Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store

Nature

Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store"


Play all audios:

Loading...

ABSTRACT Industrially, the artificial fixation of atmospheric nitrogen to ammonia is carried out using the Haber–Bosch process, but this process requires high temperatures and pressures, and


consumes more than 1% of the world's power production. Therefore the search is on for a more environmentally benign process that occurs under milder conditions. Here, we report that a


Ru-loaded electride [Ca24Al28O64]4+(e−)4 (Ru/C12A7:e−), which has high electron-donating power and chemical stability, works as an efficient catalyst for ammonia synthesis. Highly efficient


ammonia synthesis is achieved with a catalytic activity that is an order of magnitude greater than those of other previously reported Ru-loaded catalysts and with almost half the reaction


activation energy. Kinetic analysis with infrared spectroscopy reveals that C12A7:e− markedly enhances N2 dissociation on Ru by the back donation of electrons and that the poisoning of


ruthenium surfaces by hydrogen adatoms can be suppressed effectively because of the ability of C12A7:e− to store hydrogen reversibly. Access through your institution Buy or subscribe This is


a preview of subscription content, access via your institution ACCESS OPTIONS Access through your institution Subscribe to this journal Receive 12 print issues and online access $259.00 per


year only $21.58 per issue Learn more Buy this article * Purchase on SpringerLink * Instant access to full article PDF Buy now Prices may be subject to local taxes which are calculated


during checkout ADDITIONAL ACCESS OPTIONS: * Log in * Learn about institutional subscriptions * Read our FAQs * Contact customer support SIMILAR CONTENT BEING VIEWED BY OTHERS ELECTRON AND


PROTON STORAGE ON SEPARATE RU AND BAO DOMAINS MEDIATED BY CONDUCTIVE LOW-WORK-FUNCTION CARBON TO ACCELERATE AMMONIA SYNTHESIS Article 24 February 2025 ELECTROCHEMICAL REDUCTION OF NITRATE TO


AMMONIA VIA DIRECT EIGHT-ELECTRON TRANSFER USING A COPPER–MOLECULAR SOLID CATALYST Article 27 July 2020 SELECTIVE CATALYTIC OXIDATION OF AMMONIA TO NITRIC OXIDE VIA CHEMICAL LOOPING Article


Open access 07 February 2022 REFERENCES * Mittasch, A. Early studies of multicomponent catalysts. _Adv. Catal._ 2, 81–104 (1950). Google Scholar  * Honkala, K. et al. Ammonia synthesis from


first-principles calculations. _Science_ 307, 555–558 (2005). Article  CAS  Google Scholar  * Ertl, G. Elementary steps in heterogeneous catalysis. _Angew. Chem. Int. Ed. Engl._ 29,


1219–1227 (1990). Article  Google Scholar  * Gambarotta, S. & Scott, J. Multimetallic cooperative activation of N2 . _Angew. Chem. Int. Ed._ 43, 5298–5308 (2004). Article  CAS  Google


Scholar  * Pool, A. J., Lobkovsky, E. & Chirik, P. J. Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex. _Nature_ 427, 527–530 (2004). Article  CAS  Google


Scholar  * Spencer, N. D., Schoonmaker, R. C. & Somorjai, G. A. Structure sensitivity in the iron single-crystal catalyzed synthesis of ammonia. _Nature_ 294, 643–644 (1981). Article 


CAS  Google Scholar  * Aika, K., Takano, T. & Murata, S. Preparation and characterization of chlorine-free ruthenium catalysts and the promoter effect in ammonia-synthesis. 3. A


magnesia-supported ruthenium catalyst. _J. Catal._ 136, 126–140 (1992). Article  CAS  Google Scholar  * Jacobsen, C. J. H. et al. Catalyst design by interpolation in the periodic table:


bimetallic ammonia synthesis catalysts. _J. Am. Chem. Soc._ 123, 8404–8405 (2001). Article  CAS  Google Scholar  * Ozaki, A. Development of alkali-promoted ruthenium as a novel catalyst for


ammonia synthesis. _Acc. Chem. Res._ 14, 16–21 (1981). Article  CAS  Google Scholar  * Tsai, M. C., Seip, U., Bassignana, I. C., Kuppers, J. & Ertl, G. A vibrational spectroscopy study


on the interaction of N2 with clean and K-promoted Fe(111) surfaces: _π_-bonded dinitrogen as precursor for dissociation. _Surf. Sci._ 155, 387–399 (1985). Article  CAS  Google Scholar  *


Rosowski, F. et al. Ruthenium catalysts for ammonia synthesis at high pressures: preparation, characterization, and power-law kinetics. _Appl. Catal. A_ 151, 443–460 (1997). Article  CAS 


Google Scholar  * Bielawa, H., Hinrichsen, O., Birkner, A. & Muhler, M. The ammonia-synthesis catalyst of the next generation: barium-promoted oxide-supported ruthenium. _Angew. Chem.


Int. Ed._ 40, 1061–1063 (2001). Article  CAS  Google Scholar  * Rao, C. N. R. & Rao, G. R. Nature of nitrogen adsorbed on transition metal surfaces as revealed by electron spectroscopy


and cognate techniques. _Surf. Sci. Rep._ 13, 221–263 (1991). Article  CAS  Google Scholar  * Aika, K., Ozaki, A. & Hori, H. Activation of nitrogen by alkali-metal promoted


transition-metal. 1. Ammonia synthesis over ruthenium promoted by alkali-metal. _J. Catal._ 27, 424–431 (1972). Article  CAS  Google Scholar  * Hansen, T. W. et al. Atomic-resolution _in


situ_ transmission electron microscopy of a promoter of a heterogeneous catalyst. _Science_ 294, 1508–1510 (2001). Article  CAS  Google Scholar  * Ertl, G. Reactions at surfaces: from atoms


to complexity (Nobel Lecture). _Angew. Chem. Int. Ed._ 47, 3524–3535 (2008). Article  CAS  Google Scholar  * Urabe, K., Aika, K. & Ozaki, A. Activation of nitrogen by alkali


metal-promoted transition metal. _J. Catal._ 38, 430–434 (1975). Article  CAS  Google Scholar  * Ommen, J. G., Bolink, W. J., Prasad, J. & Mars, P. The nature of the potassium compound


acting as a promoter in iron–alumina catalysts for ammonia synthesis. _J. Catal._ 38, 120–127 (1975). Article  Google Scholar  * Larichev, Y. V. et al. XPS and TEM studies on the role of the


support and alkali promoter in Ru/MgO and Ru-Cs+/MgO catalysts for ammonia synthesis. _J. Phys. Chem. C_ 111, 9427–9436 (2007). Article  CAS  Google Scholar  * Siporin, S. E. & Davis,


R. J. Use of kinetic models to explore the role of base promoters on Ru/MgO ammonia synthesis catalysts. _J. Catal._ 225, 359–368 (2004). Article  CAS  Google Scholar  * Bécue, T., Davis, R.


J. & Garces, J. M. Effect of cationic promoters on the kinetics of ammonia synthesis catalyzed by ruthenium supported on zeolite X. _J. Catal._ 179, 129–137 (1998). Article  Google


Scholar  * Dye, J. L. Electrides: early examples of quantum confinement. _Acc. Chem. Res._ 42, 1564–1572 (2009). Article  CAS  Google Scholar  * Matsuishi, S. et al. High-density electron


anions in a nanoporous single crystal: [Ca24Al28O64]4+(e−)4 . _Science_ 301, 626–629 (2003). Article  CAS  Google Scholar  * Sushko, P., Shluger, A., Hayashi, K., Hirano, M. & Hosono, H.


Electron localization and a confined electron gas in nanoporous inorganic electrides. _Phys. Rev. Lett._ 91, 126401-1-4 (2003). Article  Google Scholar  * Toda, Y., Kubota, Y., Hirano, M.,


Hirayama, H. & Hosono, H. Surface of room-temperature-stable electride [Ca24Al28O64]4+(e−)4: preparation and its characterization by atomic-resolution scanning tunneling microscopy. _ACS


Nano_ 5, 1907–1914 (2011). Article  CAS  Google Scholar  * Hayashi, K. Heavy doping of H− ion in 12CaO·7Al2O3 . _J. Solid State Chem._ 184, 1428–1432 (2011). Article  CAS  Google Scholar  *


Kim, S-W. & Hosono, H. Synthesis and properties of 12CaO·7Al2O3 electride: a review of single crystal and thin film growth. _Phil. Mag._ 92, 2596–2628 (2012). Article  CAS  Google


Scholar  * Yoon, B. et al. Charging effects on bonding and catalyzed oxidation of CO on Au8 clusters on MgO. _Science_ 307, 403–407 (2005). Article  CAS  Google Scholar  * Ricci, D. et al.


Paramagnetic defect centers at the MgO surface. An alternative model to oxygen vacancies. _J. Am. Chem. Soc._ 125, 738–747 (2003). Article  CAS  Google Scholar  * Sushko, P. V., Gavartin, J.


L. & Shluger A. L. Electronic properties of structural defects at the MgO (001) surface. _J. Phys. Chem. B_ 106, 2269–2276 (2002). Article  CAS  Google Scholar  * Toda, Y. et al. Work


function of a room-temperature, stable electride [Ca24Al28O64]4+(e−)4 . _Adv. Mater._ 19, 3564–3569 (2007). Article  CAS  Google Scholar  * Michaelson, H. B. The work function of the


elements and its periodicity. _J. Appl. Phys._ 48, 4729–4733 (1977). Article  CAS  Google Scholar  * Matsuishi, S. et al. Direct synthesis of powdery inorganic electride [Ca24Al28O64]4+(e−)4


and determination of oxygen stoichiometry. _Chem. Mater._ 21, 2589–2591 (2009). Article  CAS  Google Scholar  * Liang, C., Wei, Z., Xin, Q. & Li, C. Ammonia synthesis over Ru/C


catalysts with different carbon supports promoted by barium and potassium compounds. _Appl. Catal. A_ 208, 193–201 (2001). Article  CAS  Google Scholar  * Kowalczyk, Z. et al.


Carbon-supported ruthenium catalyst for the synthesis of ammonia. The effect of the carbon support and barium promoter on the performance. _Appl. Catal. A_ 184, 95–102 (1999). Article  CAS 


Google Scholar  * Raróg-Pilecka, W. et al. Carbon-supported ruthenium catalysts for NH3 synthesis doped with caesium nitrate: activation process, working state of Cs–Ru/C. _J. Catal._ 239,


313–325 (2006). Article  Google Scholar  * Kadowaki, Y. & Aika, K. Promoter effect of Sm2O3 on Ru/Al2O3 in ammonia synthesis. _J. Catal._ 161, 178–185 (1996). Article  CAS  Google


Scholar  * Kubota, J. & Aika, K. Infrared spectra of adsorbed dinitrogen on ruthenium metal supported on alumina and magnesium oxide. _J. Chem. Soc. Chem. Commun._ 1544–1545 (1991). *


Kubota, J. & Aika, K. Infrared studies of adsorbed dinitrogen on supported ruthenium catalysts for ammonia synthesis: effects of the alumina and magnesia supports and the cesium compound


promoter. _J. Phys. Chem._ 98, 11293–11300 (1994). Article  CAS  Google Scholar  * You, Z., Inazu, K., Aika, K. & Baba, T. Electronic and structural promotion of barium hexaaluminate as


a ruthenium catalyst support for ammonia synthesis. _J. Catal._ 251, 321–331 (2007). Article  CAS  Google Scholar  * Aika, K. et al. Support and promoter effect of ruthenium catalyst. Ш.


Kinetics of ammonia synthesis over various Ru catalysts. _Appl. Catal. A_ 28, 57–68 (1986). Article  CAS  Google Scholar  * Hagen, S. et al. Ammonia synthesis with barium-promoted


iron–cobalt alloys supported on carbon. _J. Catal._ 214, 327–335 (2003). Article  CAS  Google Scholar  Download references ACKNOWLEDGEMENTS We deeply appreciate K. Aika for his suggestions.


Discussions with K. Nakajima and Y. Toda are acknowledged. We thank T. Yoshizumi, S. Nakamura and D. Lu for their technical assistance. This work was supported by a Funding Program for


World-Leading Innovative R&D on Science and Technology from the Japan Society for the Promotion of Science. A part of this work was supported by a fund from the Element Strategy


Initiative Project of the Ministry of Education, Culture, Sports and Science for Technology in Japan. AUTHOR INFORMATION Author notes * Sung-Wng Kim Present address: Present address:


Department of Energy Science, SungKyunKwan University, Suwon, Korea, AUTHORS AND AFFILIATIONS * Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,


226-8503, Yokohama, Japan Masaaki Kitano, Yasunori Inoue, Youhei Yamazaki, Shinji Kanbara, Michikazu Hara & Hideo Hosono * Frontier Research Center, Tokyo Institute of Technology, 4259


Nagatsuta, Midori-ku, 226-8503, Yokohama, Japan Fumitaka Hayashi, Satoru Matsuishi, Toshiharu Yokoyama, Sung-Wng Kim & Hideo Hosono Authors * Masaaki Kitano View author publications You


can also search for this author inPubMed Google Scholar * Yasunori Inoue View author publications You can also search for this author inPubMed Google Scholar * Youhei Yamazaki View author


publications You can also search for this author inPubMed Google Scholar * Fumitaka Hayashi View author publications You can also search for this author inPubMed Google Scholar * Shinji


Kanbara View author publications You can also search for this author inPubMed Google Scholar * Satoru Matsuishi View author publications You can also search for this author inPubMed Google


Scholar * Toshiharu Yokoyama View author publications You can also search for this author inPubMed Google Scholar * Sung-Wng Kim View author publications You can also search for this author


inPubMed Google Scholar * Michikazu Hara View author publications You can also search for this author inPubMed Google Scholar * Hideo Hosono View author publications You can also search for


this author inPubMed Google Scholar CONTRIBUTIONS H.H. proposed the idea behind this research and M.H. and H.H. directed the entire project. M.K., Y.I., Y.Y., F.H., S.M., S.K., T.Y. and


S-W.K. performed the synthesis, characterization and catalytic testing of Ru/C12A7:e−. All the authors discussed the results and commented on the study. M.K., M.H. and H.H. co-wrote the


manuscript. CORRESPONDING AUTHORS Correspondence to Michikazu Hara or Hideo Hosono. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing financial interests.


SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary information (PDF 809 kb) RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Kitano, M.,


Inoue, Y., Yamazaki, Y. _et al._ Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. _Nature Chem_ 4, 934–940 (2012).


https://doi.org/10.1038/nchem.1476 Download citation * Received: 24 May 2012 * Accepted: 06 September 2012 * Published: 21 October 2012 * Issue Date: November 2012 * DOI:


https://doi.org/10.1038/nchem.1476 SHARE THIS ARTICLE Anyone you share the following link with will be able to read this content: Get shareable link Sorry, a shareable link is not currently


available for this article. Copy to clipboard Provided by the Springer Nature SharedIt content-sharing initiative


Trending News

Forbidden fruit: an excerpt from the feature documentary fantastic fungi

Your support keeps us _ad-free_ and _financially independent_.  Our 10,000+ video & article library is 99% free, ad-...

Covid in ireland: country saw biggest household spending fall in eu during first wave

Ireland recorded the largest drop in household spending across the EU during the first Covid-19 wave, despite being one ...

Foothold in Bosnia | Nature

The world's diffidence at intervention in Bosnia is understandable, but should not be taken to extremes. Access thr...

Page not found - HW News English

NationalAfter Pahalgam, J&K CM Holds Cabinet Meeting In GulmargNews DeskMay 28, 2025May 28, 2025015The Chief Minister sa...

Tyson fury promoter frank warren issues response to dillian whyte

“I’m just glad that it is now gone and we can get back to work on making Fury against Joshua should both men win their n...

Latests News

Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store

ABSTRACT Industrially, the artificial fixation of atmospheric nitrogen to ammonia is carried out using the Haber–Bosch p...

Schools to pay $58,000 for toxic soil removal

The Santa Monica-Malibu Board of Education has awarded an emergency contract to have an estimated 30 truckloads of conta...

The page you were looking for doesn't exist.

You may have mistyped the address or the page may have moved.By proceeding, you agree to our Terms & Conditions and our ...

Emmerdale spoiler: marlon dingle and laurel potts kiss exposed

Last week saw a lovelorn Marlon (played by Mark Channock) lean in for a kiss with Laurel (Charlotte Bellamy), while his ...

Start

Memorial Day Sale! Join AARP for just $11 per year with a 5-year membership Join now and get a FREE gift. Expires 6/4  G...

Top