Abstract
We report on the detailed structure of MnO x nanoparticles (MnO x NP) which are either stabilized by cationic spherical polyelectrolyte brushes or by star-shaped cationic polyelectrolyte chains. In both cases, the polycation is composed of 2-(trimethylammonium)ethyl methacrylate chloride (TMAEMC). The analysis by transmission electron microscopy (TEM), cryogenic transmission electron microscopy (cryoTEM), and powder X-ray diffraction leads to the conclusion that the MnO x nanoparticles in aqueous dispersed state are composed of only a few or even single lamellae of c-disordered potassium birnessite (birnessite). Using star-shaped pTMAEMC homopolymer for the synthesis of composite particles, we obtain MnO x NP with an average diameter of about 5 nm. MnO x NP immobilized on cationic spherical polyelectrolyte brush have a length of about 20 nm and a width of 1.6 nm. Comparison of the extended X-ray absorption fine structure (EXAFS) spectra of the MnO x composites with reference spectra leads to the conclusion that all materials include c-disordered birnessite-type nanoparticles. A comparison of the energy shift of the Mn K-edge absorption peak of the X-ray absorption near-edge structure spectra of different manganese oxide reference materials with the different MnO x NP revealed an average oxidation state of about 3.5–3.7 for synthesized compounds. No distinct structural difference is found when comparing the dried samples to samples dispersed in water. A comparison of the EXAFS data of the birnessite nanoparticles with the crystal structure of macroscopic systems showed a compression along the c direction accompanied by a slight elongation within the ab plane of the layered material.
Similar content being viewed by others
Notes
δ-MnO2 is a synthetic analogous to the mineral vernadite [54]. According to Villalobos et al., δ-MnO2 has the same local structure as randomly stacked “acid” birnessite. The only difference is the smaller crystallite size and the fewer number of stacked layers along the c-axis as compared to birnessite [42]
References
Suib SL (2008) J Mater Chem 18:1623–1631
Wang X, Li Y (2006) Pure Appl Chem 78:1–64
Brock SL, Duan N, Tian ZR, Giraldo O, Zhou H, Suib SL (1998) Chem Mater 10:2619–2628
Suib SL (2008) Acc Chem Res 41:479–487
Cai J, Liu J, Suib SL (1998) Chem Mater 10:2619–2628
Aronson BJ, Kinser AK, Passerini S, Smyrl WH, Stein A (1999) Chem Mater 11:949–957
Shen XF, Ding YS, Liu J, Cai J, Laubernds K, Zerger RP, Vasiliev A, Aindow M, Suib SL (2005) Adv Mater 17:805–809
Sakai N, Ebina Y, Takada K, Sasaki TJ (2005) Phys Chem B 109:9651–9655
Yang DS, Wang MK (2001) Chem Mater 13:2589–2594
Zhu S, Zhou H, Hibino M, Honma I, Ichihara M (2005) Adv Funct Mater 15:381–386
Gaillot AC, Flot D, Drits VA, Manceau A, Burghammer M, Lanson B (2003) Chem Mater 15:4666–4678
Feng Qu, Kanoh H, Ooi KJ (1999) Mater Chem 9:319–333
Post JE, Veblen DR (1990) Am Mineral 75:477–489
Drits VA, Silvester EJ, Gorshkov AI, Manceau A (2002) Am Mineral 87:1631–1645
Ching S, Petrovay DJ, Jorgensen ML, Suib SL (1997) Inorg Chem 36:883–890
Feng Q, Kanoh H, Miyai Y, Ooi K (1995) Chem Mater 7:1226–1232
Lanson B, Drits VA, Gaillot AC, Silvester E, Plancon A, Manceau (2002) Am Mineral 87:1631–1645
Liu ZH, Ooi K, Kanoh H, Tang WP, Tomida T (2000) Langmuir 16:4154–4164
Kai K, Yoshida Y, Kageyama H, Saito G, Ishigaki T, Furukawa Y, Kawamata J (2008) J Am Chem Soc 130:15938–15943
Gao Q, Giraldo O, Tong W, Suib SL (2001) Chem Mater 13:778–786
Omomo Y, Sasaki T, Wang L, Watanabe M (2003) J Am Chem Soc 125:3568–3575
Oaki Y, Imai H (2007) Angew Chem Int Ed 46:4951–4955
Croguennec L, Deniard P, Brec R, Lecerf A (1997) J Mater Chem 7:511–516
Hara D, Shirakawa J, Ikuta H, Uchimoto Y, Wakihara M, Miyanaga T, Watanabe I (2003) J Mater Chem 13:897–903
Petkov V, Ren Y, Saratovsky I, Pastén P, Gurr SJ, Hayward MA, Poeppelmeier KR, Gaillard JF (2009) ACS Nano 3:441–445
Kobayashi S, Kottegoda IRM, Uchimoto Y, Wakihara M (2004) J Mater Chem 14:1843–1848
Brock SL, Sanabria M, Urban V, Thiyagarajan P, Potter DI, Suib SL (2001) J Phys Chem B 105:5404–5410
Silvester E, Manceau A, Drits VA (1997) Am Mineral 82:962–978
Gaillot AC, Drits VA, Manceau A, Lanson B (2007) Microporous Mesoporous Mater 98:267–282
Fukuda K, Nakai I, Ebina Y, Tananka M, Mori T, Sasaki T (2006) J Phys Chem B 110:17070–17075
Saratovsky I, Wightman PG, Pastén PA, Gaillard JF, Poeppelmeier KR (2006) J Am Chem Soc 128:11188–11198
Grangeon S, Lanson B, Miyata N, Tani Y, Manceau A (2010) Am Mineral 95:1608–1616
Ressler T, Brock SL, Wong J, Suib SL (1999) J Phys Chem B 103:6407–6420
Polzer F, Kunz DA, Breu J, Ballauff M (2010) Chem Mater 22:2916–2922
Sharma G, Ballauff M (2004) Macromol Rapid Commun 25:547–557
Plamper FA, Schmalz A, Penott-Chang E, Drechsler M, Jusufi A, Ballauff M, Müller AHE (2007) Macromolecules 40:5689–5697
Qiu J, Charleux B, Matyjaszewski K (2001) Prog Polym Sci 26:2083–2134
Sala T, Sargent MVJ (1978) J Chem Soc Chem Commun 31:253–254
Brock SL, Sanabria M, Urban V, Thiyagarajan P, Potter DI, Suib SL (1999) J Phys Chem B 103:7416–7428
McKenzie RM (1978) Mineral Mag 38:493–502
Kim SH, Kim SJ, Oh SM (1999) Chem Mater 11:557–563
Villalobos M, Toner B, Bargar J, Sposito G (2003) Geochim Cosmochim Acta 67:2649–2662
Crassous JJ, Rochette CN, Wittemann A, Schrinner M, Drechsler M, Ballauff M (2009) Langmuir 25:7862–7871
Erko A, Packe I, Hellwig C, Fieber-Erdmann M, Pawlitzki O, Veldkamp M, Gudat W (2000) AIP Conference Proc 521:415–418
Erko A, Packe I, Gudat W, Abrosimov N, Firsov A (2000) SPIE Rev 4145:122–128
Newville M, Livins P, Yacoby Y, Stern EA, Rehr JJ (1993) Phys Rev B 47:14126–14131
Newville M, Livins P, Yacoby Y, Rehr JJ, Stern EA (1993) Jpn J Appl Phys Part 1(32):125–127
Ravel B, Newville M, Cross JO, Bouldin CE (1995) Physica B 209:145–147
Kelly SD, Hesterberg D, Ravel B (2008) Part 5 -Mineralogical methods in Ulery AL and Drees LR (Eds). Analysis of soils and minerals using X-ray absorption spectroscopy Methods of soil analysis Soil Science Society of America, Madison, WI, pp 367–463
Ravel B, Newville M (2005) J Synchrotron Radiat 12:537–541
Zabinsky SI, Rehr JJ, Ankudinov A, Albers R, Eller MJ (1995) Phys Rev B 52:2995–3009
Schrinner M, Haupt B, Wittemann A (2008) Chem Eng J 144:138–144
Grangeon S, Lanson B, Lanson M, Manceau A (2008) Mineral Mag 72:1279–1291
Giovanelli R (1980) Miner Deposita (Berl) 15:251–253
Breu J, Seidl W, Stoll AZ (2003) Anorg Allg Chem 629:503–515
Brunelli M, Lanzara A, Saini NL, Bianconi A, Valletta A, Radaelli PG (1997) J Supercond Chem B 10:315–317
Belli M, Scafati A, Bianconi A, Mobilio S, Paladino L, Reale A, Buratini E (1980) Solid State Commun 35:355–361
Koningsberger DC, Prins R (1988) X-ray absorption: principles, applications, techniques of EXAFS, SEXAFS, and XANES. Wiley, New York, p 673
Manceau A, Combes JM (1988) Phys Chem Miner 15:283–295
Manceau A, Gorshkov AI, Drits VA (1992) Am Mineral 77:1133–1143
Ma Y, Luo J, Suib SL (1999) Chem Mater 11:1972–1979
The International Battery Material Association (1989) Handbook of manganese dioxide, battery grade. Glover D, Schumm B Jr, Kozowa A (eds). The International Battery Material Association, Strongsville. pp 25–32
Manceau A, Gorshkov AI, Drits VA (1992) Am Mineral 77:1144–1157
Manceau A, Gorshkov AI, Drits VA (1988) Phys Chem Miner 15:283–295
Lee PA, Pendry JB (1975) Phys Rev B 11:2795–2811
Teo BK (1981) J Am Chem Soc 103:3990–4001
Rechav B, Sicron N, Yacoby Y, Ravel B, Newville M, Stern EA (1993) Physica C 209:55–58
Krappe HJ, Rossner HH (2009) Phys Scr 79:048302
Stern EA (1988) Theory of EXAFS. In: Koningsberger DC, Prins R (eds) X-ray absorption. Wiley, New York, pp 3–52
Polzer F, Wunder S, Lu Y, Ballauff M (2012) J Catal 289:80–87
Acknowledgments
We thank the Deutsche Forschungsgemeinschaft and the Henkel AG & Co. KGaA for the financial support. This work has been a part of the dissertation of Frank Polzer.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(PDF 524 kb)
Rights and permissions
About this article
Cite this article
Polzer, F., Holub-Krappe, E., Rossner, H. et al. Structural analysis of colloidal MnO x composites. Colloid Polym Sci 291, 469–481 (2013). https://doi.org/10.1007/s00396-012-2725-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00396-012-2725-8