The PH Dependent Surface Charging and Points of Zero Charge. X. Update

Advances in Colloid and Interface Science 319 (2023) 102973
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Advances in Colloid and Interface Science

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Historical Perspective
The pH dependent surface charging and points of zero charge. X. Update

Marek Kosmulski
Lublin University of Technology, Nadbystrzycka 38, PL-20618 Lublin, Poland
A R T I C L E I N F O A B S T R A C T
Keywords: Surfaces are often characterized by their points of zero charge (PZC) and isoelectric points (IEP). Different au
Point of zero charge thors use these terms for different quantities, which may be equal to the actual PZC under certain conditions.
Isoelectric point Several popular methods lead to results which are inappropriately termed PZC. This present review is limited to
Electrophoresis
zero-points obtained in the presence of inert electrolytes (halides, nitrates, and perchlorates of the 1st group
Potentiometric titration
metals). IEP are reported for all kinds of materials. PZC of metal oxides obtained as common intersection points
of potentiometric curves for 3 or more ionic strengths (or by means of equivalent methods) are also reported,
while the apparent PZC obtained by mass titration, pH-drift method, etc. are deliberately neglected. The results
published in the recent publications and older results overlooked in the previous compilations by the same
author are reported. The PZC/IEP are accompanied by information on the temperature and on the nature and
concentration of supporting electrolyte (if available). The references to previous reviews by the same author
allow to compare the newest results with the PZC/IEP of similar materials from the older literature.
1. Introduction protons). When the adsorption of ions of the electrolyte (e.g., NaCl) is
only due to electrostatic interactions, ζ = 0 implies σ0 = 0. This is why
The point of zero charge (PZC) is almost obligatory in characteriza the IEP measured in the presence of 1–1 electrolytes is often identified
tion of adsorbents, especially in studies of adsorption of ions from with the PZC. The electrostatic character of adsorption of 1–1 electro
aqueous solution, and numerous papers report the values of the PZC lytes (at least at low concentrations) has been confirmed by the inde
[1–8]. Those are new, original results and PZC from the literature. pendence of the IEP of the concentration and nature (e.g., NaCl vs.
Literature data taken from original papers or from review papers are KNO3) of the electrolyte, but most IEP reported in the literature are
used alone or they accompany the new, original results. pH-dependent based on measurements with a single concentration of one electrolyte.
surface charging is a complex phenomenon, and in principle the sur The independence of the IEP on the solid-to-liquid ratio may be another
face charge density cannot be measured directly, but its sign is derived validation of the IEP, but such a test is seldom performed. The ζ potential
from other quantities using certain assumptions [1]. Special terminology is very sensitive to surface-active impurities. The presence of surface-
is used for zero-points obtained by means of various methods. The active impurities is responsible for the discrepancies between the IEP
conversion of electrophoretic mobility into zeta potential ζ is a complex reported for different specimens of nominally the same chemical com
problem, but at least both quantities have the same sign. Therefore, the pound. The results of electrokinetic measurements, especially near the
pH, at which the sign of the zeta potential reverses from positive (at low IEP, are scattered, and a random mixture of positive and negative values
pH) to negative (at high pH) can be easily determined in typical systems, (e.g., of electrophoretic mobility) is obtained in the closest vicinity of the
i.e., when the zeta potential assumes high positive values a fraction of 1 IEP. Therefore, the IEP is determined by interpolation of the data points
pH unit below the isoelectric point (IEP) and high negative values a at pH below and above the IEP rather than by a direct measurement at
fraction of 1 pH unit above the IEP. The electrokinetic charge is not pH where ζ = 0. In spite of the above disadvantages, the zero-point
equal to the surface charge, and, in general ζ = 0 does not imply that also determined by electrokinetic measurements belongs to the most reli
the surface charge density σ0 = 0. Therefore a separate term (IEP) is used able zero-points, and the IEP reported for various well-defined materials
for the zero-point determined from electrokinetic measurements. Elec are summarized in this review.
trokinetic measurements detect the net electrokinetic charge irre With metal oxides the σ0(pH) curves obtained by acid-base titration
spective of the charging mechanism. This charge may be due to positive at various concentrations of a 1–1 electrolyte intersect at one point
or negative adsorption of various ions (including but not limited to (common intersection point, CIP), and this point is identified with σ0 =
E-mail address: m.kosmulski@pollub.pl.
https://doi.org/10.1016/j.cis.2023.102973
Received in revised form 31 July 2023;
Available online 7 August 2023
0001-8686/© 2023 The Author. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M. Kosmulski Advances in Colloid and Interface Science 319 (2023) 102973
0 and pH=PZC. In this present review the term CIP (cip) is restricted to paper by Parks [8] and in [1]), but less popular in the recent liter
common intersection point of σ0(pH) curves for various ionic strengths. ature. Such an apparent PZC depends on the solid-to-liquid ratio and
Many other sets of curves in surface chemistry do show common inter on the ionic strength.
section points, but such intersection points are not considered in this • pH-drift method. Instead of titration, solutions of different initial pH
review. With pure metal oxides the PZC matches the IEP. Metal oxides are equilibrated with the same mass of the solid and the initial and
and several other materials show a CIP, but many other materials do not, final pH are compared. This method is equivalent to intersection
thus the usefulness of CIP for determination of PZC of most materials is point between potentiometric titration curve of inert electrolyte and
limited. The determination of PZC as the CIP is based on the assumption single titration curve of dispersion except that the equilibration time
that the surface charge is due to positive or negative adsorption of is long. Again, such an apparent PZC depends on the solid-to-liquid
protons, which is the case with metal oxides, but not necessarily with ratio and on the ionic strength. The pH-drift method is very popu
other materials. This is why the term “point of zero net proton charge, lar, e.g., among researchers who study activated carbons. Many
PZNPC” is often used to emphasize that the surface excess of protons is apparent PZC obtained by this method are reported in [1] and in its
measured rather than the net charge. The potentiometric titration curves early updates, but they are deliberately neglected in the recent up
are affected by the surface-charging, but also by pH-dependent disso dates of [1], and in the present review.
lution-precipitation of solid particles, and by protonation-deprotonation • Mass titration. Natural pH of a very concentrated dispersion. This
of solution species. Even “water insoluble” metal oxides show some method is very popular. Many apparent PZC obtained by this method
degree of solubility (on the order of 10− 6 M), and the solution species are reported in [1] and in its early updates, but they are deliberately
undergo protonation/deprotonation in course of titration. The role of neglected in the recent updates of [1], and in the present review.
solution monomers is negligible near the PZC, when the solid-to-liquid
ratio (expressed in m2/L) is sufficiently high. The pH-dependent disso In clay science the zero-point is often determined by uptake of Na+
lution and precipitation are slow (and often irreversible), and the course and Cl− ions [10]. The pH, at which the uptakes of Na+ and Cl− ions are
of titration curves depends on the rate of titration. With a broad range of equal is considered as the zero-point, but such zero-points are not
ionic strengths (e.g., 0.001–0.01-0.1 M) we have a better chance of included in Table 1. The IEP is correlated with a maximum in particle
obtaining a sharp CIP than with a narrow range. In spite of the above size of dispersed particles, maximum in viscosity and yield stress of
problems, the zero-point determined as CIP of metal oxides obtained by concentrated dispersions, and minimum in dispersion stability. Such
properly designed potentiometric titration belongs to the most reliable correlations are reported in Table 1, but the measurements of particle
zero-points, and such results are summarized in this review. size or of dispersions stability are not considered as standalone methods
The points of zero charge (PZC) and isoelectric points (IEP) pub of determination of the zero-point.
lished until 2008 were reviewed in [1]. More recent results (2009–2021)
were summarized in the updates [2,3,4,5,6,7] of the original review. On 2. Structure of Table 1
top of the above reviews by the present author, many other reviews of
the PZC are available. The early compilations including the seminal Table 1 reports the PZC and IEP determined by methods recom
review by Parks [8] reported the PZC obtained by all possible methods mended by the present author. A few results obtained by other methods
including the methods not recommended by the present author. Several are discussed in this review, but not included in the Table. As in the
recent reviews, e.g., [9] report mixtures of zero-points obtained as IEP previous compilations [1–7], the materials are divided into 13 groups,
and CIP, and apparent zero-points obtained by methods, which are not and they are sorted according the same scheme.
recommended here. Most surfaces are heterogeneous, that is, the local Column 1: Section in [1] or reference to [2–7]. This reference allows
surface charge density and zeta potential may be very different from the to find other data on the same or on similar material. On top of PZC/IEP,
“averaged” values obtained by pH-titration or by electrophoresis, and ref. [1] reports the physical properties of the materials including the
most PZC and IEP reported in this review are based on these “averaged” particle shape and size, specific surface area, impurity level, crystallo
values. The surface heterogeneity plays a specially important role in clay graphic data etc.
minerals. Namely the PZC of the basal vs. edge plane may differ by Column 2:
several pH units as discussed in detail in [1]. To the best knowledge of the present author the formulae in column
There are many popular methods, which produce the actual PZC 2 represent the actual composition of the specimens, but in several
provided that the sample is absolutely pure. These methods and their studies the name of the main component was used, while the specimens
limitations are discussed in detail in [1]. Surface-active impurities affect contained substantial amounts of other compounds. For example in [11]
the PZC obtained by all methods including the methods recommended in the authors refer to Al2O3 and SiC in their text, tables and figures, and
this study (IEP, CIP). Inorganic acids and bases (as HCl and NaOH) are they only reveal in Supplementary data, that their Al2O3 contained
common impurities in commercial chemicals and in materials synthe about 6% of Zr and their SiC contained about 8% of O and about 6% of
sized by the authors of cited papers. The presence of HCl or NaOH as an Zr. This is why the data from [11] were not used in Table 1, but such
impurity in the powder does not affect the IEP or CIP, but they affect the detailed information could be easily overlooked (many readers do not
natural pH of dispersions. In this respect IEP or CIP are more reliable, i. read Supplementary data at all), and sometimes it is not available at all.
e., they are sensitive to surface-active impurities while most other The materials are sorted into 13 groups (3.1–3.13) and then they are
popular methods are sensitive to all kinds of impurities including com further sorted according to the following principles in particular groups:
mon inorganic acids and bases. Even very small amounts of inorganic 3.1 Metal (hydr)oxides are sorted alphabetically by the metallic
acids and bases substantially affect the natural pH of dispersions, element, then by the oxidation state of the metallic element, then by
especially when the zero-point is in the nearly-neutral pH range (5–9). hydration level. Aluminum hydroxides and iron (hydr)oxides are addi
The apparent PZC obtained as the natural pH of dispersion are in tionally sorted by polymorph within the same oxidation and hydration
general less reliable than IEP or CIP, and apparent zero-points can only state. The materials with the same (nominal) chemical formula and
match the actual PZC when the sample is absolutely pure or when the structure are presented in the following order: commercially available
effects of different impurities cancel out. These methods (described in materials (further sorted by the manufacturer and by trade name),
more detail in [1]) include: synthetic materials (further sorted by the precursor of metal), natural
minerals (further sorted by the country of origin), and the other (origin
• Intersection point between titration curve of inert electrolyte and unknown). The same order: commercial-synthetic-natural-other is used
single titration curve of dispersion. Once very popular (multiple in the other categories of materials. The same manufacturer (e.g.,
apparent PZC obtained by this method are reported in the seminal Degussa vs. Evonik) and the same product may appear under different
2
Table 1
PZC/IEP compilation. Update of [1–7]. Asterisk: no data points reported, only PZC/IEP value.
Section in [1] or reference to [2–7]. Material Electrolyte t, oC method Instrument PZC/IEP Ref. number PZC/IEP
of in
entries [1–7].
in [1–7].
3.1 Oxides
2
3.1.1.1.1.5, VI Al2O3, γ, Alfa Aesar 10− M NaCl iep electrophoresis 9 [12] 2 8.5
3.1.1.1.1.3.11, VI, VII Al2O3, α, CT 3000 SG iep ESA 9 [13] 4 8
from Almatis
3.1.1.1.1.3.14 Al2O3, α, T60/T64 from iep ESA 7.7 [13] 1 7.5
Almatis
a
3.1.1.1.1 Al2O3, α, P162LSB from NH4OH + iep Zeta Probe 9 [14]
Alteo, 99.9% pure HCl Colloidal
Dynamics
3.1.1.1.1.11,VI Al2O3, Baikowski NaOH + HCl 25 iep Acoustosizer I 9.2 [15] 3 8.8
3.1.1.1.1.13 Al2O3, α, Buehler 10− 3 - 10− 1 25 iep ESA 8000 Matec 9 [16] 1 8.9
M NaCl
3.1.1.1.1.13 Al2O3, γ, Buehler, 3 10− 3 M iepb ESA 8000 Matec 8.3–8.9 [17]
specimens KNO3
a
3.1.1.1.1 Al2O3, α, ALG-1SH NH4OH + iep Zeta Probe 9 [14]
from Daehan, 99.9% HCl Colloidal
pure Dynamics
3.1.1.1.1.21, IV-IX AluC Degussa NaOH + 25 iep ESA 8000 Matec 9.2 [18] 50 9
HNO3
c
3.1.1.1.1.43 Al2O3, Versal GL25 NaOH + HCl 25 iep Malvern 8.8 [19]
from La Roche Zetasizer Nano
ZS
2
3.1.1.1.1 Al2O3, NGK porous 10− M KCl iep Streaming 5 [20]
ceramic membrane potential
3.1.1.1.1 Al2O3, γ, Petroraza iep electrophoresis 6.3* [21]
3.1.1.1.1 Al2O3, nanoparticles, 25 iep electrophoresis 9.2 [22]
Petroraza
2
3.1.1.1.1 SRS 333 calcined 10− M KCl iep Coulter Delsa 9.1* [23]
alumina 440SX
3.1.1.1.1.72.2 Al2O3, α, AA-04 from none 23 iep Matec ESA 8000 9.9d [24] 1 9.3
Sumitomo, 99.99%
pure
3.1.1.1.1.72 Al2O3, α, AES-11 from NH4OH + iep Zeta Probe 9.9a [14]
Sumitomo, 99.9% pure, HCl Colloidal
0.12% MgO Dynamics
intentionally added as
sintering additive
3.1.1.1.1.72.6 Al2O3, AKP-15 from NaOH + iep Zeta Probe 6.8 [25] 5 8.9
Sumitomo HNO3 Colloidal
Dynamics
3.1.1.1.1.72.8 Al2O3, α, AKP-30 from 25 iep Acoustosizer 9.5 [26] 20 9
IV-VIII Sumitomo Matec
e
3.1.1.1.1.72.9 Al2O3, AKP-50 from NH4OH + iep ESA 8.6 [27] 20 9
Sumitomo HNO3
3.1.1.1.1.73, VII Al2O3, α, from Taimei, 0.001–0.1 M 20 iep Zeta Meter 9.2 [28] 4 9
99.99% NaNO3
3.1.1.1.1 Al2O3, Dispal-180 from NH4OH + iep ESA 8.6 [27]
Vista HNO3
VII, VIII, 3.1.1.1.2.1, Al2O3, from 10− 2 M 25 iep Malvern 7.8 [29] 2 8.6
3.1.1.1.2.1.5 isopropoxide. Calcined NaNO3 Zetasizer Nano
at 600 ◦ C
3.1.1.1.2.2 Al2O3, γ, from sulfate iep 8.5 [30]
and urea. Calcined at
550 ◦ C
3
3.1.1.1.4 Al2O3 sapphire 10− M KCl iep Surpass 3 4.5 [31]
3.1.1.1.4 Al2O3 unspecified, iep DT 1200 8.7 [32]
various solid loads 9.4
3.1.1.2.2.2 AlOOH, boehmite 10− 1 M iep Malvern A 10.2 [33]
precipitated at pH 4.4 NaNO3 Zetasizer 3000, N 9.5
(A), 6.5(N), and 11.5 automatic B 8.8
(B) titration starting
at pH 3.5
3.1.1.2.2.3 AlOOH, boehmite from iep Zetasizer 9.4a [34]
nitrate and ammonia,
synthesized at 160 ◦ C,
washed, and dried at
55 ◦ C
3.1.1.4.1.1 Gibbsite from Aladdin 0.0025 M iep Brookhaven >7 if anyf [35]
KCl Zeta Plus
g
3.1.1.4.1.1.1.3 Gibbsite H 710 B from iep DT-1200 >9 if any [36] 2 9.1;
Alcoa 10.4
(continued on next page)
3
Table 1 (continued )
of in
entries [1–7].
in [1–7].
3.1.1.4.1.2 Synthetic gibbsiteh 10− 3

M NaCl 25 iep Malvern 8.7 [37]
Zetasizer Nano
ZS90
3.1.1.4.1.2.1.4, 3.1.1.4.1.2.1.6, IV- Synthetic gibbsitei 10− 3
M NaCl iep Brookhaven >9 if any [38] 12 10.2
VI Zeta Plus
3.1.1.4.2 Synthetic bayerite, β-Al 0.1 M NaCl 25 iep Malvern 6.7 [39]
(OH)3 Zetasizer Nano
ZS90
3.1.1.4.4 Electro-generated iep 6.5 [40]
aluminum hydroxide
3.1.3.1 Bi2O3, biogenic iep 5 [41]
synthesis, calcined at
550 ◦ C, mixture of γ
and α phases
3.1.6.1.1.1, 3.1.6.1.1.4, VI,VII,IX CeO2, Aldrich, cubic, 0.01, 0.1 M 25 intersection 6.3 [42] 4 8
30 nm NaCl [43]
[44]
3.1.6.1.1 CeO2, Avention HNO3 + iep ELSZ 1000 6j [45]
NaOH Otsuka
3.1.6.1.1 Ceria polishing powder HCl + NaOH iep DT 1202 <4 if any [46]
from Rodiak
3.1.6.1.1.1, 3.1.6.1.1.4, VI,VII,IX CeO2 from Sigma none 25 iep Malvern 7j [47] 4 8
Aldrich, 30 m2/g Zetasizer Nano
ZS
3.1.8.1.2 Cr2O3 obtained from 25 iep electrophoresis 6a [22]
potassium dichromate
by electrochemical
method
3.1.9.1 Cu2Ol iep 7.5 [48]
3.1.9.2.1.1, V, IX CuO from Sigma- 25 iep Malvern 10j [49] 4 8.5
Aldrich, 50 nm in Zetasizer Nano
diameter ZS900
3.1.9.2.2 CuO obtained by arc- iep Brookhaven 10 [50]
submerged Zeta Plus
nanoparticle synthesis
system
3
3.1.12.2.1 Magnetite from 10− M NaCl iep Malvern 6 [51]
NanoAmor, >98%, Zetasizer Nano
20–30 nm in diameter ZS900
2
3.1.12.2.2.2 Magnetite, from Fe II 10− M NaCl iep Malvern 6.3 [52]
and Fe III, precipitated Zetasizer Nano
with NaOH, washed ZS90
with water, dried at
40 ◦ C
3
3.1.12.2.2.2.1, V,VI,VII, IX Magnetite from FeCl3, 10− M NaCl iep Zetasizer ZEN 7.1 [53] 3 7.2
FeCl2 and ammonia, 3600
synthesized at room
temperature.
3.1.12.2.2.2.5 Magnetite from FeCl3, 10− 3 M iep Brookhaven 6.8a [54] 1 6.2
FeCl2 and ammonia, NaNO3 Zeta Plus
synthesized at 80 ◦ C
3.1.12.2.2.2.4, V,VI,IX Magnetite from FeCl3, NaOH + HCl 23 iep Malvern 6.3 [55] 3 7
FeSO4 and ammonia, Zetasizer ZEN
synthesized at 30 ◦ C 3600
3.1.12.2.2.2.4, V,VI,IX Magnetite from FeCl3, 0.05 M 25 iep Malvern 6.8 [56] 3 7
FeSO4 and ammonia KNO3 Zetasizer Nano
ZS
3.1.12.2.2 Synthetic magnetite iep 4.2 [57]
3.1.12.3.1.1.2, V, VIII Maghemite 99.95% HCl iep Zeta Probe, 7.7* [58] 3 7.5
from Alfa Aesar Colloidal
Dynamics
3.1.12.3.1.1.2, V, VIII Maghemite >99% from 0.1 M NaCl iepm Malvern Nano 8.3 [59] 3 7.5
Alfa Aesar ZS
3.1.12.3.1.2, V Maghemite obtained by NaOH + HCl iepa ELS 8000 8.3 [60]
cathodic deposition at Otsuka 7.9
pH 2, using steel rod as
the anode, at various
current densities,
washed with water, 2
specimens
3.1.12.3.1.2, VI,VII Maghemite obtained by iep Malvern 7 [61] 2 7.5
oxidation of magnetite Zetasizer 3000
nanoparticles with Fe HS
4
of in
entries [1–7].
in [1–7].
(NO3)3 solution at
80 ◦ C
3.1.12.3.2.1, VI, VII Hematite from Fisher, 10− 2 M Iep Malvern 7 [62] 2 7; 7.1
150 nm NaNO3 Salt Zetasizer Nano 6.2*
NaNO3 addition ZS
3.1.12.3.2.1.20 Hematite >99.9% from HCl iep Zeta Probe, 8.6* [58] 1 8.6
Nanostructured and Colloidal
Amorphous Materials Dynamics
3.1.12.3.2.1.2, VI,VII, IX Hematite from Sigma 10− 2 M (HCl iep Malvern 4.5 [63] 5 8.5
Aldrich + NaOH) Zetasizer Pro
Blue
3
3.1.12.3.2.1 Hematite from US 10− M NaCl 25 iep Malvern 8.3n [64]
Research Zetasizer Nano
Nanomaterials, 98%, ZS
20–40 nm
3.1.12.3.2.2.2.8, V-IX Hematite. 0.02 M FeCl3 0.0005 M Iep Malvern 9.3 [65] 39 8
in 0.002 M HCl was NaCl Zetasizer
aged for 7 d at 100 ◦ C in
PE bottle. Washed with
water, aged for 1 d at
100 ◦ C and stored as
dispersion at 4 ◦ C in
darkness.
VI, 3.1.12.3.2.2.3.5 Hematite, diluted Fe 10− 2 M Iep Malvern 9.3 [62] 1 o
(NO3)3 in 0.002 M HCl NaNO3 Salt Zetasizer Nano 9.2*

was aged for 7 d at NaNO3 addition ZS
98 ◦ C for 7 d, dialyzed,
38 nm
3.1.12.3.2.2.3.2, IV Hematite, 1 M Fe 10− 2 M Iep Malvern 8.5 [62] 2 7.5; 8.8
(NO3)3 was added to NaNO3 Salt Zetasizer Nano 8.8*
boiling water, 9 nm NaNO3 addition ZS
3.1.12.5.1.1.1 goethite >99.9% from HCl iep Zeta Probe, 8.8* [58] 1 8.8
Alfa Aesar Colloidal
Dynamics
IV,VIII, 3.1.12.5.1.1.3 Bayoxide from Lanxess 10− 2 M 20 ± iep Rank Brothers 7.4* [66] 1 7.4
commercial goethite NaNO3 1 Mark II
3.1.12.5.1.1, V-VII goethite from Sigma 10− 2 M (HCl iep Malvern 6.2 [63] 3 8.7
Aldrich + NaOH) Zetasizer Pro
Blue
3.1.12.5.1.2.1.1, IV-IX Goethite, recipe by iepg DT-1200 8.5 [36] 94 8.5
Schwertmann and
Cornell
3.1.12.5.1.2.1.1, IV-IX Goethite, from 1 M Fe 0.001, 0.7 M iep Malvern 9.8 [67] 94 8.5
(NO3)3 and 5 M KOH, NaCl Zetasizer Nano
aged at 70 ◦ C for 60 h, ZS ZEN3600
35 m2/g
3.1.12.5.1.2 Goethite, obtained by 10− 2 M iep Malvern 4.5 [68]
spontaneous NaNO3 Zetasizer Nano
conversion of
ferrihydrite
3.1.12.5.2.2.1.2, VI-IX Synthetic lepidocrocite 10− 2 M 20 ± iep Rank Brothers 7.3* [66] 5 7.2
from sulfate NaNO3 1 Mark II
3.1.12.5.3 GEH commercial 10− 2 M 20 ± iep Rank Brothers 7.2* [66]
akaganeite NaNO3 1 Mark II
3.1.12.7,VI Ferrihydrite from Alfa 10− 2 M Iep Malvern 7.1 [62] 1 o
Aesar, 4 nm, 99.95% NaNO3 Salt Zetasizer Nano 8*

NaNO3 addition ZS
3.1.12.7.1.7, IV, VII, IX Ferrihydrite from 10− 2 M iep Malvern 6.8 [68] 10 8
nitrate, obtained at pH NaNO3 Zetasizer Nano
7
3.1.12.7.1 Synthetic ferrihydrite, 10− 2 M (HCl iep Malvern 7.7 [63]
recipe by Villacis- + NaOH) Zetasizer Pro
Garcia Blue
2
3.1.12.7.1.7 6 line ferrihydrite, 10− M NaCl 25 iep Malvern 8.7p [69] 1 6.8
recipe by Cornell and Zetasizer Nano
Schwertmann ZS
3.1.12.7.1 6 line ferrihydrite, 10− 2 M 25 iep Malvern 7 [70]
precipitated at pH 3.8 NaCl, Zetasizer Nano
from nitrate NaNO3 ZS
V,VI,VIII, 3.1.12.7.1.6 Ferrihydrite iep Malvern 7.2 [71] 3 7.9
precipitated with 1 M ZEN3500
NaOH from 0.1 M FeCl3
5
of in
entries [1–7].
in [1–7].
at pH 7–7.5, dialyzed, 2
line
3.1.12.7.1.7, IV, VII, IX Ferrihydrite 0.1 M NaCl 25 iep Malvern 5.9 [39] 10 8
precipitated with 0.2 M Zetasizer Nano
NaOH from 0.375 M Fe ZS90
(NO3)3 at pH 8, and
aged for 16 h at 25 ◦ C, 2
line
3.1.12 Freshly formed iron 10− 2 M (HCl iep Malvern 7.4 [63]
oxide, from FeSO4 + NaOH) Zetasizer Pro
Blue
For iron oxyhydroxide see also section 3.8
3
3.1.14 β-Ga2O3 single crystal 10− M KCl iep Surpass 3 4.6 [31]
3.1.21.1 MgO from nitrate 25 iep electrophoresis 11.4 [22]
obtained by sol-gel
method
3.1.21.1 MgO from nitrate and iep electrophoresis 11.4* [21]
NaOH. Calcined at
450 ◦ C
3.1.21.2.2 Mg(OH)2 from MgO iep Zeta Probe from 11.9* [72]
and water Colloidal
Dynamics
3.1.21.2.2.2, VI, IX Mg(OH)2 from chloride iep Zeta Probe from 12.1 [73] 5 11.7
Colloidal
Dynamics
3.1.22.3.2 Mn3O4 52 m2/gq iep Malvern 5.6* [74]
Zetasizer Nano Z
3.1.22.3.2 Mn3O4 hausmannite, 0.1 M NaCl 25 iep Malvern 6.3 [39]
prepared from MnSO4, Zetasizer Nano
H2O2, and ammonia, ZS90
aged at 95 ◦ C for 6 h
3.1.22.6 MnOOH from KMnO4 iep Malvern 3.41 [75]
and sodium citrate, Zetasizer Nano
prepared at 180 ◦ C, ZS
washed with water and
ethanol
3.1.23.2.2.2 Nb2O5. From chloride, iep 2.7 [76]
obtained by
hydrothermal
treatment at 180 ◦ C for
12 h. Washed, and
calcined at 500 ◦ C.
3.1.24.1 Nd2O3 10− 4–10− 2
iep Malvern 10.4 [77]
M KCl Zetasizer
r o
VI, 3.1.25.1.1 NiO from BDH 30 Salt 8.4* [78] 1
addition
3.1.26.3 β PbO2 from Acros iep Malvern 5.2 [79]
Zetasizer 300 Hs
s
VI, 3.1.26.3 PbO2 plattnerite, 0.005–0.1 M cip 4.8 [80] 1
obtained from Pb NaNO3
(NO3)2 and NaClO in
basic medium in Ar
atmosphere
3.1.35.1.24.3 silica Bindzil 360 from 0.002–0.1 M room pH <3 if any [81]
Akzo Nobel NaCl
3.1.35.1 Fused silica window 0.05 M NaCl iep SurPass Anton <2 if anyt [82]
from Almaz Optics, Paar
cleaned with methanol,
and Piranha solution
3.1.35.1 Quartz sand from Carlo none 25 iep Malvern <2 if any [47]
Bernasconi, ground, Zetasizer Nano
washed with water ZS
3.1.35.1 SFP-20 M silica from 0.02% KCl iep Zeta Probe <2.5 if any [83]
Denka, >99.5% pure, Colloidal
11 m2/g, 0.14% Al2O3 Dynamics
VI, 3.1.35.1.29 Silica, Geltech 99.9% 10− 3 - 10− 1 25 iep ESA 8000 Matec <2 if any [16] 10 3
M NaCl
3.1.35.1.43 silica Klebosol 300 0.002–0.1 M room pH <3 if any [81]
from Merck NaCl
VII, VIII, 3.1.35.1.43.6 silica gel Si 60 from NaOH + HCl 25c iep Malvern 3.9 [19] 5 <3.5
Merck Zetasizer Nano
ZS
6
of in
entries [1–7].
in [1–7].
2
3.1.35.1.43.4 Monospher 250, Stober 10− M NaCl 25 iep Malvern 31 [84] (2) <4(pH)
silica from Merck Zetasizer Nano
− 1
3.1.35.1 Quartz from Mevior 0–10 M 22 iep Pen Kem Laser <2 if any [85]
KNO3 Zee Meter 501
3.1.35.1 EHT from Ransom and iep Malvern <2.5 if any [86]
Randolph Zetasizer Nano
ZS
3.1.35.1 Quartz from Real & 25 iep Malvern <2 if any [87]u
Lead Zetasizer Nano
ZS
3.1.35.1.22.1 Ludox AM from Remetv iep Malvern <3 if any [86] 4 <3
Zetasizer Nano
ZS
3.1.35.1 Remasol from Remet iep Malvern 1 [86]
Zetasizer Nano
ZS
3.1.35.1 RW microsilica iep ESA <3 if any [13]
3.1.35.1.22.4, VII silica Ludox SM from 0.002–0.1 M room pH <3 if any [81] 1 <3.5
Sigma Aldrich NaCl, 0.05 M [88]
LiCl, KCl,
CsCl
3.1.35.1.63.1 silica fumed from iep electrophoresis 2* [21] 3 2
Sigma Aldrich
− 2
3.1.35.1.63.1 silica fumed from 10 M NaCl 25 iep Malvern <3 if any [89] 3 2
Sigma Aldrich pH Zetasizer Nano
ZS
3.1.35.1.4, 3.1.35.1.63, SiO2 nanoparticles, 25 iep electrophoresis <3 if any [22]
3.1.35.1.64 Sigma Aldrich
3.1.35.2.3, IV-IX Stober silica 20 ± iep Malvern 2.3 [90]
2 Zetasizer Nano
ZSP
3.1.35.2 Silica spheresw HCl + NaOH iep Malvern 2.5 [91]
Zetasizer Nano
ZS 90
3.1.35.2.5, V,VI MCM-41 HCl + NaOH iep Malvern <2 if any [92] 2 <4
Zetasizer Nano
x − 3
IV-IX SBA-15 10 M NaCl 25 iep Malvern <2.5 if any [93] 13 3
Zetasizer [94]
a
3.1.35.3.12, IV Biosilica insulated from none 25 iep Malvern 2.1 [95]
diatoms Zetasizer
3
3.1.35.4.1 SiO2 quartz 10− M KCl iep Surpass 3 <3 if any [31]
3.1.35.3.12, IV SiO2 quartz from 22 ± iep Malvern <2 if any [96] 13 <2
Brazily 1 Zetasizer Nano [97]
ZS 90
3.1.35.3.2, VI,VII, IX SiO2 quartz from Brazil 10− 3 M 25z iep Streaming <3 if any [98] 13 <2
crushed and washed NaNO3 potential
with nitric acid
3.1.35.3.4, VII-IX SiO2 quartz from none iep Malvern <2 if any [99] 6 2
Hubei, China Zetasizer Nano
ZS 90
3.1.35.3 Quartz from Russia, 10− 3 M iep Malvern 2 [100]aa
>99%, acid-washed NaNO3 Zetasizer Nano
ZS 90
3.1.37 TaOx from ethoxide, none iep Malvern 3a [101]
synthesized in Zetasizer Nano
microemulsion, not
calcined
3.1.37.1.2 Ta2O5 from ethoxide 0–0.15 M 25 Iep Malvern 3.4j [102]
NaCl intersection Zetasizer Nano 4.2; 4.7 [103]
ZS
3.1.39.1.1, IX TiO2, anatase, Aladdin, NaOH + HCl 25 iep Malvern 20 nm 7.8 [104] 1 4.5
Macklin, and Meryer, 6 Zetasizer Nano 40 nm 6.5
specimens of different ZS 60 nm 6.2
sizes 100 nm 4.3
120 nm 3.7
140 nm 3.3
2
3.1.39.1.1.2.2, V, VI,IX TiO2, anatase, Alfa 10− M NaCl iep electrophoresis 6 [12] 5 6.1
Aesar
3.1.39.1.1.10.1, IV-IX TiO2, P25 Degussa none iepab Malvern 6.8j [105] 111 6.5
Zetamaster S
3.1.39.1.1.10.1, IV-IX TiO2, P25 Evonik iep Malvern 5.8 [106] 111 6.5
Zetasizer Nano
ZS
7
of in
entries [1–7].
in [1–7].
3.1.39.1.1.10.1, IV-IX TiO2, P25 Evonik iep 6a [107] 111 6.5

3
3.1.39.1.1.10.1, IV-IX TiO2, P25 Acros 10− M NaCl 25 iep Malvern 5.9ac [108] 111 6.5
Zetasizer Nano
ZS
3.1.39.1.1.10.1, IV-IX TiO2, P25 HCl + NaOH iep Malvern 6.4 [91] 111 6.5
Zetasizer Nano
ZS 90
3.1.39.1.1.10.1, IV-IX TiO2, P25 Degussa iep Malvern 6.7ad [109] 111 6.5
Zetasizer Nano [110]
ZS 90
3
3.1.39.1.1.10.1, IV-IX TiO2, P25 Degussa 0, 10− M iep Matec ESA 6.5 [111] 111 6.5
KCl 8000ae
3.1.39.1.1.10.1, IV-IX TiO2, Evonik, 70% iep Malvern 6–7af [112] 111 6.5
anatase 30% rutile Zetasizer Nano
ZS 90
3.1.39.1.1.12 TiO2, rutile, R746 from iep DT 1200 3.6 [32] 1 6
DuPont, 76% w/w
slurry
3.1.39.1.1.33, VI,IX TiO2, Police, heated at iep Malvern 5.5 [106] 3 6.2
100 ◦ Cag Zetasizer Nano
ZS
3.1.39.1.1.35 Rutile from Precheza, 2 none iep Malvern 4 [113]
specimens Zetasizer Nano 4.4
ZS90
3.1.39.1.1.1.2, 3.1.39.1.1.43.1, IV, Anatase from Sigma- none iep Malvern 5.5 [113] 31 5.8
VI,VII, VIII, IX Aldrich Zetasizer Nano
ZS90
3.1.39.1.1.1.2, 3.1.39.1.1.43.1, IV, Anatase from Sigma- iep Malvern 6a [114] 31 5.8
VI,VII, VIII,IX Aldrich, 99.7%, 25 nm Zetasizer Nano
ZS90
3.1.39.1.1.1.3, 3.1.39.1.1.43.2, Anatase+rutile from none iep Malvern 6 [113]
Sigma-Aldrich Zetasizer Nano
ZS90
2
3.1.39.1.1.45 TiO2, Tami porous 10− M KCl iep Streaming 5 [20] 1 6.2
3.1.39.1.3.3, IV-VII,IX Titania from HCl + NaOH iep Malvern 3 [92] 7 5.8
isopropoxide calcined Zetasizer Nano
at 500 ◦ C for 2 h
3.1.39.1.3.3.13, V,VI,VIII,IX Anatase from butoxide, iep 5.3 [115]
synthesized in aqueous
2-propanol, calcined at
500 ◦ C
3.1.39.1.3.3.13, V,VI,VIII,IX TiO2, anatase, iep Malvern 5.2 [116]
syntheticah Zetasizer Nano
ZS
3.1.39.1.3.3.13, V,VI,VIII,IX TiO2 from butoxide and iep Zetasizer Ultra, 6.1 [117]
ammonia, 100 nm in Malvern
diameter, anatase
3.1.39.1.3.1 Brookite, from TiCl3, iep Malvern 5.2*-5.9* [118]
obtained at various pH, Zetasizer Nano
calcined for 2 h at ZS
400 ◦ C, 4 specimens
3.1.39.1.3.4, V,VI,IX Titanate nanotubes, iep Malvern 3 [119] 4 5.3
calcined at 500 ◦ C in Zetasizer Nano
nitrogen ZS90
3.1.39.1.3.4, V,VI,IX TiO2, nanotubes None iepj Malvern 2.6 [109] 4 5.3
obtained by treatment 0.01 M Na Zetasizer Nano 3.7 [110]
of P25 in 10 M NaOH at ZS 90
130 ◦ C for 3 d
3.1.39.1.3.4, V,VI,IX TiO2, protonated iep Malvern 4 [120] 4 5.3
nanotubes obtained by Zetasizer Nano
treatment of P25 in 10 ZS 90
M NaOH at 130 ◦ C for 3
d
3.1.39.1.3.4, V,VI,IX TiO2, nanotubes iep Malvern 4.2–2.7 [114] 4 5.3
obtained by treatment Zetasizer Nano
of anatase from Sigma- ZS90
Aldrich in 8 M NaOH at
130 ◦ C for 1–12 h
3.1.39.1.3.4, V,VI, VII,IX Titanate nanotubes iep 3.2 [121] 4 5.3
3.1.39.1.5 TiO2, anatase, origin 0.01–0.1 M cip 6.5 [42]
unknown NaCl
3.1.39.1.5 TiO2, nanoparticles none iep Malvern ZS90 6.2 [122]
8
of in
entries [1–7].
in [1–7].
3.1.39.1.5 TiO2, nanoparticles iep 6.7 [121]

3.1.44.1.3 Y2O3, from Molycorp iep Malvern 11.2* [123] 1 8.5
Zetasizer 3
3.1.44.1.3 Y2O3, from Molycorp NH4OH + iep ESA 10.5 [27] 1 8.5
HNO3
3.1.44.1.7 Y2O3 from Shin-Etsu SU HNO3 + NH3 iep ESA 8000 Matec 9.2ai [124] 1 8.3
VIII, 3.1.44.1.8.1 Y2O3 from HC Starck, NaOH + HCl 25 iep Acoustosizer I 9.2 [15] 3 10
grade C
3.1.44.2.1 Y2O3, cubic, from iep 8.7 [30] 1 8.2
nitrate and urea.
Calcined at 550 ◦ C
2
3.1.46.1.1, IX ZnO, zincite, Alfa Aesar 10− M NaCl iep electrophoresis 8.2 [12] 1 8–8.5
3
3.1.46.1.1 ZnO, hexagonal, 4 10− M NaCl iep Malvern Nano 10.2 [125]
specimensaj ZS 9.6
9.8
<9 if any
3.1.46.1.2.2, VII ZnOak iep 8.2 [48] 1 10.2
3.1.46.1.2.3 ZnO from acetate HCl + NH3 iep Litesizer 500 9.5 [126]1 (1) 9.3al
3.1.47.1.1.19 ZrO2, Tosoh, 99.99% none 23 iep ESA Matec 9 [127]
3.1.47.1 ZrO2 monoclinic, 10 0.001–1 M 25 cip N2 purged 7.5 (table) [128]
m2/g, washed with NaNO3 7.7 (figure)
NaOH, calcined at
900 ◦ C for 8 h
3.1.47.1.2.1 ZrO2 monoclinic iep 6.3 [115]
+tetragonal, from
butoxide, synthesized
in aqueous 2-propanol,
calcined at 500 ◦ C
3.1.47.1.2.1, V, VI,IX ZrO2, from 10− 3–10− 1
20 Iep Malvern 3.8 [129]
isopropoxide and M KNO3 cip Zetasizer Nano 6.6*
ammonia, 347 m2/g ZS
3
3.1.47.1.2.2 ZrO2 from chloride 10− M KCl iep Brookhaven 5.2 [130]
obtained by Zeta Plus
hydrothermal
processing at 110 ◦ C for
1d
3.1.47.1.2.3 ZrO2 from nitrate HCl + NaOH 25am iep Malvern 6.41 [131]
precipitated at pH 9,
calcined at 550 ◦ C for 4
h
3.1.47.1.2.4 ZrO2 from sulfate, 0.05 M 25 Iep Malvern 6.7 [132]
precipitated at pH 7.5 KNO3 cip Zetasizer 2000
3.2 Aluminosilicates, clay minerals, sorted by name
V, VI Albite from Mevior 0–10− 1 M 22 iep Pen Kem Laser <2 if any [85]
KNO3 Zee Meter 501
1
V, VI Albite from Shandong, iep Coulter Delsa 1.9 [133]
China, ground in agate 440 SX
mortar
3.2.14, 3.2.33.6, VII biotite from Brazilan 10− 3
M KCl 22 ± iep Malvern <2 if any [96]
1 Zetasizer Nano
ZS 90
3.2.14, 3.2.33.6, VII biotite from Hebei, iep Malvern 3ao [134]
China Zetasizer Nano
ZS 90
3
3.2.18, V, VII Chlorite from 10− M KCl iep Brookhaven 5.5 [135]
Pennsylvania Zeta PALS
3.2 Diatomite from Chinaap iep Zeta Probe from 1.9 [73]
Colloidal
Dynamics
3.2 Dravite from Hebei, iep Malvern 3.41 [136]
China Zetasizer 2000
3.2 dravite from Wadi El 10− 2 M iep Malvern 31 [137]
Gemal, Egypt NaNO3 Zetasizer Nano
ZS
3.2.27, VII Halloysite nanotubes iep Mobius 2.6 [138]
3.2.27, VII Halloysite nanotubes iep Zetasizer 3 [139]
from Hubei
3.2.27, VII Halloysite nanotubes iep Malvern 3 [140]
from Merck Zetasizer Nano
ZS
3.2.27, VII Halloysite from China HCl + NaOH iepj ESA 8000, <3 if any [141]
in Na form Matec
9
of in
entries [1–7].
in [1–7].
3.2.27, VII Halloysite nanotubes iep Brookhaven 3.8 [142]

from China, washed Zeta Plus
with water
3.2.27, VII Halloysite from China, 10− 2 M iep Malvern 2.4 [68]
original and washed NaNO3 Zetasizer Nano
with piranha solution
3.2.29.1, VII I-Mt2 from Clay 0.056 M iep Malvern <3 if any [143]
Mineral Society, NaCl Zetasizer Nano
exposed to 1 M NaCl
3
3.2.30.1 Kaolinite from Evans 0, 10− M 22.5 iep Zeta Meter 3.0+ <3 if any [144]
Clay Companyaq LiCl ± 2.5
3.2.30.1 Kaolinite from none iepar Zeta Meter, <2 if any [145]
Lewiston Streaming
potential
3.2.30.1 Kaolin from Sedlecki 0–10− 3 M iep Brookhaven <3 if any [146]
Kaolin, 2 specimens KCl Zeta Plus
3.2.30.1.12, IX K-Ga2 from Clay 0.056 M iep Malvern <3 if any [143] 7 3
exposed to 1 M NaCl
3.2.30.1, VIII K15GM Kaolinite from 10− 2 M 22 iep Acoustosizer <2.5 if any [147]as 1 <2
Unimin, 99% pure KNO3
(quartz and mica 1%)
3.2.30.1 Kaolinite from iep Streaming 4 [148]
Vanderbilt converted potential and
into Na-form electroosmosis
3.2.30.2.1, V,VII, IX Kaolinite from China 25 iep Malvern 2.5 [87]
Zetasizer Nano
ZS
3.2.30.2.1, V,VII, IX Kaolinite from China HCl + NaOH 25 ± iepat Zeta Probe 3 [149]
2
au
3.2.30.2 kaolinite from HCl + NaOH iep ESA 8000, 3.3 [141]
Indonesia in Na form Matec
3.2.30.1.11 KGa1 kaolin iep7 DT-1200 4.5 [36] 1 3.9av
3.2.30.3.1 Georgia kaolinite in Na 10− 4 M 25aw iep Streaming 5.31 [98] 1 <2ax
form NaNO3 potential
3.2.25, 3.2.34 Microcline, KAlSi3O8, 10− 3 M NaCl iepay Zeta Meter <6 if any [150] 1 <1
ground
3.2.35 Montmorillonite from 0.0025 M iep Brookhaven <2.5 if any [35]
Aladdin NaCl Zeta Plus
3.2.35 Montmorillonite from 0, 10− 3 M 22.5 iep Zeta Meter 3.0+ <3 if any [144]
Clay and Clay Mineral LiCl ± 2.5
Repositoryaz
3.2.35.18, VI, VII S-Wy2 from Clay 0.056 M iep Malvern <3 if any [143] 5 <2
exposed to 1 M NaCl
3
3.2.35.18.5,V Bentonite from China 10− M NaCl 25 iep Malvern <2 if any [37]
in Na-form Zetasizer Nano
ZS90
3.2.35.18 Montmorillonite from HCl + NaOH Iep ESA 8000, <3 if any [141]
Japan in Na form Matec
− 3 − 2
3.2.33, 3.2.38; Ruby muscovite mica 10 , 10 iep Malvern <3.5 if any [151] 2 <3
V,VI from Continental Trade M NaCl Zetasizer Nano
ZS
3.2.33, 3.2.38, VII muscovite from Hebei, iep Malvern 4.541 [134] 1 4.5
ZS 90
3.2.33 Phlogopite (mica) from 10− 2 M iep Malvern <2 if any [137]
Wadi El Gemal, Egypt NaNO3 Zetasizer Nano
ZS
3.2.33 phlogopite from iep Coulter Delsa 2.31 [133]
Liaoning, China, 440 SX
ground in agate mortar
3.2.33 phlogopite from Hebei, iep Malvern <2 if any41 [134]
ZS 90
3.2.57.4 H-β-300 zeolite NaOH + HCl 253 iep Malvern <1 if any [19]
obtained by calcination Zetasizer Nano
of NH4- β 300 from ZS
Zeolystba
3.2.57 Synthetic β zeolite 0, 0.1 M 20 iep Coulter Delsa <2 if any [152]
nanoparticles Si/Al = NaCl 440 SX
30
10
of in
entries [1–7].
in [1–7].
3.2.57 Synthetic silicate-1 0, 0.1 M 20 iep Coulter Delsa 6.5 [152]

zeolite nanoparticles NaCl 440 SX
3.2.57 Synthetic β zeolite 0.1 M NaCl 20 iep Coulter Delsa 60 < 2 if any [152]
nanoparticles various 440 SX 120 4.5
Si/Al ratios 240 4.7
2
3.2.57 Zeolite from Argentina 10− M NaCl iep Malvern <3 if any [52]
Zetasizer Nano
ZS90
3.3 Mixed oxides
3.3.1.1 Al2O3 with CeO2 (1 and 10− 2 M 25 iep Malvern 8.6 (1%) [29]
5%) obtained by NaNO3 Zetasizer Nano 8.9 (5%)
impregnation with Ce
sulfate. Calcined at
550 ◦ C
2
3.3.1.4 Al-Fe mixed 10− M KCl iep Malvern 8.3–9 [153]
hydroxidesbb Zetasizer Nano
ZS ZEN3600
3.3.1.11 Al2O3 + Y2O3, cubic, iep 25 9.3 [30]
from Al sulfate, Y 50 9.2
nitrate and urea. 75 9
Calcined at 550 ◦ C.
Different mass % of
Y2O3
3.3 BiVO4 iep 2.3* [154]
3.3 BiVO4 + 5% Cobc iep Malvern 4.5 [155]
Zetasizer 2000
3.3.6.1.3 CoFe2O4, syntheticbd iep Nicomp 380 ZLS 6.5–9.6 [156]
[157]
3.3.6.1.3, VII CoFe2O4, syntheticbe 0.05 M NaCl 25 iep Malvern 8 [158] 1 bf
Zetasizer Nano
ZS
3.3.6.1.3, VII CoFe2O4, obtained by iep Malvern 7.3* [159] 1 58
citrate sol-gel method, Zetasizer Nano
calcined at 550 ◦ C ZS
3.3.6.3 Fe-Cu binary oxidebg iep Malvern 7.3–9 [160]
Zetasizer 2000
57
3.3.6.3 CuFe2O4, synthetic 0.05 M NaCl 25 iep Malvern 8.1 [158]
Zetasizer Nano
ZS
3.3.6.3 CuFe2O4, obtained by iep Malvern 7.1* [159]
3.3.6.3 CuFe2O4, crystalline iep 7.31 [161]
from CuSO4 and
elementary Fe
3.3.6 MgFe2O4, syntheticbh iep electrophoresis 9.5 [162]
3.3.6.4 MnFe2O4, synthetic57 0.05 M NaCl 25 iep Malvern 6 [158]
Zetasizer Nano
ZS
3.3.6.4 Manganese ferroxyhite 10− 2 M 20 ± iep Rank Brothers 7.2* [66]
AquAsZero from NaNO3 1 Mark II
Loufakis
3.3.6.5.4, VII NiFe2O4, obtained by iep Malvern 7.3* [159]
3.3.6.11 ZnFe2O4, obtained by iep Malvern 7.1* [159]
3.3.8.3 Mg-Zn binary oxidebi Iep Malvern 8.41 [163]
Zetasizer Nano
ZS90
3.3.13.1.3 Al6Si2O13 mullitebj iep Malvern 6 [164]
3.3.13.1.5, VIII allophane from Japan HCl + NaOH Iep10 ESA 8000, 5.5 [141] 1 6
in Na form Matec
− 3
3.3.13.5.2 Talc from Merck, >99% 10 M iep Acoustosizer II <2 if any [165]
KNO3
3.3.13.5.2 Talc 97% pure from 10− 1 M iep 1
Coulter Delsa 3 [166]
China KNO3 440 S II
3.3.13.5.2 Talc from China 10− 3 M iep Zeta Plus <3 if any [167]
containing 5% of KNO3
chlorite
11
of in
entries [1–7].
in [1–7].
3.3.13.5; 3.2.51; V, VI,VIII,IX Pure serpentinite from 10− 3 M iep Zeta Plus 10.2bk [167] 2 8.8;10.2
China containing traces KNO3
of chlorite
3.3.13.5; 3.2.51; V, VI,VIII,IX (Mg,Fe)3Si2O5(OH)4 10− 3 M iep electrophoresis 11.9 [168]bl 2 8.8;10.2
Serpentinite from KNO3
China with traces of
chlorite and amphibole
3
3.3.13.5.3 Forsterite from 10− M KCl 25 iep Brookhaven 2.3 [169]
Norway, 41% SiO2, Zeta Plus
52% MgO, 9% Fe2O3,
ground
3.3.13 Th silicates, Si:Th 22 ± iep Malvern Si:Th 3.9: [170]
molar ratios 3.9 and 2 Zetasizer Nano 4.9
14.2 ZS Si:Th 14.2: 4
3.3.13.6 Silica-titania composite iep 2.4a [171]
3.3.13.6 Biosilica insulated from none 25 iep Malvern 3.1a [95]
diatoms doped with Ti Zetasizer
3.3.13.8.3.4, VII, IX ZrSiO4, natural, from HCl + NaOH iep Streaming 4.8 [172]
sea sand potential
3
3.3 Ta2O5 from ethoxide, 10− M NaCl 25 iepbm Malvern 3.7 [102]
Eu-doped (1.5 mol%) Zetasizer Nano
ZS
3.3.15.1 4% Al2O3, 8% SiO2, iep Malvern 7.6 [173]
88% TiO2, synthesized Zetasizer Nano
by pyrogenic method ZS
3.3.15.7, 3.3.18.2 TiO2 + ZrO2 iep 5.4–5.9 [115]
amorphous, from
butoxides, synthesized
in aqueous 2-propanol,
calcined at 500 ◦ C, 5
specimens
3.3 Y2O3, Eu-doped NaOH + 25 iep ESA 8000 Matec 8.7 [18]bn
HNO3
3.3.17 ZnO from acetate +5% HCl + NH3 iep Litesizer 500 8.2 [126]1
Mn
3.3.18.1 30 mass% ceria, 70 NaOH + HCl iep DT 1200 8.1 [174]
mass% zirconia from
Luxferbo
3.3.18.1 50 mass% ceria, 50 NaOH + HCl iep DT 1200 9.2 [174]
mass% zirconia from
Luxfer
3.4 Salts, sorted by anion
2
3.4.3.1.2.1 SiC, LiqTech porous 10− M KCl iep Streaming <3 if any [20]
3.4.3.1.2.1 SiC, from HC Starck iep Malvern 7* [123]
Zetasizer 3
3.4.3.1.2.1 SiC from HC Starck, β, NaOH + HCl 25 iep Acoustosizer I 3.8 [15]
0.9 mass% oxygen
3.4.3.2.3.1 CaCO3 from Specialty 0.001 M KCl 25 iep Zeta Plus <8 if any [175]
Minerals, mean Brookhaven
diameter 0.83 μm
3.4.3.2.3.3.3, V calcite from Liaoning, iep Coulter Delsa 8.6 [133]
China, ground in agate 440 SX
mortar
3.4.3.2.3.3.3, V Calcite from China, HCl + NaOH iep PALS 190 Plus <7.5 if any [176]
ground Brookhaven
3.4.3.2.3.3, V Calcite 98.2% pure HCl + NaOH iep DT 300 8.8 [177]
from Norwaybp
3.4.3.2.3.3 Natural calcite 98.2% iep EMTA 1202 8.2 [178]
pure, 1.4% SiO2, 0.4% Micromeritics
MgO
3.4.3.2.11.2, IX dolomite from iep Coulter Delsa 6.2 [133]
Liaoning, China, 440 SX
3.4.3.2.11.2, IX dolomite from Hubei, none iep Malvern <9.5 if any [99]
ZS 90
3.4.3.2.7 Malachite from Richard 10− 3 M iep Malvern 9.5 [100]
Tayler, >99% NaNO3 Zetasizer Nano
ZS 90
3
3.4.3.2.7, VII Malachite from Junsei, 10− M NaCl iep ELS-Z from 9.6a [179] 1 9
ground Otsuka
12
of in
entries [1–7].
in [1–7].
2
3.4.3.2.7, IX Malachite from Congo 10− M KCl iep Brookhaven 8.7 [180] 1 8.5
ZetaPlus
− 3
3.4.3.2.7 Malachite from Mexico, 10 M KCl iep Zeta Probe 9.1 [181]
90% pure (4% of Colloidal
pseudomalachite) Dynamics
3
3.4.3.2.7 Malachite from Mexico, 10− M KCl iep Zeta Probe 8.2 [182]bq
(4% of Colloidal [183]
3
3.4.3.2.7 Malachite from Mexico, 10− M KCl iep Zeta Probe 7.8 [184]bqo
(4% of Colloidal
3.4.3.2.9 Fe6(OH)12CO3 0.006–0.7 M cip 8.4 [185]
Carbonated green rust, KNO3
synthetic
2
3.4.3.2.11 Hydrotalcite 10− M NaCl 25 iep Malvern >11.5 if any [186]
Mg6Al2CO3(OH)16 ⋅4 Zetasizer
H2O, precipitated from
chlorides
3
3.4.3 Copper salicylaldoxime 10− M KCl iep Malvern <4.5 if any [181]
Zetasizer Nano
ZS 90
3.4.13 AlN, from Dow iep Malvern 5* [123]
Zetasizer 3
3.4.13.2.1.2.1 Si3N4 from Denki iep Malvern 8.9* [123] 1 15
Kagaku, P 21 B Zetasizer 3
3.4.13.2.1.2 Si3N4 from Denka, SN- HNO3 + NH3 iep ESA 8000 Matec 4 [124]
9S
3.4.13.2.1.11.1 Si3N4 from HC Starck, iep Malvern 5.7* [123] 4 7.5
LC 10 Zetasizer 3
3.4.13.2.1.14.1, 3.4.13.2.3 Si3N4 from Ube, SNE-3 iep Malvern 5.4* [123] 4 5.1
Zetasizer 3
3.4.13.2.1.14.1, 3.4.13.2.3 Si3N4 from Ube, SNE-3 NH4OH + iep ESA 5.1 [27] 4 5.1
HNO3
3.4.13.2.1.14.2 Si3N4 from Ube, SNE- 0.001–0.1 M iepbr ESA 8000 Matec 6.4 [187] 15 6.2
10 NaNO3 [188]
[189]
3.4.15.6.3 Fluorapatite from none iep Malvern 3.4bs [99]
Madagascar Zetasizer Nano
ZS 90
3.4.17.1.3 Co9S8 10− 3 M KCl iep electrophoresis 2 [190]
3.4.17.1.4.1 Cu1.94S djurleite from 10− 2 M iep DT 310 4 [191]
Englandbt NaNO3
3.4.17.1.4.2 CuS synthetic covellite HCl + NaOH iep Malvern <1.5 if any [192]
Zetasizer Nano
ZS
2
3.4.17.1.4.3.6 CuFeS2 chalcopyrite 10− M KCl iep Rank Brothers <3 if any [193] 1 <5
from Ward'sbu Mark II
3.4.17.1.4.3.6 CuFeS2 chalcopyrite 10− 3 M 27 iep Zeta Meter 3.0 <3 if any [194] 1 <5
from Ward's, high KNO3
purity, ground
3.4.17.1.4.3 chalcopyrite 90% pure 10− 1 M iepa Coulter Delsa 4.2 [166]
from China, 0.3% SiO2 KNO3 440 S II
3.4.17.1.4.3 CuFeS2 chalcopyrite, 10− 3 M iep Zeta Meter 3.2 [195]
containing 9% of KNO3
bornite Cu5FeS4
3.4.17.1.4.3 CuFeS2 chalcopyrite none iep A80030E Zeta 5.9 [196]
ground Probe
3.4.17.1.5.1.2 FeS2 pyrite from iep Brookhaven <2 if any [197]
Australia, >95% pure Zeta Plus
− 3
3.4.17.1.5.1.2 FeS2 pyrite from India, 10 M iep Malvern <3 if any [198]
>99.9% pure KNO3 Zetasizer 3000
3.4.17.1.5.1.2 FeS2 pyrite ground none iep A80030E Zeta 4.8bv [196]
Probe
3.4.17.1.5.1.2 FeS2 pyrite, 98.7% 10− 3 M iep Zeta Meter 2 [195]
pure, 1.1% nonmetallic KNO3
gangue
3.4.17.1.5.2 FeS, synthetic 0.005 M iep Sephy 33 MDV <4 if any [199] 1 5.7
mackinawite NaClbw 9444
VIII, 3.4.17.1.9 Pentlandite (Fe,Ni)9S8 10− 1 M iepa Coulter Delsa 4 [166]
92% pure from China, KNO3 440 S II
0.9% SiO2
3.4.17.1.8, VII,VIII MoS2 molybdenite 0.001 M iep Zeta Meter 9.1 [200]bx
from Molymet, Chile KNO3
13
of in
entries [1–7].
in [1–7].
3
3.4.17.1.8, VII,VIII MoS2 10− M KCl iep electrophoresis 2.8 [190]
3
3.4.17.1.10.3.1.13.4.17.1.10.3.1.2 PbS galena from Wards' 10− M NaCl iep Acoustosizer <4 of any [201] 3 <3
3.4.17.1.10.3.1.3, IV, V >99.8% Rank Brothers
Mark II
3.4.17.1.10.3, IV, V PbS galena from India, 10− 3 M iep Malvern <3 if any [198]
>99.6% pure KNO3 Zetasizer 3000
3.4.17.1.10, IV, V PbS galena of unknown 0.0005–0.1 iep Malvern Nano <2 if any [202]
origin M NaCl ZS90
3.4.17.1.12.3.1, V ZnS sphalerite from 10− 3,10− 2 M iep Acoustosizer 8.5 [201] 3 3
Wards' >98.5% NaCl Rank Brothers 7
Mark II
3.4.17.2.4.1, VIII Synthetic 10− 2 M 20 ± iep Rank Brothers 7.2* [66] 1 7.2
schwertmannite NaNO3 1 Mark II
3.4.17.2.4.1 Fe6(OH)12SO4 0.006–0.5 M cip 8.3 [185]
Sulfated green rust, KNO3
synthetic
3.4.16.3 MgCaSi2O6 diopside iep Coulter Delsa 2.1a [133] 2 3; 3.4
from Shandong, China, 440 SX
3.5 Glasses
3
VIII Schott Borofloat 10− M KCl iep EKA Anton Paar 3 [203]
borosilicate glass
washed with acid,
macroscopic sheet
3.6 Carbon-rich materials
3.6.1 Detonation iep Malvern <2 of any [204]
nanodiamond Zetasizer Nano
produced from ZS
trinitrotoluene and
hexogen
3.6.1 Synthetic diamond HCl + KOH 25 iep Matec ESA 8000 3.4 [205]by
3.6.1 natural diamond HCl + KOH 25 iep Matec ESA 8000 2 [205]
3.6.2 Graphite AF 96/97 iepbz ESA 4.5 [13]
from Graphit
Kropfmuhl
3.6.4.1.2.6 Activated carbon iep Malvern 4.5 [119]
Filtrasorb 400 from Zetasizer Nano
Calgon ZS90
3
3.6.4.1 Biochar from Shanghai 10− M NaCl iep Malvern <2 if any [206]
Hainuo Charcoal 79% Zetasizer Nano
C, 19% O, 1% H, 0.4% ZS90
N
3.6.4.1 Carbon black, thermal, iep78 ESA 3.8 [13]
Luvomaxx MT N-991
from Lehmann&Voss
VII, VIII Graphene oxide iep Malvern <2 of any [207]
LayerOne 2.5% Zetasizer Nano
ZS
3.6.4.2.2.3 MWCNT from iepa Malvern O 4.9 [208]
Nanotech <10 nm in Zetasizer P < 2 if any
diameter, original and ZEN1001
purified
3.6.4.2.2.3 SWCNT from Nanotech iepa Malvern O 4.6 [208]
<2 nm in diameter, Zetasizer P < 2 if any
original and purified ZEN1001
3.6.4.2.2.3 single wall CNT from iep Malvern 6.2* [209]
Shenzhen Zetasizer Nano
ZS90
3
3.6.4.2.2.3 MWCNT from 10− M NaCl iep Malvern 3.7a [51]
Shenzhen, 40–60 nm in Zetasizer Nano
diameter, 1–2 μm long, ZS90
oxidized
3.6.4.2.2.3 Multi wall CNT from iep Malvern 5.8* [209]
Shenzhen Zetasizer Nano
ZS90
3.6.4.2.2.3 Double wall CNT from iepa Malvern Original 6.5 [209]
Shenzhen Zetasizer Nano Oxidized 5.5
ZS90
3.7 Other well-defined inorganic compounds
VII B4C HC Starck, HD7, 3 HCl + NaOH 25 iep Malvern 7 [210] 1 <2
specimens Mastersizer 4a
2000 <3 if anyca
14
of in
entries [1–7].
in [1–7].
3
3.7.6.1, VI Crushed Ottawa sand 0, 10− M 22.5 iep Zeta Meter 3.0+ <3 if any [144] 3 <2
LiCl ± 2.5
3.8 Coatings
3.8.4.1 Iron oxyhydroxidecb on 10− 4
M NaCl iep 8.4 [211]
sand
3.8.10, VI Silica on Si, 1.9 nm 10− 2 M iep SurPass 3.5* [212]
thick layer Me4NCl
3.8.12.2, VII TiO2 on silica, calcined none iep Malvern ZS90 4.8 [122]
at 900 ◦ C
3.8.12.2, VII TiO2 on silica, calcined HCl + NaOH iep Malvern 2.9 [91]
at 500 ◦ C for 3 h Zetasizer Nano
ZS 90
3.9 Low-molecular-mass organic compounds
3.9.1, VIII hexadecane 0.0004 M iep Acoustosizer <5 if any [213] 1 3.4
NaCl, NaI,
NaClO4
3.10 Polymers, macroscopic specimens
3
3.10.1 NF90 fully aromatic 10− M KCl iep Anton Paar Original 3.3 [214]
polyamide membrane SurPass Ozonated
from Dow Filmtec, <3
original and ozonated
3
3.10.1 NF270 semi-aromatic 10− M KCl iep Anton Paar Original 2.9 [214]
polyamide membrane SurPass Ozonated
from Dow Filmtec, <3
original and ozonated
3
3.10.7, IV,V PMMA reference plate 10− M KCl iep EKA Anton Paar 3.8cc [203]
from Anton Paar
VI Poly(ethylene 0–0.01 M 25 ± iep Zeta Meter 3.0 4.8 [215]
terephthalate) from NaCl, KCl 2
Petkim, 0.8% Cr2O3,
0.8% TiO2
3
VI PVC ultrafiltration 10− M KCl iep Anton Paar 4.3 [216]
membrane from SurPass
Shenzhen
3.10 Polysulfone 0.0005, iep EKA Anton Paar <3.5 if any [217]
ultrafiltration 0.002 M
membrane from NaCl
Pridesa
VI Polyethersulfone 10− 4–10− 2
iep Streaming 20 2.4 [218]
ultrafiltration M KCl potential 100 < 2 if
membranes from any
Techsep, 20 and 100cd
kDa
3.11 Latexes
2
3.11.1 Polystyrene latex, 1 μm 10− M NaCl 25 iep Malvern <3 if any [69]
in diameter, from Zetasizer Nano
Microparticles ZS
3.11.1 Polystyrene latex, 100 0.0005 M Iep Malvern <4 if any [65]
nm, fluorescent from NaCl Zetasizer
Thermo Fisher
3.11.2.7, 3.11.3.1 Polystyrene latex, 10− 3, 10− 2
iep Malvern <3 if any [151]
synthetic, Goodwin M NaCl Zetasizer Nano
method ZS
3.11.2.7, 3.11.3.1, V Polystyrene latexce 10− 2 M (HCl iep Malvern <3 if any [63]
+ NaOH) Zetasizer Pro
Blue
3.11.2 Zwitterionic latex, 10− 4–10− 2 iep 4.1 [219]
synthetic M NaCl
3.12 Natural high-molecular-mass organic compounds, and their derivatives
3.12.1.2.7, VII,IX Humic acid, Suwannee 10− 3 M NaCl iep Malvern <4 if any [220] 2 <3
River Zetasizer Nano
ZS90
3.12.1.2 Humic acid extracted 10− 3 M iep Malvern Nano Z 4.2 [221]
from coal. Washed with KNO3
HCl and HF
3
3.12.1.2 Fulvic acid, Suwannee 10− M NaCl iep Malvern <4 if any [220]
River Zetasizer Nano
ZS90
2
VII, VIII Bovine serum albumin 10− M NaCl 25 iep Malvern 5a [84] 2 4.7; 5.1
>96% from Sigma Zetasizer Nano
Aldrich
3.13 Microorganisms
15
of in
entries [1–7].
in [1–7].
3
3.13.4, IX Rhodococcus opacus, 10− M NaCl iep ELS-Z from Mid- [179] 5 3
different growth phases Otsuka exponential
2.7
Stationary
3.2
a
Few data points.
b
The IEP was confirmed by measurements at different solid loads. In 10− 1 M KNO3 the IEP shifted to high pH.
c
Also 50 and 65 ◦ C.
d
Matches the maximum in sediment volume.
e
Atypical electrokinetic curve: zeta potential close to zero at pH 7.8–8-6. In another paper [123] the same authors report IEP at pH 7.6* (data points not reported)
obtained by Malvern Zetasizer 3.
f
An unsupported IEP of 8.55 is reported in the text.
g
Back and forth titration.
h
0.5 M Al nitrate was titrated with 0.25% ammonia at 75 ◦ C to pH 9.2. The precipitate was separated, dispersed in water, and titrated with HNO3 to pH 3.7 at 80 ◦ C.
Stored as a dispersion.
i
1 M AlCl3 was titrated with 4 M NaOH to pH 4.6. The slurry was aged for 2 h at 40 ◦ C, electro-dialyzed for 3 months, and dried at 60 ◦ C. Finally ground to pass
through a 100 mesh sieve.
j
Matches the maximum in particle size.
k
The natural pH of dispersion (10) and low IEP suggest that the commercial powder contains surface-active additives.
l
CuSO4 solution was poured into 0.1 M LiOH. The precipitate was reduced with ascorbic acid, and washed with water.
m
Dispersions prepared in a glove box to exclude oxygen.
n
Potentiometric titration curves for 10− 3–10− 1 M NaCl did not show a clear CIP.
o
Another paper of the same authors, probably reporting the same results.
p
A maximum in particle size does not match the IEP. Few data points.
q
The same study reports an IEP of Mn3O4 + MnO2 composite prepared in the presence of PVP at pH 2.5.
r
Also 60 ◦ C.
s
PZC at pH 7.4 is claimed in the text. Actually there was no sharp CIP.
t
Also in H2O-D2O mixture. Unlike in most similar studies, electrokinetic charge density rather than zeta potential is plotted as a function of pH.
u
The same paper reports an electrokinetic study of alumina (few data points).
v
The same study reports IEP of Ludox SK from Remet at pH 3.5. Ludox SK contains a polymer.
w
Prepared from TEOS, chitosan, and Aerosil silica. Calcined at 550 ◦ C for 3 h.
x
The same study presents electrokinetic curves of two composites: titania deposited on SBA-15.
y
0.9% Fe2O3.
z
Also 10, 35, and 75 ◦ C.
aa
The same study reports an IEP of natural hematite containing 1% of quartz at pH 6.
ab
Argon atmosphere.
ac
Correlation between zeta potential, and the results obtained from Turbiscan measurements (Stokes radius, turbidity, backscattering) is demonstrated.
ad
Broad maximum in size near the IEP.
ae
The same paper reports the electrophoretic mobilities obtained by Rank Brothers' Mk II. The results from the both instruments match at pH <6, but at pH > 7 the
electrophoretic mobilities obtained by electrophoresis are more negative. This may suggest an IEP at pH about 6.3 obtained by Rank Brothers' Mk II, although data
points in the closest vicinity of the apparent IEP are not reported.
af
Atypical electrokinetic curve. The zeta potential was almost constant at pH 5.8–6.7.
ag
Hydrothermal treatment with ammonia shifted the IEP to pH 6.6.
ah
Solution 0.5 M in Ti butoxide and 1 M in trimethanoloamine was heated for 10 min. at 180 ◦ C. The precipitate was centrifuged and washed with water. The same
study reports electrokinetic curves and apparent IEP for 8 other TiO2 powders which were not used in Table 1 because of too few data points or unknown composition
of the commercial specimens (Surface active additives possible).
ai
Matches the minimum in supernatant turbidity, and maximum in dispersion viscosity.
aj
From feed industry, manufacturer or purity not specified. Specific surface area of 28, 2, 38, and 0.5 m2/g, respectively.
ak
Zn nitrate solution was poured into 0.1 M LiOH. The precipitate was washed with water.
al
Obtained by methods not recommended by the present author.
am
Also 40 and 70 ◦ C.
an
38.2% SiO2, 11.8% Al2O3, 11% Fe2O3, 19.3% MgO, 1.5% CaO, 0.3% Na2O, 11% K2O, 2.9% TiO2. The same study reports data points for phlogopite, which were
not used in this study (too few data points).
ao
Based on information received from the authors.
ap
67.3% SiO2, 15.4% Al2O3, 7.1% Fe2O3, 4% K2O.
aq
46.9% SiO2, 35.5% Al2O3, 0.9% Fe2O3, 0.1% MgO, 0.04% CaO, 0.1% Na2O, 0.2% K2O.
ar
CO2-free atmosphere.
as
The same study reports an electrokinetic curve for Na-smectite containing 5% of quartz.
at
An unusually high zeta potential of − 174 mV is reported.
au
Broad maximum in particle size near the IEP.
av
Multiple studies report apparent PZC from titration, but IEP is only reported in one study.
aw
Also 75 ◦ C.
ax
Georgia kaolinite is the proper title of section 3.2.30.3.1 (error in [1]).
ay
PZC of quartz and of microcline obtained by titration are also reported (only numerical values, no data points)
az
59.5% SiO2, 18.6% Al2O3, 3.5% Fe2O3, 2.2% MgO, 0.6% CaO, 0.4% Na2O, 0.3% K2O.
16
ba
Two other H-zeolites obtained by calcination of commercial NH4-zeolites showed atypical electrokinetic curves with negative values at very low and very high pH
and positive values at pH about 5. Similar atypical behavior was observed in a synthetic β zeolite.
bb
Precipitated at pH 7 from nitrates, 5 specimens, Al/(Al + Fe) molar ratios of 5–25%. The same study reports IEP of pure 2-line ferrihydrite, which is not reported in
Table 1 (few data points).
bc
A solution of diethylenetriamine pentaacetic acid, Bi2O3 and V2O5 in ammonia (pH 11), DTPA:Bi:V molar ratio of 3:1:1, and a calculated amount of Co(NO3)2 (to
achieve a desired Co load) was heated at 80 ◦ C until complete dissolution. Then water was evaporated and the gel was calcined for 4 h at 600 ◦ C. ζ expressed in atypical
units (eV).
bd
11 specimens. Solution of metal nitrates (Fe:Co = 1:1) and 1 M NaOH were added to water at 70 ◦ C and at pH 6 or 8 in the presence or absence of fulvic or humic
acid. The precipitate was washed, filtered, dried at 100 ◦ C, and calcined at 300 ◦ C or 500 ◦ C for 4 h, 18–54 m2/g, XRD patterns reported.
be
Solution of metal nitrates (Fe:Co (or Cu or Mn) = 2:1) was titrated with 2 M NaOH to pH 12.5, and then autoclaved at 80 ◦ C (160 ◦ C for Mn) for 12 h. Washed with
water to reach neutral pH, then with ethanol, and dried at 100 ◦ C for 2 h.
bf
7.7 (figure) or 3.6 (text).
bg
Fe:Cu molar ratio of 2:1, precipitated from FeCl3 and CuSO4 at pH 9–13, 4 different specimens.
bh
From FeCl3, Mg(NO3)2 and CTAB solution. Precipitated with NaOH, filtered, washed, dried at 100 ◦ C, and calcined at 500 ◦ C for 3 h.
bi
A solution of Mg nitrate and Zn acetate 1:1 M ratio with a 7:1 excess of triethanoloamine was heated at 200 ◦ C at pH 5–6 adjusted by means of HNO3. Then water
was evaporated and the residue was calcined for 2 h at 600 ◦ C.
bj
Acicular alumina and kaolin were mixed to produce 3:1 Al:Si molar ratio. 3% of AlF3 by mass were added. The mixture was ball-milled, pressed into disks, and
sintered at 1400 ◦ C. Then crushed, milled, washed, and dried at 105 ◦ C.
bk
The same study reports an IEP of acid-leached serpentinite at pH 6.2 (text). However, this result is based on arbitrary extrapolation from a few data points.
bl
The same authors as in [167].
bm
Surface-charging curved did not show a sharp intersection point.
bn
The same paper reports IEP of several commercial phosphors, chiefly REE-doped phosphates and aluminates of the 2nd group elements.
bo
The same study reports IEP of 4 mixed ceria-zirconia oxide containing La, Pr and Y. The presence of La and Y shifted the IEP to high pH.
bp
1.6% dolomite, 0.2% quartz. The IEP reported in text (8.8) is based on an atypical electrokinetic curve: zeta potential was close to zero at pH 7–10. Most data
points are in the pH range where calcite undergoes dissolution. The same study reports apparent IEP of pyrite and pyrthotite, but these materials showed high level of
impurities (calcite, quartz), and the results were not used in Table 1.
bq
From the same laboratory as [181].
br
The IEP was confirmed by titrations at different solid loads, slow and fast titration, and multiple back and forth titrations. Moreover, replacement of NaNO3 with
KCl, KBr or KI (0.01 M) did not affect the IEP.
bs
The reported IEP is beyond the range of stability of fluorapatite against dissolution in acid.
bt
86.4% pure, but the main impurities (13.6%) are other copper sulfides: chalcocite, anilite, and digenite.
bu
Conditioned at various pH in nitrogen and in oxygen atmosphere
bv
ζ ≈ 0 at pH 3–5.
bw
In N2 atmosphere, in glovebox.
bx
Other IEP of sulfides reported in this study are not included due to insufficient purity of the minerals used.
by
The same study reports electroacoustic studies of acid-washed, and plasma-treated diamond.
bz
ESA signal rather than ζ is plotted against pH.
ca
The IEP in Table 1 refer to original samples. After heat treatment in argon at 450 ◦ C for 1 h all specimens had IEP at pH < 2 if any.
cb
The title of section S8 in [211] suggests iron-coated sand, but the text of the same section suggests iron oxyhydroxide nanoparticles.
cc
Very low zeta potentials (in absolute value) near the IEP.
cd
100 kDa (section 3.3) or 200 kDa (section 2.2) in [218].
ce
5.5 mL of styrene were added under nitrogen atmosphere to a solution of 125 mg of potassium persulfate and 150 mg of SDS in 50:20 v/v methanol-water mixture.
After 8 h stirring at 70 ◦ C the latex was centrifuged, washed with methanol and with water, and dried.
names in original publications, in compilations [1–7], and in Table 1 Column 4. Temperature in oC. Empty cells in column 4 denote that
below. the information on temperature was not available, but missing infor
3.2 Aluminosilicates and clay minerals are sorted alphabetically by mation suggest that the zero-points were obtained at room temperature
name (used in the original paper). Similar materials may appear under or with factory settings of an instrument (usually 25 ◦ C). The PZC is
different names, because the classification of clay minerals is complex relatively insensitive to the temperature (typically 0.03 pH unit/1 ◦ C
and multi-level. [1]), so exact information about the temperature is not crucial.
3.3 Mixed oxides (both single oxides are insoluble in water) are Column 5. Method. IEP denotes the zero-point obtained from elec
sorted by the first (usually more abundant) and then by the second trokinetic or electroacoustic measurements. CIP denotes a common
metallic element. Thus similar materials may be found in two sections, e. intersection point of titration curves obtained for at least 3 ionic
g., Al-first, Fe-second and Fe-first, Al-second. strengths. In principle the PZC obtained as intersection points of two
3.4 Salts are sorted alphabetically by non-metallic element, then by titration curves were not used in Table 1, but a few results (marked as
anion, and then by cation. Salt-type compounds like FeTiO3 (ilmenite) “intersection”) are reported for less common materials. Addition of inert
are considered as mixed oxides when both acid and base are water- electrolyte (powder or concentrated solution) to a dispersion shifts the
insoluble. pH towards the PZC. “Salt addition” in column 5 denotes a pH, at which
3.8 Coatings. Core-shell materials are sorted by shell and then by addition of inert electrolyte to a dispersion does not affect the pH. This
core. method is nearly equivalent to CIP, and a few results are reported in
Short descriptions of materials (e.g., trade name) are presented in the Table 1. Unlike in metal oxides, the titration curves of silica obtained for
table, and longer descriptions (e.g., detailed recipes for synthetic ma different ionic strengths do not show a CIP, but they merge into one
terials) are in footnotes. master curve at sufficiently low pH. The exact value of PZC cannot be
Column 3. Electrolyte. A hyphen denotes a concentration range (3 or derived from such titration curves, but the results are reported in Table 1
more concentrations). A semicolon is used when exactly 2 concentra and marked as “pH”.
tions were studied. The zero-points obtained without addition of elec Column 6. The names of commercial zetameters are reported. A few
trolyte (particles dispersed in water) are marked as such, and empty cells studies report only the principle of measurements (electrophoresis,
in column 3 denote that the information on electrolyte was not streaming potential).
available. Column 7. Asterisk denotes that the original work reports only the
17
PZC/IEP value (σ0 vs. pH or ζ vs. pH curves not reported). Multiple electrolyte was acid or base added to adjust the pH. The inert character
values or ranges are reported in column 7 when the zero-point is re of 1–1 electrolytes is only observed in their dilute solutions. In
ported for several samples or when the results obtained at different concentrated solutions of 1–1 electrolytes (>1 M) specific adsorption of
conditions (back and forth titration, different electrolytes) differ. ions occurs [226].
Extrapolation is not used. The zero-points beyond the data range are In absence of surface-active compounds the IEP obtained at different
marked as such, e.g., “IEP at pH<3 if any”. concentrations of different 1–1 electrolytes (including the IEP in “pure”
Column 8. Zero-points reported in multiple papers of the same water) should match, so single electrokinetic curve (one electrolyte, one
author(s), which are likely to represent the same experiment are pre concentration) is sufficient to determine the IEP. Relatively few studies
sented as one entry. present multiple electrokinetic curves (different electrolytes, different
Columns 9 and 10. Two PZC/IEP from [1–7] are reported explicitly concentrations). Different 1–1 salts were used in an electroacoustic
(unless both values are equal). With 3 or more PZC/IEP from [1–7] their study of Si3N4 [187]. Electrokinetic curves of quartz and of albite at 4
median is reported. Numbers in parentheses denote zero-points deter different ionic strengths (no electrolyte, and 3 concentrations of KNO3)
mined by methods not recommended in this study. are presented in [85]. The electrokinetic curves showed the expected
Additional information (other than reported in columns 1–10) is dependence on the ionic strength (absolute value of ζ potential drops
given in footnotes. They may include insufficient quality of data (such when the ionic strength increases) in KNO3 solutions, but substantial
zero-points are only reported for less common materials), and special deviations from this trend were observed when no electrolyte was
experimental setup (e.g., inert gas atmosphere in electrokinetic studies). added. Formally the electrokinetic curves presented in [146] represent
five different ionic strengths ranging from 0 to 10− 3 M. However, most
3. Discussion electrolyte concentrations were low, and except for pH ≈ 7 the amount
of acid or base (which are also electrolytes) used to adjust the pH was
3.1. Recent reviews high as compared to the declared ionic strength, so the actual ionic
strength was substantially higher than the declared one. Usually, the
Several recent reviews include large compilations of PZC/IEP and/or absolute value of ζ potential drops when the ionic strength increases, but
related results, e.g., ζ(pH) curves. Such compilations may cover the re such a systematic effect was not observed in [146], and the latex studied
sults deliberately omitted in [1–7] and in the present review, e.g., in [151] showed even higher absolute value of ζ potential in 10− 2 M
referring to complex or ill-defined materials or to the zero-points ob NaCl than in 10− 3 M NaCl. Several electrokinetic studies were per
tained by methods not recommended by the present author. Pawlik formed at high ionic strengths, e.g., 10− 1 M KNO3 was used in [166],
[222] reviewed froth flotation with a special emphasis on the correlation 10− 1 M NaNO3 was used in [33], and 10− 1 M NaCl was used in [39]
between flotability and ζ potential. Zeta potentials obtained by elec [59]. High ionic strengths are not recommended for determination of
troacoustic methods were summarized in [223]. Zeta potentials of crude pristine IEP by electrophoresis because of instability of dispersions
oil were summarized in [224]. against coagulation and because of low absolute values of ζ potentials,
which result in poor precision of IEP obtained by interpolation. More
3.2. Experimental conditions over, ion-specific effects occur at high ionic strengths, that is, the IEP
obtained in different 1–1 salts may differ as discussed in detail in [1].
Many results presented in Table 1 were obtained at temperatures Electrophoretic and electroacoustic measurements are often per
between 20 and 30 ◦ C (usually 25 ◦ C) or the temperature was not re formed in titration mode. Usually, only one titration curve is presented
ported. Probably the latter studies were also conducted at room tem (low to high or high to low pH), but the titration curves may show a
perature, that is, about 25 ◦ C. Very few papers report the effect of hysteresis as discussed in detail in [1]. The IEP obtained by slow and fast
temperature on the surface charging. The effect of the temperature on titration and in multiple back and forth titrations were compared in an
the ζ potentials of silica, alumina and zeolites was studied in [19]. The electroacoustic study of Si3N4 [187].
effect of the temperature on ζ potential of zirconia was studied in [131]. Determination of the PZC of metal oxides by potentiometric titration
The IEP shifts to low pH as the temperature increases, but there are too used to be very popular, and many examples of such PZC can be found in
few data points in the electrokinetic curves in [131] to quantitatively [1–7]. Only a few examples of PZC obtained as CIP were found in
evaluate the effect. The effect of the temperature on the PZC (obtained recently published papers [42,80,128,129,132]. A few studies present
by salt addition) of NiO was studied in [78]. unsuccessful attempts, that is, the charging curves did not show a sharp
Most results presented in Table 1 were obtained by electrophoresis, CIP. In most studies reporting the PZC, three titration curves at different
by means of commercial instruments, but the other instruments use ionic strengths were used to determine the CIP, and studies involving
streaming potential and electroacoustics, and the IEP obtained by such more than 3 ionic strengths are rare, also in older literature. Titrations
instruments are also marked as iep in Table 1. A term iep (lowercase) in were performed at four different ionic strengths in [185], and according
Table 1 is used to emphasize that the zeta potential is positive at pH to the expectations, the absolute value of σ0 increased with the ionic
below and negative above the zero-point (to be distinguished from IEP strength. Apparent σ0(pH) curves for hematite in 0.1, 0.3 and 0.7 M NaCl
(uppercase): any conditions, where zeta equals to zero). The principles are presented in [227]. The authors claim PZC at pH 7.04, but this result
of operation of common instruments are summarized in [1,5]. There is a is not included in Table 1. This is because the apparent charging curves
family of instruments based on common principle discussed in detail in do not show a clear CIP, but they merge over a wide pH-range. In most
[1] (Mutek, Stabino), which allegedly measure ζ potentials, but these other studies the electrolyte concentrations differ by several orders of
instruments often produce absolute values of ζ potentials of several magnitude (e.g., 10− 3–10− 1 M) thus the difference between particular
hundred mV, that is, higher by an order of magnitude than the ζ po charging curves is more significant. Apparently the range of NaCl con
tentials reported in other studies. The IEP determined by means of centrations in [227] was too narrow to obtain a sharp CIP. This can very
Stabino, e.g., 8.6 for AlOOH, boehmite reported in [225] are often in well be that with a broader range of ionic strengths and otherwise the
line with the IEP determined by the other methods, but such results are same conditions, a sharp CIP might have been obtained.
not reported in Table 1. The titrations were performed over a relatively narrow pH range
Many electrokinetic studies were performed in 10− 4–10− 2 M 1–1 (7.8–9) in [185] to avoid dissolution/reprecipitation reactions, which
electrolytes, and NaCl was the most popular one. In several studies no may occur in acidic and basic media. These reactions are often slow and
electrolyte was added other than acid or base used to adjust the pH. irreversible, and they may be responsible for difficulties in obtaining one
Many other studies do not reveal information on the electrolyte. Prob sharp CIP. In general, a narrow range (3–4 pH units) is recommended in
ably their authors dispersed particles in pure water, and the only determination of CIP. Nitrogen or argon atmosphere are used in most
18
studies reporting CIP. Namely the dissolved carbonate species undergo apparent IEP of titania layer was below the apparent IEP of silica layer,
protonation and deprotonation, and they affect the course of potentio in contrast with the results obtained with bulk materials.
metric titrations, thus the presence of atmospheric CO2 must be avoided.
Dissolved oxygen does not affect the titration curves of materials unless 3.5. Results deliberately neglected in Table 1
these materials are redox-sensitive. N2 + H2 atmosphere was used in
[185] to avoid atmospheric CO2 and oxygen, which might have oxidized Several studies were not used in Table 1 due to atypical, controver
iron II to iron III. The effect of CO2 on the PZC of iron (hydr)oxides sial or contradictory results, although they used methods recommended
obtained by salt addition was studied in [62]. With commercial hematite by the present author. A few examples are presented in this section, but
the PZC in air-saturated electrolyte and in inert-gas atmosphere were the list is not complete, and many other problematic results can be found
identical. In contrast with commercial ferrihydrite and with synthetic in the recent literature.
hematite, the presence of air shifted the apparent PZC to low pH. Several recent results were not included in Table 1 due to problems
Although salt titration is nearly equivalent to CIP as a method of with sample purity. Electrokinetic curves of 6 specimens of titania are
determination of the PZC (in absence of CO2), the effects of CO2 on the reported in [231]. These specimens were obtained in quartz reactor and
apparent PZC determined by these methods may be different. this might have resulted in low IEP due to silica-contamination.
Ref. [232] illustrates the difficulties faced in electrokinetic studies in
3.3. Choice of the specimens mixtures of different powders. They studied valleriite, which is 4(Fe,Cu)
S⋅3(Mg,Al)(OH)2. Coarse grains (75–125 μm) of synthetic and of natural
As in [1–7], the PZC and IEP in Table 1 mostly refer to oxides, mineral produced negative zeta potentials measured by streaming po
especially to alumina, silica, titania and iron oxides. A few less common tential over the entire pH range. In contrast fine grains (<20 μm) pro
oxides were also studied. The zero-points of Cu2O (studied in [48]) are duced an IEP at pH 6.5, determined by electrophoresis. The authors
seldom reported and the published zero-points are very scattered. The attribute the difference in the IEP to the presence of serpentinite in the
IEP at pH 7.5 reported in [48] is very different from the “predicted” natural sample.
value, which ranges from 10.7–12.9. The zero-points of Ga2O3 (studied Titration curves obtained for 3 ionic strengths are presented in
in [31]) are seldom reported. The IEP of Ga2O3 single crystal at pH 4.6 [128]. With ZrO2 a sharp CIP was observed. The authors report apparent
reported in [31] is much lower than the IEP at pH 9 reported in [1–7] for PZC (equivalent to CIP) for alumina and titania, but the charging curves
dispersions. This discrepancy is similar to the effect reported in [1–7] for for alumina and titania merged over a broad pH range (no sharp CIP).
alumina, and widely discussed in scientific literature, namely alumina This result is not surprising in view of low specific surface areas of these
single crystals also show very low IEP (about pH 5) as compared with oxides (4 and 6 m2/g respectively). The apparent PZC of alumina and
dispersions (pH 9). The zero-points of Nd2O3 (studied in [77]) are titania reported in [128] are not included in Table 1. While the apparent
seldom reported. The IEP of Nd2O3 at pH 10.4 reported in [77] is lower PZC of alumina reported in [128] (8.8) is in line with the previously
than previously reported IEP at pH >11 (if any) for Nd oxide and hy reported values [1–8], the apparent PZC of titania (8.9) is not.
droxide. The IEP are not reported in [228], but the authors report the Several recently published IEP were not included in Table 1 due to
zeta potentials of Pr6O11, Gd2O3, and Nd2O3 (and of other materials) in atypical electrokinetic behavior. Normally we expect high positive ζ
distilled water. Although only single values of ζ potential are reported, potentials (typically 40–100 mV) at low pH, ζ potentials close to zero
ref. [228] deserves a special attention, because the IEP of Pr6O11 and over a narrow pH range (less than 1 pH unit) near the IEP, and high
Gd2O3 are seldom studied, and the previously reported zero-points are negative ζ potentials at high pH. The ζ potential monotonically de
controversial as discussed in detail in [1]. creases as a function of pH, and only small deviations (<10 mV) from a
Substantial numbers of recent studies were devoted to aluminosili monotonic master curve occur. Zeta potential of carbon fibers and of
cates and clay minerals, to mixed oxides and to salts, and other cate polycarbonate nanoparticles was studied as a function of pH in [233].
gories of materials were seldom visited. Most surface-charging studies While the zeta potentials of polycarbonate nanoparticles were negative
were performed with materials which have been studied before, and the over the entire studied pH range, which is often the case with materials
recent research confirms well-established values. Several papers having an IEP at low pH, the zeta potential of carbon fibers, was negative
reviewed in [1–7] suggest that the zero-points of mixed oxides are at low pH, and positive at high pH. This is opposite to the generally
weighted averages of the zero-points of their components, and indeed, observed trend, and such a sign reversal point is not considered as an
most experimental results confirm such an allegation. Interestingly IEP. The preparation method of polycarbonate nanoparticles suggests
enough, the IEP of yttria-alumina composites reported in [30] were that the particles might have contained SDS. The IEP obtained (prob
higher than the IEP of the components reported in the same paper. ably) in the presence of SDS is not a pristine IEP, and it is not reported in
Table 1.
3.4. Coatings vs. thin layers Unusual zeta potential of 490 mV is reported for allophane at pH 2 in
[141], but the other data points are in the usual range.
Several examples of zero-points of core-shell particles are presented Ordinartsev et al. [234] studied the zeta potentials of reagent-grade
in [1–7] and in Table 1. The coatings in such particles are thick enough anatase and rutile, original and ground in isopropanol for different
to define the surface properties of materials while the nature of the core times. All apparent IEP (Table 2 in [234]) were below pH 5, apparently
had rather insignificant effect on the surface properties [1]. In contrast, due to the presence of specifically adsorbing anions in commercial re
the IEP of very thin layers are not included in Table 1. agents. This problem was widely discussed elsewhere [1]. Moreover the
Xia et al. [229] report IEP and electrokinetic curves (pH 4–10) for electrokinetic curves in [234] are of peculiar shape (multiple maxima
layers of 14 metal oxides obtained by atomic layer deposition, as well as and minima, multiple zero-points, Fig. 2 in [234]). Therefore the IEP
IEP of these oxides taken from the literature. Their results are not re from [234] are not included in Table 1. The electrokinetic curve of
ported in Table 1 because they are not representative for bulk metal zeolite in [235] is of peculiar shape (multiple maxima and minima,
oxides. Several IEP reported in [229], e.g., 4.9 for silica, 8.2 for SnO2, multiple zero-points, Fig. 2 in [235]). Therefore the IEP from [235] is
and < 4.5 for NiO are substantially different from the results reported in not included in Table 1.
the literature [1–7] for bulk materials. Electrokinetic curve of atypical shape with zeta potential equal to
Electrokinetic curves of 10–15 nm-thick layers of silica, alumina and zero at pH 6 and 7 for titania (obtained from butoxide) is presented in
titania on mica are reported in [230]. The apparent IEP from [230] are [236]. The authors claim IEP at pH about 6 in the text, but actually the
not included in Table 1, because of insufficient number of data points or IEP can be anywhere between pH 5 (the highest pH with clearly positive
because of their scatter in the vicinity of IEP. Interestingly enough, the ζ potential) and 8 (the lowest pH with clearly negative ζ potential), and
19
the apparent IEP from [236] is not included in Table 1. 3.8. Atypical methods
Electrokinetic curves of two zeolites of atypical shape with multiple
maximums and minimums, with an absolute value of zeta potential in The methods presented in this section are not recommended for
excess of 200 mV, and with positive zeta potentials at very high pH are determination of the zero-point, but the results obtained by these
reported in [237]. The apparent IEP from [237] are not included in methods are likely to represent the actual zero-point.
Table 1. Surface potentials of silica calculated from second-harmonic-
generation SHG measurements are reported in [263]. Miller et al.
3.6. Surface charging in nonaqueous and mixed solvents [135] studied the surface charging of various faces of chlorite by atomic
force microscopy AFM. The mica-like face and brucite-like face carried
Commercial zetameters are designed for aqueous systems, and charges of opposite signs over a pH range 4.5–9. Correlation between the
measurements in non-aqueous media bring about problems, which are morphology of boehmite crystals and their IEP was studied in [33].
discussed in detail in [1]. Zeta potentials of P25 titania in methanol as a Exposed area of particular faces differs from one specimen to another.
function of pH and in 15 other nonaqueous solvents (pure or containing Different IEP are assigned to different faces, and the IEP of a specimen
10− 3 M of acid or base) are reported in [108]. Zeta potentials of titania was estimated as a weighted average of the IEP of particular faces.
and alumina in 50% aqueous ethylene and propylene glycols as a Indeed, the difference in exposure or particular faces may be one of the
function of pH are reported in [238]. Zeta potentials of zinc oxide in 50% reasons for discrepancies between PZC/IEP of various specimens of the
aqueous ethylene glycol as a function of pH are reported in [239]. Zeta same chemical compound.
potentials of zeolite A in 50:50 aqueous ethanol as a function of pH were Contact angle vs. pH curves of mica and silica are reported in [264].
studied in [240]. Zeta potentials of silica in glycerol as a function of pH They match second degree polynomials, and show maximums at pH 3.6
are reported in [241]. Exact description of pH measurement is missing in and 3.8, respectively. Maximums in contact angle vs. pH curves are often
the above studies, and this can very well be that the authors just interpreted as the PZC as discussed in detail in [1].
immersed a pH-electrode calibrated with aqueous buffers into their Inflection point in pH(titrant volume) curve at pH 6 was interpreted
dispersions. The measurement and even definition of pH in nonaqueous as the PZC of titania in [112]. Similar method was discussed in older
and mixed solvents are not trivial. Therefore most electrokinetic studies literature [1], but it is not recommended by the present author.
in nonaqueous and mixed solvents were performed without pH-
measurements. 3.9. Other correlations
Zeta potentials of alumina [242] [243], Fe3O4 [244], magnesia
[245], silica [246], titania [247] [248] [249], WS2 [250], carbon Correlations between IEP and maximum in particle size (due to ag
nanotubes [251] [252], and hydroxylated graphene [253] in glycols and gregation of primary particles near the IEP), minimum in dispersion
in aqueous glycols (no additives) have been reported. On top of ζ po stability (aggregation enhances sedimentation), maximum in dispersion
tentials of nanoparticles dispersed in “pure” solvent, the above studies viscosity and in its yield stress are reported in Table 1, in the footnotes.
report ζ potentials with acid, base and/or surface-active agents added, In a few studies the above quantities were measured, but the expected
and otherwise the same systems. Special interest in ζ potentials in gly correlations with IEP were not observed.
cols is due to application of dispersions of nanoparticles in glycols or in Rogov et al. [265] demonstrated limited correlation between in
their mixtures with water (”nanofluids”) as heat-transfer fluids. High duction period in bipolar plasma electrolytic oxidation process at pH
dispersion stability is desired in heat-transfer nanofluids, and highly 12.4 and oxide IEP in six metals. A linear dependence was observed for
charged particles are likely to produce stable dispersions. Ta, Ti, Zr, Al and Mg, but not for Nb.
Strubbe et al. studied the electrophoretic mobility of silica [254] and IEP of anatase decreased from pH 7.8 to 3.3 in a series of commercial
of PMMA microspheres [255] in dodecane. The mobility of silica varied specimens with particle sizes increasing from 20 to 140 nm [104]. This
over time. Kokot et al. studied the electrophoretic mobility of silica in result may suggest that the IEP strongly depends on the size of primary
ethanol and in acetonitrile [256]. Medrano et al. studied the electro particles (Attention: many discussions on particle size in this review
phoretic mobility of silica in toluene-ethanol 70:30 mixture at various refer to the size of aggregates of primary particles, but in this paragraph,
solid loads [257]. Apparently, the mobility decreased with the solid the size of primary particles is meant). Allegations about the correlation
load. Ichinose et al. [258] studied ζ potentials of various polymers in between IEP and primary particle size can be found in older literature
cyclohexane using a home-made apparatus. They have not attempted to summarized in [1–7]. A simple correlation between size and IEP is hard
remove water from the solvent or from the solid particles. to demonstrate. It would be practically impossible to produce a series of
specimens which only differ in size and do not differ in other properties,
3.7. Model calculations which may potentially affect the IEP, e.g., in the level of impurities or in
exposition of particular crystalline faces. A few selected specimens were
Predota et al. [259] used MD calculation to estimate the zeta po used in [104], and hundreds of other specimens of nano-TiO2 studied in
tential of 0001 quartz in 0.4 M NaCl, NaBr, KCl, and KBr. Interestingly the literature (and summarized in this present paper and in [1–7]) do not
enough, the increase of pH from 6 to 9 induced a substantial decrease in show this kind of correlation, that is, sometimes, relatively small par
the absolute value of the negative zeta potentials, which is against the ticles show a low IEP, and relatively large particles show a high IEP.
experimentally observed trends. IEP of metal oxide nanoparticles was used to estimate their con
Facet-dependent PZC of rutile and anatase was calculated from duction band energy, which in turn was used (as one of the descriptors)
crystallographic data in [260]. According to a MD calculation presented to assess their toxicity [266]. Correlation between electronegativity and
in [261] and in a previous paper of the same authors cited therein, PZC of numerous metal oxides was studied in [267]. A few unusual PZC,
anatase is supposed to have a higher PZC than rutile. Analysis of data for example 5.1 for Al(OH)3 and 10.5 for ZrO2 taken from the literature
from [1–7] does not confirm this allegation, that is, the median of re were used (see [1–7] and Table 1 for typical values).
ported zero-points is around 6 both in rutile and in anatase.
Lutzenkirchen et al. [262] presented the results of their model cal 3.10. Examples of erroneous procedures and interpretations
culations using various codes to calculate the σ0(pH) and ζ(pH) curves,
as well as force-distance curves (at specific pH and ionic strength). The results obtained by the methods discussed in this section are
unlikely to represent the actual zero-points. This section is not aimed as
a complete compilation or as in-deep analysis of erroneous methods
(detailed discussion of the methods can be found elsewhere [1]) and
20
results, and only a few representative examples are presented.

Kolokolov et al. [268] claimed a “zero-charge point” of SnO2 at pH 3
in the text. Apparently, the graph upon which the above statement is
based does not present the ζ potential as a function of equilibrium pH of
dispersion of particles from the same lot, but rather as a function of
initial pH of dispersion, which was autoclaved during the synthesis of
SnO2 (multiple lots of SnO2 were obtained at various initial pH).
An example of erroneous determination of IEP (incorrectly termed
PZC) from electrokinetic data is presented in [269]. The electrokinetic
curve consisted of two data points only: ca 2 pH units above and ca 2 pH
units below the IEP, and the result of linear interpolation was reported as
the IEP with 2 decimal digits. Interpolation of the IEP with such preci
sion is meaningless, and the actual IEP could be anywhere between these
two pH values.
The following formula.
pHpzc = 2 (pHKCl ) − pHH2O (1)
was used in [169] to calculate apparent PZC of 5 materials, where pHKCl

and pHH2O are the pH of dispersions of 1 g of certain material in 2.5 mL
Fig. 1. The number of entries in [3–7] and in Table 1, which report PZC
of 1 M KCl or of water. This approach gained certain popularity, e.g., it determined as CIP.
was used for 5 other materials in [270], for next 9 materials in [271],
and for another material in [272], but the present author does not
recommend such a procedure.
Substantial discrepancies between IEP and apparent PZC, the later
probably obtained as natural pH of dispersion in a series of iron (hydr)
oxides are reported in [66]. This result demonstrates that IEP and nat
ural pH of dispersion are two different quantities.
4. Conclusions
Although determination of the point of zero (proton) charge as CIP is

superior to its determination as the natural pH of dispersion, the former
method is seldom used and the later (less reliable) method becomes
more and more popular. The number of entries in [3–7] and in Table 1,
which report CIP is illustrated in Fig. 1. The PZC obtained by methods
equivalent to CIP (e.g., salt titration) are not included. Extrapolation of
the trend shown in Fig. 1 suggests that the determination of the point of
zero charge as CIP will be completely forgotten soon. Fig. 2 shows the
same results as Fig.1, but normalized to the number of references in
particular updates. Fig. 2. The number of entries in [3–7] and in Table 1, which report PZC
Although the superiority of CIP is (still) well-known, and it has been determined as CIP normalized to the number of references in particular reviews.
discussed in classical textbooks (Lyklema [273], Hunter [274]), and in
many journal papers including, but not limited to [2–7], the contem Data availability
porary scientists prefer mass titration or pH-drift method. Interestingly
the popularity of salt titration and related methods has been at nearly Data will be made available on request.
constant level over many decades. The preference for erroneous
methods shows a positive feedback: because of the popularity of Acknowledgment
apparent PZC determined by mass titration or pH-drift method and
declining interest of CIP in the recent literature, an unaware reader may This research was supported by Lublin University of Technology,
have an impression that CIP is obsolete while determination of PZC as grant number FD-EE-407.
natural pH of dispersion is a modern approach. This results in further
growth of the popularity of mass titration and of pH-drift method, but a References
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[7] Kosmulski M. The pH dependent surface charging and points of zero charge IX
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The pH dependent surface charging and points of zero charge. X. Update

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3.1.1.4.1.2 Synthetic gibbsiteh 10− 3

(NO3)3 in 0.002 M HCl NaNO3 Salt Zetasizer Nano 9.2*

Aesar, 4 nm, 99.95% NaNO3 Salt Zetasizer Nano 8*

3.1.39.1.1.10.1, IV-IX TiO2, P25 Evonik iep 6a [107] 111 6.5

3.1.39.1.5 TiO2, nanoparticles iep 6.7 [121]

3.2.27, VII Halloysite nanotubes iep Brookhaven 3.8 [142]

3.2.57 Synthetic silicate-1 0, 0.1 M 20 iep Coulter Delsa 6.5 [152]

results, and only a few representative examples are presented.

was used in [169] to calculate apparent PZC of 5 materials, where pHKCl

Although determination of the point of zero (proton) charge as CIP is

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