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Energy-Efficient Ammonia Production from Air and Water Using Electrocatalysts with Limited Faradaic Efficiency

Mechanisms of alloy degradation in a fireside N-S-O-C-H-Cl-Na-K atmosphere at 880 degrees C were elucidated using SEM-EDS, chemical equilibrium calculations, and XRD. Alloys 310S, 800H/HT, and 600 were studied after 0, 8000, and 16,000 h exposure in a boiler co-firing biomass waste. For 310S and 800H/HT it was shown that nitrogen formed internal Cr nitrides lowering the Cr activity and inhibiting internal alloy Cr permeation, and that NaCl and Na2SO4 reacted with Cr oxide to form chromate and to accelerate the S and the Cl pickup. Alloy 600 showed no nitride or major chromate formation. Bio4Energy

The dissociation process of hydrogen molecules on W(110) was studied using density functional theory and classical molecular dynamics. We have calculated the dissociation probability for molecules with energies below 300 meV and analyzed the dynamics of the adsorption process. Our results show that the fate of each trajectory is determined at distances relatively far from the surface, at roughly 2–2.5 Å. This distance varies slightly with the initial kinetic energy of the molecule. Part of our simulations include van der Waals dispersion effects in the interaction between molecule and surface. We present a comparison between these results and other theoretical and experimental results previously published. The inclusion of the van der Waals term provokes an increase in the far-distance attraction that is compensated by a stronger repulsion at short distances. The combination of both effects appreciably decreases the value of the dissociation probability. The successful comparison of our results with experimental information confirms that the methodology employed can be considered as a rich and accurate instrument to study the dissociation of hydrogen on surfaces., A. R. F. acknowledges financial support by the University of Bordeaux. This work was conducted in the scope of the transborder joint Laboratory “QuantumChemPhys: Theoretical Chemistry and Physics at the Quantum Scale” (ANR-10-IDEX-03-02). This work has been supported in part by the Basque Departamento de Educación, Universidades e Investigación, the University of the Basque Country UPV/EHU (Grant No. IT1246-19) and the Spanish Ministerio de Ciencia e Innovación (PID2019-107396GB-I00/AEI/10.13039/501100011033).

Nuclear and electronic dynamics in a wavepacket comprising bound Rydberg and valence electronic states of nitrogen from 12 to 15 eV are investigated using attosecond transient absorption. Vibrational quantum beats with a fundamental period of 50 femtoseconds persist for a picosecond in the b′ 1Σ+u valence state. Multi-state calculations show that these coherences result primarily from near infrared-induced coupling between the inner and outer regions of the b′ 1Σ+u state potential and the dark a″ 1Σ+g state. The excellent spectral and temporal resolution of this technique allows measurement of the anharmonicity of the b′ 1Σ+u potential directly from the observed quantum beats.

The electrochemical synthesis of ammonia from nitrogen under mild conditions using renewable electricity is an attractive alternative1–4 to the energy-intensive Haber–Bosch process, which dominates industrial ammonia production. However, there are considerable scientific and technical challenges5,6 facing the electrochemical alternative, and most experimental studies reported so far have achieved only low selectivities and conversions. The amount of ammonia produced is usually so small that it cannot be firmly attributed to electrochemical nitrogen fixation7–9 rather than contamination from ammonia that is either present in air, human breath or ion-conducting membranes9, or generated from labile nitrogen-containing compounds (for example, nitrates, amines, nitrites and nitrogen oxides) that are typically present in the nitrogen gas stream10, in the atmosphere or even in the catalyst itself. Although these sources of experimental artefacts are beginning to be recognized and managed11,12, concerted efforts to develop effective electrochemical nitrogen reduction processes would benefit from benchmarking protocols for the reaction and from a standardized set of control experiments designed to identify and then eliminate or quantify the sources of contamination. Here we propose a rigorous procedure using 15N2 that enables us to reliably detect and quantify the electrochemical reduction of nitrogen to ammonia. We demonstrate experimentally the importance of various sources of contamination, and show how to remove labile nitrogen-containing compounds from the nitrogen gas as well as how to perform quantitative isotope measurements with cycling of 15N2 gas to reduce both contamination and the cost of isotope measurements. Following this protocol, we find that no ammonia is produced when using the most promising pure-metal catalysts for this reaction in aqueous media, and we successfully confirm and quantify ammonia synthesis using lithium electrodeposition in tetrahydrofuran13. The use of this rigorous protocol should help to prevent false positives from appearing in the literature, thus enabling the field to focus on viable pathways towards the practical electrochemical reduction of nitrogen to ammonia. A protocol for the electrochemical reduction of nitrogen to ammonia enables isotope-sensitive quantification of the ammonia produced and the identification and removal of contaminants.

We employ a synergistic material and process development strategy to improve the performance of a single-cycle vacuum pressure swing adsorption (VPSA) process for the hydrogen purification and the CO2 separation from reforming-based hydrogen synthesis. Based on process-informed adsorbent selection criteria, including high CO2 cyclic capacity and selective uptake of impurities like CO, N2, and CH4 over H2, a metal organic framework (MOF), Cu-TDPAT, is selected. First, adsorption isotherms of CO2, CO, CH4, N2 and H2 are measured. Subsequently, a column model is used for optimization-based analysis of the VPSA cycle with Cu-TDPAT as the adsorbent to assess both the separation performance, and the process performance in terms of energy consumption and productivity. The adsorption characteristics of Cu-TDPAT require an adaptation of the original VPSA process to increase the CO2 separation performance of the process. After this adaptation, Cu-TDPAT clearly outperforms the benchmark material, zeolite 13X, in several metrics including higher H2 purities and recoveries and fewer columns needed for a continuous separation process. Most importantly, Cu-TDPAT offers a two-fold improvement in CO2 productivities when compared to zeolite 13X, thus substantially decreasing the bed size required to achieve the same throughput. However, zeolite 13X remains the better adsorbent for reaching high CO2 purities and recoveries due to its higher selectivity for CO2 over all other components in the gas stream, which leads to an overall lower energy consumption. The obtained results show that the final performance strongly depends on an interplay of various factors related to both material and process. Hence, an integrated process and material design approach should be the new paradigm for developing novel gas separation processes., Chemical Engineering Journal, 414, ISSN:0300-9467, ISSN:1385-8947, ISSN:1873-3212, ISSN:0923-0467

The compression of ammonium azide (AA) has been considered to be a promising route for producing high energy-density polynitrogen compounds. So far though, there is no experimental evidence that pure AA can be transformed into polynitrogen materials under high pressure at room temperature. We report here on high pressure (P) and temperature (T) experiments on AA embedded in N2 and on pure AA in the range 0–30 GPa, 300–700 K. The decomposition of AA into N2 and NH3 was observed in liquid N2 around 15 GPa–700 K. For pressures above 20 GPa, our results show that AA in N2 transforms into a new crystalline compound and solid ammonia when heated above 620 K. This compound is stable at room temperature and on decompression down to at least 7.0 GPa. Pure AA also transforms into a new compound at similar P–T conditions, but the product is different. The newly observed phases are studied by Raman spectroscopy and X-ray diffraction and compared to nitrogen and hydronitrogen compounds that have been predicted in the literature. While there is no exact match with any of them, similar vibrational features are found between the product that was obtained in AA + N2 with a polymeric compound of N9H formula.

Among microporous adsorbents, zeolites constitute the reference materials in CO2-capture technologies, because of their high CO2 affinity, high chemical and thermal stability, and low cost. Being synthesized in powder form, they need to be shaped in pellets or monolith to be suitable for real applications. The process has a direct effect on CO2-capture properties of the material creating, in this sense, substantial differences between lab-scale (adsorbents) and plant-scale systems (adsorbers). The ability of the honeycomb monolith to efficiently separate gases of interest arises from the properties of its single components such as an active phase and a phase resulting from the decomposition of a binder. Moreover, the textural (i.e., pore distribution and exposed surface) and structural properties (e.g., amorphization) of the active phase can be modified in the conditions adopted during the process that leads to the final artifact. These modifications can affect the CO2-capture performances of the active p...

Atomically detailed simulations were used to examine CO2/N-2 separation potential of metal organic framework- (MOF-) based mixed matrix membranes (mmms) in this study. Gas permeability and selectivity of 700 new mmms composed of 70 different mofs and 10 different polymers were calculated for CO2/N-2 separation. This is the largest number of MOF-based mmms for which computational screening is done to date. Selecting the appropriate mofs as filler particles in polymers resulted in mmms that have higher CO2/N-2 selectivities and higher CO2 permeabilities compared to pure polymer membranes. We showed that, for polymers that have low CO2 permeabilities but high CO2 selectivities, the identity of the MOF used as filler is not important. All mofs enhanced the CO2 permeabilities of this type of polymers without changing their selectivities. Several MOF-based mmms were identified to exceed the upper bound established for polymers. The methods we introduced in this study will create many opportunities to select the MOF/polymer combinations with useful properties for CO2 separation applications., Scientific and Technological Research Council of Turkey (TÜBİTAK)

Adsorption, 18 (1), ISSN:0929-5607, ISSN:1572-8757

International audience; Combined spatially resolved electron-energy loss spectroscopy (EELS) and high resolution near-edge X-ray absorption fine structure (NEXAFS) spectroscopy have been used to investigate the nitrogen doping of multi-walled carbon nanotubes (N-MWNT). EELS indicates that most of the tubes are nitrogen-doped. NEXAFS spectroscopy reveals pyridine-like and nitrile N structures. High resolution NEXAFS experiments show that the main nitrogen concentration originates from a high amount of molecular N-2 encapsulated into only a small quantity of tubes.

International audience; Rotational coherent anti-Stokes Raman spectroscopy (CARS) is a well-established spectroscopic technique for thermometry at pre-combustion temperatures an atmospheric pressure. However, at pressures of several MPa, a previous investigation revealed large discrepancies between experimental data and the theoretical model. A re-evaluation has been made of these data (at room temperature and in the range 1.5-9 MPa) with two improvements to the spectral code. The first is the inclusion of an inter-branch interference effect, which is described in detail in Paper I. The second is the use of experimental S-1-branch Raman line widths measured at 295 K, with a temperature dependence extracted from semi-classical calculations following the Robert-Bonamy formalism. It is shown that these two modifications significantly improve the theoretical model, since both the spectral fits and the accuracy of the evaluated temperatures are considerably improved.

International audience; The paper presents high resolution Raman investigations of the Q(1) line of H-2 in Ar mixture from low density (Doppler regime) to high density (collisional regime) analyzed with a unique line shape profile. Measurements are performed by stimulated Raman gain spectroscopy between 300 and 1000 K in a wide density range (from 0.2 to 11 amagat). All the observed spectral features are accurately described by a unified model recently proposed by two of the authors. This model accounts for a velocity-memory process, not restricted to the usual hard and soft limits. It also includes correlation between velocity- and phase-changing collisions. An exhaustive analysis of various possible mechanisms on the line shape is achieved. These mechanisms are the Dicke narrowing, the radiator speed dependence of the collisional broadening and shifting parameters, the collisionally induced speed-class exchange and the nonimpact effect. The present test shows the high consistency of the unified model, since it allows one to get a remarkable agreement with all the data by using a unique set of parameters. This model should be useful for optical diagnostics at moderate density, as required for combusting media or atmospheric work.