The Haber-Bosch process to produce ammonia for fertilizer currently relies on carbon-intensive steam reforming of methane as a hydrogen source. We present an electrochemical pathway in which ammonia is produced by electrolysis of air and steam in a molten hydroxide suspension of nano-Fe2O3. At 200°C in an electrolyte with a molar ratio of 0.5 NaOH/0.5 KOH, ammonia is produced at 1.2 volts (V) under 2 milliamperes per centimeter squared (mA cm(-2)) of applied current at coulombic efficiency of 35% (35% of the applied current results in the six-electron conversion of N2 and water to ammonia, and excess H2 is cogenerated with the ammonia). At 250°C and 25 bar of steam pressure, the electrolysis voltage necessary for 2 mA cm(-2) current density decreased to 1.0 V.
Carbon nanofibers, CNFs, due to their superior strength, conductivity, flexibility, and durability have great potential as a material resource but still have limited use due to the cost intensive complexities of their synthesis. Herein, we report the highyield and scalable electrolytic conversion of atmospheric CO 2 dissolved in molten carbonates into CNFs. It is demonstrated that the conversion of CO 2 → C CNF + O 2 can be driven by efficient solar, as well as conventional, energy at inexpensive steel or nickel electrodes. The structure is tuned by controlling the electrolysis conditions, such as the addition of trace transition metals to act as CNF nucleation sites, the addition of zinc as an initiator and the control of current density. A less expensive source of CNFs will facilitate its adoption as a societal resource, and using carbon dioxide as a reactant to generate a value added product such as CNFs provides impetus to consume this greenhouse gas to mitigate climate change.
Contemporary models are shown to significantly underestimate the attainable efficiency of solar energy conversion to water splitting, and experimentally a cell containing illuminated AlGaAs/Si RuO2/Ptblack is demonstrated to evolve H2 and O2 at record solar driven water electrolysis efficiency. Under illumination, bipolar configured Al0.15Ga0.85As (E g = 1.6 eV) and Si (E g = 1.1 eV) semiconductors generate open circuit and maximum power photopotentials of 1.30 and 1.57 V, well suited to the water electrolysis thermodynamic potential: H2O → H2 + 1/2O2; E°H 2 O = E O 2 − E H 2 ; E°H 2 O(25 °C) = 1.229 V. The E°H 2 O/photopotential matched semiconductors are combined with effective water electrolysis O2 or H2 electrocatalysts, RuO2 or Ptblack. The resultant solar photoelectrolysis cell drives sustained water splitting at 18.3% conversion efficiencies. Alternate dual band gap systems are calculated to be capable of attaining over 30% solar photoelectrolysis conversion efficiency.
The first experimental evidence of a new solar process, combining electronic and chemical pathways, to isolate CO2 (carbon capture) is presented. This solar thermal electrochemical photo (STEP) process is a synergy of solid-state and solar thermal processes, and is fundamentally capable of converting more solar energy than photovoltaic or solar thermal processes alone. Here, CO2 is captured using a 750−950 °C electrolysis cell powered by a full spectrum solar simulator in a single step. The process uses the full spectrum; solar thermal energy decreases the energy required for carbon capture, while visible sunlight generates electronic charge to drive the electrolysis. CO2 can be captured from 34% to over 50% solar energy efficiency (depending on the level of solar heat inclusion), as solid carbon and stored, or used as carbon monoxide to be available for a feedstock to synthesize (with STEP generated hydrogen) solar diesel fuel, synthetic jet fuel, or chemical production.
Higher capacity batteries based on an unusual stabilized iron(VI) chemistry are presented. The storage capacities of alkaline and metal hydride batteries are largely cathode limited, and both use a potassium hydroxide electrolyte. The new batteries are compatible with the alkaline and metal hydride battery anodes but have higher cathode capacity and are based on available, benign materials. Iron(VI/III) cathodes can use low-solubility K(2)FeO(4) and BaFeO(4) salts with respective capacities of 406 and 313 milliampere-hours per gram. Super-iron batteries have a 50 percent energy advantage compared to conventional alkaline batteries. A cell with an iron(VI) cathode and a metal hydride anode is significantly (75 percent) rechargeable.
Because of its high resistivity and subsequent low electroactivity, sulfur is not normally considered a room-temperature battery cathode. An elemental sulfur cathode has been made with a measured capacity of over 900 ampere.hours per kilogram, more than 90 percent of the theoretical storage capacity of solid sulfur at room temperature, accessed by means of a lightweight, highly conductive, aqueous polysulfide interface through the electrocatalyzed reaction S + H(2)O + 2e(-) --> HS(-) + OH(-). This solid sulfur cathode was first used in a battery with an aluminum anode for an overall discharge reaction 2Al + 3S + 3OH(-) + 3H(2)O --> 2Al(OH)(3) + 3HS(-), giving a cell potential of 1.3 volts. The theoretical specific energy of the aluminum-sulfur battery (based on potassium salts) is 910 watt.hours per kilogram with an experimental specific energy of up to 220 watt.hours per kilogram.
The most accurate values to date were determined for conductivity of water from 0-100°C, permitting new determination of high-temperature hydroxide ion equivalent conductance. These values were incorporated into a fundamental water coefficient table including hydroxide and hydrogen ion mobilities, water ionization constant, density, conductivity, and resistivity. The conductivity/resistivity values were measured with a multiple-pass, closed, recirculating flow conductivity system, with improved multiple resistance temperature device measurement, and improved analysis of temperature and impurity effects. An accurate conductivity knowledge is necessary to understand water-limiting processes and to facilitate the analysis of trace ionic impurities in water.
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.
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