Scribd Logo
Upload

Welcome to Scribd!

  • NH3 Cheng Science

    Uploaded by

    Luis Pedrero Ojeda
    52 views10 pages

    Original Title

    NH3 cheng science

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Report this Document

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    52 views10 pages

    NH3 Cheng Science

    Uploaded by

    Luis Pedrero Ojeda

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 10
    RESEARCH Lee INORGANIC CHEMISTRY Beyond fossil fuel-driven nitrogen transformations ingguang.G. Chen,” Richard M. Crooks,” Lance C. Seefelat,” Kara I. Bren, 1. Morris Bullock, Marcetta Y. Darensbourg, Patrick L. Holland, Brian Hoffman, ‘Michael J. Janik, Anne K. Jones, Mercouri G. Kanatvidis, Paul King, Kyle M. Laneaster, Sergei V. Lymar, Peter Pfromm, William F. Schneider, Richard K. Schrock BACKGROUND: The invention ofthe Haber- Bosch (H-B) process in the early 1900s to produce ammonia industrially from nitrogen. and hydrogen revolutionized the manufacture of fertilizer and led to fundamental changes In the way food is produced. Its impact is ‘underscored by the fact that about 50% of ‘the nitrogen atoms in humans today originate rom this single industrial process. In the cen- ‘tury after the H-B process was invented, the chemistry of earbon moved to center stage, resulting in remarkable discoveries and a vast array of products ineluding plastis and phar- macenticals. In contrast, ite has ehangea in Industrial nitrogen chemistry. This scenario, reflects both the inherent efficiency of the H-B. process and the particular challenge of breaking the strong dinitrogen bond. Nonetheless, the rellance ofthe H-B process on fosi fuels and its associated high CO, emissions have spurred recent interest in finding more sustainable and environmentally benign alternatives, Nitrogen ints more oxidized forms i also industrially, biologically, and environmentally important, Possible routes for nitrogen ‘transformations that eliminate ‘oF minimize the need for fossil fuels. A more thorough understanding of nitrogenase may lead to more efficient homogeneous catalysts for reduction of No to NH Coupling of theory and ‘experiment wil ead to ‘more effective and stable heterogeneous and lactrocatalysts. Innovative energy sources, such as plasmas, which involve roneuilrium chemistry. may lead to new nitrogen = conversion mechanisms, ey Nirogenase ymes ‘and synergies in new combinations of oxi- dative and reduetive transformations across the nitrogen cycle could lead to improved efficiencies. ADVANCES: Major effort has been devoted to {developing alternative and environmentally {endl processes that would allow NH pro- duction at distributed sources under more benign conditions, rather than through the large-scale centralized H-B process, Hydro- carbons (particularly methane) and water are ‘the only two sourees of hydrogen atoms that ‘ean sustain longterm, large-scale NH produe- ton, The use of water as the hydrogen source for NH production requires substantially more ‘energy than using methane, but its also more ‘environmentally benign, does not contribute to the accumulation of greenhouse gases, and does not compete for valuable and limited hydro- carbon resources, Microbes living in all major ‘ecosystems are able to reduce N, to NH, by using the enzyme nitrogenase. A deeper under- standing of this enzyme could lead to more @ %8 gm, ‘ead Heterogeneous catasts serous ficient catalysts for nitrogen reduction under ambient conditions. Model molecular catalysts have been designed that mimic some of the functions of the ative site of nitrogenase. Some modest sucess has also been achieved in design- ingeleetroeaalysts for dinitrogen reduetion. leetrochemistry avoids the expense and envi- ronmental damage of steam reforming of me- ‘thane (whieh aecounts for most ofthe cost of the H-B proces) and it may provide a means for distributed production of ammonia. On ‘the oxidative side, nitric acid isthe principal ‘commodity chemical containing oxidized nitro sen. Neary all nitric acid is manufactured by cidation of Ny throush ‘the Ostwald process, but Read the ful article Amore direct reaction of EthitayaedouNewith Op mightbe prac- org/1026/ tically feasible through seleneeax0ll_— further development of nonthermal plasma tech- nology. Heterogeneous NH oxidation with Os is at the heart of the Ostwald process and is practiced in a variety of environmental pro- ‘ection applications as well. Precious metals, remain the workhorse catalysts, and oppor- tunities therefore exist to develop lower-cost materials with equivalent or beter activity and selectivity. Nitrogen oxides are also environ- mentally hazardous pollutants generated by industrial and transportation activities, and ‘extensive research has gone into developing and applying reduction eialyst. Three-way catalytic ‘omvestersare operating on hundreds of milion ‘of icles worldwide. However, increasingly stringent emissions regulations coupled with ‘the low exhaust temperatures of high-efficiency ‘engines, present challenges for future combus- tion emissions control Bacterial denititcation is the natural analog of this chemistry and another source of study and inspiration for catalyst design. ‘OUTLOOK: Demands for greater enerzyeff- ciency, smaller-scale and mote flexible pro- ‘esses, and environmental protection provide ‘rowing impetus for expanding the scope of nitrogen chemistry. Nitrogenase, as well as nitrifying and denitrfying enzymes, will even- ‘tually be understood in suticient detail that robust molecalareaalytie mimics wil emerge Hreetrochemical and photochemical methods also demand more sty. ther intriguing areas of research that have provided tantalizing result inelude chemiea! looping and plasma- driven processes. The grand challenge in the field of nitrogen chemistry is the development ‘of catalysts and processes that provide simple, low-energy routes to the manipulation of the redox states of nitrogen. *Canespndeg ata: Era erence (0.0) colscmuas ed (RC) cesta (LC) ‘Ge aca 1G. Chen a, Se 380 eal (2s) DoE scenes alt 1202 ‘bt fine wo Sie BewooVo.9s o9u9}95/ren WOH popEoLUNOR, RESEARCH INORGANIC CHEMISTRY Beyond fossil fuel-driven nitrogen transformations ‘ingguang G. Chen,'* Richard M. Crooks,"* Lance C. Seefeldt,** Kara L. Bren,” R. Morris Bullock,” Marcetta Y. Darensbourg,’ Patrick L, Holland,” Brian Hoffinan,” ichael J. Janik," Anne K. Jones," Mercouri G. Kanatzidis," Paul King,” Kyle M. Lancaster, Sergei V. Lymar,® Peter Promm,!* William F. Schneider,” Richard R. Schrock" Nitrogen is fundamental to al of lfe and many industrial processes. The interchange of nitrogen oxidation states in the industrial production of ammonia, nitric acid, and other ‘commodity chemical largely powered by fossil fuels. A key goal of contemporary ‘esearch in the field of nitrogen chemistry is to minimize the use of fossil fuels by developing more efficient heterogeneous, homogeneous, photo-, and electrocatalytic processes or by adapting the enzymatic processes underiying the natural nitrogen cycle, ‘These approaches, as well as the challenges involved, are discussed in this Review. duced forms of nitrogen, partially ame ‘monia (NH,), are vital to life. Before the arly 19005 all reluced N came from bio- logical nitrox fixation by microbes, This landseape changed in the early 1900s with {he invention by Haber and Bosch ofan indus- ‘rial process to reduce No to NH, (Np + SEs = NHL). The Haber-Bosch (HB) process has led ‘tw fundamental changes in the way food is pro- 13,this 10 dasron rection sore hee: ‘modynamically favorable than the parasitic four- ecto water oxidation to O,, Ths, tis possibe {or NO,” to be the only preauet of an anoxic pro- ‘es particulary in neutral and alkaline solutions, ‘fasufidently active an selective eleetrocatalyst ‘or Ba 6 ean be dscns The eoresponding cell ‘eompletng athodi reaction ean be either water ‘reduction to H oF O, reduction to water. Little apparent progresshas yet been made in develop- ingsuet catalysts, but theres no reason to believe that they eannot eventually be discovered. By coupling eathodie Nz reduction (Ea. 2) ‘with anodic Nz oxidation (Bq. 6), an eleetro- ‘chemical cell consuming only atmospheric Np and water as feedstock to yield aqueous NHNOS (Bq, 7) ean be envisioned. Nap + 31100) # NU a) 4 NOs i) * Ha o ‘The additional H, produetion is necessary {for matching eathodie and anodic currents and maintaining the electrolyte pH constant. Such cell would require a minimum of 108 V to ‘operate in neutral or alkaline eletrolte, which {is slightly lower than the minimum water elec- ‘woljsis voluge of 123 V. Advanees relating to ‘lectrochemical N, oxidation wil require devel- ‘opment of catalysts that are sufiiently active (capable of good current densities at low over- Potentials, sleetive (with respeet to water oxt- dation), and stable (toward deactivation under harsh redax and pH operating conditions). NO, reduction and NH; oxidation Overview ‘The redox chemistry of forms of nitrogen other ‘han Nis immense and rich, and it is extensively incorporated into biological systems. Both NO,, and NH, are environmentally hazardous pollu- tants generated by industrial and transportation activity, and thus much research has gone into ‘developing and applying NO, reduction andl NT, ‘oxidation eatalysts As soften the case the under standing of these catalysts lags their applications “Ammonia oxidation and NO, reduction are tal to environmental protetion and are much less well understood or optimized than the syn thesis of Ny. There are appealing opportunities ‘twapply the experimental and eomputational tools ‘of modern heterogeneous catalysis to these re- actions, both to develop a fundamental under standing of the processes and o identify superior materials and catalytic transformations—for ex. ample, catalysts that can selectively reduce NO, ‘to N, using hytrocarbon reductant, Environ- ‘mental applications generally demand high lon- sevity, durability, and tolerance to poisons. Key ‘gaps in understanding indlude how activity and selectivity can be acheved in relatively e001 gas streams how catalyst structure evolves overlong periods of time, how sulfur and other common Doisons interfere with reactions, and especially how these effects can be mitigated. NO, reduction [NO decomposition, the reverse of a, 3s ther= ‘morlynamically dovnhil but dieu to eatalyze under the oxygen-rich conditions of interest or ‘environmental protection (00). Nevertheless, NO ‘decompastion has een demonstrated using both homogeneous and heterogencons catalysts. De- ‘composition appears to involve a two-electron redliction of two NO molecules to ahyponitrite (E48). 2NO + €° + NOs wn NOs +e + N02 wn NOP 42H NO+1,0 60 Coordination complexes of hyponitrtes are not uncommon, and a tr+Cu hyponitite coved nation complex has been isolated as an inter- mediate in the catalytic decomposition of NO to Nz (0). A Ga dimer has similarly been m= plicated as the active site fa Cx-exehangedre0- lite catalyst for NO decomposition (63). NO, can be catalytically reduced to N, via several routes Precious metals are active fr NO, reduetion by CO and hydrocarbons, but only ‘under conditions in which O, concentrations are low (10). Vanadiatitania catalysts and metal- ‘exchanged zeolites catalyze selective reduction ‘ofNO, by NH, (69) Nitrsamine appears to be the key Na forming intermediate inthe catalytic Pathway (Eq, 9. NH, +NO—HANNO+H' +e A) HLNNO +N, + 1.0 on) “This Nforming reaction is exothermic, imply- Ing substantial, but perhaps not insurmountab kinetic eallengs to reversing the chemistry NO, can also be catalytically reduce with Hy ‘over Pd. and Pt catalysts (13), and Ny is typically the desired product (66). By suitable selection ‘of promoters and control of the NO/H, ratio, however, NH, can be produced over P catalysts (70), Likewise, NHy competes with Nz as the product ofthe catalytic reduction of NO, and NOs” by Hy over Pd eatalysts (12). Certain bacteria analogously reduce NO,” and NO, through a series of gaseous interme ates, leading ultimately to Ny in a process called 1202 “bt Kine wo soso Bewsaouores eou9}9s/-ery WOH papeqLUMEA, RESEARCH | REVIEW

    You might also like