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At least 667 records · Page 37

Oxygen Evolution Reaction in Alkaline Environment: Material Challenges and Solutions

Abstract The oxygen evolution reaction (OER) generally exists in electrochemistry‐enabled applications that are coupled with cathodic reactions like hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. The OER heavily impacts the overall energy efficiency of these devices because the sluggish OER kinetics result in a huge overpotential, thus, a large amount of efficient catalysts are needed. The benchmark iridium and ruthenium (Ir/Ru)‐based materials (mostly used in acid media) are, however, significantly limited by their scarcity. Non‐precious metal‐based catalysts (NPMCs) have emerged as the most promising alternatives; however, they tend to degrade quickly under the harsh operating conditions of typical OER devices. Another challenge is the unsatisfying performance of OER catalysts when integrated in real‐world devices. Herein, the OER active sites for three mainstream types of NPMCs including non‐precious transition metal oxides/(oxy)hydroxides, metal‐free carbon materials, and hybrid non‐precious metal and carbon composites are reviewed. In addition, possible degradation mechanisms for active sites and mitigation strategies are discussed in detail. This review also provides insights into the gaps between R&D of NPMCs for the OER and their applications in practical devices.

Xie, Xiaohong↗

Electrochemical approach for passivating steel and other metals and for the simultaneous production of a biocide to render water potable

Potentiostatic polarization curves indicated that the cathodic reactions in deaerated KI-I2 water solutions were due to iodine reduction and hydrogen evolution. In the presence of oxygen an additional reduction wave appeared. Anodic polarization curves revealed that iodine could be produced in the region of potential from +600 to +1000 nv vs. SCE.

Source record↗

A reaction mechanism for plasma electrolysis of AgNO 3 forming silver nanoclusters and nanoparticles

In plasma-driven solution electrolysis (PDSE), gas-phase plasma-produced species interact with an electrolytic solution to produce, for example, nanoparticles. An atmospheric pressure plasma jet (APPJ) directed onto a liquid solution containing a metallic salt will promote reduction of metallic ions in solution, generating metallic clusters that nucleate to form nanoparticles. In this article, results from a computational investigation are discussed of a PDSE process in which a radio-frequency APPJ sustained in helium impinges on a silver nitrate solution, resulting in growth of silver nanoparticles. A reaction mechanism was developed and implemented in a global plasma chemistry model to predict nanoparticle growth. To develop the reaction mechanism, density functional theory was used to generate probable silver growth pathways up to Ag 9 . Neutral clusters larger than Ag 9 were classified as nanoparticles. Kinetic reaction rate coefficients for thermodynamically favorable growth pathways were estimated based on an existing, empirically determined base reaction mechanism for smaller Ag particle interactions. These rates were used in conjunction with diffusion-controlled reaction rate coefficients that were calculated for other Ag species. The role of anions in reduction of Agn ions in forming nanoparticles is also discussed. Oxygen containing impurities or admixtures to the helium, air entrainment into the APPJ, and dissociation of saturated water vapor above the solution can produce additional reactive oxygen species in solution, resulting in the production of anions and O 2 – in particular. For a given molarity, delivering a sufficient fluence of reducing species will produce similar nanoparticle densities and sizes for all applied power levels. In conclusion, comparisons are made to alternate models for nanoparticle formation, including charged nanoparticles and use of direct current plasmas.

36 MATERIALS SCIENCE↗

Elucidation of Ce/Zr ratio effects on the physical properties and catalytic performance of CuO x /Ce y Zr 1− y O 2 catalysts

Although cerium oxide (CeO 2 ) is widely used as a catalyst support, its limited defect sites and surface oxygen vacancy/mobility should be improved. The incorporation of zirconium (Zr) in the cerium (Ce) lattice is shown to increase the number of oxygen vacancies and improve catalytic activity. Using a fixed surface density (SD) of copper (∼2.3 Cu atoms per nm 2 ) as a surface species, the role of the support (Ce y Zr 1−y O 2 (y = 1.0, 0.9, 0.6, 0.5, and 0.0)) and defect site effects in the CO oxidation reaction was investigated. Spectroscopic (e.g., Raman, XRD, XPS) and microscopic (e.g., SEM-EDX, HR-TEM) characterization techniques were applied to evaluate the defect sites, crystallite size, lattice parameters, chemical composition, oxidation states of elements and microstructure of the catalysts. Here, the CO oxidation reaction with varied CO : O 2 ratios (1 : 5, 1 : 1, and 1 : 0.5 (stoichiometric)) was used as a model reaction to describe the relationship between the structure and the catalytic performance of each catalyst. Based on the characterization results of Ce y Zr 1−y O 2 materials, the addition of Zr causes physical and chemical changes to the overall material. The inclusion of Zr into the structure of CeO 2 decreased the overall lattice parameter of the catalyst and increased the number of defect sites. The prepared catalysts were able to reach complete CO conversion (∼100%) at low temperature conditions (<200 °C), each showing varied reaction activity. The difference in CO oxidation activity was then analyzed and related to the structure, wherein Cu loading, surface oxygen vacancies, reduction–oxidation ability, CuO x –support interaction and oxygen mobility in the catalyst were the crucial descriptors.

36 MATERIALS SCIENCE↗

The onsite manufacture of propellant oxygen from lunar resources

The Aerojet carbothermal process for the manufacture of oxygen from lunar materials has three essential steps: the reduction of silicate with methane to form carbon monoxide and hydrogen; the reduction of carbon monoxide with hydrogen to form methane and water; and the electrolysis of water to form hydrogen and oxygen. The reactions and the overall process are shown. It is shown with laboratory experimentation that the carbothermal process is feasible. Natural silicates can be reduced with carbon or methane. The important products are carbon monoxide, metal, and slag. The carbon monoxide can be completely reduced to form methane and water. The water can be electrolyzed to produce hydrogen and oxygen. A preliminary engineering study shows that the operation of plants using this process for the manufacture of propellant oxygen has a large economic advantage when the cost of the plant and its operation is compared to the cost of delivering oxygen from Earth.

Rosenberg, Sanders D.↗

Reduction Thermodynamics of Sr 1– x Ce x MnO 3 and Ce x Sr 2– x MnO 4 Perovskites for Solar Thermochemical Hydrogen Production

Herein, the compositional families Sr 1–x Ce x MnO 3 (SCMX, X = 100x, x = 0.10, 0.20, and 0.30) and Ce x Sr 2–x MnO 4 (CSMX, X = 100x, x = 0.10, 0.20, and 0.30) are studied to determine the effects of perovskite structure and cerium content on thermal reduction thermodynamics and the resulting impact on solar thermochemical hydrogen production (STCH). Relying on thermogravimetric results from oxygen nonstoichiometry experiments, fits for various thermodynamic quantities are produced, including defect-reaction specific enthalpy (Δ H) and entropy (Δ S ), as well as the δ-dependent standard partial molar enthalpy, Δh¯$^{°}_{Ο}$, and entropy Δs¯$^{°}_{Ο}$, of oxygen as a function of composition within these two perovskite families. Here, the results of this thermodynamic study are also discussed in the context of structure and cerium dopant level. Experimental hydrogen production results show that the SCM family produces slightly larger amounts of hydrogen per mole of oxide compared with the CSM family under similar reduction and oxidation temperature conditions, however, a direct correlation between structure, cerium content, and water-splitting capacity could not be discerned.

08 HYDROGEN↗

Protocol for Screening Water Oxidation or Reduction Electrocatalyst Activity in a Three-Electrode Cell for Alkaline Exchange Membrane Electrolysis

Accurate and reproducible screening of the electrocatalytic activity of novel materials for Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) requires establishing an easily adoptable harmonized testing protocol. Herein, we describe a robust, instrumentation-independent testing technique utilizing a three-electrode cell with a fully immersed working electrode. Compared to rotating disk electrode (RDE) techniques, this protocol produces current densities close to those obtained in real electrolyzers and eliminates the usage of the expensive RDE apparatus.

08 HYDROGEN↗

The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

Summers, David P.↗

Reduction kinetics of hercynite redox materials for solar thermochemical water splitting

Solar thermochemical water splitting (STWS) using a hercynite redox cycle is a promising technology for producing renewable H 2 . Here, the reduction kinetics of hercynite (FeAl 2 O 4 ) is evaluated using thermogravimetric and XRD analyses. The results indicate that as-prepared hercynite materials undergo reduction via two different reaction mechanisms. The reaction first proceeds by a nucleation and growth mechanism (AE1), followed by a third-order kinetic model (F3). XRD analyses show the occurrence of superstoichiometric oxygen in the spinel structure of FeAl 2 O 4+δ in the second reaction mechanism, which indicates the formation of cationic vacancies. TGA and XRD analyses confirm that hercynite maintains its spinel structure when the materials are thermally reduced and oxidized with steam. Differential scanning calorimetry (DSC) performed on FeAl 2 O 4 particles shows two heats of reaction in agreement with the two observed mechanisms. This is the first kinetics study to report on the thermal reduction of hercynite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical CO 2 Reduction Reaction over Cu Nanoparticles with Tunable Activity and Selectivity Mediated by Functional Groups in Polymeric Binder

Electrochemical carbon dioxide reduction reaction (CO 2 RR) using copper (Cu)-based catalysts has received significant attention mainly because Cu is an element capable of producing hydrocarbons and oxygenates. One possible way to control the CO 2 RR performance at the electrode interface is by modifying catalysts with specific functional groups of different polymeric binders, which are necessary components in the process of electrode fabrication. However, the modification effect of the key functional groups on the CO 2 RR activity and selectivity is poorly understood over Cu-based catalysts. In this work, the role of functional groups (e.g., -COOH and -CF 2 groups) in hydrophilic and hydrophobic polymeric binders on the CO 2 RR of Cu-based catalysts is investigated using a combination of electrochemical measurements, in-situ characterization and density functional theory (DFT) calculations. DFT results reveal that functional groups influence the binding energies of key intermediates involved in both CO 2 RR and the competing hydrogen evolution reaction, consistent with experimental observation of binder-dependent product distributions among formic acid, CO, CH 4 , and H 2 . This study provides a fundamental understanding that the selection of desired polymeric binders is a useful strategy for tuning the CO 2 RR activity and selectivity.

25 ENERGY STORAGE↗

Bosch CO2 reduction unit research and development.

Development of Bosch CO2 reduction units for manned spacecraft application has been in progress for a decade. The Bosch process catalytically reacts CO2 with H2 to produce water and carbon. The water may then be electrolyzed to close the biological oxygen and process hydrogen loops. A critical problem has been to confine the reaction so that carbon does not block flow and stop the process. Reaction isolation within a replaceable catalyst cartridge has been successfully demonstrated. Objectives of the current development program are a 25% reduction in operating power, an 80% reduction in expendable weight, and minimized resupply volume.

Holmes, R. F.↗

Investigation of the NO reduction by CO reaction over oxidized and reduced NiO x /CeO 2 catalysts

CeO 2 -supported NiO x catalysts have been widely studied in various catalytic reactions including NO reduction by CO. This work is mainly focused on investigation of the impact of catalyst synthesis conditions (e.g., oxidation and reduction) on the physicochemical properties of NiO x /CeO 2 catalysts and the catalytic response for the NO reduction by CO reaction. The oxide NiO x /CeO 2 sample was prepared by an incipient wetness impregnation (IWI) method and reduced under hydrogen reduction treatment at high temperatures (500 and 700 °C). The physicochemical properties of the synthesized samples were characterized by BET analysis, Raman spectroscopy, XRD, XPS, EELS and high-resolution transmission electron microscopy (HR-TEM). The results showed that higher reduction temperature led to the decrease in specific surface area (SSA), fewer oxygen vacancy/defect site, larger crystallite size of the CeO 2 support, and formation of metallic Ni on the surface. The oxidized NiO x /CeO 2 catalyst showed the highest catalytic activity, indicating that the presence of oxygen vacancy/defect sites, Ni 2+ oxidation state, and smaller crystallite size are believed to enhance the catalytic activity. In situ DRIFTS confirmed the generation of several intermediate species, such as nitrate, carbonate, and N 2 O. Finally, on the basis of in situ DRIFTS and activity results, the possible reaction mechanism of NO reduction by CO over NiO x /CeO 2 was proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reaction mechanisms for electrical doping of organic semiconductors using complex dopants

Electrical doping of organic semiconductors (OSCs) can be achieved using simple one-electron reductants and oxidants as n- and p-dopants, respectively, but for such dopants, increased doping strength is accompanied by increased sensitivity to ambient moisture and/or oxygen. “Indirect” or “complex” dopants—defined here as those that generate OSC radical cations or anions via pathways more complex than a single simple electron transfer, i.e., by multistep reactions—represent a means of circumventing this problem. Further, this review highlights the importance of understanding the reaction mechanisms by which such dopants operate for: (i) ensuring a researcher knows the composition of a doped material; (ii) predicting the thermodynamic feasibility of achieving doping with related dopant:OSC combinations; and (iii) predicting whether thermodynamically feasible doping reactions are likely to be rapid or slow, or to require subsequent activation. The mechanistic information available to date for some of the wide variety of complex n- and p-dopants that have been reported is then reviewed, emphasizing that in many cases our knowledge is far from complete.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessment of Bulk Oxygen Capacity and Transient Redox Behavior of Foamed Lanthanum Strontium Manganese Perovskites

Synthesis of solar thermochemical hydrogen (STCH) production redox materials with engineered structures, for example, replica foams, can enable efficient heat and mass transport and are critical for scaled-up systems. Prior work has motivated the use of lanthanum strontium manganese (LSM)-type perovskites as foamed STCH materials, but the effect of their morphology on bulk and kinetic behavior has not been reported. In this work, replica and direct foamed samples of La 0.65 Sr 0.35 MnO 3-δ (LSM35) were fabricated and compared to synthesized powders and dense monoliths, and similarly synthesized CeO 2-δ (ceria) foams, regarding their specific reaction rates and bulk oxygen capacity/H 2 yields. Changes in oxygen capacity (Δδ) and reaction rates were measured between 1200 °C and 1400 °C by using fixed ratios of steam and hydrogen during both reduction and oxidation steps, allowing for analysis under practical high conversion conditions. Results suggest bulk behavior and reaction rates of the foamed LSM materials are comparable to their powder analogues. Differences in reaction rates were observed only when replica foamed samples were subjected to rapid laser heating (emulating conditions expected in solar furnaces), which is expected but has not been demonstrated at such a small scale. Here, foamed samples were further subjected to 50 redox cycles at 1400 °C to evaluate their stability. Results show no statistically significant decrease in hydrogen production for any of the foamed samples, but the direct foamed samples became brittle with time. Together, these results demonstrate the viability of replica foamed LSM perovskites for integration in scaled-up STCH systems.

08 HYDROGEN↗

Supported-Single Nickel Atom Catalysts for the Methanation of Carbon Dioxide

Synthesis of twenty-seven bimetallic catalysts consisting of nickel and one of nine different dopants (B, Co, Cu, Fe, Mg, Mn, Sn, V, and Zn) supported on three different metal oxides (Al 2 O 3 , CeO 2 , and SiO 2 ) is carried out via organometallic grafting. The catalysts are evaluated for their activity and selectivity for the CO 2 methanation reaction at a feed ratio of H 2 /CO 2 of 4 at 300 °C in a high-throughput flow reactor system. After in situ pre-activation (500 °C in H 2 ), Ni/Co/CeO 2 exhibited high conversion (84.3%) and selectivity for methane (99.6%). Ni/Co/CeO 2 was characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, H 2 -temperature-programmed reduction (H 2 -TPR), and CO 2 -temperature-programmed desorption (CO 2 -TPD). HRTEM showed the presence of single Ni and Co atoms on ceria after pre-reduction at 500 °C and after the methanation reaction at 300 °C for 15 h. XPS determined that the strong interaction between Ni, Co, and ceria increased after the reduction, leading to a charge transfer between Ni and Ce that created oxygen vacancies in ceria. Nickel was found to be Ni 2+ in the as-prepared material and was partially reduced in the presence of cobalt and after the activation in H 2 at 500 °C. The DFT results show that both nickel and cerium exhibit lower Bader charges in the Ni/Co/CeO 2 system, confirming that the presence of cobalt enhances the reduction of both Ni and Ce through electronic interactions. This indicates that single cationic Ni atoms are highly effective for the methanation reaction. In conclusion, the organometallic grafting technique is found to be efficient for synthesizing catalysts with highly homogeneous dispersed species at low metal loadings (0.16 wt % Ni–0.15 wt % Co), which leads to high turnover frequency (up to 248.7 h –1 ) and durability for methanation.

CO2 conversion↗

Biogenic Methane and the Rise of Oxygen

Oxygenic photosynthesis does not make the rise of oxygen inevitable. What is required is that reductant and oxygen be separated and permanently segregated. The usual picture for Earth is that oxygenic photosynthesis split CO2 into carbon and oxygen, with the carbon buried in sediments and the oxygen mostly taken up by oxides of iron and sulfur. The relatively small atmospheric reservoir of O2 is regulated by the carbon burial rate, reaction with volcanic and metamorphic gases, and oxidation of reduced carbon released as old sediments weather. Absent from this picture is a distinction between the Archean and modern times: on average, carbon burial fluxes would have been matched by oxygen losses then as now. Separation of reductant from oxidant is only provisional. No net oxidation of the continents occurs, and so no change of diagenetic, metamorphic, or volcanic gases is expected. Nor would any change in oxidative weathering be expected. Something more than carbon burial is required to make the Archean different. The escape of hydrogen to space permanently separates the reductant from the oxidant. Hydrogen escape is widely believed to have led to the present highly oxidized states of Mars and Venus. Hydrogen escape has usually been thought small for Archaean Earth, because water vapor is cold-trapped at the troposphere and thus held to levels of a few ppmv in the stratosphere. This cold trapping renders hydrogen escape negligible. However, methane is not cold trapped, and its expected abundance in the Archaean, given low oxygen levels and a biogenic source, would have been high, probably more than 100 times present. At such levels methane would have driven geologically significant levels of hydrogen escape. Additional information is contained in the original extended abstract.

Catling, David↗

Biofuel production from palm oil deoxygenation using nickel-molybdenum on zirconia catalyst using glycerol as a hydrogen donor

The growing demand for renewable energy has generated interest in biofuels as alternatives to fossil fuels. Second-generation biofuels, derived from deoxygenating fats and oils, have garnered a higher level of interest from industry and academia due to their potential for direct replacement of diesel and jet fuels. Palm oil, mostly cultivated in Thailand and composed of C16 and C18 fatty acids, is a primary feedstock sought for biofuel production. Palm oil deoxygenation contains several pathways that may or may not require hydrogen gas. This study aimed to produce biofuels in different fuel ranges, such as gasoline, jet fuel, and diesel, through palm oil deoxygenation using glycerol as a hydrogen source. Glycerol, a low-value byproduct, was used as a hydrogen donor, whereas nickel-molybdenum-supported catalysts were chosen for their high efficiency in deoxygenation and cost-effectiveness. The study investigated the impact of reaction time, temperature, and catalyst activation method on palm oil deoxygenation. Catalyst characterization methods, including XRD, SEM, TEM, XPS, FTIR, TGA, and nitrogen-sorption, were employed to understand the role of catalysts’ activity during palm oil upgrading. Findings indicated that alkane hydrocarbons are the major components in liquid products. The presence of excess hydrogen in post reaction gaseous phase proves the hydrogen donation capability of glycerol. Increased reaction time and temperature facilitated the removal of oxygen from palm oil. Nickel-molybdenum on zirconia activated by sulfidation demonstrated higher stability than by reduction activation.

09 BIOMASS FUELS↗

Sabatier Reactor System Integration with Microwave Plasma Methane Pyrolysis Post-Processor for Closed-Loop Hydrogen Recovery

The Carbon Dioxide Reduction Assembly (CRA) designed and developed for the International Space Station (ISS) represents the state-of-the-art in carbon dioxide reduction (CDRe) technology. The CRA produces water and methane by reducing carbon dioxide with hydrogen via the Sabatier reaction. The water is recycled to the Oxygen Generation Assembly (OGA) and the methane is vented overboard resulting in a net loss of hydrogen. The proximity to earth and the relative ease of logistics resupply from earth allow for a semi-closed system on ISS. However, long-term manned space flight beyond low earth orbit (LEO) dictates a more thoroughly closed-loop system involving significantly higher recovery of hydrogen, and subsequent recovery of oxygen, to minimize costs associated with logistics resupply beyond LEO. The open-loop ISS system for CDRe can be made closed-loop for follow-on missions by further processing methane to recover hydrogen. For this purpose, a process technology has been developed that employs a microwave-generated plasma to reduce methane to hydrogen and acetylene resulting in 75% theoretical recovery of hydrogen. In 2009, a 1-man equivalent Plasma Pyrolysis Assembly (PPA) was delivered to the National Aeronautics and Space Administration (NASA) for technical evaluation. The PPA has been integrated with a Sabatier Development Unit (SDU). The integrated process configuration incorporates a sorbent bed to eliminate residual carbon dioxide and water vapor in the Sabatier methane product stream before it enters the PPA. This paper provides detailed information on the stand-alone and integrated performance of both the PPA and SDU. Additionally, the integrated test stand design and anticipated future work are discussed.

Abney, Morgan B.↗