Ezra L. Clark

Core–shell MoO3–MoS2 Nanowires for Hydrogen Evolution: A Functional Design for Electrocatalytic Materials

We synthesize vertically oriented core-shell nanowires with substoichiometric MoO(3) cores of ∼20-50 nm and conformal MoS(2) shells of ∼2-5 nm. The core-shell architecture, produced by low-temperature sulfidization, is designed to utilize the best properties of each component material while mitigating their deficiencies. The substoichiometric MoO(3) core provides a high aspect ratio foundation and enables facile charge transport, while the conformal MoS(2) shell provides excellent catalytic activity and protection against corrosion in strong acids.

MoO 3−x Nanowire Arrays As Stable and High-Capacity Anodes for Lithium Ion Batteries

In this study, vertical nanowire arrays of MoO(3-x) grown on metallic substrates with diameters of ~90 nm show high-capacity retention of ~630 mAhg(-1) for up to 20 cycles at 50 mAg(-1) current density. Particularly, they exhibit a capacity retention of ~500 mAhg(-1) in the voltage window of 0.7-0.1 V, much higher than the theoretical capacity of graphite. In addition, 10 nm Si-coated MoO(3-x) nanowire arrays have shown a capacity retention of ~780 mAhg(-1), indicating that hybrid materials are the next generation materials for lithium ion batteries.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

Significance Direct capture of CO2 from the air and its conversion to fuels using solar energy offers a means for mitigating global warming while also supporting future energy demands. Whereas natural photosynthesis converts CO2 and water to carbohydrates, this process is only 0.5–2.0% efficient and the energy content of the resulting biomass is low. Increasing CO2 levels in the atmosphere combined with rising energy needs motivate the search for an artificial photosynthetic system that is at least 10 times as efficient as that used by nature. Identification of light absorbers that provide a photocurrent density >10 mA cm-2 and a photovoltage >2 V are prerequisites for a >10% efficient artificial photosynthetic system. Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

Kinetically limited de-lithiation behavior of nanoscale tin-covered tin oxide nanowires

In this paper, we report that Sn-nanocluster-covered SnO2 nanowire (“hybrid architectures”) electrodes exhibited stage-wise de-lithiation suggesting complete lithium extraction. The lithiation and de-lithiation behavior explains that the high capacity retention of 814 mAh g−1 and durability over hundred cycles is because of low irreversible capacity loss. Mono-layers of un-agglomerated, sub 60 nm size Sn clusters supported on metallic electrodes also exhibited similar stage-wise de-lithiation while the microscale Sn clusters exhibited single-phase lithium extraction. This can be attributed to shorter lithium ion diffusion lengths and high surface area of the nanomaterials. The cyclic voltammetric studies of Sn nanoclusters (sub 60 nm size) confirm the reaction kinetics limited behavior of lithiation and de-lithiation characteristics. The Sn-nanocluster-covered SnO2 nanowires showed a capacity retention of 458 mAh g−1 at 500 mAg−1 current density indicating an excellent rate capability.

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

The electrochemical reduction of CO2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably for HCOO-, C2H4, and C2H5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO- over polycrystalline Ag and Sn. Interpretation of the findings for CO2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. The observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.

Electrochemical CO2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity

The electrochemical reduction of carbon dioxide using renewably generated electricity offers a potential means for producing fuels and chemicals in a sustainable manner. To date, copper has been found to be the most effective catalyst for electrochemically reducing carbon dioxide to products such as methane, ethene, and ethanol. Unfortunately, the current efficiency of the process is limited by competition with the relatively facile hydrogen evolution reaction. Since multi-carbon products are more valuable precursors to chemicals and fuels than methane, there is considerable interest in modifying copper to enhance the multi-carbon product selectivity. Here, we report our investigations of electrochemical carbon dioxide reduction over CuAg bimetallic electrodes and surface alloys, which we find to be more selective for the formation of multi-carbon products than pure copper. This selectivity enhancement is a result of the selective suppression of hydrogen evolution, which occurs due to compressive strain induced by the formation of a CuAg surface alloy. Furthermore, we report that these bimetallic electrocatalysts exhibit an unusually high selectivity for the formation of multi-carbon carbonyl-containing products, which we hypothesize to be the consequence of a reduced coverage of adsorbed hydrogen and the reduced oxophilicity of the compressively strained copper. Thus, we show that promoting copper surface with small amounts of Ag is a promising means for improving the multi-carbon oxygenated product selectivity of copper during electrochemical CO2 reduction.

Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO2 reduction electrocatalysts

In the last few years, there has been increased interest in electrochemical CO2 reduction (CO2R). Many experimental studies employ a membrane separated, electrochemical cell with a mini H-cell geometry to characterize CO2R catalysts in aqueous solution. This type of electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. We show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences due to the complexity of the physical phenomena taking place on electrode surfaces during CO2R, particularly as they relate to the cell temperature and bulk electrolyte CO2 concentration. Both effects were evaluated quantitatively in high S/V cells using Cu electrodes and a bicarbonate buffer electrolyte. Electrolyte temperature is a function of the current/total voltage passed through the cell and the cell geometry. Even at a very high current density, 20 mA cm-2, the temperature increase was less than 4 °C and a decrease of <10% in the dissolved CO2 concentration is predicted. In contrast, limits on the CO2 gas-liquid mass transfer into the cells produce much larger effects. By using the pH in the cell to measure the CO2 concentration, significant undersaturation of CO2 is observed in the bulk electrolyte, even at more modest current densities of 10 mA cm-2. Undersaturation of CO2 produces large changes in the faradaic efficiency observed on Cu electrodes, with H2 production becoming increasingly favored. We show that the size of the CO2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO2 concentration in the electrolyte, and we have designed a high S/V cell that is able to maintain the near-equilibrium CO2 concentration at current densities up to 15 mA cm-2.

Inorganic nanowires: a perspective about their role in energy conversion and storage applications

There has been tremendous interest and progress with synthesis of inorganic nanowires (NWs). However, much of the progress only resulted in NWs with diameters much greater than their respective quantum confinement scales, i.e. 10?100?nm. Even at this scale, NW-based materials offer enhanced charge transport and smaller diffusion length scales for improved performance with various electrochemical and photoelectrochemical energy conversion and storage applications. In this paper, these improvements are illustrated with specific results on enhanced charge transport with tin oxide NWs in dye sensitized solar cells, higher capacity retention with molybdenum oxide (MoO3) NW arrays and enhanced photoactivity with hematite NW arrays compared with their nanoparticle (NP) or thin film format counterparts. In addition, the NWs or one-dimensional crystalline materials with diameters less than 100?nm provide a useful platform for creating new materials either as substrates for heteroepitaxy or through the phase transformation with reaction. Specific results with single crystal phase transformation of hematite (a-Fe2O3) to pyrite (FeS2) NWs and heteroepitaxy of indium-rich InGaN alloy over GaN NW substrates are presented to illustrate the viability of using NWs for creating new materials. In terms of energy applications, it is essential to have a method for continuous manufacturing of vertical NW arrays over large areas. In this regard, a simple plasma-based technique is discussed that potentially could be scaled up for roll-to-roll processing of NW arrays.

Differential Electrochemical Mass Spectrometer Cell Design for Online Quantification of Products Produced during Electrochemical Reduction of CO2

The discovery of electrocatalysts that can efficiently reduce CO2 to fuels with high selectivity is a subject of contemporary interest. Currently, the available analytical methods for characterizing the products of CO2 reduction require tens of hours to obtain the dependence of product distribution on applied potential. As a consequence, there is a need to develop novel analytical approaches that can reduce this analysis time down to about an hour. We report here the design, construction, and operation of a novel differential electrochemical mass spectrometer (DEMS) cell geometry that enables the partial current densities of volatile electrochemical reaction products to be quantified in real time. The capabilities of the novel DEMS cell design are demonstrated by carrying out the electrochemical reduction of CO2 over polycrystalline copper. The reaction products are quantified in real time as a function of the applied potential during linear sweep voltammetry, enabling the product spectrum produced by a given electrocatalyst to be determined as a function of applied potential on a time scale of roughly 1 h.

Standards and Protocols for Data Acquisition and Reporting for Studies of the Electrochemical Reduction of Carbon Dioxide

Objective evaluation of the performance of electrocatalysts for CO_2 reduction has been complicated by a lack of standardized methods for measuring and reporting activity data. In this perspective, we advocate that standardizing these practices can aid in advancing research efforts toward the development of efficient and selective CO_2 reduction electrocatalysts. Using information taken from experimental studies, we identify variables that influence the measured activity of CO_2 reduction electrocatalysts and propose procedures to account for these variables in order to improve the accuracy and reproducibility of reported data. We recommend that catalysts be measured under conditions which do not introduce artifacts from impurities, from either the electrolyte or counter electrode, and advocate the acquisition of data measured in the absence of mass transport effects. Furthermore, measured rates of electrochemical reactions should be normalized to both the geometric electrode area as well as the electrochemically active surface area to facilitate the comparison of reported catalysts with those previously known. We demonstrate that, when these factors are accounted for, the CO_2 reduction activities of Ag and Cu measured in different laboratories exhibit little difference. Adoption of the recommendations presented in this perspective would greatly facilitate the identification of superior catalysts for CO_2 reduction arising solely from changes in their composition and pretreatment.