An analysis of ammonia synthesis by the model of Selective Energy Transfer (SET)
Article Sidebar
Main Article Content
Abstract
The SET theory implies that energy is transferred from the catalyst system via infrared radiation to the molecules that are supposed to react. In previous investigations it has been demonstrated that the activation of the reacting species-as long as the molecules are infrared active-can occur at low adsorption strength. However, for molecules that are IR inactive, e.g. dinitrogen, this is not possible. Hence the N2 molecule has to be adsorbed on the catalyst surface to give rise to vibrations that can interact with IR quanta of the catalyst. By analyzing the activation energies for a series of reactions between hydrogen and nitrogen under slightly differing conditions this critical vibration has been found at wave numbers such as 374, 374 and 355cm-1. The critical vibration is identified as the degenerate bending vibration of the M-N-N unit. When this bending is activated, the N2 triple bond is weakened and makes place for hydrogen addition. Two different routes of reaction are scheduled, of which one is the most likely one, using the metal-atomic nitrogen stretch vibration as the catalyst vibrator.
For the classical Fe3O4 a perfect resonance (1:1) with the above-mentioned critical vibrations exist. This is also the case for the catalyst from Co3Mo3N, where a surface cover of, inter alia, MoO42- seem to act likewise in full resonance.
Downloads
Article Details
Copyright (c) 2019 Larsson R.
This work is licensed under a Creative Commons Attribution 4.0 International License.
Licensing and protecting the author rights is the central aim and core of the publishing business. Peertechz dedicates itself in making it easier for people to share and build upon the work of others while maintaining consistency with the rules of copyright. Peertechz licensing terms are formulated to facilitate reuse of the manuscripts published in journals to take maximum advantage of Open Access publication and for the purpose of disseminating knowledge.
We support 'libre' open access, which defines Open Access in true terms as free of charge online access along with usage rights. The usage rights are granted through the use of specific Creative Commons license.
Peertechz accomplice with- [CC BY 4.0]
Explanation
'CC' stands for Creative Commons license. 'BY' symbolizes that users have provided attribution to the creator that the published manuscripts can be used or shared. This license allows for redistribution, commercial and non-commercial, as long as it is passed along unchanged and in whole, with credit to the author.
Please take in notification that Creative Commons user licenses are non-revocable. We recommend authors to check if their funding body requires a specific license.
With this license, the authors are allowed that after publishing with Peertechz, they can share their research by posting a free draft copy of their article to any repository or website.
'CC BY' license observance:
|
License Name |
Permission to read and download |
Permission to display in a repository |
Permission to translate |
Commercial uses of manuscript |
|
CC BY 4.0 |
Yes |
Yes |
Yes |
Yes |
The authors please note that Creative Commons license is focused on making creative works available for discovery and reuse. Creative Commons licenses provide an alternative to standard copyrights, allowing authors to specify ways that their works can be used without having to grant permission for each individual request. Others who want to reserve all of their rights under copyright law should not use CC licenses.
Larsson R (2013) Concluding remarks on the theory of selective energy transfer and exemplification on a zeolite kinetics study. Monatsh Chem 144: 21-28. Link: http://bit.ly/2mYqnvl
a) Kitte CWD, Knightt MA. Ruderman, Mechanics Berkeley Physics Course, Vol. 1, Chapt. 7, McGraw-Hill, New York, 1965.
b) Larsson R (1989) A Model of Selective Energy Transfer at the Active Site of the Catalyst. J Mol Catal 55: 70-83. Link: http://bit.ly/2n66HWA
Larsson R (1987) On the Stepwise Change of the Energy of Activation of Catalytic Reactions. Z Physik Chemie, Leipzig 268: 721-732. Link: https://tinyurl.com/y3e28253
Ertl G (2008) Reactions at Surfaces. From Atoms to Complexity (Nobel Lecture) Angew Chem Int Ed Engl 47: 3524-3535. Link: https://tinyurl.com/y6582s5f
Chatt J (1969) Nitrogen Complexes of the Platinum Metals; Pointers to a Mechanism of Fixation. Platinum Metals Rev 13: 9-14. Link: https://tinyurl.com/y59lloh4
Bee MW, SFA Kettle, DB Powell (1974) Vibrational spectra of ruthenium and osmium pentammine carbonyls and nitrogenyls. Spectrochim Acta 30: 585-596. Link: https://tinyurl.com/y2jqfkmt
Wang HP, Yates JT (1984) Infrared Spectroscopic Study of N2 Chemisorption on Rhodium Surfaces. J Phys Chem 88: 852-856. Link: https://tinyurl.com/yy6bo8ns
Folkesson B (1973) ESCA Studies on the Charge Distribution in Some Dinitrogen Complexes of Rhenium, Iridium, Ruthenium and Osmium, Acta Chem Scand 27: 287-302. Link: https://tinyurl.com/y6gs59qb
Aika K, Tamaru K (1995) Ammonia Synthesis over Non-Iron Catalysts and Related Phenomna, Chapter 3, Ammonia Catalysis and Manufacture, A Nielsen (Ed), Springer Verlag, Berlin Heidelberg. Link: https://tinyurl.com/y6axmsfk
Aika K, Hori H, Ozaki A (1972) Activation of Nitrogen by Alkali Metal Promoted Transition Metal, I. Ammonia Synthesis over Ruthenium Promoted by Alkali Metal. J Catal 27: 424-431. Link: https://tinyurl.com/y64nnazh
Aika K, Ohya A, Ozaki A, Inoue Y, Yasumori I (1985) Support and Promoter Effect of Ruthenium Catalyst; II. Ruthenium/Akaline Earth Catalyst for Activation of Dinitrogen. J Catal 92: 305-311. Link: https://tinyurl.com/y5xk3z5z
de Paola RA, Hoffmann FM, Heskett D, Plummer EW (1987) Adsorption of molecular nitrogen on clean and modified Ru(001) surfaces: The role of s bonding. Physical Review B 35: 4236–4249. Link: https://tinyurl.com/yyfh6us4
Anton AB, Avery NR, Toby BH, Weinberg WH (1983) The Chemisorption of Nitrogen on the (001) Surface of Ruthenium. J Electron Spectrosc Relat Phenom 29: 181-186. Link: https://tinyurl.com/yxrr5q97
Greenler RG, Snider DR, Witt D, Sorbello RS (1982) The Metal-Surface Selection Rule for Infrared Spectra of Molecules Adsorbed on Small Metal Particles. Surf Sci 118: 415-428. Link: https://tinyurl.com/y25cak5f
Keane MA, Larsson R (2007) Isokinetic behaviour in gas phase catalytic hydrodechlorination of chlorobenzene over supported nickel. J Mol Catal 268: 87-94. Link: https://tinyurl.com/yy9efubl
Mittasch A (1950) Early Studies of Multicomponent Catalysts. Adv Catal 2: 81-104.
Roonasi P, Holmgren A (2009) A study on the mechanism of magnetite formation based on iron isotope fractionation. Proc. EPD Congress sponsored by the Extraction and Processing Division (EPD) of the Minerals, Metals & Materials Society (TMS); Howard,S.M. (Ed.); Warrendale, Pa. Minerals Metals Mater Soc 829-836. Link: https://tinyurl.com/yxj3jxsx
Ertl G, Prigge D, Schlögl R, Weiss M (1983) Surface Characterization of Ammonia Synthesis Catalysts. J Catal 79: 359-377. Link: https://tinyurl.com/yy8ncqt2
Cremer PS, Su X, Shen YR, Somorjai GA (1996) The first measurement of an absolute surface concentration of reacting intermediates in ethylene hydrogenation. Catal Lett 40: 143-145. Link: https://tinyurl.com/y5w8w9fx
Cremer PS, Su X, Shen YR, Somorjai GA (1996) Ethylene Hydrogenation on Pt(111) Monitored in Situ at High Pressure Using Sum Frequency Generation. J Am Chem Soc 118: 2942-2949. Link: https://tinyurl.com/y2rfvwz8
Bozso F, Ertl G, Grunze M, Weiss M (1977) Interaction of Nitrogen with Iron Surfaces. I. Fe(100) and Fe(111). J Catal 49: 18-41. Link: https://tinyurl.com/y6ouuas5
Rosowski F, Hornung A, Hinrichsen O, Herein D, Muhler M et al. (1997) Ruthenium catalysts for ammonia synthesis at high pressures: Preparation, characterization, and power-law kinetics. Appl Catal A 151: 443-460. Link: https://tinyurl.com/y3g78pnj
Aika K, Ozaki A (1969) Kinetics and Isotope Efects of Ammonia Synthesis over an Unpromoted Iron Catalyst. J Catal 13: 232-237. Link: https://tinyurl.com/yxh2g4bj
Ruch E (1960) Zur Theorie der koordinativen Verbindungen. 10 Jahre Fonds der Chemischen Industrie, Düsseldorf 163-173.
Brill R (1970) Another Rate Equation for the Catalytic Synthesis of Ammonia. J Catal 16: 16-19. Link: https://tinyurl.com/y28xrb5g
Schmidt WA (1968) Mass-spectroscopic Study of the Synthesis of NH3 on Iron Tips. Angew. Chem., Intern. Ed 7: 139-139. Link: https://tinyurl.com/y2jdk2yc
Brill R, Richter EL, Ruch E (1967) Adsorption of Nitrogen on Iron. Angew Chem Intern Ed 6: 882-883.
Brill R, Jiru P, Schultz G (1969) Infrarotspektren von N2 – H2- Adsorptionskomplexen an einem Eisenkatalysator. Z Physik Chem NF 64: 215-224. Link: https://tinyurl.com/y4g2empz
Takezawa N, Emmett PH (1968) Interaction of Nitrogen and Carbon Monoxide on Iron. Synthetic Ammonia Catalysts. J Catal 11: 131-134. Link: https://tinyurl.com/y2gae58e
Dietrich H, Jacobi K, Ertl G (1996) Coverage, lateral order, and vibrations of atomic nitrogen on Ru (0001). J Chem Phys 105: 8944-8950. Link: https://tinyurl.com/yy52kwsd
Erley W, Ibach H (1982) Vibrational spectra of ammonia adsorbed on Fe(110). Surface Sci 119: L357-L362. Link: https://tinyurl.com/y24ulecz
Okawa T, Onishi T, Tamaru K (1977) Infrared study of chemisorbed ammonia on an evaporated Iron Film. Chm Lett 1077-1078. Link: https://tinyurl.com/y3xdwdv9
Cremer E (1955) The Compensation Effect in Heterogeneous Catalysis. Adv Catal 7: 75-91. Link: https://tinyurl.com/yyrer4yr
Larsson R (1996) Catalysis as a resonance effect. V. Factors that determine the isokinetic temperature in catalytic reactions. React Kinet Catal Lett 8: 115-124. Link: https://tinyurl.com/y6nbcymq
Kitano M, Kanbara S, Inoue Y, Kuganathan N, Sushko P, et al. (2015) Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottle neck on ammonia synthesis. Nature Communications 6. Link: https://tinyurl.com/y27yrevj
Zeinalipour-Yadzi CD, Hargreaves JSJ, Catlow CR (2016) DFT-D3 Study of MolecularN2 and H2 Activation on Co3Mo3N surfaces. J Phys Chem 120: 21390-21398. Link: https://tinyurl.com/y5umovc9
Zeinalipour-Yadzi CD, Hargreaves JSJ, Catlow CR (2018) Low-T Mechanisms of Ammonia Synthesis on Co3Mo3N. J Phys Chem 122: 6078-6082. Link: https://tinyurl.com/yy2emvn8
Alshibane I, Laassiri S, Rico JL (2018) Methane Cracking over Cobalt Molybdenum Carbides. Catal Lett 148: 1643-1650. Link: https://tinyurl.com/y4cvqogk
Xu K, Chao J, Li W, Liu Q, Wang Z, et al. (2014) CoMoO4·0.9H2O nanorods grown on reduced graphene oxide as advanced electrochemical pseudocapacitor materials. RSC Adv 4: 34307-34314. Link: https://tinyurl.com/y4a2hq73
Alconchel S, Sapina F, Martinez E (2004) Daöton Trans 16: 2463.
Frost RL, Cejka MJ, Dickfos MJ (2008) Raman and infrared spectroscopic study of the molybdate conaining uranyl mineral calcurmolite. J Raman Spectroscopy 39: 779-785. Link: https://tinyurl.com/y2gzsnom
AlShibane I, Hargreaves JSJ, HectorAL, Levason W, McFarlane A (2017) Dalto Trans 46: 8782.
Brown RG, Denning J, Hallett A, Ross SD (1970) Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy; .Selection Rules for Molecular and Lattice Vibrations and the Correlation Method 26: 963.
Farmer VC (1974) The Infraed Spectra of Minerals; Mineralogical Society Monograph 4; The Mineralogical Society, London, UK. Link: https://tinyurl.com/y33888ng
Leigh J (2001) All quiet on the N front, Chem. Br 37: 23-24.