The effect of electrolyte composition on the electroreduction of CO2 to CO on Ag based gas diffusion electrodes.

The electroreduction of CO2 to C1-C2 chemicals can be a potential strategy for utilizing CO2 as a carbon feedstock. In this work, we investigate the effect of electrolytes on the electroreduction of CO2 to CO on Ag based gas diffusion electrodes. Electrolyte concentration was found to play a major role in the process for the electrolytes (KOH, KCl, and KHCO3) studied here. Several fold improvements in partial current densities of CO (jCO) were observed on moving from 0.5 M to 3.0 M electrolyte solution independent of the nature of the anion. jCO values as high as 440 mA cm(-2) with an energy efficiency (EE) of ≈ 42% and 230 mA cm(-2) with EE ≈ 54% were observed when using 3.0 M KOH. Electrochemical impedance spectroscopy showed that both the charge transfer resistance (Rct) and the cell resistance (Rcell) decreased on moving from a 0.5 M to a 3.0 M KOH electrolyte. Anions were found to play an important role with respect to reducing the onset potential of CO in the order OH(-) (-0.13 V vs. RHE) < HCO3(-) (-0.46 V vs. RHE) < Cl(-) (-0.60 V vs. RHE). A decrease in Rct upon increasing electrolyte concentration and the effect of anions on the cathode can be explained by an interplay of different interactions in the electrical double layer that can either stabilize or destabilize the rate limiting CO2˙(-) radical. EMIM based ionic liquids and 1 : 2 choline Cl urea based deep eutectic solvents (DESs) have been used for CO2 capture but exhibit low conductivity. Here, we investigate if the addition of KCl to such solutions can improve conductivity and hence jCO. Electrolytes containing KCl in combination with EMIM Cl, choline Cl, or DESs showed a two to three fold improvement in jCO in comparison to those without KCl. Using such mixtures can be a strategy for integrating the process of CO2 capture with CO2 conversion.

Synthesis, characterization, and photoactivity of Ta2O5-grafted SiO2 nanoparticles.

Herein, we discuss the synthesis as well as material and photochemical characterization of nanometer-sized Ta(2)O(5) decorated, in a controlled fashion, on top of 20 nm diameter SiO(2) particles to yield a composite oxide with a tunable band-gap width. Particular emphasis is paid to control of particle size, and control of the distribution of the overlying oxide. The nanoscale dimension imparts a high surface area and introduces quantum confinement effects that displace the conduction band more negatively and the valence band more positively on the electrochemical scale of potentials. This band shift results in an increase of the number of possible participants in photocatalytic reactions. The band shift is shown to result in an increase in driving force for thermodynamically feasible reactions. By decorating SiO(2) with smaller-sized Ta(2)O(5), the interplay of the Lewis acidity of SiO(2) and the contact area between Ta(2)O(5) and SiO(2) is utilized to develop a photocatalyst with higher photoactivity than pure Ta(2)O(5).

An industrial perspective on catalysts for low-temperature CO2 electrolysis.

Electrochemical conversion of CO2 to useful products at temperatures below 100 °C is nearing the commercial scale. Pilot units for CO2 conversion to CO are already being tested. Units to convert CO2 to formic acid are projected to reach pilot scale in the next year. Further, several investigators are starting to observe industrially relevant rates of the electrochemical conversion of CO2 to ethanol and ethylene, with the hydrogen needed coming from water. In each case, Faradaic efficiencies of 80% or more and current densities above 200 mA cm-2 can be reproducibly achieved. Here we describe the key advances in nanocatalysts that lead to the impressive performance, indicate where additional work is needed and provide benchmarks that others can use to compare their results.

Effects of molecular sieving and electrostatic enhancement in the adsorption of organic compounds on the zeolitic imidazolate framework ZIF-8.

In this work, the adsorption behavior of a range of organic vapors and gases on the zeolitic imidazolate framework, ZIF-8, is investigated using an inverse gas chromatography (IGC) methodology at the zero-coverage limit and elevated temperatures. The measured thermodynamic values and surface energies for the adsorption of n-alkanes on ZIF-8 are found to be reduced from those previously reported for IRMOF-1. This reduction is most likely an effect of the predominately organic accessible surface of ZIF-8 and the resulting weaker interactions in comparison to IRMOF-1. The pore aperture size of ZIF-8, which is significantly reduced from that of IRMOF-1, is seen to introduce molecular sieving effects for branched alkanes, aromatics, and heavily halogenated compounds. Deformation polarizabilities of the adsorbates were used to calculate the specific adsorption free energy, and it is determined that the specific effects account for around 1-5 kJ/mol, or between 10% and 70% of the total free energy of adsorption for the sorbates studied (at 250 °C). The importance of electrostatic forces was seen in the significantly enhanced adsorption of propylene and ethylene in comparison to their respective alkanes and in the direct correlation shown between the specific components of the free energy of adsorption and the adsorbate's dipole moment.

Trends in the adsorption of volatile organic compounds in a large-pore metal-organic framework, IRMOF-1.

Metal-organic frameworks have been proposed as useful sorbents for the capture of a variety of compounds. In this work, inverse gas chromatography (IGC) utilizing micropacked capillary columns was used to probe the adsorption of more than 30 volatile organic compounds (VOCs) on IRMOF-1. In an attempt to study the effect of structural degradation upon VOC adsorption, multiple samples of IRMOF-1 with widely ranging properties were investigated. Trends in the differential enthalpies and equilibrium constants for the adsorption of VOCs were determined on the basis of the molecular properties of the adsorbate and the structural properties of the MOF sample. The results indicate that samples of IRMOF-1 that are affected by a moderate amount of structural degradation interact with adsorbed species more strongly than does a sample with fewer defects, resulting in higher heats of adsorption. Samples of IRMOF-1 with specific surface areas of around 1000 m(2)/g show heats of adsorption for alkanes that are higher than those estimated previously via Monte Carlo calculations. Although the data for nonpolar (and weakly polar) species showed many of the anticipated trends for the interactions with IRMOF-1, the equilibrium behavior of polar VOCs did not correlate well with the molecular properties of the adsorbate (i.e., vapor pressure and deformation polarizability), leaving some uncertainty about the nature of the interaction mechanism. The equilibrium data and the heats of adsorption were found to fit well to a small group of molecular descriptors through the application of the Abraham linear free-energy relationship, thus providing insight into the complex interactions between the MOF structure and the VOC compounds. Hydrogen bonding interactions were determined to be the primary contributors to specific interactions between adsorbates and the MOF surface. Size exclusion also seems to play a role in the adsorption of larger species. These results show that the interaction of VOCs with MOFs is more complex than previously assumed and that more work is needed to probe the mechanisms of these processes.

Nonbiological inhibition-based sensing (NIBS) demonstrated for the detection of toxic sulfides.

The purpose of this paper is to report on a new technique in chemical detection: nonbiological inhibition-based sensing (NIBS). This method uses a new approach to chemical amplification, where the analyte inhibits rather than enhances the rate of catalytic reaction. Although there are many possible catalysts for this technique, such as enzymes, this paper focuses on using the selective binding found in colorimetric detection. Colorimetric methods are selective; however, they are not particularly sensitive. Using nonbiological-based molecules allows for selective detection without the shelf-life issues that are associated with enzymes. In practice, we can use the active substances in Draeger tubes and related systems as catalysts. Analytes of interest inhibit the catalysts that leads to a large signal. The work presented here focuses on the detection of toxic sulfide compounds. Using NIBS, we observe that we can enhance the sensitivity of the system by 2 orders of magnitude with no apparent loss in selectivity. We can also decrease the detection time from 5 h to 10 min. So far, we have demonstrated the technique for sulfide detection; however, we believe that the technique can have general use in the detection of toxic compounds.

Partially buried microcolumns for micro gas analyzers.

This article demonstrates the feasibility of making a partially buried micro gas chromatography (micro-GC) column with a rounded channel wall profile, which enables coating the stationary phase more uniformly and shows better separation characteristics than a square deep reactive ion etched (DRIE) wall profile. A buried structure fabrication method was adapted to fabricate 34 cm long, 165 microm wide, and 65 microm deep partially buried microcolumns, which had a unique rounded microcolumn wall profile similar to that of a flattened circular tube. The separation characteristics were compared to that of a 34 cm long, 100 microm x 100 microm square DRIE microcolumn, which had a similar hydraulic diameter. Minimum height equivalent to a theoretical plate (HETP) and reduced HETP of 0.39 mm and 6.02, respectively, with a retention factor of 6.3 were obtained on the coated partially buried microcolumn compared to 0.66 mm and 6.73, respectively, on the coated square DRIE microcolumn with a similar retention factor. The partially buried microcolumn was found to perform closer to the theoretical approximation and this could be attributed to the uniform phase deposition in the partially buried microcolumn compared to the square DRIE microcolumn. A 10 component mix was separated on the partially buried microcolumn in 3.8 s with the maximum peak width at half-height equal to 0.2 s, while a similar mix separated at higher pressure and temperature conditions on the square DRIE microcolumn in 4.6 s. The rounded corners allowed depositing thinner stationary phase, which was reflected in the faster elution of n-C(12) on the partially buried microcolumn compared to the square DRIE microcolumn. The better performance of the partially buried microcolumn may be attributed to either the rounded channel wall profile, the clean channel structures produced by the fabrication process, or the double-etched wall profile, which lowers the Taylor-Aris dispersion.

Non-equilibrium electrokinetic micro/nano fluidic mixer.

We propose a new type of micro/nano fluidic mixer based on non-equilibrium electrokinetics and demonstrate its mixing performance. We fabricate the device with two-step reactive ion etching, one for nanochannels and one for microchannels. Mixing is achieved by strong vortex structures formed near the micro/nano channel interface. We expect the proposed device to be beneficial in the development of micro total analysis systems, since it is simple in its design with minimal fabrication complications.

Micromachined GC columns for fast separation of organophosphonate and organosulfur compounds.

This article demonstrates how to prepare microfabricated columns (microcolumns) for organophosphonate and organosulfur compound separation that rival the performance of commercial capillary columns. Approximately 16,500 theoretical plates were generated with a 3 m long OV-5-coated microcolumn with a 0.25 microm phase thickness using helium as the carrier gas at 20 cm/s. Key to the advance was the development of deactivation procedures appropriate for silicon microcolumns with Pyrex tops. Active sites in a silicon-Pyrex microcolumn cause peak tailing and unwanted adsorption. Experimentally, we found that organosilicon hydride deactivation lowers adsorption activity in microcolumns more than silazane and silane treatments. But without further treatment, the phosphonate peaks continue to tail after the coating process. We found that heat treatment with pinacolyl methylphosphonic acid (PMP) eliminated the phosphonate peak tailing. In contrast, conventional resilylation employing N, O-bis(trimethylsilyl)acetamide, hexamethyldisilazane, and 1-(trimethylsilyl)imidazole does not eliminate peak tailing. Column activity tests show that the PMP treatment also improves the peaks for 2,6-dimethyl aniline, 1-octanol, and 1-decanol implying a decrease in the column's hydrogen bonding sites with the PMP treatment. FT-IR analysis shows that exposure to PMP forms a bond to the stationary phase that deactivates the active sites responsible for organophosphonate peak tailing.

Carbon Dioxide and Water Electrolysis Using New Alkaline Stable Anion Membranes.

The recent development and market introduction of a new type of alkaline stable imidazole-based anion exchange membrane and related ionomers by Dioxide Materials is enabling the advancement of new and improved electrochemical processes which can operate at commercially viable operating voltages, current efficiencies, and current densities. These processes include the electrochemical conversion of CO2 to formic acid (HCOOH), CO2 to carbon monoxide (CO), and alkaline water electrolysis, generating hydrogen at high current densities at low voltages without the need for any precious metal electrocatalysts. The first process is the direct electrochemical generation of pure formic acid in a three-compartment cell configuration using the alkaline stable anion exchange membrane and a cation exchange membrane. The cell operates at a current density of 140 mA/cm2 at a cell voltage of 3.5 V. The power consumption for production of formic acid (FA) is about 4.3-4.7 kWh/kg of FA. The second process is the electrochemical conversion of CO2 to CO, a key focus product in the generation of renewable fuels and chemicals. The CO2 cell consists of a two-compartment design utilizing the alkaline stable anion exchange membrane to separate the anode and cathode compartments. A nanoparticle IrO2 catalyst on a GDE structure is used as the anode and a GDE utilizing a nanoparticle Ag/imidazolium-based ionomer catalyst combination is used as a cathode. The CO2 cell has been operated at current densities of 200 to 600 mA/cm2 at voltages of 3.0 to 3.2 respectively with CO2 to CO conversion selectivities of 95-99%. The third process is an alkaline water electrolysis cell process, where the alkaline stable anion exchange membrane allows stable cell operation in 1 M KOH electrolyte solutions at current densities of 1 A/cm2 at about 1.90 V. The cell has demonstrated operation for thousands of hours, showing a voltage increase in time of only 5 µV/h. The alkaline electrolysis technology does not require any precious metal catalysts as compared to polymer electrolyte membrane (PEM) design water electrolyzers. In this paper, we discuss the detailed technical aspects of these three technologies utilizing this unique anion exchange membrane.

Experimental technique using FTIR to estimate IR optical properties at variable temperatures: application to PMDA-ODA polyimide thin films from 100 to 380 degrees C.

An experimental technique is presented to measure reflectance at high sample temperature with respect to room temperature in the infrared using Fourier transform infrared fitted with a reflectometer. Sample temperature artifacts are accounted for by sequential measurements taken with the lamp source on and with the lamp source off. The sequential measurements are shown mathematically to correct for the modulation of sample and detector thermal emissions. Further, the technique is applied to a polyimide (PMDA-ODA) film on a layer of gold deposited on a thermally oxidized Si wafer. It is shown that the optical properties (index of refraction and extinction coefficient) remain relatively constant with temperature (from room temperature to 380 degrees C) in the 4000-6000 cm(-1) spectral region. The significant changes that occur with temperature are the change in thickness of the film and also the spectral properties in the 2000-4000 cm(-1) region. Also, by using a Lorentz oscillator model, it is shown that this method is able to discern that spectral features corresponding to the OH stretching bands at 3630 and 3470 cm(-1) show significant variation with increasing temperature.

Charge transfer from metallic single-walled carbon nanotube sensor arrays.

This paper explores the possibility of using arrays of metallic carbon nanotubes as sensors. Unlike their semiconducting counterparts, single-walled carbon nanotube arrays or networks that are dominated by metallic conduction pathways have not been investigated for their environmental sensitivity. In this work, we demonstrate transduction of molecular adsorption via charge transfer through predominantly metallic single-walled carbon nanotubes. Raman spectroscopy and electric field dependent transport confirm that signal transduction takes place through primarily large diameter metallic nanotubes. This unique signal transduction mechanism might have implications for novel sensors. The scaling of the signal with array impedance is well described using an irreversible binding model developed previously. The arrays have several advantages including a simple, two-electrode fabrication, rapid regeneration, and a responsivity that scales predictably and linearly with the number of adsorption sites. An array-assisted hydrolysis of reactive analytes is found to regenerate the nanotube surface from hydrolyzable species which include important organophosphate nerve agents.

Mechanical activation of CaO-based adsorbents for CO(2) capture.

The reversible cycling of CaO adsorbents to CaCO(3) for high-temperature CO(2) capture is substantially improved by mechanical treatment. The mechanical milling intensity and conditions of grinding (e.g., wet vs. dry, planetary vs. vibratory milling) were determined to be the main factors that control the effectiveness of the mechanochemical synthesis to enhance the recycling stability of the sorbents prepared. In addition, MgO was used as an example of an inert binder to help mitigate CaCO(3) sintering. Wet planetary milling of MgO into CaCO(3) allowed efficient particle size reduction and the effective dispersion of MgO throughout the particles. Wet planetary milling yielded the most stable sorbents during 50 cycles of carbonation-calcination.

An acetylcholinesterase-inspired biomimetic toxicity sensor.

This work demonstrates the ability of an acetylcholinesterase-inspired biomimetic sensor to accurately predict the toxicity of acetylcholinesterase (AChE) inhibitors. In surface waters used for municipal drinking water supplies, numerous pesticides and other anthropogenic chemicals have been found that inhibit AChE; however, there is currently no portable toxicity assay capable of determining the potential neurotoxicity of water samples and complex mixtures. Biological assays have been developed to determine the toxicity of unknown samples, but the short shelf-life of cells and other biological materials often make them undesirable for use in portable assays. Chemical methods and structure-activity-relationships, on the other hand, require prior knowledge on the compounds of interest that is often unavailable when analyzing environmental samples. In the toxicity assay presented here, the acetylcholinesterase enzyme has been replaced with 1-phenyl-1,2,3-butanetrione 2-oxime (PBO) a biomimetic compound that is structurally similar to the AChE active site. Using a biomimetic compound in place of the native enzyme allows for a longer shelf-life while maintaining the selective and kinetic ability of the enzyme itself. Previous work has shown the success of oxime-based sensors in the selective detection of AChE inhibitors and this work highlights the ability of an AChE-inspired biomimetic sensor to accurately predict the toxicity (LD50 and LC50) for a range of AChE inhibitors. The biomimetic assay shows strong linear correlations to LD50 (oral, rat) and LC50 (fish) values. Using a test set of eight AChE inhibitors, the biomimetic assay accurately predicted the LC50 value for 75% of the inhibitors within one order of magnitude.

Non-biological inhibition-based sensing (NIBS) demonstrated for the detection of toxic arsenic compounds.

This work demonstrates the success of a recently developed technique in chemical amplification, non-biological inhibition-based sensing (NIBS), for the detection of toxic arsenic compounds. Screening for toxic arsenic compounds is especially important due to their prevalence in wastewater and water sources. The detection method presented in this work amplifies the chemical response of toxic arsenic compounds by developing a sensor chemistry where the analyte inhibits, rather than enhances, the rate of a catalytic reaction. This technique mimics the work done with enzyme inhibition; however, using non-biological molecules allows for selective detection without the shelf-life issue associated with biological molecules. Using NIBS we find that we can enhance the sensitivity of the system by two orders of magnitude with no apparent loss in selectivity. This work demonstrates the versatility of NIBS, showing that the technique can be of general use for the detection of toxic compounds.

Fast carbon nanotube detectors for micro gas chromatographs.

Highly sensitive and completely reversible chemiresistor detectors based on carbon nanotubes (CNTs) were fabricated for multi-component chemical analysis. CNT detectors were used in a series configuration with a gas chromatography column and exposed to a mixture of nine different compounds. It is shown that CNT detectors were able to show parts per billion (pbb) sensitivity responses to each individual component of the mixture and detect nine distinct chemical compounds in roughly 210 s when the detector operates in current stimulated desorption (CSD) mode. This is the first demonstration of an uncoated CNT detector to analyze multi-component chemical mixtures providing an alternative yet simple sensing approach for online air quality control and health monitoring applications.

Ionic liquid-mediated selective conversion of CO2 to CO at low overpotentials.

Electroreduction of carbon dioxide (CO(2))--a key component of artificial photosynthesis--has largely been stymied by the impractically high overpotentials necessary to drive the process. We report an electrocatalytic system that reduces CO(2) to carbon monoxide (CO) at overpotentials below 0.2 volt. The system relies on an ionic liquid electrolyte to lower the energy of the (CO(2))(-) intermediate, most likely by complexation, and thereby lower the initial reduction barrier. The silver cathode then catalyzes formation of the final products. Formation of gaseous CO is first observed at an applied voltage of 1.5 volts, just slightly above the minimum (i.e., equilibrium) voltage of 1.33 volts. The system continued producing CO for at least 7 hours at Faradaic efficiencies greater than 96%.

On the sensing mechanism in carbon nanotube chemiresistors.

There has been recent controversy whether the response seen in carbon nanotube (CNT) chemiresistors is associated with a change in the resistance of the individual nanotubes or changes in the resistance of the junctions. In this study, we carry out a network analysis to understand the relative contributions of the nanotubes and the junctions to the change in resistance of the nanotube network. We find that the dominant mode of detection in nanotube networks changes according to the conductance level (defect level) in the nanotubes. In networks with perfect nanotubes, changes in the junctions between adjacent nanotubes and junctions between the contacts and the CNTs can cause a detectable change in the resistance of the nanotube networks, while adsorption on the nanotubes has a smaller effect. In contrast, in networks with highly defective nanotubes, the changes in the resistance of the individual nanotubes cause a detectable change in the overall resistance of a chemiresistor network, while changes in the junctions have smaller effects. The combinational effect is also observed for the case in between. The results show that the sensing mechanism of a nanotube network can change according to the defect levels of the nanotubes, which may explain the apparently contradictory results in the literature.

Nonthermal current-stimulated desorption of gases from carbon nanotubes.

The desorption of gases from carbon nanotubes is usually a slow process that limits the nanotubes' utility as sensors or as memristors. Here, we demonstrate that flow in the nanotube above the Poole-Frenkel conduction threshold can stimulate adsorbates to desorb without heating the sensor substantially. The method is general: alcohols, aromatics, amines, and phosphonates were all found to desorb. We postulate that the process is analogous to electron-stimulated desorption, but with an internally conducted rather than externally applied source of electrons.