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At least 55 records · Page 3

Solar-Thermal Ammonia Production: A Renewable, Carbon-Neutral Route to Ammonia via Concentrating Solar Thermochemistry [Slides]

Solar Thermal Ammonia Production has potential to produce green ammonia using CSP, air, and water. Air separation to purify N 2 was successfully demonstrated with BSF1585 in packed bed reactor; on-sun reduction reactor under construction. Metal nitrides (MNy) were successfully synthesized and characterized under both ambient and pressurized conditions. Co 3 Mo 3 N shown to successfully produce NH 3 when exposed to pure H 2 at pressures between 5 – 20 bar 600 – 750 °C. Ambient reaction experiments imply there may be a catalytic aspect as well. Technoeconomic and systems analyses show a path towards scale-up.

14 SOLAR ENERGY↗

Thermophilic Geobacillus WSUCF1 Secretome for Saccharification of Ammonia Fiber Expansion and Extractive Ammonia Pretreated Corn Stover

A thermophilic Geobacillus bacterial strain, WSUCF1 contains different carbohydrate-active enzymes (CAZymes) capable of hydrolyzing hemicellulose in lignocellulosic biomass. We used proteomic, genomic, and bioinformatic tools, and genomic data to analyze the relative abundance of cellulolytic, hemicellulolytic, and lignin modifying enzymes present in the secretomes. Results showed that CAZyme profiles of secretomes varied based on the substrate type and complexity, composition, and pretreatment conditions. The enzyme activity of secretomes also changed depending on the substrate used. The secretomes were used in combination with commercial and purified enzymes to carry out saccharification of ammonia fiber expansion (AFEX)-pretreated corn stover and extractive ammonia (EA)-pretreated corn stover. When WSUCF1 bacterial secretome produced at different conditions was combined with a small percentage of commercial enzymes, we observed efficient saccharification of EA-CS, and the results were comparable to using a commercial enzyme cocktail (87% glucan and 70% xylan conversion). It also opens the possibility of producing CAZymes in a biorefinery using inexpensive substrates, such as AFEX-pretreated corn stover and Avicel, and eliminates expensive enzyme processing steps that are used in enzyme manufacturing. Implementing in-house enzyme production is expected to significantly reduce the cost of enzymes and biofuel processing cost.

Bhalla, Aditya↗

Preliminary data on the optical properties of solid ammonia and scattering parameters for ammonia cloud particles.

The infrared absorption spectrum of solid ammonia is obtained from 2 to 125 microns as a composite of the published measurements. From this, the absorption coefficient and the complex refractive index are calculated as a function of frequency by integration of the Kramers-Kroenig dispersion relations. These data are used in a Mie theory analysis to obtain the basic parameters for scattering of long wavelength radiation by solid ammonia particles; this is believed to be an important process in radiative transfer within the atmospheres of the giant planets.

Taylor, F. W.↗

Ammonia Formation by the Reduction of Nitrite/Nitrate by FeS: Ammonia Formation Under Acidic Conditions

FeS reduces nitrite to, ammonia at pHs lower than the corresponding reduction by aqueous Fe+2. The reduction follows a reasonable first order decay, in nitrite concentration, with a half life of about 150 min (room temperature, CO2, pH 6.25). The highest ammonia product yield measured was 53%. Under CO2, the product yield decreases from pH 5.0 to pH 6.9. The increasing concentration of bicarbonate at higher pH interferes with the reaction. Bicarbonate interference is shown by comparing runs under N2 and CO2. The reaction proceeds well in the presence of such species as chloride, sulfate, and phosphate though the yield drops significantly with phosphate. FeS also reduces nitrate and, unlike with Fe+2, the reduction shows more reproducibility. Again, the product yield decreases with increasing pH, from 7% at pH 4.7 to 0% at pH 6.9. It appears as if nitrate is much more sensitive to the presence of added species, perhaps not competing as well for binding sites on the FeS surface. This may be the cause of the lack of reproducibility of nitrate reduction by Fe+2 (which also can be sensitive to binding by certain species).

Summers, David P.↗

Ammonia-Assisted Light Alkane Anti-coke Reforming on Isolated ReO x Sites in Zeolite

The conventional reforming produces H 2 with stoichiometric amounts of CO and CO 2 from hydrocarbons. Here, we show that CO x -free H 2 can be produced from ammonia-assisted reforming (ammoreforming) of natural gas liquids (C n H 2n+2 + nNH 3 = nHCN + (2n + 1) H 2 , n = 2 or 3) at the same conditions as the steam reforming. Such a process co-produces HCN, which can be easily separated from H 2 and used as value-added chemicals or for NH 3 recycling through hydrolysis. In addition, the ammoreforming of ethane and propane was realized over the Re-modified HZSM-5 zeolite rather than the traditional Pt-based catalyst for the BMA process (methane ammoreforming). The specific activity of the Re/HZSM-5 catalysts at 650 °C is up to 1 mol H2 /g Re /min (or 180 min –1 ) during ethane ammoreforming. The catalyst is highly coke resistant and shows only slight deactivation with a time-on-stream up to 20 h. Characterization of the fresh and used catalysts by X-ray absorption and Raman spectroscopies suggested that the isolated ReO x site grafted by AlO 4 – tetrahedral in the zeolite framework is responsible for the outstanding catalytic activity and coke resistibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vibrational predissociation and vibrationally induced isomerization of 3-aminophenol-ammonia

We investigate the vibrational predissociation dynamics of the hydrogen-bonded 3-aminophenol-ammonia cluster (3-AP-NH{sub 3}) in the OH and NH stretching regions. Vibrational excitation provides enough energy to dissociate the cluster into its constituent 3-AP and NH{sub 3} monomers, and we detect the 3-AP fragments via (1 + 1) resonance-enhanced multiphoton ionization (REMPI). The distribution of vibrational states of the 3-AP fragment suggests the presence of two distinct dissociation pathways. The first dissociation channel produces a broad, unstructured feature in the REMPI-action spectrum after excitation of any of the OH or NH stretching vibrations, pointing to a nearly statistical dissociation pathway with extensive coupling among the vibrations in the cluster during the vibrational predissociation. The second dissociation channel produces distinct, resolved features on top of the broad feature but only following excitation of the OH or symmetric NH{sub 3} stretch in the cluster. This striking mode-specificity is consistent with strong coupling of these two modes to the dissociation coordinate (the O–H⋯N bond). The presence of clearly resolved transitions to the electronic origin and to the 10a{sup 2} + 10b{sup 2} state of the cis-3-AP isomer shows that vibrational excitation is driving the isomerization of the trans-3-AP-NH{sub 3} isomer to the cis-3-AP-NH{sub 3} isomer in the course of the dissociation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tall Tower Vertical Profiles and Diurnal Trends of Ammonia in the Colorado Front Range: Tall Tower Vertical Profiles of Ammonia

Ammonia (NH 3 ) mixing ratios were measured between the surface and 280 m aboveground level from a moveable carriage at the Boulder Atmospheric Observatory tower in summer 2014 as part of the Front Range Air Pollution and Photochemistry Éxperiment. The campaign median mixing ratio was 3.3 ppb, ranging from below detection limits to 192 ppb. Median vertical profiles show an overall increase in NH 3 mixing ratios toward the surface of 6.7 ppb (89%) during the day and 3.9 ppb (141%) at night. In contrast to the overall increasing trend, some individual profiles show decreasing NH 3 in the lowest 10 m. This suggests that the local surface is capable of acting as either a source or a sink, depending on the relative amounts of NH 3 at the surface, and in advected air parcels. We further use this data set to investigate the variation in diurnal patterns of NH 3 as a function of height above the surface. At higher altitudes (100 ± 5 and 280 ± 5 m), NH 3 mixing ratios reach a gradual maximum during the day between 9:00 and 16:00 local time, likely driven by changes in source region. At lower altitudes (10 ± 5 m), the daytime maximum begins earlier at about 7:00 local time, followed by a sharper increase at 9:00 local time. At this height we also observe a peak in NH3 mixing ratios during the night, likely driven by the trapping of emitted NH 3 within the shallower nocturnal boundary layer.

54 ENVIRONMENTAL SCIENCES↗

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Putting chromium on the map for N 2 reduction: production of hydrazine and ammonia. A study of cis -M(N 2 ) 2 (M = Cr, Mo, W) bis(diphosphine) complexes

The first complete structurally and spectroscopically characterized series of isostructural Group 6 N 2 complexes is reported in this paper. Protonolysis experiments on cis-[M(N 2 ) 2 (P Et N R P Et ) 2 ] (M = Cr, Mo, W; R = 2,6-difluorobenzyl) reveal that only Cr affords N 2 H 5 + and NH 4 + from the reduction of the N 2 ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗