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Mediated Fuel Cells: Soluble Redox Mediators and their Applications to Electrochemical Reduction of O2 and Oxidation of H2, Alcohols, Biomass, and Complex Fuels
Mediated fuel cells are electrochemical devices that produce power in a manner similar to that of conventional proton exchange membrane fuel cells (PEMFCs). They differ from PEMFCs in their use of redox mediators dissolved in liquid electrolyte to conduct oxidation of the fuel or reduction of the oxidant, typically O2, in bulk solution. The mediators transport electrons (and often protons) between the electrode and the catalysts or chemical reagents in solution. This strategy can help overcome many of the challenges associated with conventional fuel cells, including managing complex multi-phase reactions (as in O2 reduction) or the use of challenging or heterogeneous fuels, such as hydrocarbons, polyols and biomass. Mediators are also commonly used in enzymatic fuel cells, where direct electron transfer from the electrode to the enzymatic active site can be slow. This review provides a comprehensive survey of historical and recent mediated fuel cell efforts, including applications using chemical and enzymatic catalysts. Our research on in this field has been exploring a number of different topics and has been supported different funding sources: the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (molecular mediators for catalytic oxygen reduction); the Great Lakes Bioenergy Research Center, DOE Office of Science DE-SC0018409 (research on biomass-based fuels; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Program, DE-FG02-05ER15690 (copper-catalyzed oxidation reactions); and the NIH NIGMS, R01 GM100143 and R35 GM134929 (use of molecular mediators for organic chemical synthesis).
Fractal Model for Drag Reduction on Multiscale Nonwetting Rough Surfaces
Rough surfaces in contact with a flow of fluid exhibit alternating no-slip and free shear boundary conditions at the solid–liquid and air–liquid interfaces, respectively, thereby potentially offering drag reduction benefits. The balance between the dynamic pressure in the flow and the restoring capillary pressure in the interasperity spaces determines the stability of the Cassie state of wettability and is a function of the relative extent of no-slip and free shear regions per unit surface area. In the present study, using a fractal representation of rough surface topography, an analytical model is developed to quantify the stability of the Cassie state of wettability as well as drag reduction and the friction factor for laminar flow in a rectangular channel between nonwetting multiscale rough surfaces. A systematic study is conducted to quantify the effects of fractal parameters of the surfaces and the flow Reynolds number on drag reduction and the friction factor. The studies are used to develop friction factor curves extending the classical Moody diagram to hydrophobic and superhydrophobic surfaces. On the basis of the studies, regime maps are derived for estimating the extent of drag reduction offered by hydrophobic and superhydrophobic surfaces, revealing that superhydrophobic surfaces do not always offer the best drag reduction performance. The application of the fractal model to practical topographies of nonwetting surfaces of copper, aluminum, and zinc oxide fabricated via electrodeposition and etching is also discussed.
Brønsted Acid Scaling Relationships Enable Control over Product Selectivity from O2 Reduction with a Mononuclear Cobalt Porphyrin Catalyst
The selective reduction of O2, typically with the goal of forming H2O, represents a long-standing challenge in the field of catalysis. Macrocyclic transition-metal complexes, and cobalt porphyrins in particular, have been the focus of extensive study as catalysts for this reaction. Here, we show that the mononuclear Co-tetraarylporphyrin complex, Co(porOMe) (porOMe = meso-tetra(4-methoxyphenyl)porphyrin), catalyzes either 2e-/2H+ or 4e-/4H+ reduction of O2 with high selectivity simply by changing the identity of the Bronsted acid in dimethylformamide (DMF). The thermodynamic potentials for O2 reduction to H2O2 or H2O in DMF are determined and exhibit a Nernstian dependence on the acid pKa, while the CoIII/II redox potential is independent of the acid pKa. The reaction product, H2O or H2O2, is defined by the relationship between the thermodynamic potential for O2 reduction to H2O2 and the CoIII/II redox potential: selective H2O2 formation is observed when the CoIII/II potential is below the O2/H2O2 potential, while H2O formation is observed when the CoIII/II potential is above the O2/H2O2 potential. Mechanistic studies reveal that the reactions generating H2O2 and H2O exhibit different rate laws and catalyst resting states, and these differences are manifested as different slopes in a linear free energy correlation between the log(rate) vs. effective overpotential for the reactions. This work shows how the manipulation of thermodynamic scaling relationships may be used to control product selectivity, and it provides a mechanistic basis for the pursuit of molecular catalysts that achieve low overpotential reduction of O2 to H2O.
Efficient Simulation of Welding Distortion in Large Structures and Its Reduction by Jig Constraints
Two large construction machinery structures were welded separately with and without jig constraints. The welding distortion of the entire structure was measured by a 3D coordinate measuring system and simulated by elastic FEM using the inherent deformation method. To obtain an accurate inherent deformation, a thermal elastoplastic FE analysis of simple one-side fillet joints with and without jig constraints was performed. Efficient simulation of welding distortion in large structures was accomplished by applying inherent deformation in a localized region, and the effect of jig constraint on the reduction of welding distortion was clarified. The computation of inherent deformation, the weld zone definition and the conversion of inherent deformation into inherent strain were automated. Measured and computed welding distortions in large structures had a good correspondence with respect to both tendency and magnitude. Further investigation of jig configuration was performed for enhanced reduction of welding distortion. Alternative controlling techniques for common welded structures were also addressed.
Biogeochemical fate of ferrihydrite-model organic compound complexes during anaerobic microbial reduction
Abstract not provided
Discovery of a Hybrid System for Photocatalytic CO 2 Reduction via Attachment of a Molecular Cobalt-Quaterpyridine Complex to a Crystalline Carbon Nitride
While recent reports have demonstrated the attachment of molecular catalysts to amorphous, graphitic carbon nitrides (g-CN) for light-driven CO 2 reduction, approaches to the utilization of crystalline carbon nitrides have remained undiscovered. Herein, a functional hybrid photocatalyst system has been found using a crystalline carbon nitride semiconductor, poly(triazine imide) lithium chloride (PTI-LiCl), with a surface-attached CoCl 2 (qpy-Ph-COOH) catalyst for CO 2 reduction. The molecular catalyst attaches to PTI-LiCl at concentrations from 0.10 to 4.30 wt % and exhibits ∼96% selectivity for CO production in a CO 2 -saturated, aqueous 0.5 M KHCO 3 solution. Optimal loadings were found to be within 0.42–1.04 wt % with rates between 1,400 and 1,550 μmol CO/g·h at an irradiance of 172 mW/cm 2 (λ = 390 nm) and apparent quantum yields of ∼2%. This optimized loading is postulated to represent a balance between maximal turnover frequency (TOF; 300+ h –1 ) and excess catalyst that can limit excited-electron lifetimes, as probed via transient absorption spectroscopy. An increase in the incident irradiance yields a concomitant increase in the TOFs and CO rates only for the higher catalyst loadings, reaching up to 2,149 μmol CO/g·h with a more efficient use of the catalyst surface capacity. The lower catalyst loadings, by comparison, already function at maximal TOFs. Higher surface loadings are also found to help mitigate deactivation of the molecular catalysts during extended catalytic testing (>24 h) owing to the greater net surface capacity for CO 2 reduction, thus representing an effective strategy to extend lifetime. The hybrid particles can be deposited onto an FTO substrate to yield ∼60% Faradaic efficiency for photoelectrochemical CO production at −1.2 V vs Ag/AgCl bias. In conclusion, these results demonstrate the synergistic combination of a crystalline carbon nitride with a molecular catalyst that achieves among the highest known rates in carbon-nitride systems for the light-driven CO 2 reduction to CO in aqueous solution with >95% selectivity.
Accessing Organonitrogen Compounds via C–N Coupling in Electrocatalytic CO 2 Reduction
Given the limited product variety of electrocatalytic CO 2 reduction reactions solely from CO 2 and H 2 O as the reactants, it is desirable to expand the product scope by introducing additional reactants that provide elemental diversity. The integration of inorganic heteroatom-containing reactants into electrocatalytic CO 2 reduction could in principle enable the sustainable synthesis of valuable products, such as organonitrogen compounds, which have widespread applications but typically rely on NH 3 derived from the energy-intensive and fossil-fuel-dependent Haber-Bosch process for their industrial scale production. Here, in this Perspective, research progress towards building C-N bonds in N-integrated electrocatalytic CO 2 reduction is highlighted, and the electrosyntheses of urea, acetamides, and amines are examined from the standpoint of reactivity, catalyst structure, and most fundamentally, mechanism. Mechanistic discussions of C-N coupling in these advances are emphasized and critically evaluated, with the aim of directing future investigations on improving the product yield and broadening the product scope of N-integrated electrocatalytic CO 2 reduction.
Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction
An effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@P nL (n = 1-6) core-shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations on model (100) surfaces suggest that the enhancement in specific activity can be attributed to the weakening of OH binding through ligand and strain effects, which, in turn, increases the rate of OH hydrogenation. A volcano-type relationship between the ORR specific activity and the number of Pt atomic layers was derived, in good agreement with the experimental results. Both theoretical and experimental studies indicate that the ORR specific activity was maximized for the catalysts based on Pd@Pt 2-3L nanocubes. Because of the reduction in Pt content used and the enhancement in specific activity, the Pd@Pt 1L nanocubes showed a Pt mass activity with almost three-fold enhancement relative to the Pt/C catalyst.
Non-perturbative measurement of cross-field thermal diffusivity reduction at the O-point of 2/1 neoclassical tearing mode islands in the DIII-D tokamak
Neoclassical tearing modes (NTMs) often lead to the decrease of plasma performance and can lead to disruptions, which makes them a major impediment in the development of operating scenarios in present toroidal fusion devices. Recent gyrokinetic simulations predict a decrease of plasma turbulence and cross-field transport at the O-point of the islands, which in turn affects the NTM dynamics. In this paper, a heat transport model of magnetic islands employing spatially non-uniform cross-field thermal diffusivity (χ{sub ⊥}) is presented. This model is used to derive χ{sub ⊥} at the O-point from electron temperature data measured across 2/1 NTM islands in DIII-D. It was found that χ{sub ⊥} at the O-point is 1 to 2 orders of magnitude smaller than the background plasma transport, in qualitative agreement with gyrokinetic predictions. As the anomalously large values of χ{sub ⊥} are often attributed to turbulence driven transport, the reduction of the O-point χ{sub ⊥} is consistent with turbulence reduction found in recent experiments. Finally, the implication of reduced χ{sub ⊥} at the O-point on NTM dynamics was investigated using the modified Rutherford equation that predicts a significant effect of reduced χ{sub ⊥} at the O-point on NTM saturation.
“Defense by other means”: future evolution(s) of cooperative threat reduction
This article discusses likely future contexts of, and options for, global threat-reduction activities to support nonproliferation goals over the next five to ten years. Threat-reduction activities span a continuum from unilateral actions that the United States might take with little cooperation and transparency at one end to cooperative actions associated with negotiated treaties and agreements at the other. This study focuses on cooperative approaches embodied in the Cooperative Threat Reduction (CTR) program, which has been the most visible program reducing the threats posed by weapons of mass destruction for over two decades. Here, we argue that CTR’s evolution can be described in terms of the relationship between the desired US influence on outcomes, the ability to generate a common threat definition, and appetite for collaboration on threat reduction. To that end, this article provides an introduction and overview of CTR initiatives over its twenty-seven-year history and a review of relevant legislation and trends. After introducing and describing the CTR Possible Futures Framework, this article offers five possible options for—and discusses the implications of—CTR’s future evolution.
Selling reduction versus Niggli reduction for crystallographic lattices
The unit-cell reduction described by Selling and used by Delone (whose early publications were under the spelling Delaunay) is explained in a simple form. The transformations needed to implement the reduction are listed. The simplicity of this reduction contrasts with the complexity of Niggli reduction.
Emissions and Energy Impacts of the Inflation Reduction Act
If goals set under the Paris Agreement are met, the world may hold warming well below 2 degrees C (1); however, parties are not on track to deliver these commitments (2), increasing focus on policy implementation to close the gap between ambition and action. Recently, the US government passed its most prominent piece of climate legislation to date - the Inflation Reduction Act of 2022 (IRA) - designed to invest in a wide range of programs that, among other provisions, incentivize clean energy and carbon management, encourage electrification and efficiency measures, reduce methane emissions, promote domestic supply chains, and address environmental justice concerns (3). IRA's scope and complexity make modeling important to understand impacts on emissions and energy systems. We leverage results from nine independent, state-of-the-art models to examine potential implications of key IRA provisions, showing economy-wide emissions reductions between 43 and 48% below 2005 levels by 2035.
Online data analysis and reduction: An important co-design motif for extreme-scale computers
A growing disparity between supercomputer computation speeds and I/O rates means that it is rapidly becoming infeasible to analyze supercomputer application output only after that output has been written to a file system. Instead, data-generating applications must run concurrently with data reduction and/or analysis operations, with which they exchange information via high-speed methods such as interprocess communications. The resulting parallel computing motif, online data analysis and reduction (ODAR), has important implications for both application and HPC systems design. Here we introduce the ODAR motif and its co-design concerns, describe a co-design process for identifying and addressing those concerns, present tools that assist in the co-design process, and present case studies to illustrate the use of the process and tools in practical settings.
Calcium Chloride-Assisted Segregation Reduction of Chromite: Influence of Reductant Type and the Mechanism
This paper describes an innovative process for the production of ferrochromium alloy via segregation reduction of chromite at 1300 °C in the presence of calcium chloride. Both charcoal and petroleum coke were used as the reductant. Individual polycrystalline ferrochrome carbide particles were produced, with their particle size and shape resembling that of the starting carbon particles. Interactions among calcium chloride, clinochlore, and chromite resulted in the formation of Ca-bearing chromite, wadalite, and gaseous chlorides. Monocrystalline ferrochrome carbide whiskers were formed only when charcoal in the presence of calcium chloride was used to reduce the chromite fraction containing large amounts of siliceous gangue. Incorporating thermodynamic evaluations, a possible segregation reduction mechanism is suggested based on the characterization of the products using scanning electron microscopy, energy dispersive spectroscopy, X-ray powder diffraction, and electron probe microanalysis, combined with thermogravimetric analysis. Metallization within chromite particles was minimized, which is suggested to be due to the ubiquitous presence of molten and gaseous calcium chloride between the chromite and carbon particles, and especially in the porous rim of the chromite particles during reduction, resulting in restricted metallization only on the carbon particles.
Highly Efficient Solar-Driven Carbon Dioxide Reduction on Molybdenum Disulfide Catalyst Using Choline Chloride-Based Electrolyte
Conversion of CO2 to energy-rich chemicals using renewable energy is of much interest to close the anthropogenic carbon cycle. However, the current photoelectrochemical systems are still far from being practically feasible. Here the successful demonstration of a continuous, energy efficient, and scalable solar-driven CO2 reduction process based on earth-abundant molybdenum disulfide (MoS2) catalyst, which works in synergy with an inexpensive hybrid electrolyte of choline chloride (a common food additive for livestock) and potassium hydroxide (KOH) is reported. The CO(2 )saturated hybrid electrolyte utilized in this study also acts as a buffer solution (pH approximate to 7.6) to adjust pH during the reactions. This study reveals that this system can efficiently convert CO(2 )to CO with solar-to-fuel and catalytic conversion efficiencies of 23% and 83%, respectively. Using density functional theory calculations, a new reaction mechanism in which the water molecules near the MoS(2 )cathode act as proton donors to facilitate the CO2 reduction process by MoS2 catalyst is proposed. This demonstration of a continuous, cost-effective, and energy efficient solar driven CO2 conversion process is a key step toward the industrialization of this technology.