DOI: 10.

1021/cg9004938

Hollow Nanospheres and Flowers of CuS from Self-Assembled 2009, Vol. 9

Cu(II) Coordination Polymer and Hydrogen-Bonded Complexes 4461–4470
of N-(2-Hydroxybenzyl)-L-serine

Mangayarkarasi Nagarathinam,† Kuppan Saravanan,† Wei Lee Leong,† Palani Balaya,‡

and Jagadese J. Vittal*,†
†
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, and
‡
Department of Mechanical Engineering, National University of Singapore, Singapore 119260

Received May 6, 2009; Revised Manuscript Received August 31, 2009

ABSTRACT: Utilization of a novel two-dimensional coordination polymer generated from a trinuclear building block
[Cu3(HSser)3(H2O)2] 3 2H2O (1) as a precursor in the synthesis of copper sulfide serendipitously resulted in CuS nanospheres
with hollow interiors. The formation of CuS nanocrystals with the three-dimensional hierarchical flower-like morphology from
the hydrogen-bonded metal complex [Cu(H2Sser)2] 3 H2O (2) as a precursor may be understood from the spatial arrangement of
the metal atom and the organic ligand in the crystal lattice plays a major role in determining the shape of the nanomaterials.
Detailed investigation on the effect of experimental conditions and the packing patterns of the complexes in the crystal lattice
reveals the formation mechanism of the morphologically different CuS. The electrochemical behavior of these nanosized CuS
meso-assemblies as a cathode material for lithium ion batteries reveals that the reaction proceeds through an insertion and
deinsertion mechanism and the CuS with a hollow interior is more efficient and has good cyclability compared to that with a
flower-like morphology.

Introduction From a literature survey, it is well understood that extensive

studies have been carried out on the application of nanosized
Micro/nanostructures with hollow interiors are one of the
CuS as a thermoelectric cooling material, optical filler, optical
most promising candidates in catalysis, gas sensors, nanoelec-
recording material, solar cell and super ionic conducting
tronics, biomedical applications and electrochemical cells.1-6
material, gas sensor, and biomedical application, and there
This is apparently due to the large surface area, low material
are only very few attempts on utilization of bulk CuS as
density, and ability to withstand cyclic changes in volume
cathode materials for lithium ion batteries.11-13 This is due to
compared to the nonhollow counterparts. Fabrication of
the main problem of a rapid drop in capacity and the forma-
hollow structures has been achieved mostly using the conven-
tion of electrolyte soluble Li2S during the course of the
tional multistep hard template (e.g., polymeric, ceramic, and
reaction.13 To our knowledge, for the first time, we report
metallic spheres), sacrificial template (metallic or inorganic
nanomaterials), soft template (emulsion droplets, supramole- the utilization of two-dimensional (2D) coordination polymer
cular miscelles/vesicles, polymer aggregates and gas bubbles) assembled from a trinuclear building block [Cu3(HSser)3-
and simple one-pot template-free methods.2 The formation of (H2O)2] 3 2H2O (1) [N-(2-hydroxybenzyl)-L-serine, H3SSer]
a hollow trait in the nanomaterials has been explained with the with a predetermined arrangement of metal atoms in the
aid of mechanisms such as the Kirkendall effect, galvanic generation of nanomaterials with hollow structures. Though
replacement, and inside out Ostwald ripening.2 Though many it has been obtained serendipitously, the isolation of hierarch-
reports available on nanometer-sized CuS with hollow inter- ical three-dimensional (3D) flower-like CuS using the hydro-
iors, existing synthetic methods have been used in the genera- gen-bonded mononuclear complex [Cu(H2Sser)2] 3 H2O (2)
tion of CuS.7-10 For example, the hollow nanostructured CuS with the same ligand and the detailed investigations on
spheres of diameter 200 nm with a shell thickness of 30 nm varying the reaction conditions clearly reveal the role of the
could be synthesized from oil/water emulsion droplet - the predetermined arrangement of metal atoms in the formation
soft template method at room temperature.7 Though there are of hierarchical self-assembly of nanocrystals.
a few exceptions, the isolation of pure CuS phase with hollow The novel 2D coordination polymer 1 obtained from a
nature by the sacrificial template method could most probably trinuclear building block is an exclusive one among the
be achieved only at high temperatures.8,9 There are other complexes synthesized from the same type of ligand systems
literature available where simple metal salts have been used as N-(2-hydroxybenzyl)-aminoacid (L) generated from various
a precursor, but formation of hollow CuS has been explained amino acids.14 These ligands on complexation with metal ions
mostly with the support of a bubble template mechanism (Cu2þ, Zn2þ, Ni2þ) generally result in a dimeric unit (M2L2)
which arises mainly due to the evolution of gases such as H2S consisting of two ligands and two metal atoms and very few
and CO2 by the decomposition of the reactants.10 Several from the monomeric unit (ML). There are also a few reports
methods have been developed to synthesize hollow structures, with monomeric (ML2) and tetrameric ({M2L2}2) moieties.15
but still it remains a challenge to develop a fast and facile one- Indeed, multinuclear (Cu2þ and Fe3þ) complexes without a
pot synthetic route to inorganic hollow materials. phenoxo-bridge and mononuclear (Mn3þ, Co3þ, Cu2þ) com-
plexes of similar ligands have also been reported.16 These
*Corresponding author. Fax: þ65-6779-1691; tel: þ65-6516-2975; e-mail:
systems usually result in the formation of either metal com-
[email protected]. plexes or 1D coordination polymers depending on the spatial
r 2009 American Chemical Society Published on Web 09/16/2009 pubs.acs.org/crystal
4462 Crystal Growth & Design, Vol. 9, No. 10, 2009 Nagarathinam et al.

arrangement of the ligands, and the higher dimension was (nujol mull) d-d transition, 662, LMCT, 377. TGA weight loss
achieved only through noncovalent interactions.14 Higher observed for water 3.6%; found 3.3%.
dimensional (2D, 3D) coordination polymeric structures have Hydrothermal Reaction. For a typical reaction, the precursor
solid 1 (0.127 g, 0.143 mmol) was treated with thiourea (0.543 g,
been reported from these types of ligands only when there is an
0.713 mmol) in 25 mL of H2O (precursor: 5 sulfur source) in a
absence of an aqua ligand.17 Though the flexibility to the Teflon-lined stainless steel autoclave. The autoclave was then placed
ligand skeleton is offered by the -CH2-NH- moiety, the in an oven at the desired temperature and time. The obtained
formation of the final basic structure is guided by the flex- product was washed several times with water and ethanol and dried
ibility introduced by the methylene moiety in the side chain of under vacuo. The reaction conditions were varied to explore the
the ligands.11 For example, the introduction of -CH2- group in effect of different reaction parameters on the size and morphology
the side chain usually leads to a helical/zigzag structure and of the product.
Effect of Time. The above procedure was followed at a constant
the substituted group supports the spatial orientation.18 This molar ratio (1:5) and constant reaction temperature of 100 °C, but
prompted us to investigate the role of a simple side chain such the reaction time was varied at 0.5, 1, 2, 3, 4, 8, and 12 h.
as CH2OH in the ligand H3Sser on the self-assembly of Effect of Molar Ratio of Precursor. In this procedure, molar
coordination polymers. ratios of the precursor to thiourea of 1:3, 1:5, and 1:10 were used, but
In this paper, we report the synthesis, characterization, constant reaction time (24 h) and constant reaction temperature
and single crystal X-ray structure determination of complexes (100 °C) were maintained.
All the above reactions with the same reaction conditions were
1 and 2 and their subsequent transformation to shape con- carried out for complex 2 with the respective molar ratios.
trolled CuS nanomaterials. The electrochemical behvavior of Instruments and Characterization. Elemental analyses were per-
these as a cathode material for lithium ion batteries where the formed in the Microanalytical laboratory, Department of Chem-
CuS with a hollow interior is more efficient and has better istry, National University of Singapore. 1H NMR and 13C NMR
cyclability compared to that with flower-like morphology. spectra were recorded on a Bruker ACF 300FT-NMR spectrometer
operating in the quadrature mode at 300 MHz with TMS as internal
Experimental Section reference at 25 °C. The infrared spectra (KBR pellet) were recorded
using FTS165 Bio-Rad FTIR spectrophotometer in the range
All the chemicals and solvents used were commercially available 4000-450 cm-1. The UV-visible spectra were recorded on a
and used as received. Shimadzu UV-2501 PC UV-vis spectrophotometer in nujol mull
Synthesis of Ligand, H3Sser. To a solution of L-serine (0.105 g, and in methanol solution. Mass spectra were recorded on a Finni-
1.0 mmol) in H2O (10 mL) containing KOH (0.056 g, 1.0 mmol) was gan MAT LCQ mass spectrometer in MeOH solution. Water
added salicylaldehyde (0.122 g, 1.0 mmol) in ethanol (10 mL). The present in the compounds were determined from an SDT 2960
yellow solution was stirred for 30 min at room temperature prior to TGA thermal analyzer with a heating rate of 5 °C min-1 in a N2
cooling in an ice bath. To this intermediate Schiff base solution, atmosphere using a 5-10 mg sample per run. The identity and the
NaBH4 (0.460 g, 1.20 mmol) was added in portions with gentle phase of the products were verified by the X-ray powder diffraction
stirring while the yellow color slowly discharged. After 30 min, the (XRPD) using a D5005 Siemens X-ray diffractometer with the Cu
pH of the solution was adjusted to ∼5-6 using acetic acid, and KR line as the irradiation source (λ = 1.5417 Å). All diffraction data
stirred for 10 min. The colorless precipitate separated out was were acquired in the reflection mode with a step size of 0.016°,
filtered, washed with cold ethanol, ether and dried under vacuo. conducted at 40 kV and 20 mA, in the 2θ range of 2-60°. The
Yield: 0.172 g (80%), Anal. Calcd. For C10H13NO4: C, 56.86; H, sample was either packed tightly on the sample holder or dispersed
6.20; N, 6.63. Found: C, 56.50; H, 6.32; N, 6.56%. 1H NMR (D2O): in ethanol and transferred to a piece of small glass slide and fixed on
δ 3.33 (t, 1H, -CHCOOH), 3.73-3.78 (m, 2H, -CH2OH), 3.86 the holder after the sample was dried. The surface morphology and
(q, 2H, Ar-CH2), 6.66-6.72 (m, 2H, Ar), 7.15-7.18 (m, 2H, Ar). the distribution of the product were analyzed using field emission
13
C NMR (D2O): 48.26 (Ar-CH2), 61.67 (-CH2OH), 63.43 scanning electron microscope (FESEM) in which the images were
(-CH2COOH). 117.12 117.57, 123.03, 129.42, 129.86, 159.66 acquired using the JEOL JSM-6700F model instrument. The sam-
(Ar), 176.97 (-COOH). IR (KBr, cm-1): υ(OH) 3447, υ(NH) ples were placed over carbon tape attached on the metal holder and
3250, υas(COO-) 1626, υs(COO-) 1471, υ(phenolic, CO) 1285. coated with a thin layer of platinum using JEOL JFC-1600 auto fine
Synthesis of [Cu3(HSser)3(H2O)2] 3 2H2O, 1. To H3Sser (0.211 g, coater to increase their conductivity. On the other hand, energy
1.0 mmol) and LiOH (0.048 g, 2.0 mmol) in 10 mL of water was dispersive X-ray (EDX) was acquired using another model, JEOL
added Cu(CH3COO)2 3 H2O (0.2 g, 1.0 mmol) in 10 mL of water. JSM-6701F field emission scanning electron microscope. Similar
The clear green solution was filtered immediately and the solution sample preparation was performed for EDX except that no coating
was kept for slow evaporation. After a week, thin green needle-like of the platinum was required. The size and morphology of the
crystals separated out, were filtered, washed with ethanol, and dried products were determined from transmission electron microscope
under vacuo. Yield: 0.2 g (50%). Anal. Calcd. for Cu3C30H41N3O16: (TEM and HRTEM) images which were taken using the JEOL 2010
C, 40.47; H, 4.64; N, 4.72. Found: C, 40.70; H, 4.70; N, 4.86%. IR and 3010 instruments. A drop of the sample dispersed in ethanol was
(KBr, cm-1): υ(OH) 3429, υ(NH) 3227, υas(COO-) 1650, υs(COO-) placed on the carbon-coated copper grid of mesh size 300 before it
1486, υ(phenolic, CO) 1276. ESI-MS: [Cu3(HSser)3]þ 817.2, was moved to the sample chamber of the TEM for viewing. As for
[Cu2(HSser)2]þ 543.3. UV-vis (λmax (nm), ε (M-1 cm-1)): (metha- the SAED images, they were captured during the acquisition
nol) d-d transition, 677(100), LMCT, 379 (695); (nujol mull) d-d process of TEM images.
transition, 690, LMCT, 331. Calcd. TGA weight loss observed for Single Crystal X-ray Crystallography. Single crystal X-ray dif-
water 8.1%; found 7.8%. fraction measurements were carried out on a Bruker AXS SMART
Synthesis of [Cu(H2Sser)2] 3 H2O, 2. To H3Sser (0.211 g, 1 mmol) CCD diffractometer. Unit cell dimensions were obtained with least-
and LiOH (0.048 g, 2 mmol) in 15 mL of water was added Cu- squares refinements, and all structures were solved by direct meth-
(CH3COO)2 3 H2O (0.150 g, 0.75 mmol) in 15 mL of water. The clear ods. The program SMART19 was used for collecting frames of data,
green solution was filtered immediately and the solution was kept for indexing reflections, and determination of lattice parameters.
slow evaporation. After a day, thin blue needle like crystals separated SAINT19 for integration of intensity of reflections and scaling;
out, filtered, washed with ethanol and dried under vacuo. The green SADABS20 was used for empirical absorption correction and
filtrate on slow evaporation resulted only in green trinuclear complex. SHELXTL21 was used for space group determination, structure
Yield of blue crystals: 0.12 g (23%). Anal. Calcd. for CuC20H26N2O9: solution, and least-squares refinements on F2. Selected crystallo-
C, 47.85; H, 5.22; N, 5.58. Found: C, 48.09; H, 5.32; N, 5.47%. IR graphic data and refinement details are displayed in Table 1.
(KBr, cm-1): υ(OH) 3407, υ(NH) 3212, υas(COO-) 1607, υs(COO-) Electrochemical Studies. For electrochemical studies, composite
1468, υ(phenolic, CO) 1280. ESI-MS: [Cu(H2Sser)2]þ 482, [Cu2- electrodes were fabricated with the active material (CuS), super P
(HSser)2]þ 542.9, [Cu3(HSser)3]þ 816.8. UV-vis (λmax (nm), ε carbon black and binder (Kynar 2801) in the weight ratio of
(M-1cm-1)): (methanol) d-d transition, 645(76), LMCT, 377(342); 70:15:15 using N-methylpyrrolidone (NMP) as a solvent and the
Article Crystal Growth & Design, Vol. 9, No. 10, 2009 4463

Figure 2. A perspective view of the packing of the 2D coordination

polymer, 1.

Figure 1. The ball and stick diagram of the asymmetric unit of in a bidentate fashion. Another ligand completes the coordi-
complex 1. Lattice H2O molecules are omitted for clarity. nation sites of Cu3. Cu2 and Cu3 have square pyramidal
geometry. The deviation from ideal square-pyramidal geo-
Table 1. Selected Crystal Data and Structure Refinement Details metry around Cu2 and Cu3 is reflected in angular structural
for 1 and 2 parameters, τ values of 0.08 and 0.2.17,18 But Cu1 has [4 þ 2]
1 2 octahedral geometry where O2N2 forms the basal plane and
formula C30H41Cu3N3O15 C20H26CuN2O9 the oxygen atoms of two water molecules in the axial posi-
formula weight (g M-1) 874.28 501.97 tions complete the distorted octahedral environment. The Cu1-
temperature (K) 223(2) 223(2) Cu2 distance is 2.99 Å and similar to the reported dimeric
crystal system monoclinic orthorhombic systems,14-18 while Cu1-Cu3 and Cu2-Cu3 distances are
space group P21 P21212
a (Å) 13.5406(14) 8.3764(12)
4.4 and 6.58 Å.
b (Å) 7.9202(8) 22.157(3) In the crystal structure of 1, the trinuclear moiety is con-
c (Å) 16.5960(19) 5.6982(8) nected along the b-axis through coordination of the Cu2 with
R (°) 90 90 carboxylate oxygen O7 of another trinuclear unit and forms a
β (°) 99.731(3) 90 chain. The Cu2-O7 bond distance, 2.547(2) Å, is similar to
γ (°) 90 90
V (Å3) 1754.2(3) 1057.6(3) the reported Cu-O(carboxylate) bonds in coordination poly-
Z 2 2 mers. Two chains of this type are connected through hydroxyl
density (calculated) (mg m-3) 1.655 1.576 oxygen of the serine moiety along the c-direction and form a
reflections collected 10161 6151 2D coordination polymer. It appears that the introduction of
independent reflections 6085 2193
Rint 0.0287 0.0363
flexible CH2OH side chain results in helical structures which
data/restraints/parameters 6085/19/496 2193/1/153 are fused to form a 2D network structure as shown in Figure 2.
absolute structure parameter -0.005(15) 0.08(4) Table S1 in Supporting Information contains selected hydro-
goodness-of-fit on F2 1.028 1.254 gen bond parameters of 1.
final R [I > 2σ(I)], R1a 0.0406 0.0619 Crystal Structure of 2. The asymmetric unit in 2 contains
wR2b 0.1105 0.1416
half of the molecule as there is a crystallographic 2-fold axis
a
R1 = Σ||Fo| - |Fc||/Σ|Fo|. b wR2 = [Σw(Fo2 - Fc2)2/Σw(Fo2)2]1/2. passing through the Cu(II) center along the c-axis. There is a
water molecule present in the lattice for each formula unit.
details of the cell fabrication have been followed as described in the
The ball and stick diagram of the complex is shown in
literature.22
Figure 3a. The secondary amine and carboxylato oxygen
atoms of the two ligands occupy the equatorial plane of the
Results and Discussion
octahedral Cu(II) site, and the axial positions are occupied
When the Cu/H3Sser ratio is 1:1, 1 forms exclusively but when by phenolic oxygen atoms of the two ligands (Cu(1)-O(1) =
the metal ratio is decreased mononuclear blue crystals of 2 are 2.596(5) Å). The Cu-OH(phenolic) bond distances observed in
obtained in low yield followed by the green crystals of 1. This the reported systems similar to this type of ligands are in the
reveals that the metal to ligand ratio dictates the formation of 1 range of 2.2-2.9 Å.14
and 2. The molecular structure of 1 with atom numbering scheme A view along the b-axis of the 2D hydrogen-bonded sheet
is shown in Figure 1. The asymmetric unit consists of the neutral like structure is shown in Figure 3b. The neutral complexes
trinuclear copper complex with two lattice water molecule. Each aggregates along the ac plane through the O-H 3 3 3 O hydro-
Cu(II) atom is coordinated through the tridentate ligand HSser. gen bonds from the hydrogen of the aqua ligand and oxygen
Cu1 and Cu2 are bridged through phenoxo oxygen and form the of the hydroxyl group of amino acid and N-H 3 3 3 O hy-
Cu2O2 core similar to the several reported dimeric systems drogen bonds from the hydrogen of the amino group
derived from this type of reduced Schiff base ligands.11 The and carboxylate oxygen of the amino acid and results in a
Cu1 and Cu3 are bridged by the carboxylate group of the ligand 2D hydrogen bonded sheet like structure. Table S1 in
4464 Crystal Growth & Design, Vol. 9, No. 10, 2009 Nagarathinam et al.

Figure 3. (a) The ball and stick diagram of 2. Lattice H2O molecule is omitted. (b) Packing pattern of 2 showing the hydrogen-bonded 2D
network structure (view along the b axis).

shell of thickness 70 ( 7 nm as shown in Figure 6. The

HRTEM image and ring-like pattern in SAED confirm the
polycrystalline nature of the hollow spheres which occurs
through the self-assembly of crystalline nanoplates. The
interplanar spacing of the parallel fringes in the HRTEM
image is 0.304 nm and agrees well with the (102) plane of the
hexagonal CuS (Figure 6d).
At the same time, the TEM image of the CuS-2 at 24 h
shows the absence of any hollow trait and the existence of
only flower-like morphology self-assembled with very
loosely packed petals. The interplanar spacing of the parallel
fringes in the HRTEM image (Figure 7c) is 0.304 nm which
agrees well with the (102) plane of the hexagonal CuS. The
polycrystalline nature of the SAED pattern supports that
the plates constituting the flowers are of small size at around
120 nm (Figure 7b).
The observation of two different morphologies from 1 and
2 synthesized from the same ligand H3Sser prompted us to
investigate the effect of time and molar ratio with water as
solvent.
The formation of the pure hexagonal covellite phase of
Figure 4. XRPD patterns of CuS produced at 100 °C, 24 h, with a
CuS (JCPDS 00-006-0464) in all these methods confirms that
1:5 molar ratio of precursor to thiourea and the bar graph of the
standard from JCPDS data. varying the time and molar ratio did not have any effect on
phase formation or composition. The FESEM image of the
Supporting Information contains selected hydrogen bond CuS-1 formed in 30 min shows very few plate beds in
parameters of 2. addition to the mixture of microspheres assembled on plate
CuS Nanomaterials from 1 and 2. Hydrothermal reactions beds and completely popped out microspheres in the range of
of 1 and 2 with thiourea as the sulfurating reagent in a 1:5 180-470 nm, and this is supported by the TEM image
molar ratio at 100 °C for 24 h in an autoclave resulted in the (Figure 9a). The HRTEM image as given in the Figure S3
formation of black products. All the peaks in the X-ray in Supporting Information reveals that the spheres are made
powder diffraction (XRPD) of the above two samples have of plates of 20-30 nm which are single crystalline nature.
been indexed to the hexagonal covellite phase of CuS The observation of a hollow sphere of 180 nm inside the
(JCPDS 00-006-0464) as shown in Figure 4. The quantitative broken hollow sphere of 450 nm as highlighted in Figure 8a
analysis of the energy dispersive X-ray (EDX) spectra reveals gives us a clear understanding that hollow spheres of differ-
that the atomic ratio of Cu to S in the samples is nearly equal ent sizes were formed initially. As the stability of hollow
to 1:1 (Figures S1 and S2 in Supporting Information) which spheres decreases, the size increases which results in the
is very close to the expected stoichiometric ratio of CuS-1 breakage of the shells of the big hollow spheres. At 1 h, there
and CuS-2. was an absence of plate beds in the mixture and on further
The typical FESEM images of CuS-1 and CuS-2 show the increase of time resulted only in microspheres.
formation of hierarchical 3D spherical and flower-like ma- The TEM image of the CuS-1 at 4 h shows that hollow
terials through self-assembly of nanoparticles (Figure 5). The spheres have an average size of 250 ( 21 nm (Figure 9a,b).
size of the spherical CuS-1 and the flower-like CuS-2 are in Still one or two hollow spheres exist of size 300 nm among the
the range of 250-300 nm and 0.65-1.1 μm. 40 spheres counted. The magnified view of the hollow
Interestingly, the TEM image of CuS-1 shows the presence spheres clearly shows that it is loosely packed all over and
of a dark edge and the pale centered spherical particles all the shell walls are not completely formed. The crystallite size
through the grid with an average size of 259 ( 17 nm. This of the nanorods/plates constituting the shell of the nano-
reveals the hollow nature of the spherical particles with a spheres is at around 30 nm.
Article Crystal Growth & Design, Vol. 9, No. 10, 2009 4465

Figure 5. FESEM images of CuS-1 and CuS-2 produced via hydrothermal reaction at 100 °C for 24 h with a 1:5 molar ratio of precursor to
thiourea.

Figure 6. TEM images under different magnifications (a and b) of CuS-1 produced via hydrothermal reaction at 100 °C with a 1:thiourea
molar ratio of 1:5 for 24 h. (c) SAED pattern and (d) the magnified HRTEM.

On observing the TEM image of the CuS-1 formed at 12 h, at 12 h that some of the broken shells are on the top of
one can see very clearly that there is an increase in the size of the microspheres and suggests that the darkness in the
the nanorods/plates (at around 50 nm) near the shell and a TEM image is only due to broken shells and this is suppor-
complete shell is formed with a thickness of 60 nm. The ted by the magnified view of the TEM image shown in
appearance of a few dark centered hollow spheres in addition Figure 9f.
to the hollow spheres (290 ( 20 nm) with a shell thickness Varying the molar ratio of complex 1 to thiourea from 1:3
of 60 nm raises a question of whether there is any core and 1:10 at 100 °C for 24 h results in the formation of
shell formation or it involves only an inside out Ostwald’s spherical spheres with self-assembled nanoplates/-rods. At
ripening process. It is seen from the FESEM image of CuS-1 the same time, plate beds are also seen in addition to the
4466 Crystal Growth & Design, Vol. 9, No. 10, 2009 Nagarathinam et al.

Figure 7. TEM images (a) of CuS-2 produced via hydrothermal reaction at 100 °C with a 2:thiourea molar ratio of 1:5 for 24 h. (b) SAED
pattern and (c) the magnified HRTEM.

Figure 8. FESEM images of CuS-1 produced via hydrothermal reaction at 100 °C for 0.5 and 4 h with a 1:5 molar ratio of 1 to thiourea.

Figure 9. TEM images under different magnifications of CuS-1 produced via hydrothermal reaction at 100 °C with a 1:thiourea molar ratio of
1:5 for (a) 0.30 h, (b, c) 4 h, and (d-f) 12 h.

spheres in the FESEM image (Figure 10b). As the plates or indicates the very loosely packed nature. To minimize the
rods grow in the self-assembled plate beds, the spheres pops interfacial energy, the loosely packed plates/rods aggregate
out and leave a hollow in the self-assembled structure and as a spherical particle.
Article Crystal Growth & Design, Vol. 9, No. 10, 2009 4467

Figure 10. FESEM images of CuS-1 produced via hydrothermal reaction at 100 °C for 24 h with (a) 1:3 and (b) 1:10 molar ratio of precursor
1 to thiourea.

Figure 11. FESEM images of CuS-2 produced via hydrothermal reaction at 100 °C for (a) 4 h, (b) 8 h with a 1:5 molar ratio of 2 to thiourea.
(c) TEM image (d) SAED pattern and (e) the magnified HRTEM of CuS-2 of 4 h.

Varying the reaction time for the CuS-2 from 4, 8, 12, and metal atoms in the crystal lattice and the product formation.
24 h may demonstrate that the 3D flower morphology results As explained in our earlier report, 1 and 2 acts as a sacrificial
from the self-assembly of nanoplates. The representative template in the formation of shape controlled nanomaterials;
images of 4 and 8 h has been shown in Figure 11, panels a that is, the Cu2þ ions on the surface of the coordination
and b, respectively. The presence of microspheres with some polymer react with the S2- ions generated from thiourea at
sharp platelike edges as seen in the TEM image of 8 h samples high temperature to form CuS and the next layer starts
(Figure 11c) indicates that the 3D flower-like nanomaterials reacting once the CuS in the surface of the crystals got peeled
have a densely packed arrangement of petals. The average off to the solution.23
size of flower is around 0.76 ( 0.2 μm. The ring-like pattern With respect to the predetermined array of metal atoms in
in the SAED indicates that the flower-like mesostructure is the trinuclear or mononuclear complexes, CuS results pre-
an assembly of many plate-like petals (Figure 11d). The liminarily in plates or rods which in turn self-assemble to
interplanar spacing of the parallel fringes in the HRTEM form plate beds made of self-assembled plates or rods. As the
image (Figure 11e) is 0.304 nm, which agrees well with the plates grow with time, they pop out of the big self-assembled
(102) plane of the hexagonal CuS. As the time increases, the plates as a sphere or flower. The above stated self-assembly is
size of the flower decreases in addition to the loss of thickness promoted by the -COOH, -OH, and -NH groups of the
or dense nature of the flower at 24 h. ligand.
Formation Mechanism of Hollow Spheres and Flowers. Since both complexes 1 and 2 are synthesized from the
Formation of CuS with different morphologies from 1 and same ligand, and the morphologically different CuS are
2 under the same reaction conditions appears to reveal the produced from similar reaction conditions, it can be well
existence of some correlation between the arrangement of understood that there is an existence of another force which
4468 Crystal Growth & Design, Vol. 9, No. 10, 2009 Nagarathinam et al.

Scheme 1. Schematic Representation of the (a, b) Packing Pattern of 1a

a
(Orange and purple bonds are the bonds connecting the trinculear units and the ligands are omitted for clarity in (b)). (c) The magnified portion of the
part highlighted in image (a) where the ligands in plane are represented as red and the ligand in a folded way is represented as blue. (d) Packing pattern of
Cu2þ ions in crystal lattice and (e) Layered arrangement of Cu2þ ions in 2.

directs the formation of spherical morphology of CuS-1 with

a hollow interior in addition to the self-assembly of plates.
Though the solubility or decomposition rate of both the
precursors also account for the product formation, this could
be well addressed only when the packing pattern of the
complexes 1 and 2 in the crystal lattice are considered.
The packing pattern of 1 as shown in Scheme 1 highlights
the exclusive angular arrangement of metal atoms in 1 which
is entirely different from the sheet-like arrangement of Cu(II)
atoms in 2 and the slightly corrugated sheet-like packing in
CuHsglu as reported earlier.23 The ligand is same in both the
precursors 1 and 2, but the denticity/chelating abililty is
different in 1 compared to 2. This probably indicates that
the decomposition rate or solubility of the precursor 1 should
be different from 2. The isolation of morphologically differ-
ent products CuS-1 and CuS-2 tends to reveal that the self-
assembly of the preformed nanomaterials depends not only
on the coordinating and hydrogen bonding ability of the Figure 12. Galvonostatic cycling of hollow spheres of CuS-1.
ligands, but also from which direction or plane the ligand
was expelled from crystal system while the metal is coordi- and density; that is, the spheres formed at the earlier stage
nating with the S2- ions. For example, self-assembly of CuS have rods of small crystallite size and with incompletely
nanocrystallites in CuS-1 and CuS-2 is due to the disassem- formed shells. The crystallite growth is well observed parti-
bly of the H3Sser ligands. The third H3Sser ligand is folded cularly in the nanorods assembled near the surface layers
between the chains in 1 in addition to the two ligands packed of the spherical particles due to its contact with the solution
in a plane, and this results in angular packing of Cu(II) atoms as seen in 12 h samples, Figure 9d. At the same time, the
which in turn are responsible for loose packing of hierarch- small particles in the inner cores are loosely packed with
ical assembly of CuS-1 compared to the tightly packed high surface energies compared to that of the particles in the
mesostructure in CuS-2. From this it is inferred that the surface layer. This provides a strong tendency to dissolve
packing pattern in the crystals is an important component in the inner materials, and the subsequent inside out Ost-
deciding the solubility and the decomposition rate of the wald’s ripening process results in the formation of hollow
precursor during the self-assembly of the nanomaterials. spheres.2,6b As the void formation is complete after 12 h, shell
Now, the extent of loose packing is supported by the with uniform thickness appears with rods or plates having
presence of holes in the plate beds (Figure 10b) as the less crystallite size.
spherical nanomaterials pop out of the petal beds. The It is worth mentioning here that synthesis of CuS from the
angular arrangement of metal atoms (Scheme 1b) seems to reaction mixture of H3Sser ligand, copper salt, and thiourea
be dictating the preliminary loose packed spherical structure in a molar ratio of 1:1:5 and 1:0.75:5 under the same reac-
and the hollow nature. As the reaction time increases, the tion conditions resulted only in CuS with flower-like mor-
self-assembled spherical particles continuously grow in size phology (Figure S4 of Supporting Information). This also
Article Crystal Growth & Design, Vol. 9, No. 10, 2009 4469

Figure 13. (a, b) Galvonostatic cycling of CuS-1 and CuS-2; (c) cycle number Vs capacity plots of CuS-1 and CuS-2; (d) cyclic voltammograms
of hollow CuS-1.

demonstrates that isolation of hollow spheres by a very nanocomposite. Cycling within the same potential window
simple methodology is facile only when the 2D coordination (1.5-2.6 V) causes drastic capacity fading (cycles are not
polymer 1 was used. In summary, the shape of the obtained shown here) within a few cycles due to the formation of Li2S
CuS could be determined from the arrangement of metal which is soluble in liquid electrolyte.4 Upon subsequent
atoms and ligands in the crystal lattice. charging, considerable irreversible storage behavior has been
Li-Ion Storage Performance of Nanostructured CuS. Fig- noticed (see Figure 12), due to the instability of nanosized
ure 12 presents the galvonostatic cycling of hollow CuS-1 Li2S as described above. Overall, first discharge capacity of
spheres in the voltage window of 1.5-2.6 V at a current rate hollow CuS-1 spheres is found to be 400 mAh g-1, which is
of 5 mA g-1. During the first discharge process, voltage 71.6% of the theoretical capacity of CuS. First charging
drops from the OCV to 2.09 V and reaches a plateau at this results in the plateau at 2.27 V, which corresponds to a
potential. Followed by this, a second plateau occurs at 1.72 V capacity of 229 mAh g-1 as shown in Figure 12.
and reaches the cutoff voltage (1.50 V). First and second To investigate the storage behavior during insertion reac-
plateaus at 2.09 and 1.72 V correspond to a capacity of tion by avoiding the conversion reaction, we limited the
149 and 252 mAh g-1 respectively. The voltage profile during voltage window within 1.8-2.6 V. Figure 13a-c presents
first discharge suggests that this electrochemical process is a the galvonostatic charge/discharge curves of CuS-1 (hollow
combination of two step reactions as shown below: structure) and CuS-2 (flower-like structure). It is found that
First discharge plateau reaction: CuS-1 exhibits higher capacity and good cyclability in
comparison with CuS-2. The improvement in the perfor-
CuSþxLiþxe - f Lix CuS ð1Þ mance of CuS-1 might probably be due to the high surface
Second discharge plateau reaction: area and large surface-to-volume ratio of the hollow archi-
tecture which in turn reduces transport length for both Liþ
ions and electrons. The porous microstructured CuS-1 thus
Lix CuSþLiþ þe - f Li2 SþCu ð2Þ
provides more access for lithium insertion from liquid elec-
The electrochemical storage behavior of nanostructured trolyte and a capability to withstand local volume change
CuS (hollow and flower-like) reported here during first cycle during electrochemical lithiation processes. The cyclic volta-
is quite similar to those reported earlier on commercially mmogram in Figure 13d shows only one pair of cathodic/
available bulk CuS.12c-d,13 During the first discharge, the anodic peaks located at 2.06 and 2.35 V, which are in good
plateau at 2.09 V corresponds to the Liþ insertion into agreement with the insertion (cathodic) and extraction
the covellite CuS lattice forming a homogeneous phase of (anodic) plateaus found in the galvanostatic cyclic process.
LixCuS. Further insertion of lithium results in the conver- Thus, we present the electrochemical behavior of
sion reaction as shown in eq 2, forming Cu and Li2S different nanostructured CuS at 5 mAg-1 up to 40 cycles.
4470 Crystal Growth & Design, Vol. 9, No. 10, 2009 Nagarathinam et al.

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