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To provide guidelines to accelerate the Haber–Bosch (HB) process for synthesis of ammonia from hydrogen and nitrogen, we used Quantum Mechanics (QM) to determine the reaction mechanism and free energy reaction barriers under experimental reaction conditions (400 °C and 20 atm) for all 10 important surface reactions on the Fe(211)R surface.
A membrane-free electrochemical cell provides a green and economic way of lithium deposition and its utilization for lithium-mediated ammonia synthesis.
Perovskite oxyhydrides such as BaTiO 2.5 H 0.5 have been found to be able to catalyze NH3 synthesis, but the mechanism and the role of the catalyst's lattice hydrides in the catalytic reaction remain unknown. Here we employ first principles density functional theory to investigate the mechanism of ammonia synthesis and the role of lattice hydrides on a prototypical perovskite oxyhydride, BaTiO 2.5 H 0.5 (BTOH). Two mechanistic hypotheses, the distal and alternating pathways, have been tested on the Ti2O 2 termination of the BTOH (210) surface, previously determined to be the most stable surface termination under the reaction conditions considered. In the distal pathway, H atoms hydrogenate N 2 to form the *N–NH x key intermediates, followed by N–N bond breaking. In the alternating pathway, H atoms hydrogenate N 2 in an alternating fashion to form the *NH x –NH y intermediates before N–N bond breaking and formation of co-adsorbed *NH x /*NH y on the surface. We find that the subsurface hydride vacancy formed after reaction of *N 2 with the lattice hydride is key to the distal pathway, leading to surface nitride formation after breaking the *N–NH 3 bond, while the neighboring surface Ti sites are key to bridging and stabilizing the *NNH intermediate in the alternating pathway. In both pathways, desorption of NH 3 is the most uphill in energy. Our results provide important insights into the role of hydrides and surface vacancies in hydrogenation reactions over BTOH, which will be useful to guide future spectroscopic experiments such as operando IR and inelastic neutron scattering to verify the key intermediates.
To understand the exceptional adsorption of ammonia (NH 3 ) in MFM-300(Sc) (19.5 mmol g -1 at 273 K and 1 bar without hysteresis), we report a systematic investigation of the mechanism of adsorption by a combination of in situ neutron powder diffraction, inelastic neutron scattering, synchrotron infrared microspectroscopy, and solid-state 45 Sc NMR spectroscopy. These complementary techniques reveal the formation of reversible host–guest supramolecular interactions, which explains directly the observed excellent reversibility of this material over 90 adsorption–desorption cycles.
Rapid development of new ammonia (NH 3 ) synthesis techniques that enable modular, intermittent production is essential to actualizing NH 3 's potential as a clean energy carrier, since contemporary methods are configured to centralized, continuous production methods with high emissions and are incompatible with renewable sources. Here, in this mission, microwave-driven catalysis is promising for its ability to enhance reaction kinetics and apply targeted heating for efficient energy use. However, owing to an incomplete understanding of the interaction between microwave fields and catalyst beds, the development of such microwave-catalysis systems remains underexplored and challenging. This paper investigates the 10× scale-up of a microwave-based NH 3 synthesis reactor using numerical and experimental approaches, achieving the largest reported microwave-driven NH 3 reactor to date. Results elucidate phenomena unique to microwave processes that are only predictable through numerical modeling, including how a catalyst's dielectric properties influence microwave field distribution by affecting penetration depth and how energy utilization can be poor even with sufficient attenuation. These dynamics change with scale, constrain reactor geometry, and potentially hamper performance. Nonetheless, we demonstrate a production rate of 56.6 g NH$_3$ per day, the highest reported NH 3 synthesis rate for laboratory-scale alternative techniques; correspondingly, the benchmark energy efficiency achieved in this paper (45.6 g NH$_3$ kW h -1 ) is the highest reported for such reactors of sufficient scale. Even with this exemplary energy efficiency, energy losses were found in excess of 50%, an issue resolvable through scale and reactor design. The efficiencies imparted by microwaves were key in these achievements, warranting further investigation toward development of microwave-driven NH 3 systems.
Electrocatalytic nitrate reduction to ammonia offers a sustainable approach for nitrogenous waste upcycling. This review outlines recent advances in the design of electrocatalysts through cross-scale structural engineering.
2D SnO 2 nanosheets based chemiresistive sensor with microporosity and oxygen rich-surface detects ammonia at room temperature in extreme humidity at ppb levels for breath based early disease diagnostics and healthcare.
Active learning based on literature and experimental data enabled the discovery of highly active novel catalysts for ammonia synthesis. Pathway analysis implies that these activities have been achieved by both structural and electronic promotion.
To improve the confinement of two-dimensional electron gas (2DEG) in AlGaN/GaN high electron mobility transistor (HEMT) heterostructures, AlGaN/GaN/AlGaN double heterojunction HEMT (DH-HEMT) heterostructures were grown using ammonia-MBE on 100-mm Si substrate. Prior to the growth, single heterojunction HEMT (SH-HEMT) and DH-HEMT heterostructures were simulated using Poisson-Schrödinger equations. From simulations, an AlGaN buffer with “Al” mole fraction of 10% in the DH-HEMT was identified to result in both higher 2DEG concentration (∼10{sup 13 }cm{sup −2}) and improved 2DEG confinement in the channel. Hence, this composition was considered for the growth of the buffer in the DH-HEMT heterostructure. Hall measurements showed a room temperature 2DEG mobility of 1510 cm{sup 2}/V.s and a sheet carrier concentration (n{sub s}) of 0.97 × 10{sup 13 }cm{sup −2} for the DH-HEMT structure, while they are 1310 cm{sup 2}/V.s and 1.09 × 10{sup 13 }cm{sup −2}, respectively, for the SH-HEMT. Capacitance-voltage measurements confirmed the improvement in the confinement of 2DEG in the DH-HEMT heterostructure, which helped in the enhancement of its room temperature mobility. DH-HEMT showed 3 times higher buffer break-down voltage compared to SH-HEMT, while both devices showed almost similar drain current density. Small signal RF measurements on the DH-HEMT showed a unity current-gain cut-off frequency (f{sub T}) and maximum oscillation frequency (f{sub max}) of 22 and 25 GHz, respectively. Thus, overall, DH-HEMT heterostructure was found to be advantageous due to its higher buffer break-down voltages compared to SH-HEMT heterostructure.
Here, we report a NH{sub 3} and Volatile Organic Compounds (VOCs) sensing prototype of CuO nanorods with peculiar sensing characteristics at room temperature. High quality polycrystalline nanorods were synthesized by a low temperature hydrothermal method. The rods are well oriented with an aspect ratio of 5.71. Luminescence spectrum of CuO nanorods exhibited a strong UV-emission around 415 nm (2.98 eV) which arises from the electron-hole recombination phenomenon. The absence of further deep level emissions establishes the lack of defects such as oxygen vacancies and Cu interstitials. At room temperature, the sensor response was recorded over a range of gas concentrations from 100-600 ppm of ammonia, ethanol and methanol. The sensor response showed power law dependence with the gas concentration. This low temperature sensing can be validated by the lower value of calculated activation energy of 1.65 eV observed from the temperature dependent conductivity measurement.
We report that about 40% of our food would not exist without synthetic ammonia (NH 3 ) for fertilization. Yet, NH 3 production is energy intensive. About 2% of the world's commercial energy is consumed as fossil fuels for NH 3 synthesis based on the century-old Haber-Bosch (H.-B.) process. The state of the art and the opportunities for reducing the fossil energy footprint of industrial H.-B. NH 3 synthesis are discussed. It is shown that even a hypothetical utterly revolutionary H.-B. catalyst could not significantly reduce the energy demand of H.-B. NH 3 as this is governed by hydrogen production. Renewable energy-enabled, fossil-free NH 3 synthesis is then evaluated based on the exceptional and continuing cost decline of renewable electricity. H.-B. syngas (H 2 , N 2 ) is assumed to be produced by electrolysis and cryogenic air separation and then supplied to an existing H.-B. synthesis loop. Fossil-free NH 3 could be produced for energy costs of about $232 per tonne NH 3 without claiming any economic benefits for the avoidance of about 1.5 tonnes of CO 2 released per tonne NH 3 compared to the most efficient H.-B. implementations. Research into alternatives to the H.-B. process might be best targeted at emerging markets with currently little NH 3 synthesis capacity but significant future population growth in markets such as Africa. Reduced capital intensity, good scale-down economics, tolerance for process upsets and contamination, and intermittent operability are some desirable characteristics of NH 3 synthesis in less developed markets and for stranded resources. Lastly, processes that are fundamentally different from H.-B. may come to the fore under these specific boundary conditions.
Combining ammonia fiber expansion (AFEX™) pretreatment with a depot processing facility is a promising option for delivering high-value densified biomass to the emerging bioenergy industry. However, because the pretreatment process results in a high moisture material unsuitable for pelleting or storage (40% wet basis), the biomass must be immediately dried. If AFEX pretreatment results in a material that is difficult to dry, the economics of this already costly operation would be at risk. This work tests the nature of moisture sorption isotherms and thin-layer drying behavior of corn (Zea mays L.) stover at 20°C to 60°C before and after sequential AFEX pretreatment and pelletization to determine whether any negative impacts to material drying or storage may result from the AFEX process. The equilibrium moisture content to equilibrium relative humidity relationship for each of the materials was determined using dynamic vapor sorption isotherms and modeled with modified Chung-Pfost, modified Halsey, and modified Henderson temperature-dependent models as well as the Double Log Polynomial (DLP), Peleg, and Guggenheim Anderson de Boer (GAB) temperature-independent models. Drying kinetics were quantified under thin-layer laboratory testing and modeled using the Modified Page's equation. Water activity isotherms for non-pelleted biomass were best modeled with the Peleg temperature-independent equation while isotherms for the pelleted biomass were best modeled with the Double Log Polynomial equation. Thin-layer drying results were accurately modeled with the Modified Page's equation. The results of this work indicate that AFEX pretreatment results in drying properties more favorable than or equal to that of raw corn stover, and pellets of superior physical stability in storage.
Pretreatment and densification of biomass can increase the viability of bioenergy production by providing a feedstock that is readily hydrolyzed and able to be transported greater distances. Ammonia Fiber Expansion (AFEX) is one such method targeted for use at distributed depots to create a value-added and densified feedstock for bioenergy use. However, the pretreatment process results in a high-moisture material that must be dried, further size reduced, and pelletized; all of which are energy intensive processes. This work quantifies the energy consumption required to dry, grind, and densify AFEX pretreated corn stover compared to non-pretreated stover and explores the potential of reduced drying as a means to conserve energy. The purpose of this work is to understand whether material property changes resulting from AFEX pretreatment influence the material performance in downstream formatting operations. Material properties, heat balance equations, and a rotary drum dryer model were used to model a commercial scale rotary drum dryer for AFEX pretreated corn stover, showing the potential to reduce dryer energy consumption by up to 36% compared to non-pretreated corn stover. Laboratory measured grinding and pelleting energies were both very sensitive to material moisture content. Overall, the total energy required for drying, grinding, and pelleting amounts to a savings of up to 20 kWh/dry ton for the AFEX pretreated material when dried to a low moisture content, equating to up to 0.55 /kg savings for gas and electricity. Grinding and pelleting of high moisture AFEX pretreated stover was shown to be more costly than the savings collected through reduced drying. Furthermore, while the energy and cost savings shown here are modest, the results help to highlight operational challenges and opportunities for continued improvement.
We present deep NH{sub 3} observations of the L1495-B218 filaments in the Taurus molecular cloud covering over a 3° angular range using the K-band focal plane array on the 100 m Green Bank Telescope. The L1495-B218 filaments form an interconnected, nearby, large complex extending over 8 pc. We observed NH{sub 3} (1, 1) and (2, 2) with a spectral resolution of 0.038 km s{sup −1} and a spatial resolution of 31″. Most of the ammonia peaks coincide with intensity peaks in dust continuum maps at 350 and 500 μm. We deduced physical properties by fitting a model to the observed spectra. We find gas kinetic temperatures of 8–15 K, velocity dispersions of 0.05–0.25 km s{sup −1}, and NH{sub 3} column densities of 5 × 10{sup 12} to 1 × 10{sup 14} cm{sup −2}. The CSAR algorithm, which is a hybrid of seeded-watershed and binary dendrogram algorithms, identifies a total of 55 NH{sub 3} structures, including 39 leaves and 16 branches. The masses of the NH{sub 3} sources range from 0.05 to 9.5 M{sub ⊙}. The masses of NH{sub 3} leaves are mostly smaller than their corresponding virial mass estimated from their internal and gravitational energies, which suggests that these leaves are gravitationally unbound structures. Nine out of 39 NH{sub 3} leaves are gravitationally bound, and seven out of nine gravitationally bound NH{sub 3} leaves are associated with star formation. We also found that 12 out of 30 gravitationally unbound leaves are pressure confined. Our data suggest that a dense core may form as a pressure-confined structure, evolve to a gravitationally bound core, and undergo collapse to form a protostar.
When non-equilibrium, low-temperature plasmas and catalysts interact, they can exhibit synergistic behavior that enhances the chemical activity above what is possible with either process alone. Unlike thermal catalysis, in plasma-assisted catalysis the non-equilibrium state of the plasma produces reactive intermediates, such as excited species, that may play an important role in the catalytic process. There are two primary plasma-surface mechanisms that could produce this synergy: the effect of the plasma on the catalyst (e.g. enhanced adsorption/reaction of plasma-activated species, change of surface structure/morphology, hot spots, etc) and the effect of the catalyst on the plasma state. This work focuses on the latter. We use a laboratory-scale, packed bed, dielectric barrier discharge (DBD) reactor to observe the influence of multiple alumina (Al 2 O 3 3 ) synthesis catalysts on the plasma electrical and optical properties. We find that while the rates of ammonia synthesis over the materials considered, including Fe/Al 2 O 3 , Ni/Al 2 O 3 , and Co/Al 2 O 3 , are different, the macroscopic properties of the DBD are statistically indistinguishable. These results support the argument that the observed synergy in our catalysis experiments is not due to the catalyst modifying the characteristics of the plasma itself, but rather arises from differences in how the plasma environment and plasma-generated species modify chemistry at the catalyst surface, although the specific mechanism is still an outstanding question.
The war in Ukraine caused Europe to more than double its imports of liquefied natural gas (LNG) in only one year. In addition, imported LNG remains a crucial source of energy for resource-poor countries, such as Japan, where LNG imports satisfy about a quarter of the country's primary energy demand. However, an increasing number of countries are formulating stringent decarbonization plans. Liquefied hydrogen and liquefied ammonia coupled with carbon capture and storage (LH 2 -CCS, LNH 3 -CCS) are emerging as the front runners in the search for low-carbon alternatives to LNG. Yet, little is currently known about the full environmental profile of LH 2 -CCS and LNH 3 -CCS because several characteristics of the two alternatives have only been analyzed in isolation in previous work. Here we show that the potential of these fuels to reduce greenhouse gas (GHG) emissions throughout the supply chain is highly uncertain. Our best estimate is that LH 2 -CCS and LNH 3 -CCS can reduce GHG emissions by 25%–61% relative to LNG assuming a 100 year global warming potential. However, directly coupling LNG with CCS would lead to substantial GHG reductions on the order of 74%. Further, under certain conditions, emissions from LH 2 -CCS and LNH 3 -CCS could exceed those of LNG, by up to 44%. These results question the suitability of LH 2 -CCS and LNH 3 -CCS for stringent decarbonization purposes.
ABSTRACT Understanding the chemical processes during starless core and prestellar core evolution is an important step in understanding the initial stages of star and disc formation. This project is a study of deuterated ammonia, o-NH2D, in the L1251 star-forming region towards Cepheus. Twenty-two dense cores (20 of which are starless or prestellar, and two of which have a protostar), previously identified by p-NH3 (1,1) observations, were targeted with the 12m Arizona Radio Observatory telescope on Kitt Peak. o-NH2D J$_{\rm {K_a} \rm {K_c}}^{\pm } =$$1_{11}^{+} \rightarrow 1_{01}^{-}$ was detected in 13 (59 per cent) of the NH3-detected cores with a median sensitivity of $\sigma _{T_{mb}} = 17$ mK. All cores detected in o-NH2D at this sensitivity have p-NH3 column densities >1014 cm−2. The o-NH2D column densities were calculated using the constant excitation temperature (CTEX) approximation while correcting for the filling fraction of the NH3 source size. The median deuterium fraction was found to be 0.11 (including 3σ upper limits). However, there are no strong, discernible trends in plots of deuterium fraction with any physical or evolutionary variables. If the cores in L1251 have similar initial chemical conditions, then this result is evidence of the cores physically evolving at different rates.
We present that ab initio theoretical studies and momentum-imaging experiments are combined to provide a consistent picture of the dynamics of dissociative electron attachment to ammonia through its 5.5- and 10.5-eV resonance channels. The present study clarifies the character and symmetry of the anion states involved and the dynamics that leads to the observed fragment-ion channels, their branching ratios, and angular distributions.