Journal of Colloid and Interface Science 298 (2006) 730741 www.elsevier.

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pH-dependent surface charging and points of zero charge III. Update

Marek Kosmulski
Department of Electrochemistry, Lublin University of Technology, Nadbystrzycka 38 A, 20-618 Lublin, Poland Received 16 November 2005; accepted 4 January 2006 Available online 8 February 2006

Abstract The recently published points of zero charge (PZC) of various materials are compiled to update previous compilations [M. Kosmulski, Chemical Properties of Material Surfaces, Dekker, New York, 2001; M. Kosmulski, J. Colloid Interface Sci. 253 (2002) 77; M. Kosmulski, J. Colloid Interface Sci. 275 (2004) 214]. The recent results corroborate the previously found PZC with a few exceptions. The PZC of alumina obtained from the second-harmonic generation response is substantially lower than the PZC obtained by means of standard methods, while for titania the difference is less signicant. PZC of Tl2 O3 at pH 7.9 was reported for the rst time. A surprisingly insignicant temperature effect on the IEP of rutile was found. Recent model studies aimed at explanation of the effect of the nature of 11 electrolytes on the course of charging curves and of discrepancies in the PZC of different materials having the same chemical formula are summarized. 2006 Elsevier Inc. All rights reserved.
Keywords: Point of zero charge; Isoelectric point; Surface charge; Zeta potential

1. Introduction The present review is devoted to the pH-dependent surface charging of metal oxides and related materials in the presence of 11 electrolytes at room temperature. The points of zero charge (PZC) of these materials obtained in the presence of alkali halides, nitrates(V), or chlorates(VII) and in the absence of other solutes are referred to as pristine points of zero charge, and they are widely used to characterize the proton afnity of materials. The most comprehensive compilations of pristine PZC published till 2003 were completed by Parks [1], and by Kosmulski [24]. A few more selective or more specialized compilations of pristine PZC have been published by various authors. Very recent results (20042005) and a few older results (overlooked in previous compilations) are compiled in the present paper in Table 1. The style of the present compilation is based on the previous publications [24]. Original papers were selected, in which the material (the manufacturer and the trademark of commercial materials or the origin of natural materials or preparation of
E-mail address: mkosmuls@hektor.umcs.lublin.pl. 0021-9797/$ see front matter 2006 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2006.01.003

synthetic materials), as well as the experimental method used to determine the PZC and the conditions of the experiment, are adequately described. There are a few blank cells in Table 1, because the relevant data (temperature, ionic strength) are not always reported in the cited papers. The following abbreviations are used for experimental methods (see Ref. [2] for detailed descriptions): cip (common intersection point of potentiometric titration curves obtained at three or more ionic strengths); intersection (intersection point of potentiometric titration curves obtained at two ionic strengths); merge (the titration curves obtained at different ionic strengths merge below an above a certain pH); pH (natural pH of the dispersion); IEP (isoelectric point obtained by means of electrophoresis or electroosmosis); acousto (isoelectric point obtained by means of the electroacoustic method). In principle, the results presented in Table 1 were obtained by means of the above methods, at standard temperature (about

Table 1 Zero points of metal (hydr)oxides and other materials Formula Al2 O3 Al2 O3 Al2 O3 Al2 O3 Al2 O3 Al2 O3 Al2 O3 Al2 O3 Description , 99.995%, Showa Denko , Aerosil, puried P152SB Pechiney Whatman, Anodisc 47 Stark , Baikowski CR6 , ALCOA 16SG Fumed 0.001 mol dm3 KCl 0.01 mol dm3 NaCl 0.0010.1 mol dm3 NaCl 0.0010.1 mol dm3 NaCl 0.001 mol dm3 NaCl 25 25 25 0.0010.1 mol dm3 NaNO3 Electrolyte T ( C) 25 Method IEP cip Acousto IEP pH cip Acousto cip Acousto IEP pH0 9.2 8.3 8 8 Original, 8.6 plasma sprayed + 8.8 8.8 Merge 8.3 9.5 Literature K. Esumi, M. Goino, Langmuir 14 (1998) 44664470 C.H. Wu, S.L. Lo, C.F. Lin, C.Y. Kuo, J. Colloid Interface Sci. 233 (2001) 259264 S. Bou, S. Baklouti, C. Pagnoux, J.F. Baumard, J. Eur. Ceram. Soc. 22 (2002) 14931500 B.H. Winkler, R.E. Baltus, J. Membr. Sci. 226 (2003) 7584 M. Harju, E. Levnen, T. Mntyl, J. Colloid Interface Sci. 276 (2004) 346353 P. Mikkola, P. Ylh, E. Levnen, J.B. Rosenholm, Ceram. Int. 30 (2004) 291299 P. Mikkola, P. Ylh, E. Levnen, J.B. Rosenholm, Ceram. Int. 30 (2004) 291299 V.M. Gunko, V.I. Zarko, I.F. Mironyuk, E.V. Goncharuk, N.V. Guzenko, M.V. Borysenko, P.P. Gorbik, O.A. Mishchuk, W. Janusz, R. Leboda, J. Skubiszewska-Zieba, W. Grzegorczyk, M. Matysek, S. Chibowski, Colloids Surf. A 240 (2004) 925 R.J. Kershner, J.W. Bullard, M.J. Cima, Langmuir 20 (2004) 41014108 H. Sieger, M. Winterer, H. Muhlenweg, G. Michael, H. Hahn, Chem. Vap. Depos. 10 (2004) 7176 R.J. Kershner, J.W. Bullard, M.J. Cima, Langmuir 20 (2004) 41014108 K. Rezwan, L.P. Meier, M. Rezwan, J. Voros, M. Textor, L.J. Gauckler, Langmuir 20 (2004) 10,05510,061; K. Rezwan, L.P. Meier, L.J. Gauckler, Langmuir 21 (2005) 34933497; K. Rezwan, A.R. Studart, J. Voros, L.J. Gauckler, J. Phys. Chem. B 109 (2005) 14,46914,474 B.P. Singh, R. Manchavez, C. Takai, M. Fuji, M. Takahashi, J. Colloid Interface Sci. 291 (2005) 181186 M.R. Das, S. Mahiuddin, Colloids Surf. A 264 (2005) 90100 S.B. Johnson, G.E. Brown, T.W. Healy, P.J. Scales, Langmuir 21 (2005) 63566365 L. Saravanah, S. Subramanian, J. Colloid Interface Sci. 284 (2005) 363 377 M. Fan, T. Boonfueng, Y. Xu, L. Axe, T.A. Tyson, J. Colloid Interface Sci. 281 (2005) 3948 J.V. Rinella, J.L. White, S.L. Hem, J. Colloid Interface Sci. 205 (1998) 161165 M.C. Jodin, F. Gaboriaud, B. Humbert, J. Colloid Interface Sci. 287 (2005) 581591 (continued on next page) 731

M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

Al2 O3 Al2 O3 Al2 O3 Al2 O3

AKP-30 Sumitomo From tri-sec-butylate, chemical vapor synthesis AA-2, IEP of individual faces , Taimei TM-DAR

KNO3 HCl + NaOH 0.0010.1 mol dm3 KCl 25 2

IEP IEP IEP Acousto

8 8.8 4-6 1 h aged dispersion 9.3, 16 h aged dispersion 9

Al2 O3 Al2 O3 Al2 O3 Al2 O3 Al2 O3 Al(OH)3 Al(OH)3

, Showa Denko, AL160 SG4 , Aldrich, heated at 700 C , AKP-30 A 12, Alcoa, From nitrate, hydrous Rehydragel, Reheis Gibbsite with 1012% of bayerite 0.0010.1 mol dm3 NaNO3 25 00.005 mol dm3 NaCl 0.01 mol dm3 KNO3 0.001 mol dm3 KNO3 25 25 25

IEP IEP Acousto IEP pH IEP pH

9.1 6.46.7 9.4 9.2 8.6 11.5 78 (no cip)

732

Table 1 (continued) Formula Al(OH)3 CeO2 CeO2 Cr2 O3 Cr(OH)3 Cr(OH)3 Fe3 O4 Fe2 O3 From chloride FeCl2 + FeCl3 + NH3 Aldrich, 0.13% Al, 0.08% Si, 0.2% Mn Reakchim Hematite, Alfa Aesar Monodispersed hematite, from FeCl3 Hematite, natural, heated at 700 C, 0.68% SiO2 , 0.29% Al2 O3 Synthetic, Commercial Minerals, 99.5%, hematite with admixture of lepidocrocite Hematite, from nitrate Hematite, synthetic , from nitrate , from chloride From nitrate, hydrous From chloride 00.001 mol dm3 NaCl 0.001 mol dm3 KNO3 Stark, eskolaite Description Freshly precipitated from chloride 99.9%, Dervey None KOH + HCl 0.01 mol dm3 NaCl 0.002 mol dm3 KNO3 104 102 mol dm3 KCl 0.001 mol dm3 NaCl 0.001, 0.01 mol dm3 NaNO3 0.1 mol dm3 NaCl 0.03 mol dm3 NaCl 23 25 25 IEP IEP IEP IEP Electrolyte T ( C) 25 Room Method IEP Acousto IEP IEP pH pH0 9.2 6 6 Original 5.4 plasma sprayed 5.5 8.6 8.5 6.7 8 Literature H. Pommerenk, G.C. Schafran, Environ. Sci. Technol. 39 (2005) 6429 6434 J.P. Hsu, A. Nacu, J. Colloid Interface Sci. 274 (2004) 277284 J.T. Abiade, W. Choi, R.K. Singh, J. Mater. Res. 20 (2005) 11391145 M. Harju, E. Levnen, T. Mntyl, J. Colloid Interface Sci. 276 (2004) 346353 A.I. Zouboulis, K.A. Kydros, K.A. Matis, Water Res. 29 (1995) 1755 1760 B.Y. Medina, M.L. Torem, L.M.S. Mesquita, Miner. Eng. 18 (2005) 225 231 Y.C. Chang, D.H. Chen, J. Colloid Interface Sci. 283 (2005) 446451 M.M. Ramos-Tejada, A. Ontiveros, J.L. Viota, J.D.G. Duran, J. Colloid Interface Sci. 268 (2003) 8595. The maximum in the yield stress roughly matches the IEP O.N. Karaseva, L.I. Ivanova, L.Z. Lakshtanov, Geochim. Int. 41 (2004) 11831193; also 50 and 75 C Z. Pan, P. Somasundaran, N.J. Turro, S. Jockusch, Colloids Surf. A 238 (2004) 123126 L.J. Kirwan, P.D. Fawell, W. van Bronswijk, Langmuir 20 (2004) 4093 4100 M.R. Das, D. Bordoloi, P.C. Borthakur, S. Mahiuddin, Colloids Surf. A 254 (2004) 4955 J. Addai-Mensah, J. Ralston, Hydrometallurgy 74 (2004) 221231. The IEP matches the maximum in the settling rate and in the yield stress

M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

Fe2 O3 Fe2 O3 Fe2 O3 Fe2 O3

25

pH IEP IEP IEP

8.5 6.5 10 5.8

Fe2 O3

22

Acousto

5.6

Fe2 O3 Fe2 O3 Fe2 O3 Fe2 O3 Fe2 O3 Fe2 O3 nH2 O

0.0030.1 mol dm3 NaNO3 0.01 mol dm3 NaCl 0.1 mol dm3 NaNO3 0.1 mol dm3 NaNO3

25 25 25 25 25

cip IEP pH pH IEP pH IEP

8.8 8.5 7.5 6.5 6.2 7.6 5.5

C.L. Peacock, D.M. Sherman, Geochim. Cosmochim. Acta 68 (2004) 26232637 S. Chibowski, J. Patkowski, E. Opala-Mazur, Mater. Chem. Phys. 92 (2005) 519525 M. Jarlbring, L. Gunneriusson, B. Hussmann, W. Forsling, J. Colloid Interface Sci. 285 (2005) 212217 M. Jarlbring, L. Gunneriusson, B. Hussmann, W. Forsling, J. Colloid Interface Sci. 285 (2005) 212217 M. Fan, T. Boonfueng, Y. Xu, L. Axe, T.A. Tyson, J. Colloid Interface Sci. 281 (2005) 3948 D.I. Kreller, G. Gibson, G.W. van Loon, J.H. Horton, J. Colloid Interface Sci. 254 (2002) 205213 (continued on next page)

Table 1 (continued) Formula Fe2 O3 nH2 O FeOOH FeOOH FeOOH FeOOH Description From nitrate Goethite, from nitrate Lepidocrocite, hydrolysis and oxidation of FeCl2 From nitrate Goethite, from sulfate Electrolyte 0.1 mol dm3 NaCl 0.0030.1 mol dm3 NaNO3 0.0030.1 mol dm3 NaNO3 0.0020.093 mol dm3 KNO3 0.01 mol dm3 KNO3 25 25 25 T ( C) Method pH cip cip Merge IEP pH0 7.7 8.5 7.7 9.2 8.1 Literature M. Davranche, O. Pourret, G. Gruau, A. Dia, J. Colloid Interface Sci. 277 (2004) 271279 C.L. Peacock, D.M. Sherman, Geochim. Cosmochim. Acta 68 (2004) 17231733; 26232637 C.L. Peacock, D.M. Sherman. Geochim. Cosmochim. Acta 68 (2004) 26232637 T. Saito, L.K. Koopal, W.H. van Riemsdijk, S. Nagasaki, S. Tanaka, Langmuir 20 (2004) 689700 L.C. Varanda, M.P. Morales, G.F. Goya, M. Imaizumi, C.J. Serna, M. Jafelicci, Mater. Sci. Eng. B 112 (2004) 188193. IEP of rare earth hydroxides is also reported at pH 5.57.5 J.F. Boily, S. Sjoberg, P. Persson, Geochim. Cosmochim. Acta 69 (2005) 32193235 R.S. Juang, J.Y. Chung, J. Colloid Interface Sci. 275 (2004) 5360 Y. Xu, L. Axe, J. Colloid Interface Sci. 282 (2005) 1119 J. Antelo, A. Avena, S. Fiol, R. Lopez, F. Arce, J. Colloid Interface Sci. 285 (2005) 476486 U.G. Nielsen, Y. Paik, K. Julmis, M.A.A. Schoonen, R.J. Reeder, C.P. Grey, J. Phys. Chem. B 109 (2005) 18,31018,315 U.G. Nielsen, Y. Paik, K. Julmis, M.A.A. Schoonen, R.J. Reeder, C.P. Grey, J. Phys. Chem. B 109 (2005) 18,31018,315 J. Jonsson, P. Persson, S. Sjoberg, L. Lovgren, Appl. Geochem. 20 (2005) 179191 W. Janusz, A. Gagan, E. Skwarek, Adsorption Sci. Technol. 22 (2004) 795806 D.A. Shaughnessy, H. Nitsche, C.H. Booth, D.K. Shuh, G.A. Waychunas, R.E. Wilson, H. Gill, K.J. Cantrell, R.J. Serne, Environ. Sci. Technol. 37 (2003) 33673374 A.G. Xyla, B. Sulzberger, G.W. Luther, J.G. Hering, P. van Cappellen, W. Stumm, Langmuir 8 (1992) 95103 C.J. Matocha, E.J. Elzinga, D.L. Sparks, Environ. Sci. Technol. 35 (2001) 29672972 D.A. Shaughnessy, H. Nitsche, C.H. Booth, D.K. Shuh, G.A. Waychunas, R.E. Wilson, H. Gill, K.J. Cantrell, R.J. Serne, Environ. Sci. Technol. 37 (2003) 33673374 M. Ramstedt, B.M. Andersson, A. Shchukarev, S. Sjoberg, Langmuir 20 (2004) 82248229 J.W. Tonkin, L.S. Balistrieri, J.W. Murray, Appl. Geol. 19 (2004) 2953 733 (continued on next page) M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

FeOOH FeOOH FeOOH FeOOH FeOOH FeOOD Fe8 O8 (OH)5.02 (SO4 )1.49 0.5H2 O HfO2 Mn3 O4

Goethite, from nitrate, 2 samples Goethite, from nitrate Goethite, from nitrate Goethite, from nitrate Nanoparticles, from chloride Nanoparticles, from chloride Schwertmannite, Kristineberg, Sweden Aldrich, washed Hausmannite, Chemetals

0.1 mol dm3 NaNO3 0, 0.1 mol dm3 NaNO3 0.0010.1 mol dm3 NaNO3 0.0050.1 mol dm3 KNO3

25 25

pH IEP cip

9.2 7.8 8.8 9.3 9.3 8.3 4.3 7.2 7.5 6.9 >10 if any

25

IEP cip IEP IEP

0.1 mol dm3 NaNO3 NaCl 0.0050.1 mol dm3 NaClO4 0.01 mol dm3 25 25

IEP cip IEP cip

MnOOH MnOOH MnOOH

Manganite, from MnSO4 Manganite, from MnSO4 Manganite, Chemetals

Titration IEP

6.2 6.3 7.4

0.0050.1 mol dm3 NaClO4 0.010.1 mol dm3 NaCl

25

cip

MnOOH MnO2

Manganite, from MnSO4 Review with 7 references

Acousto pH Titration

8.28.5 8.1

734

Table 1 (continued) Formula MnO2 MnO2 NiO Ni(OH)2 SiO2 SiO2 SiO2 SiO2 Description Delta EMD, treated at 100 500 C for 1 d (9 samples) NaMnO4 + Mn(NO3 )2 Aldrich, <1% C From nitrate CabOSil M5 C800 Sifraco CabOSil M5 Grown on seeds (EverGreen) from dispersion obtained from Na2 SiO3 solution by cation exchange Ludox HS Ludox AM (0.2% Al2 O3 ) Fumed 103 mol dm3 KCl 0.001 mol dm3 NaCl 20 25 0.1 mol dm3 KNO3 0.001 mol dm3 KCl N(CH3 )4 OH + HNO3 HNO3 + KOH 25 Electrolyte 0.01 mol dm3 NaNO3 25 pH IEP IEP IEP Acousto IEP IEP 2.4 3.54 9.2 = 0 at pH 2 <2 if any 0 at pH < 2.5 1.5 T ( C) 25 Method pH pH0 4.26 Literature A.P. Malloy, G.J. Browning, S.W. Donne, J. Colloid Interface Sci. 285 (2005) 653664 M. Fan, T. Boonfueng, Y. Xu, L. Axe, T.A. Tyson, J. Colloid Interface Sci. 281 (2005) 3948 N. Hernandez, R. Moreno, A.J. Sanchez-Herencia, J.L.G. Fierro, J. Phys. Chem. B 109 (2005) 44704474 M. Meyer, A. Bee, D. Talbot, V. Cabuil, J.M. Boyer, B. Repetti, R. Garrigos, Colloid Interface Sci. 277 (2004) 309315 X. Meng, R.D. Letterman, Environ. Sci. Technol. 27 (1993) 970975 S. Bou, S. Baklouti, C. Pagnoux, J.F. Baumard, J. Eur. Ceram. Soc. 22 (2002) 14931500 W.H. Kuan, S.L. Lo, M.K. Wang, J. Colloid Interface Sci. 272 (2004) 489497 M.S. Tsai, W.C. Wu, Mater. Lett. 58 (2004) 18811884

M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

SiO2 SiO2

IEP IEP

<2 if any 2.2

P. van der Meeren, H. Saveyn, S. Bogale Kassa, W. Doyen, R. Leysen, Phys. Chem. Chem. Phys. 6 (2004) 14081412 V.M. Gunko, V.I. Zarko, I.F. Mironyuk, E.V. Goncharuk, N.V. Guzenko, M.V. Borysenko, P.P. Gorbik, O.A. Mishchuk, W. Janusz, R. Leboda, J. Skubiszewska-Zieba, W. Grzegorczyk, M. Matysek, S. Chibowski, Colloids Surf. A 240 (2004) 925 H. Sieger, M. Winterer, H. Muhlenweg, G. Michael, H. Hahn, Chem. Vap. Depos. 10 (2004) 7176 J.F. Cardenas, Colloids Surf. A 252 (2004) 213219 T.N.T. Phan, N. Louvard, S.A. Bachiri, J. Persello, A. Foissy, Colloids Surf. A 244 (2004) 131140 A. Shchukarev, J. Rosenqvist, S. Sjoberg, J. Electron Spectrosc. Relat. Phenom. 137140 (2004) 171176; A. Shchukarev, S. Sjoberg, Surf. Sci. 584 (2005) 106112 Y. Xu, L. Axe, J. Colloid Interface Sci. 282 (2005) 1119 X. Ma, M. Pawlik, Colloids Surf. A 289 (2005) 4855 D. Fornasiero, J. Ralston, Int. J. Miner. Process. 76 (2005) 7581 T. Moriguchi, K. Yano, M. Tahara, K. Yaguchi, J. Colloid Interface Sci. 283 (2005) 300310 K. Rezwan, A.R. Studart, J. Voros, L.J. Gauckler, J. Phys. Chem. B 109 (2005) 1446914474 (continued on next page)

SiO2 SiO2 SiO2 SiO2

From tetraethoxysilane chemical vapor synthesis Ludox 50 From sodium silicate Ludox TM-50, Aldrich

HCl + NaOH 0.1 mol dm3 KCl 0.03 mol dm3 NaCl 0.02, 0.1 mol dm3 NaCl 0.0010.1 mol dm3 NaNO3 0.01 mol dm3 LiCl, NaCl, KCl, CsCl 0.001 mol dm3 KCl 0.01 mol dm3 NaCl

IEP pH pH pH

2.2 0 < 0 at pH > 2.17 <3 if any <3 if any

SiO2 SiO2 SiO2 SiO2 SiO2

Quartz, Alfa Aesar Quartz, Sigma-Aldrich Quartz, high purity, Bottley CARiACT, Fuji Amorphous, Snowtex ZL, Nissan

cip Acousto IEP IEP Acousto

2.9 <3.5 if any <3 if any <2 if any = 0 at pH 1.2

Table 1 (continued) Formula SiO2 SiO2 SiO2 SiO2 TiO2 TiO2 TiO2 TiO2 TiO2 Stark Fumed 0.01 mol dm3 NaCl 0.001 mol dm3 NaCl 25 Description From sodium metasilicate Nissan, nonporous, acid washed Klebosol, 3 types Stober P25 Degussa Tioxide, CLDD 1910 Electrolyte 0.001 mol dm3 NaCl 0.0010.1 mol dm3 KCl 0.0031 mol dm3 KCl 0.01 mol dm3 KNO3 0.0010.1 mol dm3 NaCl 0.01 mol dm3 KCl 25 pH IEP IEP cip IEP IEP Acousto IEP pH IEP <4 if any 2.9 7.6 6.3 6.2 7.4 Original, rutile + Ti8 O15 5 plasma sprayed, rutile, 5.3 6 T ( C) Method IEP pH pH0 <2 if any <4.5 if any Literature T. Jesionowski, Dyes Pigments 67 (2005) 8192 Y. Samoshina, T. Nylander, V. Shubin, R. Bauer, K. Eskilsson, Langmuir 21 (2005) 58725881 M. Kobayashi, F. Juillerat, P. Galletto, P. Bowen, M. Borkovec, Langmuir 21 (2005) 57615769 M. Ocana, M. Andres-Verges, R. Pozas, C.J. Serna, J. Colloid Interface Sci. 294 (2006) 355361 N. Jaffrezic-Renault, P. Pichat, A. Foissy, R. Mercier, J. Phys. Chem. 90 (1986) 27332738; P. Pichat, New J. Chem. 11 (1987) 135140 R.W. OBrien, B.R. Midmore, A. Lamb, R.J. Hunter, Faraday Discuss. Chem. Soc. 90 (1990) 301312 P.V. Liddell, Ph.D. thesis, Univ. Melbourne 1996, quoted by Z. Zhou, P.J. Scales, D.V. Boger, Chem. Eng. Sci. 56 (2001) 29012920 M. Harju, E. Levnen, T. Mntyl, J. Colloid Interface Sci. 276 (2004) 346353 V.M. Gunko, V.I. Zarko, I.F. Mironyuk, E.V. Goncharuk, N.V. Guzenko, M.V. Borysenko, P.P. Gorbik, O.A. Mishchuk, W. Janusz, R. Leboda, J. Skubiszewska-Zieba, W. Grzegorczyk, M. Matysek, S. Chibowski, Colloids Surf. A 240 (2004) 925 M. Kosmulski, J.B. Rosenholm, Colloids Surf. A 248 (2004) 121126 S. Lebrette, C. Pagnoux, P. Abelard, J. Colloid Interface Sci. 280 (2004) 400408. Also in water, 0.9 volume fractionethanol, 0.1 volume fraction mixture Y. Gao, R. Wahi, A.T. Kan, J.C. Falkner, V.L. Colvin, M.B. Tomson, Langmuir 20 (2004) 95859593 W. Janusz, A. Gagan, E. Skwarek, Adsorpt. Sci. Technol. 22 (2004) 795806 W. Janusz, A. Gagan, E. Skwarek, Adsorpt. Sci. Technol. 22 (2004) 795806 D.R.E. Snoswell, J. Duan, D. Fornasiero, J. Ralston, J. Colloid Interface Sci. 286 (2005) 526535; stability was also studied C. Jing, X. Meng, S. Liu, S. Baidas, R. Patraju, C. Christodoulatos, G.P. Koratis, J. Colloid Interface Sci. 290 (2005) 1421 P.K. Dutta, A.K. Ray, V.K. Sharma, F.J. Millero, J. Colloid Interface Sci. 278 (2005) 270275 P.K. Dutta, A.K. Ray, V.K. Sharma, F.J. Millero, J. Colloid Interface Sci. 278 (2005) 270275 (continued on next page) 735 M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

TiO2 TiO2

Anatase, Aldrich, washed Kerr McGee, rutile, >99.7%, Fe and S < 10 ppm Anatase, 3 samples: TiNano, Alfa Aesar, Sigma Rutile, from chloride Anatase, from ethoxide From ethoxide Nanocrystalline anatase, from sulfate P25 Degussa, 80% anatase, 20% rutite Hombikat UV 100, Sachtleben Chemie, 99% anatase

0.005 mol dm3 NaNO3 0.01, 0.1 mol dm3 NaCl 0.1 mol dm3 KNO3 NaCl NaCl 0.001 mol dm3 KCl 0.0010.1 mol dm3 KNO3 0.001 mol dm3 NaNO3 0.001 mol dm3 NaNO3

25

Acousto Acousto intersection pH

6.8 5.6

TiO2 TiO2 TiO2 TiO2 TiO2

66.1 5.1 6.2 6.2 6.1 5.8

25 25 25

cip cip IEP IEP Intersection IEP IEP IEP

TiO2 TiO2

6.9 6.2

736

Table 1 (continued) Formula TiO2 Description Anatase, Kronos Electrolyte T ( C) Method IEP Acousto 0.001 mol dm3 NaCl 0.0010.1 mol dm3 NaClO4 0.01 mol dm3 NaNO3 None 25 25 pH IEP cip IEP IEP cip IEP pH0 5.1 Literature K. Rezwan, A.R. Studart, J. Voros, L.J. Gauckler, J. Phys. Chem. B 109 (2005) 1446914474; K. Rezwan, L.P. Meier, L.J. Gauckler, Langmuir 21 (2005) 34933497 S. Liufu, H. Xiao, Y. Li, J. Colloid Interface Sci. 281 (2005) 155163 W. Janusz, M. Matysek, J. Colloid Interface Sci. 296 (2006) 22 M. Kosmulski, C. Saneluta, J. Colloid Interface Sci. 280 (2004) 544545 M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741 A. Degen, M. Kosec, J. Am. Ceram. Soc. 86 (2003) 20012010

TiO2 TiO2 Tl2 O3 ZnO

Anatase, from chloride, 20 nm in diameter Anatase, Aldrich Avicennite, Aldrich Johnson Matthey, Pharma, Slovak Koseca, Grillo Sigma Synthetic, nanoparticles Monoclinic, Ventron, washed Monoclinic, TZ-0, Tosoh Monoclinic, S.D. Fine Chemicals From chloride Zn(NO3 )2 + NaOH (pH 8)

5.7 5.7 5.5 5.2 7.9 9.2 8.7 8.6 9.8 9.2 9 7.6 5.8 6.2 5.5 8.2

ZnO ZnO ZrO2 ZrO2 ZrO2 ZrO2 ZnOZn(OH)2

0.01 mol dm3 KNO3 0.001 mol dm3 NaCl NaCl 25

IEP IEP cip Acousto

T.H. Muster, I.S. Cole, Corrosion Sci. 46 (2004) 23192335 S. Liufu, H. Xiao, Y. Li, Powder Technol. 145 (2004) 2024 W. Janusz, A. Gagan, E. Skwarek, Adsorpt. Sci. Technol. 22 (2004) 795806 K. Rezwan, A.R. Studart, J. Voros, L.J. Gauckler, J. Phys. Chem. B 109 (2005) 1446914474 L. Saravanah, S. Subramanian, Colloids Surf. A 252 (2005) 175185 L.P. Salgaonkar, R.V. Jayaram, J. Colloid Interface Sci. 291 (2005) 92 97 T.H. Muster, I.S. Cole, Corrosion Sci. 46 (2004) 23192335; also zinc basic chloride, basic sulfate and basic carbonate S. Condom, S. Chemlal, A. Larbot, M. Persin, J. Membr. Sci. 268 (2006) 175180 D.X. Li, W.G. Hou, S.P. Li, M.T. Hao, G.Y. Zhang, Chin. Chem. Lett. 15 (2004) 224227

0.001 mol dm3 KNO3 None 0.01 mol dm3 KNO3 30

IEP IEP IEP

CoAl2 O4 Fex Mgy Al1xy (OH)2 Clz (OH)1yz

Spinel Hydrotalcite-like compounds, 6 samples, x = 0.030.29, y = 0.420.72, z = 0.10.2 From aluminum tri-sec-butylate and tetraethoxysilane, chemical vapor synthesis Imogolite, Kitakami, Japan Chlorite

Mixed oxides and aluminosilicates IEP 0.0010.01 mol dm3 NaCl 0.0010.01 mol dm3 NaCl 25 cip IEP

108.5 10.411.1 11.111.5

Al2 O3 SiO2

HCl + NaOH

IEP

None7.5

H. Sieger, M. Winterer, H. Muhlenweg, G. Michael, H. Hahn, Chem. Vap. Deposition 10 (2004) 7176

Al2 O3 SiO2 2.5H2 O (Mg,Al,Fe)12 (Si,Al)8 O20 (OH)16

0.0010.1 mol dm3 NaCl 0.001 mol dm3 KCl

25

IEP pH IEP

>11 if any 6 5.5

H. Tsuchida, S. Ooi, K. Nakaishi, Y. Adachi, Colloids Surf. A 265 (2005) 131134 D. Fornasiero, J. Ralston, Int. J. Miner. Process. 76 (2005) 7581 (continued on next page)

Table 1 (continued) Formula Kaolinite Kaolinite Montmorillonite Stevensite Description KGa-2 Aksaray, Turkey Treated SWy-2 Si3.78 Al0.22 Mg2.92 Fe0.09 Na0.08 K0.08 O10 (OH)2 4H2 O, Morocco 72.75% SiO2 , 13.56% Al2 O3 , 2.92% Na2 O, 4.93% K2 O, 1.1% CaO Stark 00.01 mol dm3 NaCl 0.01 mol dm3 NaCl 30 Electrolyte 0.010.1 mol dm3 NaNO3 20 25 IEP pH IEP <2.4 if any 4.2 2 T ( C) 25 Method pH pH0 5.56 Literature I. Heidmann, I. Christl, C. Leu, R. Kretzschmar, J. Colloid Interface Sci. 282 (2005) 270282 M. Alkan, O. Demirbas, M. Dogan, Micropor. Macropor. Mater. 83 (2005) 5159 M. Fan, T. Boonfueng, Y. Xu, L. Axe, T.A. Tyson, J. Colloid Interface Sci. 281 (2005) 3948 A. Benhammou, A. Yaacoubi, L. Nibou, B. Tanouti, J. Colloid Interface Sci. 282 (2005) 320326 M. Alkan, M. Karadas, M. Dogan, O. Demirbas, Colloids Surf. A 259 (2005) 155166; M. Alkan, O. Demirbas, M. Dogan. Micropor. Mesopor. Mater. 84 (2005) 192200 M. Harju, E. Levnen, T. Mntyl, J. Colloid Interface Sci. 276 (2004) 346353 L.F. Li, W.G. Hou, X.N. Dai, C.X. Liu, Acta Chim. Sin. 62 (2004) 429 432 M. Harju, E. Levnen, T. Mntyl, J. Colloid Interface Sci. 276 (2004) 346353 R. Rojas Delgado, M. Arandigoyen Vidaurre, C.P. de Pauli, M.A. Ulibarri, M.J. Avena, J. Colloid Interface Sci. 280 (2004) 431441 M.S. Tsai, W.C. Wu, Mater. Lett. 58 (2004) 18811884 M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

Perlite

IEP

<2 if any

87% Al2 O3 13% TiO2

pH

Original 8.1 plasma sprayed 7.6 10.911.2 10.411 Original 8.3 plasma sprayed 5.8 >11 if any <1.5 if any

Zn(1x) Alx (OH)2+y Clxy

From chlorides, hydrotalcite-like compounds x = 0.310.52, y = 0.110.34 Stark

0.0010.1 mol dm3 NaCl 0.01 mol dm3 NaCl

IEP cip pH

75% Cr2 O3 25% TiO2

Zn2 Cr(OH)6 Cl0.7 (CO3 )0.15 2.1H2 O SiO2 + Al2 O3

From chlorides Grown on seeds (Ever-Green) from dispersion obtained from Na2 SiO3 solution by cation exchange and Al(NO3 )3 Natural sepiolite, 53.47% SiO2 , 23.55% MgO, 0.71% CaO, 0.19% Al2 O3 , 0.16% Fe2 O3 , 0.43% NiO, from Anatolia Talc

0.01 mol dm3 NaCl

IEP cip

Si12 O30 Mg8 (OH,F)4 (H2 O)4 8H2 O

HCl + NaOH 0.001 mol dm3 NaCl

IEP 20

6.6 7.8

M. Alkan, O. Demirbas, M. Dogan, J. Colloid Interface Sci. 281 (2005) 240248; M. Alkan, G. Tekin, H. Namli, Micropor. Mesopor. Mater. 84 (2005) 7583

Mg3 Si4 O10 (OH)2

0.002 mol dm3 KNO3

IEP

2.5

D.W. Fuerstenau, P. Huang, in: Proceedings XXII Int. Mineral Proc. Congress (Cape Town) S. Afr. Inst. Min. Metall. 2 (2003) p. 1034. Cited by D.W. Fuerstenau, Pradip. Adv. Colloid Interface Sci. 114115 (2005) 926 D. Fornasiero, J. Ralston, Int. J. Miner. Proc. 76 (2005) 7581 J. Sun, B.V. Velamakanni, W.W. Gerberich, L.F. Francis, J. Colloid Interface Sci. 280 (2004) 387399 J. Sun, B.V. Velamakanni, W.W. Gerberich, L.F. Francis, J. Colloid Interface Sci. 280 (2004) 387399 737 (continued on next page)

Mg3 Si2 O5 (OH)4 SnO2 + In2 O3 SnO2 + Sb2 O5

Lizardite Nanophase Technologies, 10% In2 O3 by mass Nanophase Technologies, 10% Sb3 O4 by mass

0.001 mol dm3 KCl 0.01 mol dm3 NaCl 0.01 mol dm3 NaCl

IEP IEP IEP

>10 if any 6 <0.5 if any

738

Table 1 (continued) Formula Titanomagnetite Fe2.4 Ti0.6 O4 FeTiO3 TiO2 SiO2 composites Description Natural, New Zealand Synthetic titanomagnetite, from Fe, Fe2 O3 and TiO2 Ilmenite, Alfa Aesar Fumed, 637% SiO2 by mass Electrolyte HCl + NaOH HCl + NaOH 0.0010.1 mol dm3 NaCl 0.001 mol dm3 NaCl 25 25 T ( C) Method IEP IEP cip IEP IEP pH0 Original 2.9 water rinsed 3.6 3.63.9 7.2 4.5 2.57 Literature Z. Yang, A.G. Langdon, Water Res. 38 (2004) 33043312 Z. Yang, A.G. Langdon, Water Res. 38 (2004) 33043312 W. Janusz, E. Skwarek, Physicochem. Problems Miner. Process. 39 (2005) 7788 V.M. Gunko, V.I. Zarko, I.F. Mironyuk, E.V. Goncharuk, N.V. Guzenko, M.V. Borysenko, P.P. Gorbik, O.A. Mishchuk, W. Janusz, R. Leboda, J. Skubiszewska-Zieba, W. Grzegorczyk, M. Matysek, S. Chibowski, Colloids Surf. A 240 (2004) 925, also uncorrected charging curves V.M. Gunko, V.I. Zarko, I.F. Mironyuk, E.V. Goncharuk, N.V. Guzenko, M.V. Borysenko, P.P. Gorbik, O.A. Mishchuk, W. Janusz, R. Leboda, J. Skubiszewska-Zieba, W. Grzegorczyk, M. Matysek, S. Chibowski, Colloids Surf. A 240 (2004) 925, also uncorrected charging curves J. Sun, L. Gao, J. Guo, J. Eur. Cer. Soc. 19 (1999) 17251730 C. Duran, Y. Jia, Y. Hotta, K. Sato, K. Watari, J. Mater. Res. 20 (2005) 13481355 J.X. Zhang, F. Ye, J. Sun, D.L. Jiang, M. Iwasa, Colloids Surf. A 254 (2005) 199205 O. Kangal, A.A. Sirkeci, A. Guney, Int. J. Miner. Proc. 75 (2005) 3139 M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

TiO2 SiO2 Al2 O3 composites

Fumed, TiO2 :SiO2 :Al2 O3 50:28:22, 71:8:21, 82:6:12, 87:4:9, 88:8:4 by mass Shenzhen Nanbo, 5.1% Y2 O3 by mass Aldrich, 3 mol% of Y2 O3 Tosoh, 5.1% Y2 O3 by mass

0.001 mol dm3 NaCl

25

IEP

3.59.5

ZrO2 + Y2 O3 ZrO2 + Y2 O3 ZrO2 + Y2 O3

0.0010.1 mol dm3 NaCl NaOH + HCl 0.001 mol dm3 KCl

IEP IEP IEP Salts IEP

6.8 7 7.2

Mg3 Ca(CO3 )4

Si3 N4 TiN Ca5 (PO4 )3 F BaTiO3 BaZrO3

Hunite, Egirdir lake, 0.39% SiO2 , 0.15% Na2 O, 0.08% Al2 O3 , 0.08% Fe2 O3 Shenhai, 99.5% Sanhe Yanjiao Xinyu Synthetic, carbonate free Synthetic, nanosized, Ba:Ti 0.997 Alfa Aesar

00.01 mol dm3 NaCl 0.001 mol dm3 KCl 0.001 mol dm3 KCl 0.1 mol dm3 NaNO3 0.001 mol dm3 NaCl 0.001 mol dm3 KCl 0.0011 mol dm3 NaCl, NaNO3 25

IEP IEP IEP pH IEP IEP Other IEP pH

4.6 2.2 <6 if any 5.7 2.5 5.3 original 4 calcined 800 C/12 h <2 if any 69 (species dependent)

J.X. Zhang, F. Ye, D.L. Jiang, M. Iwasa, Colloids Surf. A 259 (2005) 117123 J.X. Zhang, L. Duan, D.L. Jiang, Q.L. Lin, M. Iwasa, J. Colloid Interface Sci. 286 (2005) 209215 M. Jarlbring, L. Gunneriusson, W. Forsling, J. Colloid Interface Sci. 285 (2005) 206211 Z.G. Shen, J.F. Chen, H.K. Zou, J. Yun, J. Colloid Interface Sci. 275 (2004) 158164 F. Boschini, A. Rulmont, R. Cloots, R. Moreno, J. Eur. Ceram. Soc. 25 (2005) 31953201 A. Gelabert, O.S. Pokrovsky, J. Schott, A. Boudou, A. Feurtet-Mazel, J. Mielczarski, E. Mielczarski, N. Mesmer-Dudons, O. Spalla, Geochim. Cosmochim. Acta 68 (2004) 40394058

Diatoms

Monospecic cultures, 4 species, whole cells and frustules

M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

739

25 C). The problem of coincidence or lack of coincidence of PZC determined by different methods in various classes of materials was discussed in detail in Ref. [2]. A few interesting results obtained by nonstandard methods and/or under nonstandard conditions are discussed in the next section. 2. Experimental ndings The application of electrometric methods in studies of surface charging of metal oxides is limited by the low conductance of most ceramic adsorbents. Kallay et al. [5] designed a hematite electrode and determined its PZC (at pH 6.1) from direct measurements of its potential against a calomel electrode. The slope of the electrode potential was nearly Nernstian in the acidic range, and far less than Nernstian in the basic range. Differential potentiometric titration [6], recently proposed as a new method for determining the PZC does not substantially differ from the method based on the inection point used by Kallay and co-workers over a decade ago, and discussed in detail elsewhere [2]. The common intersection point of the second-harmonic generation response as a function of pH for three ionic strengths at pH 4.8 was identied with the PZC of the rutile 110 face [7]. This result is in fair accordance with the PZC of the rutile powders determined by means of classical methods (see Refs. [14] and Table 1). For -alumina [8] a similar method produced the PZC at pH 4.1 and 5.5 for the (0001) and (1-102) faces, respectively, which is substantially lower than the PZC of the alumina powders determined by classical methods (see Refs. [14] and Table 1). The problem of existence or nonexistence of positive charge of silica at low pH is still an open question (cf. Ref. [2] for a literature review). Recently, indirect evidence of existence of positive surface charge of SiO2 at low pH based on kinetics of dissolution was presented [9]. Duc et al. [10] reviewed acidbase properties of various clay minerals, especially the effect of the ionic strength on the PZC. The same authors [11] studied the effect of the time regime on hysteresis in the potentiometric titration curves of montmorillonite and the apparent PZC. Indeed, slow leaching and dissolution processes seem to be among the main sources of discrepancies, not only for clay minerals. While the temperature effect on the course of potentiometric titrations is well documented, studies of the temperature effect on the electrokinetic potential are rare. Recently the increase of temperature from 25 to 90 C was shown to exert a rather insignicant effect on the IEP of rutile [12]. In the cited study the actual data points are far (about 1 pH unit below and above) from the IEP; thus the position of the IEP, based on a subjective interpolation, is uncertain. The PZC of titania based on CIP (cf. Ref. [2] for references) clearly shifts to low pH as the temperature increases. Different temperature effects on the IEP on the one hand and on the PZC on the other contradict the standard model, in which the PZC and IEP match irrespective of the temperature. A shift in the PZC of granular activated carbon from pH 9.8 to 9.4 as the temperature increases from 12 to 37 C was recently reported [13]. This change is close to the change

in 1 pKw over the same temperature interval and to the typical 2 temperature effect on the PZC of metal oxides. The PZC/IEP of deuterated compounds were not reported in older literature. A recent study of deuterated goethite [14] resulted in an IEP substantially lower than that of the 1-H goethite. Further studies of isotope effects may provide valuable data to test models attempting to derive charging behavior from rst principles. 3. Model calculations In this section a few recent papers aimed at renement of existing models of the electric double layer at the solidliquid interface are reviewed. The CD (charge distribution) model, which was originally introduced for multivalent ions, was recently used to explain the specic effects of various 11 electrolytes on the charging curves of goethite [15]. In addition to the protonation constant (log K = 9, 1pK model), which is common for all 11 salts, the model involves the afnity constants, which are dened separately for each monovalent cation and anion, and fractions characterizing the distribution of the charge of the anion or of the cation between two planes. The charge of chloride (small anion) was entirely attributed to the plane closer to the surface, and the charge of cesium (large cation) was entirely attributed to the plane more remote from the surface. On the other hand, the charge of small cations (Li, Na) and of large anions (chlorate(VII)) is distributed between these two planes. This approach produces a good t between experimental and calculated charging curves for several 11 salts. The anion effect can be entirely attributed to the difference in size (the distribution coefcient varies, and the best-t afnity constant is almost constant for all studied anions), and the cations differ in size and in afnity constant, as well. The models based on protonation and deprotonation of surface sites can be generalized by allowing protonation and deprotonation of water at the portions of the surface that are free of protonable surface sites [16]. The generalized model explains rather consistent absolute values of the surface charge density 0 of samples that differ in site density. The model calculations demonstrated the independence of the PZC of titania of the site density. In contrast, the calculated PZC of alumina decreases as the site density decreases. These results explain the rather consistent PZC of various titanias (PZC at pH 6) reported in the literature, while the PZC of various aluminas (and other materials of high PZC) and of various silicas (and other materials of low PZC) show substantial scatter, which is attributed to varied site density. The IEP at pH about 4 experimentally observed for many dissimilar materials is interpreted as the IEP in the absence of surface sites, solely due to protonation and deprotonation of the surface water. Sverjensky [17] demonstrated correlations between parameters of triple-layer models (TLM) and measurable physical quantities, e.g., the permittivity of the solid. Such correlations are signicant for parameters that can be unambiguously determined from experimental data. In TLM many sets of model parameters produce practically identical model curves.

740

M. Kosmulski / Journal of Colloid and Interface Science 298 (2006) 730741

Different approaches to the prediction of the PZC by means of the bond-valence method, including the types of correlations and the set of data used in tting procedures, have been discussed [18]. The signicance of the electrostatic correction, which has to be applied for both solution monomers and surface sites was also emphasized. For solution monomers the following equations successfully predict their acidbase properties
int pKa = 61.5Sb + 22.5I 19.2 for oxyacids,

(1)

where Sb is the Lewis base strength (unsaturated valence per orbital of oxygen atom available to form bonds with hydrogen), and I is the ionicity of the bond between the central atom and oxygen calculated from the difference in the electronegativities, and
int pKa = 57.1Sb + 9.1I 18.6 for hexaquo cations.

(2)

These equations were tested for the surfaces of crystobalite and gibbsite, and Eq. (1) gave promising results. Kallay et al. [19] argue that in models of the interfacial region two parallel connected condensers can be used instead of the classical approach with two serially connected condensers. The new model produces equally good t to experimental data as the classical model. 4. Conclusions The pH-dependent surface charging of metal oxides and related materials remains an active eld of research. Many experimental studies were carried out for the materials whose surface charging behavior is already well known. Tables 2 and 3 compare the median and average PZC of Al2 O3 , Fe2 O3 , FeOOH, SiO2 , and TiO2 reported in this study with the corresponding results from the older compilations. In spite of progress in the instruments, the recent results are fairly consistent with those reported in older studies with the one exception of FeOOH (the PZC reported in Ref. [1] were substantially lower than more recent values). The differences in the average PZC of aluminum,
Table 2 Median PZC of common oxides reported in Refs. [14] and in this work Al2 O3 [1] [2, Table 3.1] [2, Appendix] [3] [4] This work 8 8.47 8.55 9 8.7 8.8 Fe2 O3 8.3 8.2 8.1 8.7 7.25 7.55 FeOOH 6.65 8.2 8.9 8.4 9 8.5 SiO2 2.1 2.95 3.45 2.4 2.7 2.2 TiO2 5.15 5.8 6 5.85 6 6.05

iron, and titanium oxides between the old results (Ref. [1]) and more recent studies (Refs. [3,4] and this study) may be due to awareness of the effect of dissolved silicates from the glassware on the IEP of metal oxides. This awareness is common now (although papers neglecting this effect are published now and then), and it was less common in the 1960s. The difference in the median PZC between the old and new results is less signicant because the median is less sensitive to the presence of a few outstanding results in the sample than the average. It should be emphasized that all types of Fe2 O3 were taken into account in the analysis of the recent studies, while only the PZC of synthetic hematites were considered for Refs. [1] and [2] (Table 3.1). This is because numerous PZC of natural iron oxides are reported in older literature, and these materials have low PZC due to impurities (chiey silica). The median and average PZC of silica from Refs. [24] and from the present study were calculated only for these samples, which actually showed a PZC. Many other samples did not show any PZC at all (negative surface charge over the entire pH range). Thus the signicance of the average and median PZC of silica is different from that for other materials, which always or almost always showed a PZC. On the other hand, in older papers, the PZC of silica was often determined by extrapolation of data, but it was not actually observed. Rather few recent publications report new data on materials for which the surface charging and PZC were less well documented or not known at all. The second-harmonic generation method offers a promise of determining the surface charging behavior of single crystallographic planes, which in turn can be used to test the theoretical models. However, such studies, involving low surface area, are very sensitive to even small concentrations of strongly adsorbing solution species, which are negligible with large surface areas (titration, electroacoustics). References
[1] G.A. Parks, Chem. Rev. 65 (1965) 177. [2] M. Kosmulski, Chemical Properties of Material Surfaces, Dekker, New York, 2001. [3] M. Kosmulski, J. Colloid Interface Sci. 253 (2002) 77. [4] M. Kosmulski, J. Colloid Interface Sci. 275 (2004) 214. [5] N. Kallay, Z. Dojnovic, A. Cop, J. Colloid Interface Sci. 286 (2005) 610 614. [6] K. Bourikas, C. Kordulis, A. Lycourghiotis, Environ. Sci. Technol. 39 (2005) 41004108. [7] J.P. Fitts, M.L. Machesky, D.J. Wesolowski, X.M. Shang, J.D. Kubicki, G.W. Flynn, T.F. Heinz, K.B. Eisenthal, Chem. Phys. Lett. 411 (2005) 399403. [8] J.P. Fitts, X.M. Shang, G.W. Flynn, T.F. Heinz, K.B. Eisenthal, J. Phys. Chem. B 109 (2005) 79817986. [9] O.S. Pokrovsky, S.V. Golubev, J.A. Mielczarski, J. Colloid Interface Sci. 296 (2006) 189. [10] M. Duc, F. Gaboriaud, F. Thomas, J. Colloid Interface Sci. 289 (2005) 139147. [11] M. Duc, F. Gaboriaud, F. Thomas, J. Colloid Interface Sci. 289 (2005) 148156. [12] A.M. Djerdjev, J.K. Beattie, R.W. OBrien, Chem. Mater. 17 (2005) 3844 3849. [13] R. Parette, F.S. Cannon, K. Weeks, Water Res. 39 (2005) 46834692.

Table 3 Average PZC of common oxides reported in Refs. [14] and in this work Al2 O3 [1] [2, Table 3.1] [2, Appendix] [3] [4] This work 7.43 8.06 8.54 8.85 8.57 8.61 Fe2 O3 7.54 7.8 7.73 8.17 7.49 7.48 FeOOH 6.12 8.14 8.81 8.32 8.73 8.54 SiO2 2.16 2.92 3.38 2.4 2.83 2.34 TiO2 5.24 5.64 6.1 5.54 5.77 6.31

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[14] U.G. Nielsen, Y. Paik, K. Julmis, M.A.A. Schoonen, R.J. Reeder, C.P. Grey, J. Phys. Chem. B 109 (2005) 1831018315. [15] R. Rahnemaie, T. Hiemstra, W.H. van Riemsdijk, J. Colloid Interface Sci. 293 (2006) 312321. [16] M. Kosmulski, Langmuir 21 (2005) 74217426.

[17] D.A. Sverjensky, Geochim. Cosmochim. Acta 69 (2005) 225257. [18] B.R. Bickmore, C.J. Tadanier, K.M. Rosso, W.D. Monn, D.L. Eggett, Geochim. Cosmochim. Acta 68 (2004) 20252042. [19] N. Kallay, D. Kovacevic, A. Cop, M. Medvidovic, Croat. Chem. Acta 77 (2004) 243249.