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Monoclonal antibody (mAb) therapy is a promising infectious disease intervention strategy but is limited to IgG1 isotypes that have restricted access to mucosal sites. IgA is well-established as the predominant antibody isotype in mucosal secretions but is clinically underutilized. To enable development of IgA-based mAbs, we exploited mRNA platform technology and demonstrated expression of functional, antigen-specific IgA (IgAmRNA) that can limit bacterial invasion in the intestine and prevent colonization in the lung. Moreover,in vivoIgAmRNAhad enhanced serum half-life and a greater degree of sialylation than a recombinantly produced IgA. The results underscore the potential of mRNA-based platforms to deliver protective human mAbs to mucosal surfaces and open new avenues to combat infectious diseases in the face of pervasive antibiotic resistance.One Sentence SummarymRNA-encoded human monoclonal IgA traffics to mucosal tissues and provides protection against bacterial challenge

An electrosynthesis is presented to transform CO2 into an unusual nano and micron dimensioned morphology of carbon, termed Carbon Nano-Scaffold (CNS) with wide a range of high surface area graphene potential usages including batteries, supercapacitors, compression devices, electromagnetic wave shielding and sensors. Current CNS value is over $323 per milligram. The morphology consists of a series of asymmetric 20 to 100 nm thick flat multilayer graphene platelets 2 to 20 µm long orthogonally oriented in a 3D neoplasticism-like geometry, and appears distinct from the honeycomb, foam, or balsa wood cell structures previously attributed to carbon scaffolds. The CNS synthesis splits CO2 by electrolysis in molten carbonate and has a carbon negative footprint. It is observed that transition metal nucleated, high yield growth of carbon nanotubes (CNTs) is inhibited in electrolytes containing over 50 wt% of sodium or 30 wt% of potassium carbonate, or at electrolysis temperatures less than 700 °C. Here, it is found that a lower temperature of synthesis, lower concentrations of lithium carbonate, and higher current density promotes CNS growth while suppressing CNT growth. Electrolyte conditions of 50 wt% sodium carbonate relative to lithium carbonate at an electrolysis temperature of 670 °C produced over 80% of the CNS desired product at 85% faradaic efficiency with a Muntz brass cathode and an Inconel anode.

Stimulated by the growing demand for sustainable and/or economical distributed ammonia synthesis, the electrochemical nitrogen reduction reaction has attracted considerable interest. The nitrogen-containing impurities in commercial metal-based nitrogen reduction reaction catalysts such as metal oxides and metallic irons have, however, been overlooked. Herein we report the presence of nitrogen-containing species in NOx− or nitrides at substantial levels revealed from many commercial catalysts. We call attention to the necessity to screen the NOx−/nitrides impurities in commercial catalysts, as the nitrogen impurities are not commonly listed in vendors’ assay documents. A simple two-step procedure (alkaline/acidic treatment followed by HPLC/UV–vis analysis) is recommended as a reliable protocol for screening NOx−/nitrides impurities in catalyst materials. A case analysis is also carried out on the previously reported H2O–NaOH–KOH system with both 15N-isotopic labelling and nitrogen elemental tracking, reassigning the true nitrogen source of the electrochemically produced NH3 from gaseous N2 to nitrogen-containing impurities in catalysts. The electrochemical nitrogen reduction reaction has recently attracted significant interest, but the true source of ammonia formation remains sometimes unclear. This Analysis reports a systematic investigation of the presence of nitrogen-containing species in a number of commercial catalysts, revealing substantial levels of NOx− and nitrides impurities for some of them.

This study describes a world of new carbon “fullerene” allotropes that may be synthesized by molten carbonate electrolysis using greenhouse CO2 as the reactant. Beyond the world of conventional diamond, graphite and buckyballs, a vast array of unique nanocarbon structures exist. Until recently, CO2 was thought to be unreactive. Here, we show that CO2 can be transformed into distinct nano-bamboo, nano-pearl, nano-dragon, solid and hollow nano-onion, nano-tree, nano-rod, nano-belt and nano-flower morphologies of carbon. The capability to produce these allotropes at high purity by a straightforward electrolysis, analogous to aluminum production splitting of aluminum oxide, but instead nanocarbon production by splitting CO2, opens an array of inexpensive unique materials with exciting new high strength, electrical and thermal conductivity, flexibility, charge storage, lubricant and robustness properties. Commercial production technology of nanocarbons had been chemical vapor deposition, which is ten-fold more expensive, generally requires metallo-organics reactants and has a highly carbon-positive rather than carbon-negative footprint. Different nanocarbon structures were prepared electrochemically by variation of anode and cathode composition and architecture, electrolyte composition, pre-electrolysis processing and current ramping and current density. Individual allotrope structures and initial growth mechanisms are explored by SEM, TEM, HAADF EDX, XRD and Raman spectroscopy.

The deployment of graphene has been slow due to its high cost and high carbon footprint. A low carbon footprint, inexpensive synthesis of graphene, consuming rather than emitting CO2, is introduced to overcome these obstacles. This is accomplished here by direct molten carbonate electrolytic splitting of the greenhouse gas CO2 to a nano-thin carbon product (carbon nanoplatelets) comprised of 25–125 graphene layers, and subsequent electrochemical exfoliation of the nanoplatelets to graphene in a carbonate soluble aqueous solution. The sole products of the carbon dioxide electrolysis are straightforward: high yield carbon nanoplatelets and oxygen. The carbon nano platelets provides a thinner starting point than a conventional graphite reactant to facilitate electrochemical exfoliation. The resultant valuable product (graphene) incentivizes utilization of the greenhouse gas carbon dioxide.

The electrochemical splitting of CO2 in molten carbonate salt electrolytes can form a valuable product, carbon nanotubes, and with this product a value-incentivized pathway of climate change mitigation by transforming CO2 from a greenhouse gas pollutant into a useful resource. Instability of the anode can provide a challenge for a commercialization of this electrochemical technology. A nickel superalloy (Inconel 718) anode is shown to be highly stable for the scalable controllable, electrosynthesis of nano-carbons from CO2 in molten carbonates salts. Unlike pure nickel anodes that degrade (corrode) in the presence of potassium carbonate containing molten electrolytes, Inconel is stable as an anode even in these electrolytes. This opens up more cost-effective electrolytes (less expensive than lithium carbonate), and the systematic variation of alkali cation carbonates is explored. Coupled with a brass cathode, uniform carbon nanotubes (CNT) are efficiently synthesized by electrolysis of CO2 in either pure Li2CO3 or in ternary electrolytes, Li2CO3-Na2CO3-LiBO2 or Li2CO3-K2CO3-LiBO2. These results increase the foundation of understanding of the electrolytic splitting of carbon dioxide and provide the data for developing a high-efficiency CO2 electroreduction for the production of carbon nanotubes.

Climate change represents one of the most important environmental issues of our time. Due to high levels of anthropogenic CO2 emissions, atmospheric CO2 has for the first time ever exceeded 415 ppm and has increased from 315 ppm in 1950. An annual increase in atmospheric CO2 of ∼2 ppm is equal to a net increase of ∼15.6 billion tons of CO2. The combustion of fossil fuels for electricity and transportation is still the main reason accounting for the CO2 accumulation. On the top of that, fossil fuels are widely used in our modern industry for the productions of indispensable social staples. For instance, the millennia old thermal reduction of iron ore by charcoal or baked coal (3C + 2Fe2O3 → 4Fe + 3CO2) continues as the main method for the production of iron. The artificial fertilizer ammonia boosts the global population and is mainly produced from the Haber-Bosch process, in which hydrogen is generated via steam reforming of methane (CH4 + 2H2O → 4H2 + CO2). Sequestration and diminution of CO2 require the development of a portfolio of technologies on (1) efficient and long-term harvesting of renewable energy, that is, solar, not only for electricity but also directly as the energy force in vital chemical processes, wherever possible, (2) carbon-neutral processes to replace current industrial processes that emit vast amounts of CO2, such as iron and ammonia production, and (3) new, low-cost technologies for CO2 capture and conversion with particular interests in the exploration of CO2 as the feedstock for fuels or other valuable chemicals and materials. To this end, we conducted some studies on the sustainable synthesis of ammonia and iron with net-zero CO2 emissions and large-scale CO2 capture and conversion into fuels and high value nanocarbon products via electrolysis in molten salt(s) with the introduction of the Solar Thermal Electrochemical Process (STEP). In STEP, solar UV-visible energy is focused on a photovoltaic device that generates the electricity to drive the electrolysis, while concurrently the solar thermal energy is focused on a second system to generate heat for the electrolysis cell. The utilization of the full spectrum of sunlight in STEP results in a higher solar energy efficiency than other solar conversion processes. STEP has been applied to conduct (1) CO2-free ammonia synthesis from nitrogen and water with the aid of nano-Fe2O3 in a molten hydroxide electrolyte, (2) CO2-free production of iron via electrochemical reduction of iron ore in molten carbonate, (3) CO2 capture and conversion into nanostructured carbon products as well as fuels in molten or mixed molten electrolytes, and (4) organic electrosynthesis of benzoic acid from benzene without overoxidizing into CO2. In this Account, we highlight some recent achievements in these topics and propose that using STEP is a highly efficient strategy for saving energy and, consequently, the environment. STEP is an ideal tool that can theoretically be applied to all endothermic reactions.

An electrosynthesis is presented to transform the greenhouse gas CO2 into an unusually thin walled, smaller diameter morphology of Carbon Nanotubes (CNTs). The transformation occurs at high yield and coulombic efficiency of the 4-electron CO2 reduction in a molten carbonate electrolyte. The electrosynthesis is driven by an unexpected synergy between calcium and metaborate. In a pure molten lithium carbonate electrolyte, thicker walled CNTs (100–160 nm diameter) are synthesized during a 4 h CO2 electrolysis at 0.1 A cm−2. At this low current density, CO2 without pre-concentration is directly absorbed by the air (direct air capture) to renew and sustain the carbonate electrolyte. The addition of 2 wt% Li2O to the electrolyte produces thinner, highly uniform (50–80 nm diameter) walled CNTs, consisting of ~ 75 concentric, cylindrical graphene walls. The product is produced at high yield (the cathode product consists of > 98% CNTs). It had previously been demonstrated that the addition of 5–10 wt% lithium metaborate to the lithium carbonate electrolyte boron dopes the CNTs increasing their electrical conductivity tenfold, and that the addition of calcium carbonate to a molten lithium carbonate supports the electrosynthesis of thinner walled CNTs, but at low yield (only ~ 15% of the product are CNTs). Here it is shown that the same electrolysis conditions, but with the addition of 7.7 wt% calcium metaborate to lithium carbonate, produces unusually thin walled CNTs uniform (22–42 nm diameter) CNTs consisting of ~ 25 concentric, cylindrical graphene walls at a high yield of > 90% CNTs.

Iron molten air is a new battery class that combines multielectron cathodic storage, high capacity air electrodes with the high redox activity of a molten electrolyte. The need for a bifunctional a...

CD73/Ecto-5'-nucleotidase is a membrane-tethered ecto-enzyme that works in tandem with CD39 to convert extracellular adenosine triphosphate (ATP) into adenosine. CD73 is highly expressed on various types of cancer cells and on infiltrating suppressive immune cells, leading to an elevated concentration of adenosine in the tumor microenvironment, which elicits a strong immunosuppressive effect. In preclinical studies, targeting CD73 with anti-CD73 antibody results in favorable antitumor effects. Despite initial studies using antibodies, inhibition of CD73 catalytic activity using small-molecule inhibitors may be more effective in lowering extracellular adenosine due to better tumor penetration and distribution. To screen small-molecule libraries, we explored multiple approaches, including colorimetric and fluorescent biochemical assays, and due to some limitations with these assays, we developed a mass spectrometry (MS)-based assay. Only the MS-based assay offers the sensitivity and dynamic range required for screening small-molecule libraries at a substrate concentration close to the Km value of substrate and for evaluating the mode of binding of screening hits. To achieve a throughput suitable for high-throughput screening (HTS), we developed a RapidFire-tandem mass spectrometry (RF-MS/MS)-based multiplex assay. This assay allowed a large diverse compound library to be screened at a speed of 1536 reactions per 40-50 min.

Helical carbon nanotubes currently cost ~15,000–19,000 USD/kg commercially and are ~10–15 times the price of straight carbon nanotubes of similar dimensions. They have not previously been made from the greenhouse gas CO2 nor had new variants of the helical morphology been demonstrated. In this study, a novel, inexpensive electrosynthesis of these helical nanocarbon materials from CO2 is presented. This material may be produced by molten carbon growth conditions that (1) maximize torsional stresses, such as those that may occur during rapid, nucleated carbon reduction, (2) enhance defects that cause formation of heptagonal, rather than the conventional hexagonal building blocks of graphene cylindrical walls, and (3) uniformly control those enhanced defects to repeatedly induce a uniform spiral conformation. These conditions are achieved with at least two of the following experimental conditions: (i) high electrolysis current density, (ii) sp3 defect-inducing agents, such as added oxide, and (iii) controlled concentration of iron added to the electrolyte or cathode. Here, it is shown with SEM, TEM, EDX, XRF, and Raman spectroscopy that a molten controlled electrolyte carbonate synthesis to induce defect formation, and a high rate of electrolysis (0.6 A/cm2) leads to a high yield of helical nanotubes, helical nanofibers, or helical nanoplatelet carbon morphologies.

A climate mitigation comprehensive solution is presented through the first high yield, low energy synthesis of macroscopic length carbon nanotube (“CNT”) wool from CO 2 by molten carbonate electrolysis. The CNT wool is of length suitable for weaving into carbon composites and textiles. Growing CO 2 concentrations, and the concurrent climate change and species extinction, can be addressed if CO 2 becomes a sought resource rather than a greenhouse pollutant. Inexpensive carbon composites formed from carbon wool as a lighter metal, textiles or cement replacement comprise major market sinks to compactly store transformed anthropogenic CO 2 . 100×-longer CNTs grow on Monel versus steel. Monel, electrolyte equilibration, and a mixed metal nucleation facilitate the synthesis. CO 2 , the sole reactant in this transformation, is directly extractable from dilute (atmospheric) or concentrated sources, and the analyzed production cost of $660 per ton CNT is cost constrained only by the (low) cost of electricity. Today's market valuation of >$100,000 per ton CNT incentivizes CO 2 removal.

This SEM, TEM and Raman Spectra and economic calculations data provides a benchmark for carbon nanotubes synthesized via molten electrolyte via the carbon dioxide to carbon nanotube (C2CNT) process useful for comparison to other data on longer length C2CNT wools; specifically: (I) C2CNT electrosynthesis with bare (uncoated) cathodes and without pre-electrolysis low current activation. (II) C2CNT Intermediate length CNTs with intermediate integrated electrolysis charge transfer. (III) C2CNT Admixing of sulfur, nitrogen and phosphorous (in addition to boron) to carbon nanotubes, and (IV) Scalability of the C2CNT process. This data presented in this article are related to the research article entitled "Carbon Nanotube Wools Made Directly from CO2 by Molten Electrolysis: Value Driven Pathways to Carbon Dioxide Greenhouse Gas Mitigation" (Johnson et al., 2017) [1].

This paper demonstrates a highly favored route for the synthesis of controlled nanostructures at high rate, high yield, and low cost by molten carbonate electrolysis splitting of CO2. We show the wide, portfolio of carbon nanotubes (CNTs) that can be produced by controlling the electrolysis conditions in this one-pot synthesis. For example solid core carbon nanofibers are formed with C-13 isotope CO2, whereas hollow core CNTs are formed with natural abundance CO2 (which contains 99% C-12 and 1% C-13). Shown are the first doped electrosynthesized carbon nanotubes, prepared with added electrolytic LiBO2 for boron doping, and salts for phosphorous, nitrogen or sulfur CNT doping is probed. Boron doping greatly enhances conductivity of the CNTs. Electrolytic CaCO3 produces thin-walled CNTs, while excess electrolytic oxide yields tangled CNTs. Addition of up to 50 mol% Na2CO3 to a Li2CO3 electrolyte, decreases electrolyte costs and improves conditions for intercalation in Na-ion CNT anodes. Addition of BaCO3 increases electrolyte density. Longer electrolysis time leads to proportionally wider diameter CNTs. Synthetic components (steel cathode, nickel anode and inorganic carbonate electrolyte) are available and inexpensive. Advantages include (1) production is limited only by the cost of electrons (electricity) providing a substantial cost reduction compared to conventional CVD and polymer spinning syntheses and (2) the only reactant consumed in the formation of the CNTs is CO2, transforming this greenhouse gas into a stable, valuable product and providing an economic incentive to the removal of anthropogenic CO2 from flue gas or from the atmosphere.

C2CNT (Carbon dioxide to carbon nanotube) cement plants have been introduced and analyzed which provide a significant economic incentive to eliminate the massive CO2 greenhouse gas emissions of current plants and serves as a template for carbon mitigation in other industrial manufacturing processes. Rather than regarding CO2 as a costly pollutant, this is accomplished by treating CO2 as a feedstock resource to generate valuable products (carbon nanotubes). The exhaust from partial and full oxy-fuel cement plant configurations are coupled to the inlet of a C2CNT chamber in which CO2 is transformed by electrolysis in a molten carbonate electrolyte at a steel cathode and a nickel anode. In this high yield 4e- per CO2 process, the CO2 is transformed into carbon nanotubes at the cathode, and pure oxygen at the anode that is looped back in improving the cement line energy efficiency and rate of production. A partial oxy-fuel process looping the pure oxygen back in through the plant calcinator has been compared to a full oxy-fuel process in which it is looped back in through the plant kiln. The second provides the advantage of easier retrofit, while the first maximizes efficiency by minimizing the volume of gas throughput (eliminating N2 from air). An upper limit to the electrical cost to drive C2CNT electrolysis is USD70 based on Texas wind power costs, but will be lower with fuel expenses when oxy-fuel plant energy improvements are taken account. The current value of a ton of carbon nanotubes is substantially in excess of a ton of cement. Hence a C2CNT cement plant consumes USD50 of electricity, emits no CO2, and produces USD100 of cement and USD60,000 of carbon nanotubes per ton of CO2 avoided. As the cement product ages, CO2 is spontaneously absorbed. This is a powerful economic incentive, rather than economic cost, to mitigate climate change through a carbon negative process., Comment: 17 pages, 14 figures

A new green methodology for the CO2-free synthesis of ammonia from air and water is presented. The conventional production of H2 utilizes fossil fuels and causes a massive greenhouse gas release, making ammonia production one of the most energy intensive and highest CO2 emitting manufacturing processes. In 2014 we introduced an alternative method for efficient ammonia synthesis that utilizes water (along with N2) instead of H2 based on electrolysis of nano-structured catalyst suspensions of Fe2O3 in low temperature aqueous or higher temperature molten hydroxide electrolytes. Here, this is replaced with a solid Fe2O3 catalyst confined to activated charcoal opening pathways to improve the rate and efficiency of ammonia production. Cyclovoltammetric studies show that Fe2O3/AC catalysts can inhibit competing hydrogen reduction and enhance reduction of iron. This iron-based catalyst supported on activated carbon (Fe2O3/AC) was prepared for use as an electrocatalyst for the electrochemical synthesis of ammonia in molten hydroxide (NaOH–KOH) directly from wet N2 at atmospheric pressure. XRD analysis shows that the catalyst exhibits a Fe2O3 structure. At 250 °C, a voltage of 1.55 V with a current density of 49 mA cm−2 yielded the highest rate of ammonia formation, 8.27 × 10−9 mol (s cm2)−1. The highest coulombic efficiency for the 3e− per ammonia formation, 13.7%, was achieved at 1.15 V with a lower average current density of 11 mA cm−2. This is a promising simple technology for the sustainable synthesis of ammonia in the future.

Despite the recent advancements in iron molten air batteries, great challenges still remain to realize cycling stability, high energy efficiency and a long-term cycling life. Herein, we demonstrate a new iron molten air battery for large-scale energy storage. We replace the KCl–LiCl–LiOH eutectic electrolyte used in our previous study with a Li0.87Na0.63K0.50CO3 eutectic electrolyte with added NaOH and LiOH. A fin air electrode configuration is designed to improve the coulombic efficiency. Cycling tests for the iron molten air battery showed a stable performance through 450 cycles with nearly 100% coulombic efficiency and an average discharge potential of ∼1.08 V when charged at a constant current of 0.05 A and discharged over a constant 100 Ω load to a 0.7 V cutoff at 500 °C. Moreover, the iron molten air battery had an excellent high-rate response up to 6.4C with a high coulombic efficiency of 95.1%. These results provide critical advances in developing iron molten air batteries with high efficiency and a long-term service life.

As the primary culprit of greenhouse effect, carbon dioxide has garnered global attention, and the technologies currently being developed to reduce the emission of CO2 vary widely. In this study, CO2 was electrochemically reduced in various molten mixtures of LiNaK carbonates to carbon nanomaterials. By regulating the electrolysis current density, electrolyte, and electrolytic temperature, the carbon products had different morphologies of honeycomb-like and nanotubular structures. A transition from a honeycomb/platelet to nanomaterial carbon morphology was observed to occur at ∼600 °C with increase in temperature. The observation of nanostructures is consistent with a higher diversity of structures possible with enhanced rearrangement kinetics that can occur at higher temperature. A high yield of a carbon nanotube (CNT) was not observed from a LiNaK electrolyte, no CNTs are formed from a NaK carbonate electrolyte, but a high yield is observed from pure Li, or mixed LiNa or mixed LiBa carbonate electrolytes, and the carbon nanotube product diameter is observed to increase with increasing electrolysis time.

The solar thermal electrochemical process synthesis of benzoic acid is an efficient way for organic synthesis based upon solar energy utilization. Graphite and platinum anodes have been developed with high yield and selectivity of benzoic acid. In this article, we present the first demonstration of the solar thermal-electro-photo field for efficient benzoic acid synthesis by using TiO2 nanotubes electrode. By adjusting the three-solar field process, toluene is oxidized at the surface of the photoactive, electrically driven, heat activated TiO2 nanotubes electrode. Results showed that, the synergistic effect of the three fields was found for enhancement of toluene oxidation at TiO2 electrode. The yield of benzoic acid and conversion of toluene is greatly improved with temperature, and arriving to 26.1% and 62.6% at 90 °C, respectively. In this process, solar thermal decreases the electrolysis potential of toluene oxidation. Hydroxyl, carboxyl and OOH groups, as well as the emergence of TiOC bond at the surface of the TiO2 nanotubes electrode, lead to an increased UV and visible absorption and a significant enhancement of TiO2 photocatalytic properties to increase the yield of benzoic acid. Simultaneously, an applied solar electric potential promotes the separation of photogenerated electrons and holes. As a result the efficiency of TiO2 photocatalysis enhanced.

Molten carbonate electrolyzers offer a pathway to capture emitted CO 2 from the flue gas of the power plants and transform this greenhouse gas emission at low energy and high yield instead into a specific, value added, hollow carbon nanofiber product, carbon nanotubes. The present day value of the carbon nanotubes product is ∼10,000 that of proposed, or in place, current carbon tax costs of $30 per ton, strongly incentivizing carbon dioxide removal. The recent progress in high-temperature molten carbonate electrolysis systems for carbon dioxide utilization and the impact these advances have on developing a CO 2 -free fossil fuel power plant for electricity generation is presented. A thermodynamic model analysis is presented for a molten Li 2 CO 3 electrolysis system incorporated within a combined cycle (CC) natural gas power plant to produce carbon nanofibers (CNF) and oxygen. Such a CC CNF plant system is shown to require 219 kJ to convert one mole of CO 2 to carbon, and generates electricity at higher efficiency due to pure oxygen looped back to the gas turbine input from the CO 2 splitting, with the added advantages that (i) the CC CNF plant emits no CO 2 and (ii) all CO 2 is converted to value added carbon nanotubes useful for strong, lightweight construction, batteries and nanoelectronics. Converting to power and ton units, per metric ton of methane fuel consumed the CC CNF plant is thermodynamically assessed to produce 8350 kW h of electricity and 0.75 ton of CNT and emits no CO 2 , while the CC plant produces 9090 kW h of electricity and emits 2.74 ton CO 2 . The required energy balance for a carbon nanotube production from an analogous coal power plant consumes a larger fraction of the coal energy, and encourages co-generation with renewable electric energy.

The inherent thermodynamic instability of FeO4 2− in water restricts its applications in water treatment, battery, and organic synthesis. The objective of this paper was to research and develop an additive for stabilization and mechanism of aqueous FeO4 2− solution on the basis of a choice of the redox equilibration. In this study, it was found that FeO4 2− in water was stabilized by the right match and adoption of KIO4 called an equalizer. The redox thermodynamic analysis and dynamic experimental results show that the adoption of KIO4 equalizer greatly increased lifetime of FeO4 2− in water by orders of magnitude. The stabilization mechanism is attributed to occur via the effect of redox equilibrium of the FeO4 2− and the IO4 − species, as well as the formation of an oxidizing chemical environment. This study opens up possibilities for stabilization of solid ferrate compounds, for example, for use in the water treatment and super-iron battery.

The cost and practicality of greenhouse gas removal processes, which are critical for environmental sustainability, pivot on high-value secondary applications derived from carbon capture and conversion techniques. Using the solar thermal electrochemical process (STEP), ambient CO2 captured in molten lithiated carbonates leads to the production of carbon nanofibers (CNFs) and carbon nanotubes (CNTs) at high yield through electrolysis using inexpensive steel electrodes. These low-cost CO2-derived CNTs and CNFs are demonstrated as high performance energy storage materials in both lithium-ion and sodium-ion batteries. Owing to synthetic control of sp3 content in the synthesized nanostructures, optimized storage capacities are measured over 370 mAh g–1 (lithium) and 130 mAh g–1 (sodium) with no capacity fade under durability tests up to 200 and 600 cycles, respectively. This work demonstrates that ambient CO2, considered as an environmental pollutant, can be attributed economic value in grid-scale and portable energy storage systems with STEP scale-up practicality in the context of combined cycle natural gas electric power generation., Carbon dioxide is transformed into carbon nanotubes which serve as high performance anodes in lithium-ion and sodium-ion batteries, offering a new route to attribute economic value to carbon dioxide.

Molten salt electrochemical CO2 conversion to value-added materials is gaining momentum in large-scale industrialization for reducing global CO2 emissions. However, the adoption of this novel technology is being limited by the environmental impact of the product purification process. A typical prior separation of raw products from a carbonate electrolyte used hydrochloric acid to dissolve the carbonate salts, and then the insoluble carbon product is filtered, rinsed, and dried. We propose and demonstrate a green High-Temperature Press Filtration (HTPF) alternative method for scalable and sustainable separation and purification of carbon products from molten salts. In our optimized experiment , 95% of the electrolyte was extracted from the cathode when pressed at 750 °C and at 493 psi for 30 min directly with a filter configuration shown to be stable through many uses. After the filtration process, the electrolyte can be conveniently recycled back to the cell which preserves heat energy and reduces waste.

This study demonstrates that CO2 can be split by molten carbonate electrolysis (1) to grow magnetic carbon nanotubes (CNTs) and (2) that the process can be initiated by carbide nucleation points acting as growth catalysts. This opens the path to other similar electrochemically prepared magnetic carbon nanomaterials. Magnetic carbon nanomaterials have a variety of applications, such as in directing medical therapy to localized regions and recoverable catalysts. In the presence of an iron or nickel containing case to house the molten carbonate electrolysis, or the presence of Fe or Ni in the electrochemical components, ferromagnetic CNTs can grow at the cathode. For example, EDS elemental analysis confirms the presence of iron in the CNTs, and XRD confirms the presence of iron carbide at the CNT nucleation site. The observed interlattice spacing of 0.20 nm of the iron carbide is distinct from the observed 0.36 nm graphene lattice spacing of the CNT walls. An excess iron release can be facilitated into the electrolyte using an iron rich alloy anode, such as Incoloy. The excess iron results in graphene layer coated iron carbide nodules on the exterior of the carbon nanotube product formed at the cathode, as well as iron carbide within these CNTs as observed by SEM and TEM.

The rate of ammonia production by the chemical oxidation of iron, N2(from air or as pure nitrogen) and water is studied as a function of (1) iron particle size, (2) iron concentration, (3) temperature, (4) pressureand (5) concentration of the alkaline reaction medium. The reaction meduium consists of an aqueous solution of equal molal concentrations of NaOH and KOH (Na0.5K0.5OH). We had previously reported on the chemical reaction of iron and nitrogen in alkaline medium to ammonia as an intermediate step in the electrochemical synthesis of ammonia by a nano-sized iron oxide electrocatlyst. Here, the intermediate chemical reaction step is exclusively explored. The ammonia production rate increases with temperature (from 20 to 250°C), pressure (from 1 atm to 15 atm of air or N2), and exhibits a maximum rate at an electrolyte concentration of 8 molal Na0,5K0,5OH in a sealed N2reactor. 1-3 µm particle size Fe drive the highest observed ammonia production reaction rate. The Fe mass normalized rate of ammonia production increases with decreasing added mass of the Fe reactant reaching a maximum observed rate of 2.2x10-4mole of NH3h-1g-1for the reaction of 0.1 g of 1-3 µm Fe in 200°C 8 molal Na0.5K0.5OH at 15 atm. Under these conditions 5.1 wt% of the iron reacts to form NH3via the reaction N2+ 2Fe + 3H2O ®2NH3+ Fe2O3.

The rate of ammonia production by the chemical oxidation of iron, N2(from air or as pure nitrogen) and water is studied as a function of (1) iron particle size, (2) iron concentration, (3) temperature, (4) pressureand (5) concentration of the alkaline reaction medium. The reaction meduium consists of an aqueous solution of equal molal concentrations of NaOH and KOH (Na0.5K0.5OH). We had previously reported on the chemical reaction of iron and nitrogen in alkaline medium to ammonia as an intermediate step in the electrochemical synthesis of ammonia by a nano-sized iron oxide electrocatlyst. Here, the intermediate chemical reaction step is exclusively explored. The ammonia production rate increases with temperature (from 20 to 250°C), pressure (from 1 atm to 15 atm of air or N2), and exhibits a maximum rate at an electrolyte concentration of 8 molal Na0,5K0,5OH in a sealed N2reactor. 1-3 µm particle size Fe drive the highest observed ammonia production reaction rate. The Fe mass normalized rate of ammonia production increases with decreasing added mass of the Fe reactant reaching a maximum observed rate of 2.2x10-4mole of NH3h-1g-1for the reaction of 0.1 g of 1-3 µm Fe in 200°C 8 molal Na0.5K0.5OH at 15 atm. Under these conditions 5.1 wt% of the iron reacts to form NH3via the reaction N2+ 2Fe + 3H2O ®2NH3+ Fe2O3.

This is a Density Functional Theory (DFT) study on the influence of an alloying mixture of Ni–Zn catalysts on carbon nanotube, CNT, growth. The study is inspired by the one pot synthesis of carbon nanofibers during the electrolysis of Li2CO3. Unlike CVD, CNT growth initiates at the liquid/solid, rather than gas/solid interface in the above process. The electrodes are an amalgamated Zn cathode and with a pure Ni crucible as the anode, and both zinc and nickel (or other transition metals) are required for high yield production. The use of transition metals as the catalyst for CNT, CVD growth is well known. However, in this study we show how a mixture of the Zn–Ni alloy can act as the catalyst for the effective CNT growth. Ni and Zn are taken as an example of first row transition metals with a partially empty and completely filled d orbital respectively. The study shows that the π–d bonding between the nanotube and the metal results in strong bond formation at the interface of the nanotube growth. The study remains valid for other such metal alloys with partially and completely filled d orbitals.

One pathway to remove the greenhouse gas carbon dioxide to mitigate climate change is by dissolution and electrolysis in molten carbonate to produce stable, solid carbon. This study determines critical knowledge to minimize the required electrolysis energy, the reaction stoichiometry in which carbon and O2 are the principal products, and that CO2 can be electrolyzed inexpensively. Thermochemical and experimental results indicate that the principal carbon-deposition reaction in molten Li2CO3 or Li2O/Li2CO3 electrolytes at 750 °C is Li2O + 2CO2 → Li2CO3 + C + O2. The reaction occurs at high Faradaic efficiency of the 4e– reduction of CO2 to carbon and oxygen at an electrolysis voltage as low as

Solar Thermal Electrochemical Process (STEP) synthesis of benzoic acid from toluene using a platinum anode has been developed as high yield and selectivity using the full spectrum of sunlight. STEP organic is an efficient process for organic synthesis based upon its use of a platinum electrode. This is a significant drawback as it is not cost effective. In this paper, the use of an active, inexpensive, graphite anode is introduced. The functionalized (aged) graphite anode was found to have a high reactivity for the oxidative conversion of toluene into benzoic acid. The yield of benzoic acid synthesized rises to 15.1% at 30 °C to 44.6% at 90 °C for the functionalized graphite anode, compared to only 12.4% and 32% respectively at a Pt anode. High conversion rate and chemical selectivity were achieved by balancing and controlling the rate of solar-to-thermal and solar-to-electric conversions. The factors influencing the efficiency and selectivity of the reaction are discussed, experimental results demonstrate the beneficial effect of increasing temperature on the yield for the process. The role of the functionalized graphite anode is considered and analyzed by SEM, FTIR and EDS. Graphite anode activity is enhanced by C OH, C O, and COOH generated on the graphite surface.

Correction for ‘Critical advances for the iron molten air battery: a new lowest temperature, rechargeable, ternary electrolyte domain’ by Shuzhi Liu et al., J. Mater. Chem. A, 2015, 3, 21039–21043.

Transition metal borides, such as VB2 and TiB2, are studied as battery anode materials both individually and as a composite anode for an air cathode battery. The combination of VB2 and TiB2 is shown to enhance anodic battery performance. In alkaline media, VB2 and TiB2 anodically discharge to yield respectively 11 and 6 electrons per molecule with VB2 intrinsic gravimetric charge capacity of 4,060 mAh/g and 2,314 mAh/g for TiB2, 3 to 5 fold higher than a conventional zinc anode. With an air cathode using external O2, these boride/air batteries discharge at ∼1 V, and exhibit unusually high, primary battery energy capacities. We show that the coulombic efficiency attained by the TiB2 anode in boride/air batteries is not a strong function of the anode capacity per unit area (cm 2 ) of anode, while the efficiency of the VB2 anode decreases with increasing anode capacity. The discharge of VB2 shows a unique singular voltage plateau, indicating that the 11 electrons discharge at a similar potential. Two voltage plateaus are observed during the TiB2 discharge indicating the possibility of a two-step anodic oxidation. The combination of VB2 and TiB2 exhibits evidence of a synergistic increase of the capacity and discharge voltage of boride/air batteries. © The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any

Cancer-associated point mutations in isocitrate dehydrogenase 1 and 2 (IDH1 and IDH2) confer a neomorphic enzymatic activity: the reduction of α-ketoglutarate to d-2-hydroxyglutaric acid, which is proposed to act as an oncogenic metabolite by inducing hypermethylation of histones and DNA. Although selective inhibitors of mutant IDH1 and IDH2 have been identified and are currently under investigation as potential cancer therapeutics, the mechanistic basis for their selectivity is not yet well understood. A high throughput screen for selective inhibitors of IDH1 bearing the oncogenic mutation R132H identified compound 1, a bis-imidazole phenol that inhibits d-2-hydroxyglutaric acid production in cells. We investigated the mode of inhibition of compound 1 and a previously published IDH1 mutant inhibitor with a different chemical scaffold. Steady-state kinetics and biophysical studies show that both of these compounds selectively inhibit mutant IDH1 by binding to an allosteric site and that inhibition is competitive with respect to Mg(2+). A crystal structure of compound 1 complexed with R132H IDH1 indicates that the inhibitor binds at the dimer interface and makes direct contact with a residue involved in binding of the catalytically essential divalent cation. These results show that targeting a divalent cation binding residue can enable selective inhibition of mutant IDH1 and suggest that differences in magnesium binding between wild-type and mutant enzymes may contribute to the inhibitors' selectivity for the mutant enzyme.