Heterogeneous Electrochemical Ammonia Oxidation with a Ru-bda Oligomer Anchored on Graphitic Electrodes via CH−π Interactions
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Results for “AMMONIA”
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Air Quality Implications of Using Ammonia as a Renewable Fuel: How Low Can NO x Emissions Go?
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Real-Time Ammonia and Humidity Monitoring with Ultra-Fast Conductometric Sensors Based on Porphyrin and Phthalocyanine Complexes
Organic semiconductors like porphyrins and phthalocyanines are attracting a wide range of researchers due to their versatile electrical properties and sensing performances in conductometric sensors. In this study, we investigate two types of π-extended porphyrins, which share the same macrocyclic structure but differ in their central metal. These porphyrins are employed as sublayers in bilayer heterojunction devices, with the lutetium bisphthalocyanine complex, LuPc 2 , serving as the common top layer. Remarkably, the central metal in the porphyrin macrocycle significantly influences the solubility of the materials and, consequently, the surface topography of the resulting bilayer heterojunction devices. This structural variation translates into distinct electrical and sensing performances. The device incorporating nickel as metal centre (AM2) demonstrates superior sensitivity towards NH3, with a relative response (RR) of ca. -7% at 90 ppm, an ultra-fast response time of about 9 s, and an impressive limit of detection (LOD) of 250 ppb, whereas, the device that has zinc as metal centre in sublayer (AM3) exhibits RR value of ca. -0.9% at 90 ppm with t 90 of ca. 120 s and LOD of 2 ppm. Both devices are evaluated under randomly varying NH 3 concentration and RH value. The results shows that the AM2-based sensor allows following NH 3 in real-time, while the AM3-based sensor delivers an average concentration over time. On the other hand, the AM2-based sensor exhibits slow kinetics under RH exposure, while the AM3-based sensor precisely mirrors the pattern of random RH changes generated by the software, demonstrating its exceptional responsiveness and accuracy in tracking humidity fluctuations. In conclusion, these findings underscore the critical role of the metal centre in tuning the electrical and sensing properties of the heterojunction devices.
99 GENERAL AND MISCELLANEOUS↗
Titanium-, Nitrogen-Doped Carbon Flowers Catalyze Electrochemical Nitrate Reduction Reaction to Ammonia
An emerging design heuristic for electrochemical nitrate reduction (NO 3 RR) catalysts is synthesizing electron-deficient sites to facilitate binding of electron-rich NO 3 – . However, this rule has rarely been applied to metal-, nitrogen-doped carbon (MNC) catalysts. Titanium (Ti), with low electronegativity and high NO 3 RR reactivity, is a compelling MNC candidate. To date, atomically dispersed TiN x motifs have eluded synthesis due to the strong oxophilicity of Ti. Here, in this work, we leverage nitrogen-rich carbon flowers (CF) to overcome synthetic challenges and produce Ti-, N-doped carbon flower (TiCF) catalysts. Advanced materials characterization demonstrates that TiCF catalysts are a mixed phase material with 3/4 of Ti atoms in TiO 2 -like nanoparticles and 1/4 of Ti atoms in novel, atomically dispersed TiN x sites. TiCF achieves 61 ± 7% NH 3 -selectivity at −0.70 V vs RHE and 14 ± 5 mA/cm 2 to NH 3 formation (| j NH 3 |) at −0.85 V vs RHE in (0.1 M NaOH + 0.1 M NaNO 3 + 0.45 M Na 2 SO 4 ) electrolyte. Control studies show both CF morphology and Ti sites are essential for high NO 3 RR activity. Density functional theory calculations attribute the NO3RR reactivity to TiN x , which facilitates multiple bond formation with surface intermediates to promote favorable NH3 synthesis pathways. Thus, TiCF exhibits 60× higher | j NH 3 | values than bulk Ti and NH 3 yield rates (>0.06 mmol NH 3 /h/cm 2 ) that are competitive with state-of-the-art MNC catalysts (e.g., FeNC, CuNC). TiCF introduces a new class of Ti electrocatalysts, advancing the MNC design space and sustainable NH 3 production.
ammonia↗
Ammonia formation from NO reaction with surface hydroxyls on rutile TiO2 (110) - 1×1
The reaction of NO with hydroxylated rutile TiO2(110)-1×1 surface (h-TiO2) was investigated as a function of NO coverage using temperature-programmed desorption. Our results show that NO reaction with h-TiO2 leads to formation of NH3 which is observed to desorb at ~ 400 K. Interestingly, the amount of NH3 produced depends nonlinearly on the coverage of NO. The yield increases up to a saturation value of ~1.3×1013 NH3/cm2 at a NO dose of 5×1013 NO/cm2, but subsequently decreases at higher NO doses. Preadsorbed H2O is found to have a negligible effect on the NH3 desorption yield. Additionally, no NH3 is formed in the absence of surface hydroxyls (HOb’s) upon coadsorption of NO and H2O on a stoichiometric TiO2(110) (s-TiO2(110)). Based on these observations, we conclude that nitrogen from NO has a strong preference to react with HOb’s on the bridge-bonded oxygen rows (but not with H2O) to form NH3. The absolute NH3 yield is limited by competing reactions of HOb species with titanium-bound oxygen adatoms to form H2O. Our results provide new mechanistic insight about the interactions of NO with hydroxyl groups on TiO2(110) .
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Proton irradiation effects on deep level states in Mg-doped p-type GaN grown by ammonia-based molecular beam epitaxy
The impact of proton irradiation on the deep level states throughout the Mg-doped p-type GaN bandgap is investigated using deep level transient and optical spectroscopies. Exposure to 1.8 MeV protons of 1 × 10{sup 13 }cm{sup −2} and 3 × 10{sup 13 }cm{sup −2} fluences not only introduces a trap with an E{sub V} + 1.02 eV activation energy but also brings monotonic increases in concentration for as-grown deep states at E{sub V} + 0.48 eV, E{sub V} + 2.42 eV, E{sub V} + 3.00 eV, and E{sub V} + 3.28 eV. The non-uniform sensitivities for individual states suggest different physical sources and/or defect generation mechanisms. Comparing with prior theoretical calculations reveals that several traps are consistent with associations to nitrogen vacancy, nitrogen interstitial, and gallium vacancy origins, and thus are likely generated through displacing nitrogen and gallium atoms from the crystal lattice in proton irradiation environment.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Communication: On the competition between adiabatic and nonadiabatic dynamics in vibrationally mediated ammonia photodissociation in its A band
Non-adiabatic processes play an important role in photochemistry, but the mechanism for conversion of electronic energy to chemical energy is still poorly understood. To explore the possibility of vibrational control of non-adiabatic dynamics in a prototypical photoreaction, namely, the A-band photodissociation of NH{sub 3}(X{sup ~1}A{sub 1}), full-dimensional state-to-state quantum dynamics of symmetric or antisymmetric stretch excited NH{sub 3}(X{sup ~1}A{sub 1}) is investigated on recently developed coupled diabatic potential energy surfaces. The experimentally observed H atom kinetic energy distributions are reproduced. However, contrary to previous inferences, the NH{sub 2}(A{sup ~2}A{sub 1})/NH{sub 2}(X{sup ~2}B{sub 1}) branching ratio is found to be small regardless of the initial preparation of NH{sub 3}(X{sup ~1}A{sub 1}), while the internal state distribution of the preeminent fragment, NH{sub 2}(X{sup ~2}B{sub 1}), is found to depend strongly on the initial vibrational excitation of NH{sub 3}(X{sup ~1}A{sub 1}). The slow H atoms in photodissociation mediated by the antisymmetric stretch fundamental state are due to energy sequestered in the internally excited NH{sub 2}(X{sup ~2}B{sub 1}) fragment, rather than in NH{sub 2}(A{sup ~2}A{sub 1}) as previously proposed. The high internal excitation of the NH{sub 2}(X{sup ~2}B{sub 1}) fragment is attributed to the torques exerted on the molecule as it passes through the conical intersection seam to the ground electronic state of NH{sub 3}. Thus in this system, contrary to previous assertions, the control of electronic state branching by selective excitation of ground state vibrational modes is concluded to be ineffective. The juxtaposition of precise quantum mechanical results with complementary results based on quasi-classical surface hopping trajectories provides significant insights into the non-adiabatic process.
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A monomeric complex of ammonia and cuprous chloride: H{sub 3}N⋯CuCl isolated and characterised by rotational spectroscopy and ab initio calculations
The H{sub 3}N⋯CuCl monomer has been generated and isolated in the gas phase through laser vaporisation of a copper sample in the presence of low concentrations of NH{sub 3} and CCl{sub 4} in argon. The resulting complex cools to a rotational temperature approaching 2 K during supersonic expansion of the gas sample and is characterised by broadband rotational spectroscopy between 7 and 18.5 GHz. The spectra of six isotopologues are measured and analysed to determine rotational, B{sub 0}; centrifugal distortion, D{sub J}, D{sub JK}; and nuclear quadrupole coupling constants of Cu, Cl, and {sup 14}N nuclei, χ{sub aa} (X). The geometry of the complex is C{sub 3v} with the N, Cu, and Cl atoms located on the a inertial axis. Bond distances and the ∠(H —N⋯Cu) bond angle within the complex are precisely evaluated through fitting of geometrical parameters to the experimentally determined moments of inertia and through ab initio calculations at the CCSD(T)(F12*)/AVQZ level. The r(Cu —Cl), r(Cu —N), and ∠(H —N⋯Cu) parameters are, respectively, evaluated to be 2.0614(7) Å, 1.9182(13) Å, and 111.40(6)° in the r{sub 0} geometry, in good agreement with the ab initio calculations. Geometrical parameters evaluated for the isolated complex are compared with those established crystallographically for a solid-state sample of [Cu(NH{sub 3})Cl].
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In-situ NC-AFM measurements of high quality AlN(0001) layers grown at low growth rate on 4H-SiC(0001) and Si(111) substrates using ammonia molecular beam epitaxy
Nitride wide-band-gap semiconductors are used to make high power electronic devices or efficient light sources. The performance of GaN-based devices is directly linked to the initial AlN buffer layer. During the last twenty years of research on nitride growth, only few information on the AlN surface quality have been obtained, mainly by ex-situ characterization techniques. Thanks to a Non Contact Atomic Force Microscope (NC-AFM) connected under ultra high vacuum (UHV) to a dedicated molecular beam epitaxy (MBE) chamber, the surface of AlN(0001) thin films grown on Si(111) and 4H-SiC(0001) substrates has been characterized. These experiments give access to a quantitative determination of the density of screw and edge dislocations at the surface. The layers were also characterized by ex-situ SEM to observe the largest defects such as relaxation dislocations and hillocks. The influence of the growth parameters (substrate temperature, growth speed, III/V ratio) and of the initial substrate preparation on the dislocation density was also investigated. On Si(111), the large in-plane lattice mismatch with AlN(0001) (19%) induces a high dislocation density ranging from 6 to 12×10{sup 10}/cm{sup 2} depending on the growth conditions. On 4H-SiC(0001) (1% mismatch with AlN(0001)), the dislocation density decreases to less than 10{sup 10}/cm{sup 2}, but hillocks appear, depending on the initial SiC(0001) reconstruction. The use of a very low growth rate of 10 nm/h at the beginning of the growth process allows to decrease the dislocation density below 2 × 10{sup 9}/cm{sup 2}.
36 MATERIALS SCIENCE↗
Study on GaN buffer leakage current in AlGaN/GaN high electron mobility transistor structures grown by ammonia-molecular beam epitaxy on 100-mm Si(111)
The effect of carbon doping on the structural and electrical properties of GaN buffer layer of AlGaN/GaN high electron mobility transistor (HEMT) structures has been studied. In the undoped HEMT structures, oxygen was identified as the dominant impurity using secondary ion mass spectroscopy and photoluminescence (PL) measurements. In addition, a notable parallel conduction channel was identified in the GaN buffer at the interface. The AlGaN/GaN HEMT structures with carbon doped GaN buffer using a CBr{sub 4} beam equivalent pressure of 1.86 × 10{sup −7} mTorr showed a reduction in the buffer leakage current by two orders of magnitude. Carbon doped GaN buffers also exhibited a slight increase in the crystalline tilt with some pits on the growth surface. PL and Raman measurements indicated only a partial compensation of donor states with carbon acceptors. However, AlGaN/GaN HEMT structures with carbon doped GaN buffer with 200 nm thick undoped GaN near the channel exhibited good 2DEG characteristics.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
The stereo-dynamics of collisional autoionization of ammonia by helium and neon metastable excited atoms through molecular beam experiments
A combined analysis of both new (energy spectra of emitted electrons) and previously published (ionization cross sections) experimental data, measured under the same conditions and concerning electronically excited lighter noble gas –NH{sub 3} collisional autoionization processes, is carried out. Such an analysis, performed by exploiting a formulation of the full potential energy surface both in the real and imaginary parts, provides direct information on energetics, structure, and lifetime of the intermediate collision complex over all the configuration space. The marked anisotropy in the attraction of the real part, driving the approach of reagents, and the selective role of the imaginary component, associated to the charge transfer coupling between entrance and exit channels, suggests that reactive events occur almost exclusively in the molecular hemisphere containing the nitrogen lone pair. Crucial details on the stereo-dynamics of elementary collisional autoionization processes are then obtained, in which the open shell nature of the disclosed ionic core of metastable atom plays a crucial role. The same analysis also suggests that the strength of the attraction and the anisotropy of the interaction increases regularly along the series Ne{sup *}({sup 3}P), He{sup *}({sup 3}S), He{sup *}({sup 1}S)–NH{sub 3}. These findings can be ascribed to the strong rise of the metastable atom electronic polarizability (deformability) along the series. The obtained results can stimulate state of the art ab initio calculations focused on specific features of the transition state (energetics, structure, lifetime, etc.) which can be crucial for a further improvement of the adopted treatment and to better understand the nature of the leading interaction components which are the same responsible for the formation of the intermolecular halogen and hydrogen bond.
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Traveling interface modulations and anisotropic front propagation in ammonia oxidation over Rh(110)
The bistable NH{sub 3} + O{sub 2} reaction over a Rh(110) surface was explored in the pressure range 10{sup −6}–10{sup −3} mbar and in the temperature range 300–900 K using photoemission electron microscopy and low energy electron microscopy as spatially resolving methods. We observed a history dependent anisotropy in front propagation, traveling interface modulations, transitions with secondary reaction fronts, and stationary island structures.
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A nitride-based epitaxial surface layer formed by ammonia treatment of silicene-terminated ZrB{sub 2}
We present a method for the formation of an epitaxial surface layer involving B, N, and Si atoms on a ZrB{sub 2}(0001) thin film on Si(111). It has the potential to be an insulating growth template for 2D semiconductors. The chemical reaction of NH{sub 3} molecules with the silicene-terminated ZrB{sub 2} surface was characterized by synchrotron-based, high-resolution core-level photoelectron spectroscopy and low-energy electron diffraction. In particular, the dissociative chemisorption of NH{sub 3} at 400 °C leads to surface nitridation, and subsequent annealing up to 830 °C results in a solid phase reaction with the ZrB{sub 2} subsurface layers. In this way, a new nitride-based epitaxial surface layer is formed with hexagonal symmetry and a single in-plane crystal orientation.
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Shockwave compression and dissociation of ammonia gas
We performed a series of plate impact experiments on NH 3 gas initially at room temperature and at a pressure of ~100 psi. Shocked states were determined by optical velocimetry and the temperatures by optical pyrometry, yielding compression ratios of ~5–10 and second shock temperatures in excess of 7500 K. A first-principles statistical mechanical (thermochemical) approach that included chemical dissociation yielded reasonable agreement with experimental results on the principal Hugoniot, even with interparticle interactions neglected. Theoretical analysis of reshocked states, which predicts a significant degree of chemical dissociation, showed reasonable agreement with experimental data for higher temperature shots; however, reshock calculations required the use of interaction potentials. Here, we rationalize the very different shock temperatures obtained, relative to previous results for argon, in terms of atomic versus molecular heat capacities.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Stimulated emission of AlGaN layers grown on sapphire substrates using ammonia molecular beam epitaxy
By optimising the growth temperature of the AlGaN layers and using high-temperature AlN buffer layers, high-quality Al{sub x}Ga{sub 1 – x}N layers (x = 0.15, 0.21, 0.26, and 0.3) were obtained, in which stimulated emission in the UV spectral range 330 – 297 nm was implemented with the threshold intensity of excitation I{sub th} ≈ 0.7 – 1.4 MW cm{sup −2}, respectively. It is found that the threshold value of the stimulated emission of AlGaN layers grown by molecular beam epitaxy is largely determined by the intensity of the process of thermal decomposition of GaN, which affects the surface morphology and, consequently, the amount of optical scattering loss. It is shown that no pronounced localisation of nonequilibrium charge carriers occurs in the AlGaN layers, which is manifested in the absence of a large Stokes shift and in the realisation of optical amplification at transitions in an electron-hole plasma, and also indicates a relatively homogeneous material composition. (paper)
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Thermal starless ammonia core surrounded by CCS in the Orion a cloud
We imaged two starless molecular cloud cores, TUKH083 and TUKH122, in the Orion A giant molecular cloud in the CCS and NH{sub 3} emission with the Very Large Array. TUKH122 contains one NH{sub 3} core 'TUKH122-n', which is elongated and has a smooth oval boundary. Where observed, the CCS emission surrounds the NH{sub 3} core. This configuration resembles that of the N{sub 2}H{sup +} and CCS distribution in the Taurus starless core L1544, a well-studied example of a dense prestellar core exhibiting infall motions. The linewidth of TUKH122-n is narrow (0.20 km s{sup –1}) in the NH{sub 3} emission line and therefore dominated by thermal motions. The smooth oval shape of the core boundary and narrow linewidth in N{sub 2}H{sup +} seem to imply that TUKH122-n is dynamically relaxed and quiescent. TUKH122-n is similar to L1544 in the kinetic temperature (10 K), linear size (0.03 pc), and virial mass (∼2 M {sub ☉}). Our results strongly suggest that TUKH122-n is on the verge of star formation. TUKH122-n is embedded in the 0.2 pc massive (virial mass ∼30 M {sub ☉}) turbulent parent core, while the L1544 NH{sub 3} core is embedded in the 0.2 pc less-massive (virial mass ∼10 M {sub ☉}) thermal parent core. TUKH083 shows complicated distribution in NH{sub 3}, but was not detected in CCS. The CCS emission toward TUKH083 appears to be extended, and is resolved out in our interferometric observations.
79 ASTRONOMY AND ASTROPHYSICS↗
Very large array observations of ammonia in high-mass star formation regions
We report systematic mapping observations of the NH{sub 3} (1, 1) and (2, 2) inversion lines toward 62 high-mass star-forming regions using the Very Large Array (VLA) in its D and DnC array configurations. The VLA images cover a spatial dynamic range from 40'' to 3'', allowing us to trace gas kinematics from ∼1 pc scales to ≲0.1 pc scales. Based on the NH{sub 3} morphology and the infrared nebulosity on 1 pc scales, we categorize three subclasses in the sample: filaments, hot cores, and NH{sub 3}-dispersed sources. The ubiquitous gas filaments found on 1 pc scales have a typical width of ∼0.1 pc and often contain regularly spaced fragments along the major axis. The spacing of the fragments and the column densities is consistent with the turbulent supported fragmentation of cylinders. Several sources show multiple filaments that converge toward a center where the velocity field in the filaments is consistent with gas flows. We derive rotational temperature maps for the entire sample. For the three hot core sources, we find a projected radial temperature distribution that is best fit by power-law indices from –0.18 to –0.35. We identify 174 velocity-coherent ∼0.1 pc scale dense cores from the entire sample. The mean physical properties for these cores are 1.1 km s{sup –1} in intrinsic linewidth, 18 K in NH{sub 3} rotational temperature, 2.3 × 10{sup 15} cm{sup –2} in NH{sub 3} gas column density, and 67 M{sub ☉} in molecular mass. The dense cores identified from the filamentary sources are closer to being virialized. Dense cores in the other two categories of sources appear to be dynamically unstable.
79 ASTRONOMY AND ASTROPHYSICS↗
NEAR-INFRARED PHOTOMETRY OF Y DWARFS: LOW AMMONIA ABUNDANCE AND THE ONSET OF WATER CLOUDS
We present new near-infrared photometry for seven late-type T dwarfs and nine Y-type dwarfs, and lower limit magnitudes for a tenth Y dwarf, obtained at Gemini Observatory. We also present a reanalysis of H-band imaging data from the Keck Observatory Archive, for an 11th Y dwarf. These data are combined with earlier MKO-system photometry, Spitzer and WISE mid-infrared photometry, and available trigonometric parallaxes, to create a sample of late-type brown dwarfs that includes 10 T9-T9.5 dwarfs or dwarf systems, and 16 Y dwarfs. We compare the data to our models, which include updated H{sub 2} and NH{sub 3} opacity, as well as low-temperature condensate clouds. The models qualitatively reproduce the trends seen in the observed colors; however, there are discrepancies of around a factor of two in flux for the Y0-Y1 dwarfs, with T {sub eff} ≈ 350-400 K. At T {sub eff} ∼ 400 K, the problems could be addressed by significantly reducing the NH{sub 3} absorption, for example by halving the abundance of NH{sub 3} possibly by vertical mixing. At T {sub eff} ∼ 350 K, the discrepancy may be resolved by incorporating thick water clouds. The onset of these clouds might occur over a narrow range in T {sub eff}, as indicated by the observed small change in 5 μm flux over a large change in J – W2 color. Of the known Y dwarfs, the reddest in J –W2 are WISEP J182831.08+265037.8 and WISE J085510.83–071442.5. We interpret the former as a pair of identical 300-350 K dwarfs, and the latter as a 250 K dwarf. If these objects are ∼3 Gyr old, their masses are ∼10 and ∼5 Jupiter-masses, respectively.
79 ASTRONOMY AND ASTROPHYSICS↗