13550-49-7Relevant articles and documents
The infrared spectrum of an adsorbate formed from NH3 on polycrystalline Pt (111)
Dunn, Douglas S.,Severson, Mark W.,Golden, W. G.,Overend, John
, p. 815 - 818 (1981)
We have studied the infrared reflection-absorption spectrum of an adsorbate formed when an annealed polycrystalline Pt foil, presumably having a (111) surface structure, is exposed to ammonia gas at pressure in the range 0.1-10 torr.Isotopic substitution establishes that the adsorbate contains N2 in addition to NHx species.There is also CN present in the adsorbate, presumably formed by reaction of nitrogen with carbon impurities on the surface.
Taylor, H. S.,Jungers, J. C.
, p. 5057 (1933)
Energy disposal in the reactions O(1D) + NH3 -> OH + NH2 and O(1D) + ND3 -> OD + ND2
Cordova, Jose F.,Rettner, Charles T.,Kinsey, James L.
, p. 2742 - 2748 (1981)
Further investigations of the reaction O(1D) + NH3 -> OH + NH2 and the first results on the reaction O(1D) + ND3 -> OD + ND2 are reported.The OH and OD rotational distributions have been found to be statistical.Hotter than statistical vibrational distributions are measured.The spin state distribution is statistical, with a strong preference to populate the energetically lower Λ component in both spin states.A preliminary study of the NH2 product shows very little rotational excitation.An analysis of this radical's vibrational hot bands was not carried out due to lack of detailed spectroscopic information.The total energy is found to be partitioned according to R(OH)> ca. 0.1, V(OH)> ca. 0.25, R(NH2)> ca. 0.04, and T> ca. 0.25.
Some thermodynamic properties of liquid ammonia and trideuteroammonia
Streatfeild, M. H.,Henderson, C.,Staveley, L. A. K.,Ferreira, A. G. M.,Fonseca, I. M. A.,Lobo, L. Q.
, p. 1163 - 1172 (1987)
The orthobaric density of liquid NH3 has been measured from about 200 to 287 K, and for liquid ND3 from about 205 to 273 K.The molar volume of liquid NH3 exceeds that of ND3 by between 0.8 and 0.9 per cent.The difference of the vapour pressures of the two compounds has been measured from about 200 to 266 K, and the vapour pressure of NH3 from the triple-point temperature to 234 K.Liquid NH3 has the higher vapour pressure, the difference being relatively large for a pair of isotopic compounds.At 200 K, the ratio of the vapour pressure of NH3 to that of ND3 is about 1.2.The available vapour pressures for NH3 have been fitted to a Wagner equation.By combining vapour pressures derived from this equation with the differential measurements, values for the vapour pressure of ND3 have been obtained.These values have likewise been fitted to a Wagner equation.The material presented in this paper has been used to estimate the molar enthalpies of vaporization of NH3(l) and of ND3(l) from the triple-point temperatures to 290 K.The molar enthalpy of vaporization of ND3 exceeds that of NH3 throughout this range.The difference amounts to about 3.5 per cent at the triple-point temperatures, and decreases with rising temperature.
Bimetallic Cooperative Cleavage of Dinitrogen to Nitride and Tandem Frustrated Lewis Pair Hydrogenation to Ammonia
Doyle, Laurence R.,Wooles, Ashley J.,Liddle, Stephen T.
, p. 6674 - 6677 (2019)
Although reductive cleavage of dinitrogen (N2) to nitride (N3?) and hydrogenation with dihydrogen (H2) to yield ammonia (NH3) is accomplished in heterogeneous Haber–Bosch industrial processes on a vast scale, sequentially coupling these elementary reactions together with a single metal complex remains a major challenge for homogeneous molecular complexes. Herein, we report that the reaction of a chloro titanium triamidoamine complex with magnesium effects complete reductive cleavage of N2 to give a dinitride dititanium dimagnesium ditriamidoamine complex. Tandem H2 splitting by a phosphine–borane frustrated Lewis pair (FLP) shuttles H atoms to the N3?, evolving NH3. Isotope labelling experiments confirmed N2 and H2 fixation. Though not yet catalytic, these results give unprecedented insight into coupling N2 and H2 cleavage and N?H bond formation steps together, highlight the importance of heterobimetallic cooperativity in N2 activation, and establish FLPs in NH3 synthesis.
Cluster size effects on hydrazine decomposition on Irn/Al 2O3/NiAl(1 1 0)
Fan, Chaoyang,Wu, Tianpin,Kaden, William E.,Anderson, Scott L.
, p. 461 - 467 (2006)
A series of planar model catalysts were prepared by deposition of size-selected Irn+ on Al2O3/NiAl(1 1 0), and hydrazine decomposition chemistry was used to probe their size-dependent chemical properties. Small Irn (n ≤ 15) on Al2O 3/NiAl(1 1 0) are able to induce hydrazine decomposition at temperatures well below room temperature, with significant activity first appearing at Ir7. Both activity and product branching are strongly dependent on deposited cluster size, with these small clusters supporting only the simplest decomposition mechanism: dehydrogenation and N2 desorption at low temperatures, followed by H2 recombinative desorption at temperatures above 300 K. For Ir15, we begin to see ammonia production, signaling the onset of a transition to clusters able to support more complex chemistry.
Hydrogen Spillover to Oxygen Vacancy of TiO2- xHy/Fe: Breaking the Scaling Relationship of Ammonia Synthesis
Mao, Chengliang,Wang, Jiaxian,Zou, Yunjie,Qi, Guodong,Yang Loh, Joel Yi,Zhang, Tianhua,Xia, Meikun,Xu, Jun,Deng, Feng,Ghoussoub, Mireille,Kherani, Nazir P.,Wang, Lu,Shang, Huan,Li, Meiqi,Li, Jie,Liu, Xiao,Ai, Zhihui,Ozin, Geoffrey A.,Zhao, Jincai,Zhang, Lizhi
, p. 17403 - 17412 (2020)
Optimizing kinetic barriers of ammonia synthesis to reduce the energy intensity has recently attracted significant research interest. The motivation for the research is to discover means by which activation barriers of N2 dissociation and NHz (z = 1-2, surface intermediates) destabilization can be reduced simultaneously, that is, breaking the scaling relationship . However, by far only a single success has been reported in 2016 based on the discovery of a strong-weak N-bonding pair: transition metals (nitrides)-LiH. Described herein is a second example that is counterintuitively founded upon a strong-strong N-bonding pair unveiled in a bifunctional nanoscale catalyst TiO2-xHy/Fe (where 0.02 ≤ x ≤ 0.03 and 0 y 0.03), in which hydrogen spillover (H) from Fe to cascade oxygen vacancies (OV-OV) results in the trapped form of OV-H on the TiO2-xHy component. The Fe component thus enables facile activation of N2, while the OV-H in TiO2-xHy hydrogenates the N or NHz to NH3 easily.
Dissociative and Associative Concerted Mechanism for Ammonia Synthesis over Co-Based Catalyst
Hosono, Hideo,Kitano, Masaaki,Li, Jiang,Lu, Yangfan,Park, Sang-Won,Sasase, Masato,Wu, Jiazhen,Ye, Tian-Nan
supporting information, p. 12857 - 12866 (2021/08/30)
The current catalytic reaction mechanism for ammonia synthesis relies on either dissociative or associative routes, in which adsorbed N2 dissociates directly or is hydrogenated step-by-step until it is broken upon the release of NH3 through associative adsorption. Here, we propose a concerted mechanism of associative and dissociative routes for ammonia synthesis over a cobalt-loaded nitride catalyst. Isotope exchange experiments reveal that the adsorbed N2 can be activated on both Co metal and the nitride support, which leads to superior low-temperature catalytic performance. The cooperation of the surface low work function (2.6 eV) feature and the formation of surface nitrogen vacancies on the CeN support gives rise to a dual pathway for N2 activation with much reduced activation energy (45 kJ·mol-1) over that of Co-based catalysts reported so far, which results in efficient ammonia synthesis under mild conditions.
