. The process employs a commonly known protein, bovine serum albumin (BSA), which not only acts as an effective exfoliation agent but also provides stability by preventing restacking of the graphene layers. The latter is demonstrated by the excellent long-term dispersibility of exfoliated graphene in an aqueous BSA solution, which exemplifies a common biological medium. The development of such potentially scalable and toxin-free methods is critical for producing cost-effective biocompatible graphene, enabling numerous possible biomedical and biological applications. A methodical study was performed to identify the effect of time and varying concentrations of BSA towards graphene exfoliation. The fabricated product has been characterized using Raman spectroscopy, powder X-ray diffraction, transmission electron microscopy and scanning electron microscopy. The BSA-FLG dispersion was then placed in media containing Astrocyte cells to check for cytotoxicity. It was found that lower concentrations of BSA-FLG dispersion had only minute cytotoxic effects on the Astrocyte cells.

Aerosol-Jet-Printed Graphene Immunosensor for Label-Free Cytokine Monitoring in Serum.

Graphene-based inks are becoming increasingly attractive for printing low-cost and flexible electrical circuits due to their high electrical conductivity, biocompatibility, and manufacturing scalability. Conventional graphene printing techniques, such as screen and inkjet printing, are limited by stringent ink viscosity requirements properties and large as-printed line width that impedes the performance of printed biosensors. Here, we report an aerosol-jet-printed (AJP) graphene-based immunosensor capable of monitoring two distinct cytokines: interferon gamma (IFN-γ) and interleukin 10 (IL-10). Interdigitated electrodes (IDEs) with 40 µm finger widths were printed from graphene-nitrocellulose ink on a polyimide substrate. The IDEs were annealed in CO2 to introduce reactive oxygen species on the graphene surface that act as chemical handles to covalently link IFN-γ and IL-10 antibodies to the graphene surfaces. The resultant AJP electrochemical immunosensors are capable of monitoring cytokines in serum with wide sensing range (IFN-γ: 0.1-5 ng/mL; IL-10: 0.1-2 ng/mL), low detection limit (IFN-γ: 25 pg/ml and IL-10: 46 pg/ml) and high selectivity (antibodies exhibited minimal cross-reactivity with each other and IL-6) without the need for sample prelabeling or preconcentration. Moreover, these biosensors are mechanically flexible with minimal change in signal output after 250 bending cycles over a high curvature (Φ = 5 mm). Hence, this technology could be applied to numerous electrochemical applications that require low-cost electroactive circuits that are disposable and/or flexible.

Heterobimetallic Single-Source Precursors: A Springboard to the Synthesis of Binary Intermetallics.

Intermetallics are atomically ordered crystalline compounds containing two or more main group and transition metals. In addition to their rich crystal chemistry, intermetallics display unique properties of interest for a variety of applications, including superconductivity, hydrogen storage, and catalysis. Because of the presence of metals with a wide range of reduction potentials, the controlled synthesis of intermetallics can be difficult. Recently, soft chemical syntheses such as the modified polyol and ship-in-a-bottle methods have helped advance the preparation of these materials. However, phase-segregated products and complex multistep syntheses remain common. Here, we demonstrate the use of heterobimetallic single-source precursors for the synthesis of 10-15 and 11-15 binary intermetallics. The coordination environment of the precursor, as well as the exact temperature used play a critical role in determining the crystalline intermetallic phase that is produced, highlighting the potential versatility of this approach in the synthesis of a variety of compounds. Furthermore, we show that a recently developed novel plasma-processing technique is successful in removing the surface graphitic carbon observed in some of the prepared compounds. This new single-source precursor approach is a powerful addition to the synthesis of atomically ordered intermetallic compounds and will help facilitate their further study and development for future applications.

Self-Limiting Processes in the Flame-Based Fabrication of Superhydrophobic Surfaces from Silicones.

Outdoor applications of superhydrophobic coatings require synthetic approaches that allow their simple, fast, scalable, and environmentally benign deployment on large, heterogeneous surfaces and their rapid regeneration in situ. We recently showed that the thermal degradation of silicones by flames fulfills these characteristics by spontaneously structuring silicone surfaces into a hierarchical, textured structure that provides wear-resistant, healable superhydrophobicity. This paper elucidates how flame processing-a simple, rapid, and out-of-equilibrium process-can be so counterintuitively reliable and robust in producing such a complex structure. A comprehensive study of the effect of the processing speed and flame temperature on the chemical and physical properties of the coatings yielded three surprising results. (i) Three thermal degradation mechanisms drive the surface texturing: depolymerization (in the O2-rich conditions of the surface), decomposition (in the O2-poor conditions found a few micrometers from the surface), and pyrolysis at excessive temperatures. (ii) The operational condition is delimited by the onset of the depolymerization at low temperatures and the onset of pyrolysis at high temperatures. (iii) The remarkably wide operational conditions and robustness of this approach result from self-limiting growth and oxidation of the silicone particles that are responsible for the surface texturing and in the extent of their deposition. As a result of this analysis we show that superhydrophobic surfaces can be produced or regenerated with this approach at a speed of 15 cm s-1 (i.e., the length of an airport runway in ∼4.5 h).

Stamped multilayer graphene laminates for disposable in-field electrodes: application to electrochemical sensing of hydrogen peroxide and glucose.

A multi-step approach is described for the fabrication of multi-layer graphene-based electrodes without the need for ink binders or post-print annealing. Graphite and nanoplatelet graphene were chemically exfoliated using a modified Hummers' method and the dried material was thermally expanded. Expanded materials were used in a 3D printed mold and stamp to create laminate electrodes on various substrates. The laminates were examined for potential sensing applications using model systems of peroxide (H2O2) and enzymatic glucose detection. Within the context of these two assay systems, platinum nanoparticle electrodeposition and oxygen plasma treatment were examined as methods for improving sensitivity. Electrodes made from both materials displayed excellent H2O2 sensing capability compared to screen-printed carbon electrodes. Laminates made from expanded graphite and treated with platinum, detected H2O2 at a working potential of 0.3 V (vs. Ag/AgCl [0.1 M KCl]) with a 1.91 µM detection limit and sensitivity of 64 nA·µM-1·cm-2. Electrodes made from platinum treated nanoplatelet graphene had a H2O2 detection limit of 1.98 µM (at 0.3 V), and a sensitivity of 16.5 nA·µM-1·cm-2. Both types of laminate electrodes were also tested as glucose sensors via immobilization of the enzyme glucose oxidase. The expanded nanographene material exhibited a wide analytical range for glucose (3.7 µM to 9.9 mM) and a detection limit of 1.2 µM. The sensing range of laminates made from expanded graphite was slightly reduced (9.8 µM to 9.9 mM) and the detection limit for glucose was higher (18.5 µM). When tested on flexible substrates, the expanded graphite laminates demonstrated excellent adhesion and durability during testing. These properties make the electrodes adaptable to a variety of tests for field-based or wearable sensing applications. Graphical abstract Expanded graphite (eGR) and expanded nanoplatelet graphene (nGN) were chemically exfoliated, thermally expanded, and manually stamped into flexible multi-layer graphene laminate electrodes. Hydrogen peroxide amperometric testing of eGR laminates compared to nGN laminates and a screen printed carbon (SPC) electrode.

Diffusional Dynamics of Tetraalkylphosphonium Ionic Liquid Films Measured by Fluorescence Correlation Spectroscopy.

Fluorescence correlation spectroscopy (FCS) is applied to investigate the diffusional dynamics of hydrophilic (Atto 590) and amphiphilic (DiD) fluorophores in a series of alkylphosphonium ionic liquid (IL) films ([P4448][Cl], [P6668][Cl], [P66614][Cl], and [P66614][NTf2]) in order to determine diffusional parameters and to elucidate nanoscale structural heterogeneities within the IL. From the measured correlation functions, the diffusion coefficients of the fluorescent molecules are estimated, rendering values that span from 0.39 to 1.2 and 0.146 to 5.2 µm2/s for Atto 590 and DiD, respectively. An increase in the diffusion coefficient values is correlated to the increase in the alkyl chain length, which in turn is correlated with a decrease in their viscosity. Interestingly, deviations from Brownian diffusion behavior of the fluorescent probes in the ILs are observed, showing a time-dependent diffusion coefficient in most of the cases. These deviations can be attributed to the presence of nanoscale structural heterogeneities in the tetraalkylphosphonium ILs. These results experimentally confirm the presence of nanosegregation in tetraalkylphosphonium ILs, which has been previously observed in molecular dynamics studies.

On the kinetics of the removal of ligands from films of colloidal nanocrystals by plasmas.

This paper describes the kinetic limitations of etching ligands from colloidal nanocrystal assemblies (CNAs) by plasma processing. We measured the etching kinetics of ligands from a CNA model system (spherical ZrO2 nanocrystals, 2.5-3.5 nm diameter, capped with trioctylphosphine oxide) with inductively coupled plasmas (He and O2 feed gases, powers ranging from 7 to 30 W, at pressures ranging from 100 to 2000 mTorr and exposure times ranging between 6 and 168 h). The etching rate slows down by about one order of magnitude in the first minutes of etching, after which the rate of carbon removal becomes proportional to the third power of the carbon concentration in the CNA. Pressure oscillations in the plasma chamber significantly accelerate the overall rate of etching. These results indicate that the rate of etching is mostly affected by two main factors: (i) the crosslinking of the ligands in the first stage of plasma exposure, and (ii) the formation of a boundary layer at the surface of the CNA. Optimized conditions of plasma processing allow for a 60-fold improvement in etching rates compared to the previous state of the art and make the timeframes of plasma processing comparable to those of calcination.

Flexible Laser-Induced Graphene for Nitrogen Sensing in Soil.

Flexible graphene electronics are rapidly gaining interest, but their widespread implementation has been impeded by challenges with ink preparation, ink printing, and postprint annealing processes. Laser-induced graphene (LIG) promises a facile alternative by creating flexible graphene electronics on polyimide substrates through the one-step laser writing fabrication method. Herein, we demonstrate the use of LIG, created with a low-cost UV laser, for electrochemical ion-selective sensing of plant-available nitrogen (i.e., both ammonium and nitrate ions: NH4+ and NO3-) in soil samples. The laser used to create the LIG was operated at distinct pulse widths (10, 20, 30, 40, and 50 ms) to maximize the LIG electrochemical reactivity. Results illustrated that a laser pulse width of 20 ms led to a high percentage of sp2 carbon (77%) and optimal peak oxidation current of 120 µA during cyclic voltammetry of ferro/ferricyanide. Therefore, LIG electrodes created with a 20 ms pulse width were consequently functionalized with distinct ionophores specific to NH4+ (nonactin) or NO3- (tridodecylmethylammonium nitrate) within poly(vinyl chloride)-based membranes to create distinct solid contact ion-selective electrodes (SC-ISEs) for NH4+ and NO3- ion sensing, respectively. The LIG SC-ISEs displayed near Nernstian sensitivities of 51.7 ± 7.8 mV/dec (NH4+) and -54.8 ± 2.5 mV/dec (NO3-), detection limits of 28.2 ± 25.0 µM (NH4+) and 20.6 ± 14.8 µM (NO3-), low long-term drift of 0.93 mV/h (NH4+ sensors) and -5.3 µV/h (NO3- sensors), and linear sensing ranges of 10-5-10-1 M for both sensors. Moreover, soil slurry sensing was performed, and recovery percentages of 96% and 95% were obtained for added NH4+ and NO3-, respectively. These results, combined with a facile fabrication that does not require metallic nanoparticle decoration, make these LIG electrochemical sensors appealing for a wide range of in-field or point-of-service applications for soil health management.

Large-Scale Synthesis of Colloidal Si Nanocrystals and Their Helium Plasma Processing into Spin-On, Carbon-Free Nanocrystalline Si Films.

This paper describes a simple approach to the large-scale synthesis of colloidal Si nanocrystals and their processing into spin-on carbon-free nanocrystalline Si films. The synthesized silicon nanoparticles are capped with decene, dispersed in hexane, and deposited on silicon substrates. The deposited films are exposed to nonoxidizing room-temperature He plasma to remove the organic ligands without adversely affecting the silicon nanoparticles to form crack-free thin films. We further show that the reactive ion etching rate in these films is 1.87 times faster than that for single-crystalline Si, consistent with a simple geometric argument that accounts for the nanoscale roughness caused by the nanoparticle shape.

Calcination does not remove all carbon from colloidal nanocrystal assemblies.

Removing organics from hybrid nanostructures is a crucial step in many bottom-up materials fabrication approaches. It is usually assumed that calcination is an effective solution to this problem, especially for thin films. This assumption has led to its application in thousands of papers. We here show that this general assumption is incorrect by using a relevant and highly controlled model system consisting of thin films of ligand-capped ZrO2 nanocrystals. After calcination at 800 °C for 12 h, while Raman spectroscopy fails to detect the ligands after calcination, elastic backscattering spectrometry characterization demonstrates that ~18% of the original carbon atoms are still present in the film. By comparison plasma processing successfully removes the ligands. Our growth kinetic analysis shows that the calcined materials have significantly different interfacial properties than the plasma-processed counterparts. Calcination is not a reliable strategy for the production of single-phase all-inorganic materials from colloidal nanoparticles.