DOI: 10.1002/anie.

201102011
Colloidal Spheres

Extension of The Stber Method to the Preparation of Monodisperse

Resorcinol–Formaldehyde Resin Polymer and Carbon Spheres**
Jian Liu, Shi Zhang Qiao,* Hao Liu, Jun Chen, Ajay Orpe, Dongyuan Zhao, and
Gao Qing (Max) Lu*
Colloidal spheres are subject to extensive research in influence their functionalities and are important for their
chemistry, materials science, and condensed-mater physics applications. A great deal of research has been directed
because of their widespread applications, such as the fabri- towards the synthesis of nanostructured phenolic resins in the
cation of photonic crystal materials, optical sensing, and drug form of nanoparticles and nanoporous structures.[2, 10–12]
delivery.[1, 2] The Stber method produces colloidal silica Despite the variety of synthetic methods and products
spheres by the hydrolysis and condensation of silicon reported, the synthesis of phenolic resin spheres with
alkoxides, such as tetraethyl orthosilicate (TEOS), in alcohol precisely controlled size has met with only limited success.[12]
solvents (e.g., ethanol) in the presence of water and a base The synthesis of phenolic resin colloidal materials would open
catalyst (e.g., ammonia aqueous solution).[3] By using the new opportunities for the design and preparation of new
Stber method, it is possible to achieve excellent control of smart materials.
particle size, narrow size distribution, smooth spherical According to the hydrolysis polymerization reaction
morphology of the resulting silica,[4] microporous silica,[5] mechanism, the organic sol–gel of resorcinol/formaldehyde
and mesoporous silica particles.[6] However, the preparation (RF) resins is analogous to silicate sol–gel process.[13] Fur-
of non-silica spheres, especially polymer spheres, by the thermore, RF precursors also have similar structures to
Stber method has not been reported to date. silanes, and both can form three-dimensional (3D) networks
Nanostructured polymers, especially phenolic resins, through the sol–gel process because of their four coordination
exhibit biocompatibility for biomedical applications, such as sites and tetrahedral coordination geometry. RF resins and
cellular delivery vehicles, cell targeting, and imaging.[2, 7, 8] In silicas with similar morphologies and nanostructures have
addition, nanostructured phenolic resins are also widely used been synthesized under similar conditions. For example,
for preparing a variety of nanostructured carbons, which have 1) both silica and RF resin aerogels were synthesized by the
attracted interest for potential applications as adsorbents, sol–gel polymerization in the presence of an acid or base;[13, 14]
super-capacitors, lithium-ion battery electrodes, drug delivery 2) by using basic amino acids, such as lysine as a catalyst, RF
carriers, as well as supports for catalysts.[2, 9, 10] The physical nanospheres[12] and silica nanospheres[15] were synthesized
and chemical properties of nanostructured phenolic resins, through polymerization of resorcinol and formaldehyde or
such as their shape, size, porosity and surface charge, TEOS, respectively; 3) using the cationic surfactant as a
template and synthesis conditions similar to those used to
[*] Dr. J. Liu, Prof. S. Z. Qiao, Dr. H. Liu, A. Orpe, Prof. G. Q. Lu prepare ordered mesoporous silica MCM-41,[16] Moriguchi
ARC Centre of Excellence for Functional Nanomaterials et al.[17] synthesized ordered mesoporous RF resin polymers;
Australian Institute for Bioengineering and Nanotechnology 4) an organic–organic assembly method[11] has been devel-
University of Queensland, QLD 4072 (Australia) oped to synthesize ordered mesoporous RF resins, which is
Fax: (+ 61) 7-3365-6074 analogous to the synthesis of mesoporous silica SBA-15[18]
E-mail: [email protected]
with various morphologies and mesostructures by using
[email protected]
triblock copolymer (e.g., Pluronic P123) as a soft template.
Prof. D. Y. Zhao
Department of Chemistry, Laboratory of Advanced Materials
We report herein for the first time the extension of the
Fudan University, Shanghai 200433 (China) Stber method for the preparation of monodisperse RF resin
Dr. J. Chen polymer spheres with uniform and controllable particle size
ARC Centre of Excellence for Electromaterials Science on the submicrometer scale. The synthesis approach is a very
Intelligent Polymer Research Institute facile and versatile procedure for making polymer beads and
University of Wollongong, NSW 2522 (Australia) is considered to be low cost and suitable for industrial
Prof. D. Y. Zhao production. We chose RF as a precursor because it can form
Department of Chemical Engineering, Monash University four-coordinate covalently bonded silica-like frameworks by
Clayton, VIC 3800 (Australia) polymerization. The effect of synthesis parameters on the
[**] This work was financially supported by the Australian Research morphologies and particle size of the resulted RF spheres was
Council (ARC) through Linkage Project program (LP0882681),
investigated in detail. We also demonstrated that these
Discovery Project program (DP1094070, DP1095861, DP0987969,
DP0879769), and the ARC Centre of Excellence for Functional polymeric spheres can be directly transformed to monodis-
Nanomaterials. J.L. gratefully acknowledges the award of ARC perse carbon spheres with a yield of 62 wt % by a carbon-
Australian Postdoctoral Fellowship. ization process. After loading with platinum nanoparticles,
Supporting information for this article is available on the WWW the carbon spheres revealed very good electrocatalytic
under http://dx.doi.org/10.1002/anie.201102011. oxygen reduction performance.

Angew. Chem. Int. Ed. 2011, 50, 5947 –5951  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 5947
Communications
In this study, the RF resin colloidal spheres are synthe-
sized by the polymerization of resorcinol/formaldehyde in a
mixture of alcohol and aqueous ammonia, a process similar to
the synthesis of silica spheres by the Stber method as
illustrated in Scheme 1. Emulsion droplets are first formed
through the hydrogen bonding of water, alcohol, resorcinol,
and formaldehyde. RF polymerization takes place from the
inside of droplets by ammonia catalysis, resulting in uniform
colloidal spheres. The detailed synthesis parameters are given
in Supporting Information (Table S1). The RF resin polymer
colloidal spheres generally have tunable diameters from 200
to 1000 nm, and can be synthesized at a temperature ranging
from 10 to 60 8C and with a wide reactant molar ratio
(NH4OH/resorcinol/formaldehyde/alcohol/H2O = 1–3/x/2 x/y/
2311 1.95 y where x = 1.4–2.8; y = 0–1186). Figure 1 a and b
show the scanning electron microscopy (SEM) images of RF
polymer particles synthesized at NH4OH concentration of
0.0529 mol L 1, ethanol/water volume ratio of 0.4, resorcinol
concentration of 0.0648 mol L 1 and at 30 8C, indicating that
RF resin polymers have regular spherical particles with a
uniform size. The high-magnification SEM image (Figure 1 b) Figure 1. a),b) SEM images of RF polymer particles at different magni-
demonstrates that these colloidal spheres have smooth sur- fications, c) TEM image, and d) DLS plot of the RF resins spheres
face and a mean diameter of 520 nm, with a standard prepared by the extended Stber method (Inset: photograph illustrat-
deviation of 29 nm. The uniformity of colloidal spheres ing the dispersivity of the RF resins spheres in ethanol).
allows them to form ordered arrays, as seen in Figure 1 a
(and Supporting Information, Figure S1). Transmission elec-
tron microscopy (TEM) image (Figure 1 c) further confirms TEOS, increasing the content of water, or using an alcohol
the RF polymer particles have spherical morphology, and that has short alkyl chains. To confirm the RF system has
some of them can self-assemble into 2D hexagonal arrays on similar hydrolysis polymerization reaction kinetics to the
the carbon film of grid when the TEM sample is prepared. silane precursors, the effect of ammonia solution concentra-
The dynamic light scattering (DLS) data (Figure 1 d) shows tion on the synthesis of RF resins was investigated. The
that the RF polymer spheres are well dispersed with particle particle size increased from 520 to 740 nm with increasing the
size around 500 nm. ammonia concentration from 0.0529 to 0.1587 mol L 1 (Fig-
In the Stber method, the diameter of silica spheres can ure S2a,b), which was consistent with the results for the
be reduced by decreasing the concentration of NH4OH or synthesis of silica spheres by the Stber method. In the
absence of ammonia, the
product had an irregular
shape and no spheres could
be obtained (Figure S2c,d).
Further studies indicated
that using other alkaline sour-
ces, such as NaOH or KOH,
did not produce RF spheres.
Thus, ammonia played an
important role for the forma-
tion of RF spherical particles
(Figure S2).
Not only the ammonia
concentration but also the
ethanol/water volume ratio
can be used to control the
size of the RF resin colloidal
spheres. By increasing the
ethanol/water volume ratio
from 0 to 0.75 under an
NH4OH concentration of
0.0529 mol L 1 at 30 8C, the
particle size increases from
Scheme 1. The formation of RF resins spheres using the extended Stber method. 340 to 850 nm (Table S1, Fig-

5948 www.angewandte.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2011, 50, 5947 –5951
ure S3 and S4). Furthermore, the precursor concentration has size, and a larger final particle size. By increasing the quotient
a significant effect on the size of these RF resin spheres. When of water or adding amphiphilic triblock copolymer (F127), the
the concentration of resorcinol is changed from 0.0324 to surface tension decreases,[19] smaller sized emulsion droplets
0.0648 to 0.0996 mol L 1, the particle size increases abruptly are formed, and RF resins colloids spheres with smaller size
from 260 to 520 to 1200 nm, respectively (Figure S4 and S5). are obtained. The longer the carbon chains of the higher
Further increasing the concentration of resorcinol to molecular weight of alcohol are, the higher the viscosity of
0.388 mol L 1, gives RF aerogels with a particle size around reaction solution is and the stronger the surface tension is, and
40 nm (Figure S5). Such aerogels are formed because the thus emulsions of larger size are formed. This increase
large number of RF molecules serves to decrease the bending emulsion size results in the production of RF resin colloidal
energy and inhibit the formation of emulsion droplets. spheres with large particle size.
The size of the RF resin colloidal spheres can also be Previously, RF with dodecahedral single-crystal morphol-
adjusted by choosing an alcohol with different alkyl chain ogy was also made in a similar way to the production of
(methanol, ethanol, isopropanol). SEM and TEM images dodecahedral single-crystal silica.[20] Our preliminary results
confirm that upon introduction of methanol, the RF resins show that nanostructured RF with various morphologies, such
spheres obtained have diameter around 430 nm (Figure S6). as mesoporous nanoparticles and hollow nanospheres, can be
When iso-propanol is used the size of the colloidal spheres successfully synthesized by applying the similar method for
obtained increases to 1100 nm. In addition, by simply chang- synthesis of the silica with the same nanostructure.
ing the reaction temperature, the size and shape of RF resins RF resins are of interest because of the high yield of
can be significantly tuned (Figure S7). Colloidal spheres with carbon conversion that can be obtained from them. Carbon
a large particle size and rough surface can be prepared at a spheres are obtained by carbonizing the RF resins spheres at
relative low temperature (10 8C), however, aggregated colloi- 600 8C for 4 h under N2 atmosphere (see Experimental
dal spheres are obtained at a high temperature (60 8C). Section for full details). TEM images (Figure 2 a and Fig-
The results shown above reveal that by decreasing the
ratio of alcohol/water, amounts of NH4OH and RF precursor,
or using alcohols with short alkyl chains, the particle size of
RF resin colloidal spheres can be gradually reduced (Fig-
ure S4). These factors have been demonstrated to be appli-
cable for the synthesis of silica spheres as well.[3–5] To our
knowledge, this is the first time that the RF resin colloidal
spheres with various diameters have been synthesized by a
facile and versatile procedure. Note that in our case the
particle size of RF resin colloidal spheres can be further tuned
by adding triblock copolymer Pluronic F127. Increasing the
initial F127 concentration used from 0 to 0.184, 1.107, and
1.476 mmol L 1 can systematically decrease the particle size Figure 2. a) TEM images and b) DLS plot of carbon spheres obtained
from 520 to 320, 230, and 60 nm, respectively (Table S2, by carbonizing the 520 nm RF colloidal spheres (inset: photograph
Figure S8). illustrating the dispersivity of the carbon spheres in ethanol).
Ammonia solution plays a critical role in the formation of
RF resin polymer nanospheres. Scheme 1 summarizes the
formation mechanism: the first step the emulsion formed is ure S9) show that all the carbon spheres preserve a spherical
stable without a surfactant because of the hydrogen-bonding morphology and have a narrow size distribution. However,
interactions between ammonia, alcohol, RF precursor, and the diameter of carbon particles is smaller than of the parent
water; ammonia molecules catalyze the polymerization of RF particles, for example, from 520 nm of the RF resin polymer
inside the droplets. The second step in the formation of spheres to 410 nm owing to shrinkage (19 %) during the
spheres is initiated by the polymerization of resorcinol with carbonization process (Figure 2 a and Figures S9 a,b). The
formaldehyde. Resorcinol can react quickly with formalde- DLS data (Figure 2 b) further confirms that the carbon
hyde to form numerous hydroxymethyl substituted species. spheres have a narrow size distribution with particle sizes
The growing hydroxymethyl substituted species are posi- around 400 nm. A high yield of carbon spheres with tunable
tioned at the surface of the emulsion droplets owing to the diameters from 150 to 900 nm can be directly produced by
electrostatic interaction with ammonia molecules, and further carbonization of the RF resins spheres (Figures S9 and S10 a).
cross-linking of these species during the hydrothermal treat- The diameter of the carbon spheres is controlled by choosing
ment results in uniform colloidal spheres (Scheme 1). As RF resin polymer sphere precursors with different particle
mentioned above, NH4+ in the emulsion can not only size. The highly cross-linked RF polymer structures are the
accelerate the polymerization of RF, but also supply the principal reason for the retention of spherical morphology
positive charges that adhere to the outer surface of spheres to under the high-temperature annealing. Nitrogen sorption
prevent the aggregation which cannot be provided by any measurement shows that the BET surface area of the carbon
other alkaline sources, such as NaOH. With increasing the spheres obtained from the 520 nm RF colloidal sphere is
concentration of ammonia or precursor, the polymerization 504 m2 g 1 and the total pore volume is approximately
rate of RF increases, resulting in emulsion droplets with larger 0.27 cm3 g 1 (Figure S10 b). These microporous carbon

Angew. Chem. Int. Ed. 2011, 50, 5947 –5951  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 5949
Communications
spheres could be promising materials for catalyst supports, RF resin polymer colloidal spheres, by a route similar to the
adsorbents, and electrode materials. synthesis of opal silica spheres. The particle size of the RF
To demonstrate the produced microporous carbon resin spheres can be tuned from 200 to 1000 nm by varying the
spheres as support materials for catalysts, platinum nano- concentration of ammonia or RF precursor, alcohol/water
particles were decorated onto the carbon-sphere surface in a ratio or the alkyl chain of alcohol. Polymerization rate of RF,
microwave-assisted reduction process performed in a mixture the surface tension, and hydrogen bonding are the main
of H2PtCl6 salt and ethylene glycol. The SEM image and X- factors to finely control the size of colloidal spheres. The
ray diffraction (XRD) pattern reveal that Pt nanoparticles are obtained resin spheres can be carbonized to carbon spheres
successfully loaded onto the carbon spheres surface with an with a high yield. Our results show that this approach is useful
average particle size around 6 nm (Figure 3 a,b and Fig- for the large-scale production of RF resin polymer and carbon
ure S11). These platinum-nanoparticle-modified carbon spheres. It can be speculated that by extending the methods
for synthesis of silica nanostructures, more nanostructured RF
resins and carbons with different morphologies could be
designed and synthesized. These polymer and carbon spheres
are potentially important for application in electrode materi-
als, photonics, adsorption and separation, water treatment,
and drug delivery.

Experimental Section
Details on the synthesis parameters of RF resins spheres are
described in the Supporting Information in Table S1. Typically,
monodisperse RF resins spheres were synthesized by using resorcinol
and formaldehyde solution as precursors. In a typical synthesis of the
RF resins spheres with 520 nm diameter, ammonia aqueous solution
(NH4OH, 0.1 mL, 25 wt %) was mixed with a solution containing
absolute ethanol (EtOH, 8 mL) and deionized water (H2O, 20 mL),
then stirred for more than 1 h. Subsequently, resorcinol (0.2 g) was
added and continually stirred for 30 mins. The formaldehyde solution
(0.28 mL) then added to the reaction solution and stirred for 24 h at
30 8C, and subsequently heated for 24 h at 100 8C under a static
condition in a Teflon-lined autoclave. The solid product was
recovered by centrifugation and air-dried at 100 8C for 48 h. The
typical yields of spheres per synthesis are around 72 %. For carbon-
ization, the RF resin spheres were heated under N2 atmosphere to
350 8C with a heating rate of 1 8C min 1, then maintained at 350 8C for
2 h, and subsequently heated to 600 8C with a heating rate of
Figure 3. a) SEM image, and b) XRD pattern of Pt/carbon spheres,
1 8C min 1 and kept at 600 8C for 4 h.
c) linear-sweep voltammograms of Pt/carbon spheres for the oxygen The samples were investigated using SEM, TEM, X-ray diffrac-
reduction reaction (ORR) in an O2-saturated and O2-free (under N2
tion (XRD), and dynamic light scattering (DLS). SEM images of
atmosphere) 0.5 m H2SO4 solution at room temperature at a scan rate samples were recorded on a JEOL 6300 and JSM-7500FA micro-
of 10 mVs 1. scope. TEM images were obtained by JEM-2100 F microscope
(JEOL, Japan). Dynamic light scattering measurements were carried
out at 25 8C on a Malvern Zetasizer NanoZS Instrument (detection
spheres (nanoPt/cs) were further investigated for the electro- range: 3–3000 nm). XRD analysis was conducted on a GBC MMA X-
ray diffractometer with 2q ranging from 308 to 908.
catalytic oxygen reduction reaction in a standard three-
The details on the preparation of nanoPt/cs and nanoPt/cs-coated
electrode electrochemical cell using nanoPt/cs-coated glassy GC electrode are described in the Supporting Information.
carbon (GC) as a working electrode. The linear sweep
voltammograms of the nanoPt/cs-coated GC electrode Received: March 22, 2011
immersed (and stationary) in a oxygen (O2) saturated 0.5 m Published online: May 31, 2011
H2SO4/H2O solution indicated a substantial catalytic oxygen
reduction process with an onset potential of ca. 0.6 V (vs. Ag/
AgCl) under an O2 atmosphere (Figure 3 c). No reduction
response is observed in this region under an N2 atmosphere.
.Keywords: carbon · colloidal spheres · nanoparticles · polymers ·
Stber method

Therefore, the current under the O2 atmosphere was unequiv-

ocally the result of electrocatalytic oxygen reduction perfor- [1] a) U. Jeong, Y. L. Wang, M. Ibisate, Y. N. Xia, Adv. Funct. Mater.
mance.[21] This result show that these carbon spheres have the 2005, 15, 1907; b) F. Li, D. P. Josephson, A. Stein, Angew. Chem.
potential to become a new kind of catalyst (metal-based) 2011, 123, 378; Angew. Chem. Int. Ed. 2011, 50, 360.
[2] a) X. M. Sun, Y. D. Li, Angew. Chem. 2004, 116, 607; Angew.
support materials, suitable to be used in energy conversion
Chem. Int. Ed. 2004, 43, 597; b) A. H. Lu, W. C. Li, G. P. Hao, B.
and other related areas. Spliethoff, H. J. Bongard, B. B. Schaack, F. Schth, Angew.
In summary, we have successfully extended the classical Chem. 2010, 122, 1659; Angew. Chem. Int. Ed. 2010, 49, 1615;
Stber method to conveniently synthesize the monodisperse c) S. R. Guo, J. Y. Gong, P. Jiang, M. Wu, Y. Lu, S. H. Yu, Adv.

5950 www.angewandte.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2011, 50, 5947 –5951
 Funct. Mater. 2008, 18, 872; d) M. Feyen, C. Weidenthaler, F. [12] a) Y. R. Dong, N. Nishiyama, Y. Egashira, K. Ueyama, Ind. Eng.
Schuth, A. H. Lu, J. Am. Chem. Soc. 2010, 132, 6791; e) K. T. Chem. Res. 2008, 47, 4712; b) A. H. Lu, B. Spliethoff, F. Schth,
Lee, Y. S. Jung, S. M. Oh, J. Am. Chem. Soc. 2003, 125, 5652. Chem. Mater. 2008, 20, 5314.
[3] W. Stber, A. Fink, E. J. Bohn, J. Colloid Interface Sci. 1968, 26, [13] a) C. J. Brinker, G. W. Scherer, Sol-Gel Science: The Physics and
62. Chemistry of Sol-Gel Processing, Academic Press, New York,
[4] D. L. Green, J. S. Lin, Y. F. Lam, M. Z. C. Hu, D. W. Schaefer, 1990; b) A. C. Pierre, G. M. Pajonk, Chem. Rev. 2002, 102, 4243;
M. T. J. Harris, J. Colloid Interface Sci. 2003, 266, 346. c) S. A. Al-Muhtaseb, J. A. Ritter, Adv. Mater. 2003, 15, 101.
[5] R. Vacassy, R. J. Flatt, H. Hofmann, K. S. Choi, R. K. Singhy, J. [14] R. W. Pekala, J. Mater. Sci. 1989, 24, 3221.
Colloid Interface Sci. 2000, 227, 302. [15] T. Yokoi, Y. Sakamoto, O. Terasaki, Y. Kubota, T. Okubo, T.
[6] M. Grn, I. Lauer, K. K. Unger, Adv. Mater. 1997, 9, 254. Tatsumi, J. Am. Chem. Soc. 2006, 128, 13664.
[7] a) X. X. Chen, M. A. Dam, K. Ono, A. Mal, H. B. Shen, S. R. [16] C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S.
Nutt, K. Sheran, F. Wudl, Science 2002, 295, 1698; b) M. Oh, Beck, Nature 1992, 359, 710.
C. A. Mirkin, Nature 2005, 438, 651; c) J. G. Park, J. D. Forster, [17] I. Moriguchi, A. Ozono, K. Mikuriya, Y. Teraoka, S. Kagawa, M.
E. R. Dufresne, J. Am. Chem. Soc. 2010, 132, 5960. Kodama, Chem. Lett. 1999, 1171.
[8] Y. Fang, D. Gu, Y. Zou, Z. X. Wu, F. Y. Li, R. C. Che, Y. H. [18] a) D. Y. Zhao, J. L. Feng, Q. S. Huo, N. Melosh, G. H. Fredrick-
Deng, B. Tu, D. Y. Zhao, Angew. Chem. 2010, 122, 8159; Angew. son, B. F. Chmelka, G. D. Stucky, Science 1998, 279, 548; b) D. Y.
Chem. Int. Ed. 2010, 49, 7987. Zhao, Q. S. Huo, J. L. Feng, B. F. Chmelka, G. D. Stucky, J. Am.
[9] A. S. Arico, P. Bruce, B. Scrosati, J. M. Tarascon, W. Van Schalk- Chem. Soc. 1998, 120, 6024.
wijk, Nat. Mater. 2005, 4, 366. [19] V. K. Lamber, R. H. Dinegar, J. Am. Chem. Soc. 1950, 72, 4847.
[10] a) C. D. Liang, Z. J. Li, S. Dai, Angew. Chem. 2008, 120, 3754; [20] a) C. Z. Yu, B. Z. Tian, J. Fan, G. D. Stucky, D. Y. Zhao, J. Am.
Angew. Chem. Int. Ed. 2008, 47, 3696; b) C. D. Liang, S. Dai, J. Chem. Soc. 2002, 124, 4556; b) F. Q. Zhang, D. Gu, T. Yu, F.
Am. Chem. Soc. 2006, 128, 5316; c) S. Tanaka, N. Nishiyama, Y. Zhang, S. H. Xie, L. J. Zhang, Y. H. Deng, Y. Wan, B. Tu, D. Y.
Egashira, K. Ueyama, Chem. Commun. 2005, 2125. Zhao, J. Am. Chem. Soc. 2007, 129, 7746.
[11] a) F. Q. Zhang, Y. Meng, D. Gu, Y. Yan, C. Z. Yu, B. Tu, D. Y. [21] a) S. H. Joo, S. J. Choi, I. Oh, J. Kwak, Z. Liu, O. Terasaki, R.
Zhao, J. Am. Chem. Soc. 2005, 127, 13508; b) Y. Meng, D. Gu, Ryoo, Nature 2001, 412, 169; b) B. Lim, M. J. Jiang, P. H. C.
F. Q. Zhang, Y. F. Shi, H. F. Yang, Z. Li, C. Z. Yu, B. Tu, D. Y. Camargo, E. C. Cho, J. Tao, X. M. Lu, Y. M. Zhu, Y. N. Xia,
Zhao, Angew. Chem. 2005, 117, 7215; Angew. Chem. Int. Ed. Science 2009, 324, 1302.
2005, 44, 7053.

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