Chemical Engineering Science 65 (2010) 169 -- 173

Contents lists available at ScienceDirect

Chemical Engineering Science

journal homepage: w w w . e l s e v i e r . c o m / l o c a t e / c e s

LiMn2 O4 spinel direct synthesis and lithium ion selective adsorption

Qin-Hui Zhang, Shao-Peng Li, Shu-Ying Sun, Xian-Sheng Yin, Jian-Guo Yu ∗
State Key Lab of Chemical Engineering, College of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, PR China

A R T I C L E I N F O A B S T R A C T

Article history: The cubic phase LiMn2 O4 spinel is synthesized via a directly soft chemistry method via hydrothermal
Received 25 June 2008 reaction of Mn(NO3 )2 , LiOH and H2 O2 at 383 K for 5–10 h, more favorable to control the nanocrystalline
Received in revised form 11 June 2009 structure with well-defined pore-size distribution and high surface area than traditional solid-phase reac-
Accepted 12 June 2009
tion at high temperature. Further, the 1D MnO2 nanorod ion-sieves with lithium ion selective adsorption
Available online 21 June 2009
property is prepared by the acid treatment process to completely extract lithium ions from the LiMn2 O4
Keywords:
lattice. The effects of hydrothermal conditions on the nanostructure, chemical stability and ion-exchange
Adsorption property of the LiMn2 O4 spinel and MnO2 ion-sieve are examined via powder X-ray diffraction (XRD), N2
Ion exchange adsorption–desorption at 77 K, high-resolution transmission electron microscopy (HRTEM), selected-area
Lithium electron diffraction (SAED) and lithium ion selective adsorption measurements. The results show that the
Manganese 1D MnO2 nanorods might be utilized in lithium extraction from aqueous environment including brine,
Nanostructure seawater and waste water.
Separation © 2009 Elsevier Ltd. All rights reserved.

1. Introduction size distribution, resulted from high-temperature calcination process

In the LiMn2 O4 spinel, the O atoms have a cubic close packing
(CCP) or face-centered close packing (FCC) structure, and contrary
to expectations based on ionic radius, the Mn atoms are in octa-
hedral sites (16d) and the Li in the tetrahedral sites (8a) as shown
in Fig. 1. The Li+ is transported via 8a–16d–8a channels in the 3D
interstitial space provided by the [Mn2 O4 ] structure unit with lit-
tle shrinking or swelling of the spinel structure, which makes the
material applicable as the selective ion-sieves for lithium adsorp-
tion from aqueous resources including brine or seawater (Chitrakar
et al., 2001; Ooi et al., 1990; Zhao and Wang, 2003). Such lithium
ion-sieve effect strongly depends on the crystal structure and mor-
phology of the LiMn2 O4 precursor, so various bulky or nanocrys-
talline MnO2 with different crystal structure are first synthesized,
followed by high-temperature solid-phase reaction between decom-
posable lithium compounds (e.g. lithium carbonate or nitrate) and
MnO2 to form LiMn2 O4 precursor and the acid treatment process to
extract lithium from the Li–Mn–O lattice to get the final ion-sieves
with selective adsorption capacity for lithium ions (Chitrakar et al.,
2000; Hunter, 1981; Shen and Clearfield, 1986; Zhang et al., 2007,
2008). However, the final ion-sieves obtained by above methods are
of irregular morphology and large aggregates with broad particle
and repeated grinding. Although the soft chemistry hydrothermal
method is proposed to obtain spinel LiMn2 O4 oxide with homo-
geneous composition and nanosize distribution, via the reaction of
-MnO2 or layered compound of Li-birnessite in 0.5–1 mol l−1 LiOH
solution at 443–473 K for about 24 days or longer (Feng et al., 1995,
2001), yet the raw material of -MnO2 or Li-birnessite has to be firstly
prepared from a complex process and the proposed hydrothermal
procedure is time consuming.
In this paper, a much milder soft chemistry conditions are opti-
mized to synthesize one-dimensional (1D) spinel LiMn2 O4 precur-
sor directly using the commercial H2 O2 , LiOH and Mn(NO3 )2 mixed
solution and reacting at 383 K for 8 h. The final low-dimensional
MnO2 nanorod ion-sieve with lithium ion selective adsorption prop-
erty is prepared further by the acid treatment process to completely
extract lithium ions from the LiMn2 O4 lattice. The structure char-
acteristics and ion-exchange properties of the samples are studied
by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), high-
resolution transmission electron microscopy (HRTEM), selected-area
electron diffraction (SAED) and lithium ion selective adsorption mea-
surement.
2. Experimental

2.1. Synthesis of 1D LiMn2 O4 nanorod and MnO2 ion-sieve

∗ Corresponding author. Tel.: +86 21 64252171; fax: +86 21 64252826. All chemicals used in this work are AR reagents, except where oth-
E-mail address: jgyu@ecust.edu.cn (J.-G. Yu). erwise indicated. 300 ml mixed solution of H2 O2 (0.20–0.90 mol l−1 )

0009-2509/$ - see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2009.06.045
170 Q.-H. Zhang et al. / Chemical Engineering Science 65 (2010) 169 -- 173
Fig. 1. LiMn2 O4 spinel structure with (1 1 1) crystal face perpendicular to the page
layout (a). Li atoms are in the red tetrahedral 8a sites (b) and the Mn in the blue
octahedral 16d sites (c).
and LiOH (0.70–1.50 mol l−1 ) is added dropwise into a teflon-coated
stainless autoclave filled with 300 ml 0.40 mol l−1 Mn(NO3 )2 solu-
tion stirred at 150 r min−1 . After the mixed solution maintained in
air at room temperature for 2 h, the autoclave is sealed and heated
at 343–453 K for 8–48 h, respectively, then cooled naturally to room
temperature. The obtained black precipitate is filtrated, washed com-
pletely with deionized water till the conductance of filtrate reaches
about 18.2 M cm−1 (the same level of the deionized water) and
dried at 343 for 12 h. By optimizing the soft-chemistry conditions
of reaction temperature, contact time, concentration of H2 O2 and
LiOH solution, pure cubic LiMn2 O4 ternary oxide (denoted as LMO-
D) could be produced at 383 K for 8 h with the mixed solution of
0.30 mol l−1 H2 O2 , 1.00 mol l−1 LiOH and 0.40 mol l−1 Mn(NO3 )2 . The
Li+ extraction from LiMn2 O4 precursor is carried out in 0.10 mol l−1
HCl solution at 303 K for 24 h until the lattice lithium is completely
extracted (in situ measured by Metrohm 861 IC with Mrtrosep C2
100/4.0 column). The acid-treated materials are filtered, washed with
deionized water and dried at 333 K for 8 h to obtain the final MnO2
ion-sieves (denoted as SMO-D). The whole process might be de-
scribed as a hydrothermal-redox-precipitation procedure as the re-
action (1) which could be divided to three steps as Eqs. (2)–(4). At
high LiOH concentration (1.00 mol l−1 ) and with the existence of Li+ ,
the MnII (OH)2 is oxidized accompanied with the Li+ insertion into
the Mn–O lattice to form the LiMnIII MnIIII O4 tri-oxide precursor.
4Mn2+ + 10OH− + 2Li+ + 3H2 O2 → 2LiMn2 O4 + 8H2 O
Precipitation reaction : Mn2+ + 2OH− → Mn(OH)2
Redox reaction : 2Mn(OH)2 + H2 O2 → 2MnOOH + 2H2 O
+ + − meter.
Li insertion : 2Li +2OH +4MnOOH + H2 O2 → 2LiMn2 O4 +4H2 O
2.2. Characterization of samples
The bulky phase of the samples is examined by XRD on a Rigaku
D/max 2550 X-ray diffractometer with monochromatized CuK ra-
diation ( = 1.54056 Å), operating at 40 kV, 100 mA and scanning
rate of 10◦ min−1 . The pore structure of the samples is character-
ized by N2 adsorption–desorption at 77 K using an adsorption appa-
ratus (Micromeritics ASAP 2010 V5.02); the surface area, from the
Brunauer–Emmett–Teller equation, and pore volume, from the total
amount of nitrogen adsorbed at relative pressures of ca. 0.96. The
microstructure and surface morphology of the samples are analyzed
by HRTEM and SAED on a JEOL JEM-2100F TEM (200 kV) after the
samples are dispersed by ultrasonic in anhydrous ethanol for 5 min
and then placed onto the cuprum grid for observations.
2.3. Lithium ion selective adsorption test
The lithium ion adsorption isotherm is carried out by stirring
(150 r min−1 ) 100.0 mg MnO2 ion-sieves in 100.0 ml LiCl solution
Table 1
Initial composition of the (LiCl+LiOH) mixed solution for pH titration of SMO-D
ion-sieve.
Solution 1 2 3 4 5 6 7 8 9 10 11
VLiCl (0.1 mol l−1 , ml) 10 9 8 7 6 5 4 3 2 1 0
VLiOH (0.1 mol l−1 , ml) 0 1 2 3 4 5 6 7 8 9 10
(pH = 10.10, adjusted by buffer solution composed of 0.1 mol l−1
NH4 Cl and 0.1 mol l−1 NH3 · H2 O with the molar ratio of 0.25) with
different initial Li+ concentration for about 72 h at 303 K. The ad-
sorption kinetics is carried out by stirring (150 r min−1 ) 100.0 mg
of MnO2 ion-sieve in 100.0 ml LiCl solution (pH = 10.10) with uni-
form initial concentration of lithium ions (10.0 mmol l−1 ) at 303 K.
The selectivity of lithium ions compared with other coexisting ions
in brine or seawater is carried out by stirring 100.0 mg of the ion-
sieves in 10.0 ml solution (pH = 10.10) containing Li+ , Na+ , K+ , Ca2+
and Mg2+ of about 10.0 mmol l−1 , respectively, for 72 h at 303 K. The
concentration of all metal ions in supernatant lucid solution is deter-
mined in situ by IC until the attainment of equilibrium. The exchange
capacity or the amount of metal ion adsorbed per gram of MnO2
ion-sieve at equilibrium (Qe ), distribution coefficient (Kd ), separation
factor (Li
Me ) and concentration factor (CF) are calculated according
to the following equations:
Qe = (C0 − Ce )V/W (5)
Kd = (C0 − Ce )V/(Ce W) (6)
Li
Me = Kd (Li)/Kd (Me), Me : Li, Na, K, Ca and Mg (7)
CF = Qe (Me)/C0 (Me) (8)
in which, Qe is the amount of metal ions adsorbed per gram of ad-
sorbent at equilibrium (mmol g−1 ); Ce the concentration of metal
ions at equilibrium (mol l−1 ); C0 the initial concentration of lithium
ions (mol l−1 ); V the solution volume (ml) and W the weight of
adsorbent (g).
The pH titration curve was measured at the same condition as the
(1) Li+ adsorption isotherm, except that the solution was the mixture
of 0.1 mol l−1 LiCl and 0.1 mol l−1 LiOH with different volume ratios
(2) as shown in Table 1. After attainment of equilibrium, the lithium
content in the supernatant solution was determined in situ by IC
(3)
and the pH of the solution was determined with a Metrohm 827 pH
(4)
3. Results and discussion
The powder XRD diffraction patterns of the nanocrystal LiMn2 O4
ternary oxide precursor (LMO-D) and MnO2 ion-sieve (SMO-D) are
presented in Fig. 2. The reflections of LMO-D can be readily indexed
to pure cubic phase [S.G.: Fd3m (227)] of LiMn2 O4 with lattice con-
stant of 8.25 Å (JCPDS 35-0782), and the reflections of SMO-D, to
cubic phase [S.G.: Fd3m (227)] of -MnO2 with lattice constant of
8.03 Å (JCPDS 44-0992) with several faint diffraction peaks at 22.16◦ ,
42.44◦ and 56.24◦ indicate trace amounts of orthorhombic phase
[S.G.: Pnma (62)] of ramsdellite-MnO2 (JCPDS 39–0375, a = 9.27 Å,
b = 2.866 Å, c = 4.5330 Å). The phenomena are different from those
of spinel LiMn2 O4 prepared by calcination method in related work
(Chitrakar et al., 2000, 2001; Hunter, 1981; Ooi et al., 1990; Shen and
Clearfield, 1986; Zhang et al., 2007, 2008; Zhao and Wang, 2003),
in which the LiMn2 O4 precursor and the final MnO2 ion-sieve fully
assemble the same spinel structure and the relative peak intensities
corresponding to (1 1 1) and (4 0 0) planes are also weaker. These are
probably resulted from the relatively low stability of LiMn2 O4 with-
out high-temperature calcination process, and further research to
obtain pure cubic phase MnO2 ion-sieve is still in process. However,
 Q.-H. Zhang et al. / Chemical Engineering Science 65 (2010) 169 -- 173
Fig. 2. XRD patterns of LiMn2 O4 precursor (LMO-D) and MnO2 ion-sieve (SMO-D).
c (h k l): cubic LiMn2 O4 crystal face;  (h k l): cubic MnO2 crystal face; r (h k l):
ramsdellite MnO2 .
it should be noticed that the XRD patterns of LMO-D and SMO-D
are still quite similar, assembling the same cubic phase with lattice
constants of 8.25 and 8.03 Å, respectively, indicating that the Mn–O
lattice is stable during the Li+ extraction process and the locations
of manganese in the crystal structure are well maintained. The rigid
structure with little swelling or shrinking in aqueous environment
is important for the strong steric or ion-sieve effect of MnO2 during
the lithium selective adsorption process.
Traditionally the final MnO2 ion-sieves are of seriously bulky
aggregates although the manganese dioxide precursor might have
nanosized distribution and morphology (Chitrakar et al., 2000, 2001;
Hunter, 1981; Ooi et al., 1990; Shen and Clearfield, 1986; Zhang
et al., 2007, 2008; Zhao and Wang, 2003). The present synthesis
conditions have been greatly alleviated and the morphology of the
LiMn2 O4 precursor and final MnO2 ion-sieve is effectively controlled
within low-dimensional nanorod structure as shown in Fig. 3. The
LiMn2 O4 precursor yields mainly mono-dispersed nanorods with
about 10–20 nm in diameter and several micrometers in length,
implying that the soft chemistry synthesis is effect for the direct
formation of 1D LiMn2 O4 nanostructure with uniform geometry ev-
idenced further by the pore-size distribution calculated from the N2
adsorption–desorption data with the peak pore size (Dp ) centered
around 30.9 nm (as shown in Table 2 and inset of Fig. 3). The pore-
size distribution, unlike the HRTEM observations, is obtained statis-
tically, thus the appearance of the obviously broad peak is attributed
to capillary condensation in the slit-shaped mesopores with par-
allel walls and implies the separation of most nanorods from one
another although some of the nanorods look thicker than others.
Fig. 3 LMO-D (B) is a typical HRTEM image of a single LiMn2 O4
nanorod with inset of SAED pattern recorded on the selected area,
showing reflection characteristic of 1D nanorod structure with the
diffraction spots elongated in the direction perpendicular to the rod
axis. The SAED pattern also confirms that the LiMn2 O4 ternary oxide
is single crystal. The derived MnO2 ion-sieves also afford the sim-
ilar 1D nanorod morphology with LiMn2 O4 precursor as shown in
Fig. 3 SMO-D, without aggregation after the acid treatment process
to extract the Li+ from Li–Mn–O lattice evidenced obviously by the
peak pore size (Dp ) centered around 31.9 nm and no other peaks in
the range of 1–100 nm (as shown in Table 2). Fig. 3 SMO-D (B) is a
typical HRTEM image of a single MnO2 nanorod with the diameter
of about 15 nm and the corresponding SAED pattern demonstrates
that the nanorod is a single crystal with a growth direction along
the (1 1 1) lattice plane.
The physical chemistry texture property of LiMn2 O4 precursor
and the derived MnO2 ion-sieve are shown in Table 2. The spe-
cific surface areas (SBET ) accordingly increased from 57.85 m2 g−1 of
the LiMn2 O4 precursor to 75.75 m2 g−1 of the final MnO2 ion-sieve
171
after Li+ are extracted from the LiMn2 O4 lattice, contrast to the phe-
nomena of solid-phase reaction, the high-temperature calcinations
always resulted in serious aggregation of the LiMn2 O4 and MnO2
bulky particles. Pore-size distribution analysis via the DFT method,
applicable for a complete range of pore size indicates that both
the samples afforded a mesoporous size distribution with the peak
pore size (Dp ) centered around 30.9 nm of LMO-D and 31.9 nm of
SMO-D, respectively. In both cases the values of external surface
area (Se ) and SBET are similar, reflecting again the lack of microp-
ores in these samples and the very little micropore volume is also
observed.
Fig. 4 shows the Li+ adsorption isotherm and kinetics of the
SMO-D nanorod ion-sieve. The equilibrium adsorption capacity (Qe )
increases apparently before the equilibrium lithium ion concen-
tration (Ce ) reaches to 3.7 mmol l−1 , then increases slowly with
the maximum lithium ion equilibrium adsorption quantity (Qe ) to
be 2.95 mmol g−1 . Although the value is only a little higher than
that of the bulky MnO2 ion-sieve (2.43 mmol g−1 ) synthesized by
high-temperature calcination method (Zhang et al., 2007), it is
probable that the current nanorod MnO2 contains trace amounts of
orthorhombic phase MnO2 besides the cubic phase MnO2 (as shown
in Fig. 2) and the orthorhombic phase MnO2 has great defect to
the lithium ion insertion process. The adsorption kinetics shows
that the adsorption rate is fast at the first 2 h with the adsorption
capacity increased quickly to about 1.7 mmol g−1 , then it increases
slowly and the adsorption process achieves the equilibrium, the to-
tal time saves about 90 h compared with the bulky MnO2 ion-sieve
synthesized by high-temperature calcination method (Zhang et al.,
2007). The theoretical content of Li+ in LiMn2 O4 is 5.53 mmol g−1 .
During the acid treatment process, with 0.10 mol l−1 HCl solution at
303 K for 24 h, totally 99.6% of the lattice lithium is extracted, that
is 5.51 mmol g−1 . The maximum lithium ion equilibrium adsorption
quantity is 53.5% of the amount of lithium removed by acid treat-
ment. This is because that the lithium ion adsorption isotherm is
carried out at pH = 10.10, adjusted by buffer solution composed of
0.1 mol l−1 NH4 Cl and 0.1 mol l−1 NH3 · H2 O with the molar ratio of
0.25. The pH value of 10 is similar with the salt lake brine in practice.
While the pH titration curve (Fig. 5) shows that the MnO2 ion-sieve
has two kinds of exchange groups. As pH < 4.46, it is the tetrahedral
8a sites with stronger acidity and easy to be exchanged; as pH > 4.46,
it is the octahedral 16d sites with weaker acidity. The acidity of the
solutions has great influence on the Li+ adsorption capacity of the
ion-sieves. With the increase of the pH values, the Li+ adsorption ca-
pacity increases till the equilibrium at pH = 12.17 and the total Li+
adsorption capacity is 3.42 mmol g−1 , which is 62.1% of the amount
of lithium removed by acid treatment. The remaining 37.9% is of very
weak acidity and cannot be exchanged in the current conditions.
Further research on the pure cubic phase nanorod MnO2 synthesis
is undergoing. Table 3 shows the selectivity of Li+ compared with
uptake behaviors of other coexisting ions in brine including Na+ , K+ ,
Ca2+ and Mg2+ . The equilibrium distribution coefficients (Kd ) of these
metal ions are in the order of Li+ ?Ca2+ > Mg2+ > Na+ > K+ , indicat-
ing high selectivity for Li+ , but much less for Na+ , K+ , Ca2+ and Mg2+ ,
similar to the cases of the bulky MnO2 ion-sieve prepared by solid-
phase reaction (Zhang et al., 2007, 2008), however, there exist more
obvious discriminations among the values of distribution coefficients
(Kd ) and separation factors (LiMe ). The distribution coefficients for Li
+
is 16770.63 ml g−1 , increased about 2.12 times compared with the
bulky MnO2 ion-sieves (7917.49 ml g−1 ) (Zhang et al., 2007), indi-
cating the remarkable improvement of the ion-sieve selectivity by
the well-maintained nanorod structure. The relatively high selectiv-
ity for Li+ can well be explained by the ion-sieve effect of the spinel
lattice with a 3D (1×3) tunnel suitable in size for fixing lithium ions
in cubic phase MnO2 nanocrystal obtained from LiMn2 O4 precursor.
The results also indicate that Na+ , K+ , Ca2+ and Mg2+ in solution
172 Q.-H. Zhang et al. / Chemical Engineering Science 65 (2010) 169 -- 173

Fig. 3. HRTEM images of LiMn2 O4 ternary oxide precursor (LMO-D) and the derived MnO2 ion-sieves (SMO-D) with insets of SAED patterns and pore distribution curves,
respectively.

Table 2
Physical chemistry texture of LiMn2 O4 precursor (LMO-D) and MnO2 ion-sieves (SMO-D).

SBET (m2 g−1 ) Total pore volume (cm3 g−1 ) Microspore volume (cm3 g−1 ) Hysteresis loop Dp (nm)

LMO-D 57.85 0.18 0.0015 H3 30.9

SMO-D 75.75 0.34 0.002 H3 31.9

Fig. 5. pH titration curve of SMO-D ion-sieve. T = 303 K, V = 10 ml, W = 100 mg.

4. Conclusions
Fig. 4. The Li+ adsorption isotherm and kinetics of the SMO-D nanorod ion-sieve.

The 1D LiMn2 O4 spinel with average size about 15–20 nm in

do not interfere with Li+ during the adsorption process since high diameter and several micrometers in length has been synthe-
concentration factors values of Li+ are observed as compared to CF sized directly via a simple soft-chemistry method with commer-
values of other metal ions. cial Mn(NO3 )2 , LiOH and H2 O2 mixed solution at 383 K for 8 h,
 Q.-H. Zhang et al. / Chemical Engineering Science 65 (2010) 169 -- 173 173

Table 3
Adsorption selectivity of lithium ions on SMO-D sample.

Metal ion C0 (mmol l−1 ) Ce (mmol l−1 ) Qe (mmol g−1 ) Kd (ml g−1 ) LiMe CF×10−3 (l g−1 )

Li+ 10.13 0.058 0.967 16770.63 1.00 95.42

Na+ 8.66 8.56 0.009 1.07 15640.12 1.06
K+ 8.22 8.18 0.004 0.46 36066.14 0.46
Mg2+ 9.48 8.17 0.126 15.47 1084.27 13.32
Ca2+ 9.54 7.14 0.230 32.26 519.80 24.15

more favorable to control the nanocrystalline structure with well- Acknowledgments

defined pore-size distribution and high surface area than traditional
high-temperature calcination method. By optimizing the reaction The research received financial support by NSFC 20576031 and
conditions, the composition and nanocrystalline structure of the as- 20706014, STCSM 0852nm02100, Key Project of Chinese Ministry of
prepared spinels are dependent on the reaction temperature, con- Education 108144 and National 863 Project 2008AA06Z111.
tact time and concentration of LiOH and H2 O2 solution, and the final
MnO2 ion-sieve with lithium ion selective adsorption capacity could References
be easily prepared via the acid treatment process to completely
extract lithium ions from the spinel LiMn2 O4 precursor, without ob- Chitrakar, R., Kanoh, H., Makita, Y., Miyai, Y., Ooi, K., 2000. Synthesis of spinel-
type lithium antimony manganese oxides and their Li+ extraction/ion insertion
vious change to the Mn–O lattice structure and the 1D nanorod mor- reactions. J. Mater. Chem. 10, 2325–2329.
phology. The Li+ adsorption property is improved compared to those Chitrakar, R., Kanoh, H., Miyai, Y., Ooi, K., 2001. Recovery of lithium from seawater
prepared by the conventional high-temperature calcination method. using manganese oxide adsorbent (H1.6 Mn1.6 O4 ) derived from Li1.6 Mn1.6 O4 . Ind.
Eng. Chem. Res. 40, 2054–2058.
Feng, Q., Kanoh, H., Miyai, Y., Ooi, K., 1995. Hydrothermal synthesis of lithium and
Notation sodium manganese oxides and their metal ion extraction/insertion reactions.
Chem. Mater. 7, 1226–1232.
Feng, Q., Higashimoto, Y., Kajiyoshi, K., Yanagisawa, K., 2001. Synthesis of lithium
C0 initial concentration of metal ions, mol l−1 manganese oxides from layer manganese oxides by hydrothermal soft chemical
Ce equilibrium concentration of metal ions, mol l−1 process. J. Mater. Sci. Lett. 20, 269–271.
Hunter, J.C., 1981. Preparation of a new crystal form of manganese dioxide: -MnO2 .
CF concentration factor, l g−1
J. Solid State Chem. 39, 142–147.
Dc critical pore diameter, nm Ooi, K., Miyai, Y., Katoh, S., Maeda, H., Abe, M., 1990. Analysis of pH titration data in
Dp peak pore size, nm a lambda−manganese dioxide+lithium hydroxide system on the basis of redox
Kd distribution coefficient, ml g−1 mechanism. Langmuir 6, 289–291.
Shen, X.M., Clearfield, A., 1986. Phase transitions and ion exchange behavior of
p0 standard atmospheric pressure, Pa electrolytically prepared manganese dioxide. J. Solid State Chem. 64, 270–282.
P pressure, Pa Zhang, Q.-H., Sun, S.-Y., Li, S.-P., Yin, X.S., Yu, J.G., 2007. Adsorption of lithium ions
Qe amount of metal ion adsorbed per gram adsorbent at on novel nanocrystal MnO2 . Chem. Eng. Sci. 62, 4869–4874.
Zhang, Q.-H., Sun, S.-Y., Li, S.-P., et al., 2008. Nanostructure ion-sieves for lithium
equilibrium, mmol g−1 adsorption. Int. J. Chem. React. Eng. 5, 1–6.
rK Kelvin radius, nm Zhao, L.L., Wang, R.S., 2003. Preparation of MnO2 (Li) and its ion exchange kinetics.
R gas constant, 8.31 J mol−1 K−1 Acta Physicochim. Sin. 19, 933–937.

R2 congruence constant
Se external surface area, m2 g−1 Qin-Hui Zhang was born in Xinjiang, China, in 1972. He received Ph.D. degree
SBET BET surface area, m2 g−1 in the field of catalysis science and technology from Tianjin University, Tianjin,
t statistical thickness, nm China, in 2002. His current and previous interests are related to adsorption/ion-
exchange process of nanocrystal oxide and photocatalysis or heterogeneous catalysis
T absolute temperature, K in the presence of semiconductor TiO2 or other nanocomposite oxides. Now he
V solution volume, ml is working at State Key Lab of Chemical Engineering, East China University of
W weight of adsorbent, g Science and Technology, Shanghai, China, and has published more than 20 papers
in peer-reviewed journals and a chapter in an edited collection (This book has been
published now. So the sentence is changed to: published in 2008 by NOVA Science
Publishers, NY USA, ISBN: 978-1-60456-964-3).
Greek letters

Li
Me separation factor
 surface tension of liquid N2 , J m2
 wave length, Å
 molar volume of liquid N2 , m3 mol−1