Photoelectrochemistry of Redox-Active Self-Assembled Monolayers Formed on n-Si/Au Nanoparticle Photoelectrodes.

Controlling the chemistry of the electrode-solution interface is critically important for applications in sensing, energy storage, corrosion prevention, molecular electronics, and surface patterning. While numerous methods of chemically modifying electrodes exist, self-assembled monolayers (SAMs) containing redox-active moieties are particularly important because they are easy to prepare, have well-defined interfaces, and can exhibit textbook photoelectrochemistry. Here, we investigate the photoelectrochemistry of redox-active SAMs on semiconductor/metal interfaces, where the SAM is attached to the metal site instead of the semiconductor. n-Si/Au photoelectrodes were fabricated using a benchtop electrodeposition procedure and subsequently modified by immersion in aqueous solutions of (ferrocenyl)hexanethiol and mercaptohexanol. We explored the relevant preparation conditions, finding that after optimization, we were able to obtain canonical cyclic voltammetry for a surface-bound redox molecule that could be turned on and off using light. We then characterized the optimized electrodes under varying illumination intensities, finding that the heterogeneous electron transfer kinetics improved under higher illumination intensities. These results lay the foundation for future studies of semiconductor/metal/molecule interfaces relevant to sensing and electrocatalysis.

Characterizing and understanding the photovoltage in n-Si/Au light-addressable electrochemical sensors.

Here, we characterize the photovoltage of n-Si/Au light-addressable electrodes (LAEs) over a range of solution potentials from ca. -1 to +1 V. We find that the n-Si/Au photoelectrodes show photovoltages consistent with a semiconductor/liquid junction in contrast to a buried junction, which opposes our previous understanding of how photovoltage originates in these sensors.

Square-Wave Voltammetry Enables Measurement of Light-Activated Oxidations and Reductions on n-Type Semiconductor/Metal Junction Light-Addressable Electrochemical Sensors.

Light-addressable electrochemical (LAE) sensing is a photoelectrochemical technique that enables high-density, individually addressed electrochemical measurements using light to activate an electrochemical reaction at the surface of a semiconducting photoelectrode. However, one major challenge is that only one electrochemical reaction (oxidation or reduction) will be activated by light. Here, we used square-wave voltammetry (SWV) to enable measurement of both types of electrochemical reactions using n-Si/Au NP LAE sensors. We demonstrated this approach for the oxidation of ferrocene methanol and the reduction of ruthenium hexamine and methylene blue. We found that for all molecules, SWV showed dramatic improvements in current under illumination in comparison with dark samples. We also demonstrated that this approach works for both fully illuminated and partially illuminated samples. Altogether, we hope these results open up new applications for LAE sensors, especially those based on semiconductor/metal junctions.

Voltammetric pH Measurements in Unadulterated Foodstuffs, Urine, and Serum with 3D-Printed Graphene/Poly(Lactic Acid) Electrodes.

The pH of a system is a critical descriptor of its chemistry-impacting reaction rates, solubility, chemical speciation, and homeostasis. As a result, pH is one of the most commonly measured parameters in food safety, clinical, and environmental laboratories. Glass pH probes are the gold standard for pH measurements but suffer drawbacks including frequent recalibration, wet storage of the glass membrane, difficulty in miniaturization, and interferences from alkali metals. In this work, we describe a voltammetric pH sensor that uses a three-dimensional (3D)-printed graphene/poly(lactic acid) filament electrode that is pretreated to introduce quinone functional groups to the graphene surface. After thoroughly characterizing the pretreatment parameters using outer-sphere and inner-sphere redox couples, we measured pH by reducing the surface-bound quinones, which undergo a pH-dependent 2e-/2H+ reduction. The position of the redox peak was found to shift -60 ± 2 mV pH-1 at 25 °C, which is in excellent agreement with the theoretical value predicted by the Nernst Equation (-59.2 mV pH-1). Importantly, the sensors did not require the removal of dissolved oxygen prior to successful pH measurements. We investigated the impact of common interfering species (Pb2+ and Cu2+) and found that there was no impact on the measured pH. We subsequently challenged the sensors to measure the pH of unadulterated complex samples, including cola, vinegar, an antacid tablet slurry, serum, and urine, and obtained excellent agreement compared to a glass pH electrode. In addition to the positive analytical characteristics, the sensors are extremely cheap and easy to fabricate, making them highly accessible to a wide range of researchers. These results pave the way for customizable pH sensors that can be fabricated in (nearly) any geometry for targeted applications using 3D printing.

Light-Addressable Electrochemical Sensing with Electrodeposited n-Silicon/Gold Nanoparticle Schottky Junctions.

Light-addressable electrochemical sensors (LAESs) are a class of sensors that use light to activate an electrochemical reaction on the surface of a semiconducting photoelectrode. Here, we investigate semiconductor/metal (Schottky) junctions formed between n-type Si and Au nanoparticles as light-addressable electrochemical sensors. To demonstrate this concept, we prepared n-Si/Au nanoparticle Schottky junctions by electrodeposition and characterized them using scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. We found that the sensors behaved almost identically to Au disk electrodes for the oxidation of an outer-sphere redox couple (ferrocene methanol) and two inner-sphere redox couples (potassium ferrocyanide and dopamine). In buffered dopamine solutions, we observed broad linear ranges and submicromolar detection limits. We then used local illumination to generate a virtual array of electrochemical sensors for dopamine as a strategy for circumventing sensor fouling, which is a persistent problem for electrochemical dopamine sensors. By locally illuminating a small portion of the photoelectrode, many measurements of fouling analytes can be made on a single sensor with a single electrical connection by moving the light beam to a fresh area of the sensor. Altogether, these results pave the way for Schottky junction light-addressable electrochemical sensors to be useful for a number of interesting future applications in chemical and biological sensing.

Scanning Line Probe Microscopy: Beyond the Point Probe.

Scanning probe microscopy (SPM) techniques have become indispensable tools for studying nano- and microscale materials and processes but suffer from a trade-off between resolution and areal scan rate that limits their utility for a number of applications and sample types. Here, we present a novel approach to SPM imaging based on combining nonlocal scanning line probes with compressed sensing (CS) signal analysis methods. Using scanning electrochemical microscopy (SECM) as an exemplar SPM technique, we demonstrate this approach using continuous microband electrodes, or line probes, which are used to perform chemical imaging of electrocatalytic Pt discs deposited on an inert substrate. These results demonstrate the potential to achieve high areal SPM imaging rates using nonlocal scanning probes and CS image reconstruction.

Solid Contact Ion-Selective Electrodes for in Situ Measurements at High Pressure.

Solid contact polymeric ion-selective electrodes (SC-ISEs) have been fabricated using microporous carbon (µPC) as the ion-to-electron transducer, loaded with a liquid membrane cocktail containing both ionophore and additive dissolved in plasticizer. These SC-ISEs were characterized and shown to be suitable for analysis in aqueous environments at pressures of 100 bar. Potassium ISEs, prepared in this manner, showed excellent performance at both atmospheric and elevated pressures, as evaluated by their response slopes and potential stability. These novel SC-ISEs were shown to be capable of measuring K+ at pressures under which traditional liquid-filled ISEs fail. Furthermore, the effect of pressure on the response of these sensors had little or no effect on potential, sensitivity, or limit of detection. High pressure sensor calibrations were performed in standard solutions as well as simulated seawater samples to demonstrate their usefulness as sensors in a deep-sea environment. These novel SC-ISE sensors show promise of providing the ability to make in situ real-time measurements of ion-fluxes near deep-ocean geothermal vents.

Direct identification and analysis of heavy metals in solution (Hg, Cu, Pb, Zn, Ni) by use of in situ electrochemical X-ray fluorescence.

The development and application of a new methodology, in situ electrochemical X-ray fluorescence (EC-XRF), is described that enables direct identification and quantification of heavy metals in solution. A freestanding film of boron-doped diamond serves as both an X-ray window and the electrode material. The electrode is biased at a suitable driving potential to electroplate metals from solution onto the electrode surface. Simultaneously, X-rays that pass through the back side of the electrode interrogate the time-dependent electrodeposition process by virtue of the XRF signals, which are unique to each metal. In this way it is possible to unambiguously identify which metals are in solution and relate the XRF signal intensity to a concentration of metal species in solution. To increase detection sensitivity and reduce detection times, solution is flown over the electrode surface by use of a wall-jet configuration. Initial studies focused on the in situ detection of Pb(2+), where concentration detection limits of 99 nM were established in this proof-of-concept study (although significantly lower values are anticipated with system refinement). This is more than 3 orders of magnitude lower than that achievable by XRF alone in a flowing solution (0.68 mM). In situ EC-XRF measurements were also carried out on a multimetal solution containing Hg(2+), Pb(2+), Cu(2+), Ni(2+), Zn(2+), and Fe(3+) (all at 10 µM concentration). Identification of five of these metals was possible in one simple measurement. In contrast, while anodic stripping voltammetry (ASV) also revealed five peaks, peak identification was not straightforward, requiring further experiments and prior knowledge of the metals in solution. Time-dependent EC-XRF nucleation data for the five metals, recorded simultaneously, demonstrated similar deposition rates. Studies are now underway to lower detection limits and provide a quantitative understanding of EC-XRF responses in real, multimetal solutions. Finally, the production of custom-designed portable in situ EC-XRF instrumentation will make heavy metal analysis at the source a very realistic possibility.

Electrochemical X-ray fluorescence spectroscopy for trace heavy metal analysis: enhancing X-ray fluorescence detection capabilities by four orders of magnitude.

The development of a novel analytical technique, electrochemical X-ray fluorescence (EC-XRF), is described and applied to the quantitative detection of heavy metals in solution, achieving sub-ppb limits of detection (LOD). In EC-XRF, electrochemical preconcentration of a species of interest onto the target electrode is achieved here by cathodic electrodeposition. Unambiguous elemental identification and quantification of metal concentration is then made using XRF. This simple electrochemical preconcentration step improves the LOD of energy dispersive XRF by over 4 orders of magnitude (for similar sample preparation time scales). Large area free-standing boron doped diamond grown using microwave plasma chemical vapor deposition techniques is found to be ideal as the electrode material for both electrodeposition and XRF due to its wide solvent window, transparency to the XRF beam, and ability to be produced in mechanically robust freestanding thin film form. During electrodeposition it is possible to vary both the deposition potential (Edep) and deposition time (tdep). For the metals Cu(2+) and Pb(2+) the highest detection sensitivities were found for Edep = -1.75 V and tdep (=) 4000 s with LODs of 0.05 and 0.04 ppb achieved, respectively. In mixed Cu(2+)/Pb(2+) solutions, EC-XRF shows that Cu(2+) deposition is unimpeded by Pb(2+), across a broad concentration range, but this is only true for Pb(2+) when both metals are present at low concentrations (10 nM), boding well for trace level measurements. In a dual mixed metal solution, EC-XRF can also be employed to either selectively deposit the metal which has the most positive formal reduction potential, E(0), or exhaustively deplete it from solution, enabling uninhibited detection of the metal with the more negative E(0).

Electrochemistry of aqueous colloidal graphene oxide on Pt electrodes.

The electrochemical behavior of colloidal solutions of graphene oxide (GO) is described here in detail. The GO reduction is shown to exhibit near-reversible electron transfer on Pt electrodes, based on E1/2 and ΔEp values. The observed peak current is found to depend linearly on the concentration of the GO and the square root of the scan rate, suggesting that the response is diffusion-limited. The difference between the experimental and diffusion-only limited theoretical current values suggests that migration may be hindering mass transport to the electrode surface. Varying the type and concentration of the supporting electrolyte showed that mass transport is weakly influenced by the presence of negative charges on the graphene particles. The effect of pH on GO was also investigated, and it was found that the reduction peak heights were directly related to proton concentration in acidic solutions. On the basis of the results presented here, we propose that the observed response of GO on Pt electrodes is a result of the reduction of protons from the colloidal double layer. This difference is observed only because the Pt electrode surface can efficiently catalyze proton reduction.

Carbon-nanofiber-based nanocomposite membrane as a highly stable solid-state junction for reference electrodes.

There is currently a need for a reliable solid-state reference electrode, especially in applications such as autonomous sensing or long-term environmental monitoring. We present here for the first time a novel solid-state nanofiber junction reference electrode (NFJRE) incorporating a junction consisting of poly(methyl methacrylate) and carbon graphene stacked nanofibers. The NFJRE operates by using the membrane polymer junction, which has a very high glass transition temperature (T(g)) and small diffusion coefficient, to control the diffusion of ions, and the carbon nanofibers lower the junction resistance and act as ion-to-electron transducers. The fabrication of the NFJRE is detailed, and its behavior is characterized in terms of its impedance, stability, and behavior in comparison with traditional reference electrodes. The NFJRE showed a response of <5-13 mV toward a variety of electrolyte solutions from 10(-5) to 10(-2) M, <10 mV over a pH range of 2-12, and excellent behavior when used with voltammetric methods.

Membraneless electrolyzers for the simultaneous production of acid and base.

This study investigates the use of membraneless electrolyzers based on angled mesh flow-through electrodes for the simultaneous production of acid and base (lye) from aqueous brine solutions. These electrolyte-agnostic flow cells are capable of producing a wide variety of acids and bases with precisely controlled pH using a simple cell design.