Contents lists av able at ScienceDirect Ce Microporous and Mesoporous Materials journal homepage: www.elsevier.com/locate/micromeso Assembly of nonionic-anionic co-surfactants to template mesoporous silica vesicles with hierarchical structures Bin Yang*, Karen Edler**, Chen Guo®, Huizhou Liu” *beparonet of Chery, University of Sth Caveron Down, ath 882 AY, UK taboraory of Separation Science an Engineering state of Process Engineering Chinese Academy of Sciences PO Boe 353 Bejing f0008, china ARTICLE INFO ABSTRACT ‘cle iy Received 25 September 2009 ‘Mesoporous silica vesicles (MSV) with a hierarchical structure were developed using uiblock copolymer Pluronic ®103 and anionic surfactant sodium dodecylsulfate (SDS) as aco-surfactant in the preset ofan inorganic sal, sodium fluoride (NaF). To some extent, variation in the particle size and vesicle cavity diameter can be achieved by adjusting che anionie-nonionic surfactant molat ratio, An onion-lke vesicle morphology was obtained by changing the inorganic sat concentration. Based on the fing of smal langle neutron scattering data, a formation mechanism has been proposed. This work opens up 2 new vay’ esoporus sa Maullayer vesicle seleassemby “snthesize mesoporous lca vesicles with controllable hirarchial structure using nonionic sr faetant P105 and anionic surfactant SDS © 2009 Elsevier In. All nights reserved. 1 Introduction In the past decades, mesostructured inorganic materials with hierarchical structures have attracted great attention from chem- {sts and material scientists not only for their potential applications, but also due to the fundamental interest in understanding and ‘emulating various biomsineralization processes [1]. Of note, meso- porous materials with vesicular morphologies have very promising applications in encapsulation, separation, targeted drug delivery and catalysis due to their minimized framework pore length, opti- ‘mal access to the interior, low density and thermal mechanical stability Previous methods for preparation of mesoporous vesicles in- volved various templates, such as polymer beads [2], emulsions [3-5] and droplets [6]. Pinnavaia's group first demonstrated the feasibility of forming vesicular mesoporous silica by utilizing bola- amphiphic amines [7,8]. In a subsequent attempt, lamellar silica with a colloid slab and onion-like core-shell structure was ob- tained using Gemini surfactants [9] Poly(ethylene oxide)-poly(propylene —oxide)-poly(ethylene oxide) (PEO-PPO-PEO, Pluronic) triblock copolymers self-assemble into several lyotropic liquid crystalline phases in a selective sol- vent, including micelles, reverse micelles, lamellar and cubic stru cures, Thus this class of surfactants has been widely used as structure directing agents to prepare mesoporous materials. How- ever, its difficult to obtain hierarchical mesoporous silica such as ‘mal odes: KEdlerobsthacuk (K Edler vesicular silica only with triblock copolymers PEO-PPO-PEO, so the ‘mixtures of nonionic surfactant solutions with other addictives such as cationic surfactants and swelling agents. have become a fo- cos for the synthesis of vesicular silica, While 1.35 trimethyl-ben- zene (TMB) has been used to expand pore size [10]. Lecren also used it to make “onion-like’ silica nano-spheres [11], 1,35-triso- propylbenzene (TIPB) was also used as a hydrophobic agent for adjusting the packing parameter of the surfactant which resulted in a multilamellar vesicular silica [12]. Yeh reported a vesicle-ike silica templated by cationic-anionic-neutral block copolymer ter- nary surfactant mixtures [13]. However, these previous results have shown little control over either the cavity size or the mor- phology of the materials. Furthermore so far, no mesoporous slicas ‘ith hierarchical structures have been synthesized using nonionic and anionic co-surfactant, Inorganic salts can increase the effective ratio of the hydropho- biclhydrophilie regions of nonionic Pluronic-type micelles by decreasing the solubility ofthe ethylene oxide and propylene oxide segments Via a “salting out” process [14], NaP is also a well known catalyst for polymerization of siliea species, and thus it has been ‘widely used to control the morphology and porosity of mesoporous ‘materials [15-19]. Pinnavaia and his coworkers reported MSU materials with a worm-like disordered channel structure formed Via fluoride-mediated synthesis [18.19]. Kim prepared highly of- dered hexagonal silicajblock copolymer mesostructured compos- ites with fluoride over a wide range of pH conditions by controlling the rate of hydrolysis and condensation of the silica source [15]. Schmidt-Winkel reported silica rods, consisting of bundles of highly ordered mesoporous silica fibers, induced by2 1 Yang ea /Miroporeus and Mesoporous Materials 131 (2010) 21-27 small amounts of fluoride added during the synthesis of SBA-15- type mesoporous silica under aqueous acidic conditions [17] In our present work, we have developed an approach to synthe- size mesoporous silica vesicles denoted as MSV) with a controlla- Dle hierarchical structure using a nonionic—anioniec co-surfactant mixture in the presence of strong acid and NaF. A mechanism thas been proposed based on the analysis of small angle neutron scattering (SANS) data. Compared to the previous reports, these vesicles are prepared in a facile way and cavities with diameters from the nanoscale to the microscale scale can be achieved by adjusting the molar ratio of anionic to nonionic surfactants. An ‘onion-like multlamellar vesicle morphology can also be obtained by changing the salt concentration, To the best of our knowledge, this isthe first time mesoporous silica witha hierarchical morphol- ‘ogy has been synthesized using nonionic and anionic co surfactants, 2. Experimental 2.1, Materials and synthesis Al chemicals were used as received without further purifica- tion, Triblock copolymer poly(ethylene oxide)-poly(propylene ‘oxide)-poly(ethylene oxide) £0,;PO,oE0,» (MW = 4950), denoted ‘as P103, was kindly received as a sample from BASF. Other chem- icals were purchased from Sigma~Aldrich. Ultra pure Milli-Q water (18.2 M? em resistance) was used forall preparations. The uiblock copolymer was dissolved in water, and stored in a refrigerator, ‘Mesoporous silica vesicles (MSV) with controllable hierarchical morphologies were synthesized using nonionic-anionic surfactant mixtures as co-templates and tetraethyl orthosilicate (TEOS) asthe silica precursor. Typically, 1.0 g triblock copolymer P103. 0.1 g NaF land 0.1 g SDS were dissolved in a mixture of 20 g water to form an Anionic-nonionic surfactant salt solution, and HCl was added to make a 2M acid aqueous solution, After sttting for 30min, 3 g ‘TEOS was added under vigorous stirring. The final reactant molar composition for a standard preparation was 1P103/1.72SDS{ 11.7BNaF/71.28TEOS. This reaction mixture was stirred at 40°C for 24h, then sealed within a Teflon autoclave and heated at 100°C for 24h. The solid products were then collected by filtra- tion, washed with water and dried, The resultant power was cal- ‘ined at 600 °C for 6h in air to remove the organic template. In the first series the molar ratio of anionic to nonionic surfactant was varied from 0.86 t0 3.44 while the amount of salt was constant at 0.2 M. In the second series, the molar ratio of anionic:nonionic ‘surfactant was constant at 1.72 and the concentration of salt varied, from 005 t0 0.1 M, To understand the formation mechanism, transparent solutions ‘of P103/SDSIHCI/NaF/D,O and P103/SDS/HCI|NaF/TEOS|D.0 were prepared for SANS experiment, at the same concentration as the standard silica vesicle forming solution above. To understand the nature of the mixed surfactant system using contrast variation, SANS patterns were also recorded for the solutions using tail-deu- terated SDS (d-SDS) as the surfactant. Since h-SDS and d-SDS have very different scattering length densities (SLD), in theory. this should allow us to highlight the scattering from different parts of the co-surfactant-silicate assembly, 22. Characterization The XRD patterns were acquired on an X-ray diffractometer (XRD, XPert Pro, Panalytical, The Netherlands) at 40 KV using CuK. radiation of wave length 2= 1.5406 A. Particle morphologies were ‘observed in afield-emission scanning electron microscope (FESEM, 4JSM-6700F, JEOL, Japan) and a transmission electron microscope (TEM, TECNAI2O;The Netherlands) operated at a voltage of 120 KV. Nitrogen adsorption/desorption measurements were per- formed at ~196 °C using a Micromerities ASAP 2000 analyzer SANS data was collected on LOQ, a small angle scattering instru- ‘ment atthe ISIS neutron scattering facility at the Rutherford Apple- ton Laboratory. Samples were held in 1 mm thick, double stopper quartz Hellma cells, This data was corrected using the LOQ pro- gram Colette, which applies a series of standard data reduction routines to correct for the background scattering and normalize ‘the transmission onto an absolute scale. In the current experiment, the background consisted of 1 mm thick Hellma cells filled with acidic D,0, which had the same concentration of HCI and D,0 as the silica vesicle forming solution. Information on the data reduc- tion procedures can be found in the Colette manual available on the LOQ website (20), The structure modeling package used to fit the data was written by the "SANS" group at the NIST Centre for Neutron Research, and is freely available on the wed [21]. To fit the mixed surfactant solu- tions (P103/SDS/HCI/NaF/D,0) without silicate, a made of polyalis- perse spheres of uniform scattering length density with a Schulz distribution of radii was used [22]-A Mayter-Penfold structure fac- tor for charged spheres was used to account for repulsive interac- ‘tions between the spheres in solution [23]. For the fits of the mixed surfactant solution containing TEOS (P103/SDS/HCI/NaF/TEOS} D0), it was necessary to use a combination of a model for a ran- domly distributed two-phase system (the “DAB” model) and 2 ‘model for a lyotropic lamellar phase. The DAB model was used to calculate the scattering from a randomly distributed two-phase system based on the Debye~Anderson-Brumberger (DAB) model for such systems [24] The model used to calculate the scattered intensity from a Iyotropic lamellar phase can also be applied & large, multilamellar vesicles [25] 3. Results 3.1. Effect of nonionic-anionic surfactant molar ratio. Fig. 1 shows the field-emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) images of the calcined vesicular mesoporous silica samples synthesized at various molar ratios (denoted as X) of nonionic surfactant P103 to anionic surfactant SDS. When X= 086, Fig. 1A and B confirms the vesicle structure with a cavity size of nearly 100 nm and wall thickness about 20 nm, Some of the vesicles show an onion-like structure with two or three layers. The silicate wall is composed of small silicate particles, and small openings in the wall are visible due to the incomplete compaction of these silicate nanoparticles. ‘When Xs increased to 1.72 (Fig 1C and D), most vesicles show uni form onion-lke vesicle structures and the cavity is around 100- 200 nm in diameter. TEM performed on the calcined samples re- veals a shell with a multilayer structure, having an interlayer spac- ing of 10 nm and a layer thickness of Sm. As shown in Fig. 1E and F, wen the X value was increased to 3.44, the vesicle diameter changes from nanometers to micrometers with a cavity size of around 0.5~1 4am while the wall thickness is around 50 nm. In this case, the increase of cavity size from nanometer scale to microme- ter scale will benefit applications such as catalysis or drug delivery. Al the samples maintain a uniform vesicle morphology even after calcination at 600°C for 6 h, indicating a high thermal stability 3.2. Fffect of salt concentration Fig. 2 provides TEM images of vesicular mesoporous silica pre~ pared at different concentrations of salt while Xis constant. When ‘the salt concentration is 0.05 M as shown in Fig. 2A, vesicles with,15 Yang el /Mroporous ond Mesoporous Motels 181 (2010) 21-27 2 Fig. 1. FESEM and TEM images ofthe calcined vesicular mesoparaus sca samples synthesized 2 varios molar ratios denoted as X) ef anionic surfactant SDS to rononie ‘fate F103 fra canrant Naf concentration of 02 M (and 8 "5086 (Cand) Xe 172, and (@ sna X= 3.44 Fig. 2. TEM images ofthe clened mesoporous sce vesicles synthesized using diferent amounts of NaF 05M (A) an 0.1 M(B inset imaze sata higher magnification} ten P102 SDS 11.72, 200-300 nm cavity size and wall thickness of 20 nm can be seen. Only one broad peak is visible in the small angle X-ray diffraction (XRD) pattern, reflecting a wormlike porous framework structure, When the salt concentration is increased to 0.1 M, as shown in Fig. 28, vesicles with a multilayer shell can be obtained, possessing. an interlayer spacing of 20 nm and a layer thickness of S nm, the cavity size is around 200-300 nm, tn order to better quantify this evaluation, small angle X-ray diffraction experiments on calcined,ca 1 Yang ea /Miroporeus and Mesoporous Materials 131 (2010) 21-27 an ‘ted sctenng eng ey of ech component Sean gh ea A) rms de x10 55 Se cio aa B Do Shiee Intensity(a.u.) oT 2 3 4 6 2theta/degree ig. small angle XRD ates of clined vesicular mesoporous sea syathe- sized at feent amounts of sat 005M (A) ane 1M) wen the molar ae of ‘he two surfactants was aed at 108 SDS 1:12, ppoweler samples were carried out, as shown in Fig. 3B. The XRD pattern exhibits two well-resolved diffraction peaks around 0.4° and 0.8", which are typical of the (001) and (002) reflections of the lamellar framework. These two peaks are in good agreement with layer-to-layer distance extracted from TEM observation (Fig. 28) and the d spacing is 21.78 nm. These two peaks indicate that the vesicular silica possesses an ordered framework an the mesoporous vesicle-like silica structure is very stable even alter calcination, Nitrogen adsorption and desorption isotherms and the corre sponding Barrett-Joyner-Halenda (BJM) pore size distribution determined from the adsorption branch have also been recorded (Fig. 4). As shown in Fig. 4A, when the salt concentration is (0.05 M, the isotherm is broad and seems to He between a Type Il and Type IV isotherm shape, suggesting the presence of both macro- and mesoporosity. BJH analysis indicates that the frame- ‘work pores are about 4-5 1m in diameter. Considering Fig 2A ‘we hypothesize that the porosity comes not only from the frame- ‘work pores but also from the macroporous voids between aggre- sated vesicles, We also note that the wide hysteresis loops ‘observed for both samples could be due to instabilities in the lamellar regions in the sample during the sorption measurements, as lamellar materials are not very mechanically stable upon capil- lary condensation. For the sample prepared with 0.1M_ salt (Fig. 4B), the sorption isotherms have a distinct hysteresis loop ‘which does nos close until the saturation pressure is reached. This result may be due to the peculiar vesicular morphology [8.12,26,27]. For the sample prepared with 0.1 M salt the pore size distribution is wider. and the BJH analysis indicates thatthe frame- work pores are about 4-5 nm while the other larger pores, around 15:nm, may be from the porous areas between multilayers. These vesicle materials exhibit large Brunauer-Emmett-Teller (BET) sur- face areas of 582.9 and 655.2 m* g ? as well as large total adsorp- tion pore volumes of 1.27 and 2.16cm*g” for samples synthesized with 0.05 and 0.1 M sal, respectively. 3.3 Nonionic—anionic co-suyfactant and silicate precursor mixture studies by SANS ‘To investigate the synthetic mechanism, the mixed surfactant- saltaid solutions with and without the silica precursor (molar ra- tio 1P123/1.72SDS/11.78NaF) were examined by SANS. For the analysis of SANS data, scattering length densities (SLD) ofall the components were calculated using the standard equation [28] and listed in Table 1. There is very good contrast between the hydrophobic core of the micelles and the solvent while there is a ‘very poor contrast between the hydrated shell and the solvent ‘when the Plutonic micelle solutions are prepared in D.0. AS are= sul, the structure factor mainly depends on the hydrophobic core radius and which aso probably contains some ofthe PEO segments since these become mote hydrophobic when salt is present and collapse against the micellar core. As shown in Fig. 5, SANS pat- ‘ems of the solutions of P103/SDSjICl/NaF/D,0 and P103/SDSj HCI/NaF/TEOS)D,0 as well as the corresponding solutions with deuterated SDS were fitted, The main fitting parameters for the models used are shown in Table 2 and 3. 5 3 2 zg ® 2 3 3 RétreprenrePP, 5 ¥ 3 3 3 RehivepresuePP, Fig 4. trogen asorption-desoiption eterns for akcined vescla mesoporous sic synthesized a ferent amounts of salt 0.05 M (A) and 01M (8) when the malar ‘aa of Pek. 30S 72 The Bip ‘ice distibutiens calaltd from each thera ae shown inthe ses Co AaB1 Yang eal /Miroporus and Mesoporous Motels 151 (2010) 21-27 a Intensity oangston © PtonmsosasrTe0s Intensity B ig 5 A) SANS patter fr P105/h-SDSF4NaFD50 and P103]4-DSp4C/NAF|D,0.The soles ae te bes ito she aa using the model for sen paries with a Schule poiydspe fold ies ae the be SANS fing rests for 103/SDSICIINAFsluone wing model a spheres having Senulepliiepersiy wit a Hayer-Peafold sete factor. he sl oncetraton ware (001 Mints mods fo match the concentration f Nain te sation the FLOSIRSDSINGF FIO3/SDSINGF ‘ean damever so=2 sez Plyaspesity o2s001 eat toot SLD of sphere (A) 44220040107 1152001 <10+ SLD of solton (A sax10" eaxi0 Charge onthe miceles 71 ne Fitting the scattering patterns of mixtures without silicate pre~ cursor (Fig. 5A and Table 2) indicates that only micelles exist inthis solution, the same result was observed by Chen [25], in which mi- celles and large aggregates were observed in similar solutions. The large aggregates, around 200-300 nm, were not able to be ob- served in these SANS patterns because ofthe limitations of the Q ange available on the LOQ instrument. The scattering length den- sity (SLD) of the spheres indicate thatthe SDS is dissolved into the ‘micelle core, and the aggregates have a mean radius of about 50 A which is consistent with the normal size of the micelle hydropho- bic core for P103, with some of the PEO probably also contributing 1 the core size [14], When silicate species were added into the solutions, as shown in Fig, 5B and Table 3, the scattering patterns no longer correspond to a simple micellar system. but could be fit- ted with a combined DAB-lamellar model. The lamellar spacing is around 13 nm and the silicate layer thickness is around 4 nm, cor- responding to the width of the two-phase region when the internal structure is masked by using d-SDS to contrast match the surfac- tant contributions, The DAB form factor model suggests the aver- ty dstbuton abd a Hayer-eatld structure factor and (8) SANS patterns for P10)h-SDSIHCINA 5 he cata the combined DAB ane tpi ames phase models 05[9,0 and P103/-SDS/CINGE/TEOS,0. The age spacing between regions of two different phases is about 10A, Here we assign this to the distance between regions within the hydrophobic regions ofthe lamellae (see Scheme 1), filled with stretched PPO polymer chains decorated with SDS micelies interca- lated with silicate precursors and/or SiQ) since the scattering length density of h-SDS and PPO chains are similar and quite difer= ent than that for amorphous silicate. When the h-SDS was substi- tuted by d-SDS, the apparent distance between regions of PPO chain to amorphous silica becomes larger since the SLD of the d- SDS is very clase to that ofthe solvent, D;0, masking d-SDS rich re- gions in the two-phase structure. 4. Discussion Until now, numerous studies on the interactions between the anionic surfactant SDS and Pluronic tiblock copolymers have been reported in the literature [30-35], For our analysis ofthe structure of the mixed surfactant system, we have assumed that the SDS ‘molecules are largely dissolved in the micellar core, This assump- tion was made on the basis of the previous studies which found ‘that the interaction between SDS and PPO units in PEO-PPO-PEO polymers is significantly stronger than that between SDS and PEO units of micelles [30-35], Also recently, our colleagues re- ported spontaneous vesicle formation when P123 (which differs from the P103 used here mainly by the length of the PPO block) is mixed with anionic surfactant SDS and the inorganic salt NaF [28]. The micelles of the block copolymer were first destroyed by the addition of the SDS micelles to form a pearl-necklace-like “complex ionic surfactant” with the PPO threaded through the hydrophobic regions of the SDS micelles, Addition of the fluoride salt then leg to the screening of the electrostatic repulsion between, SDS head groups and may also cause the polymer to become less th the TEM mages, and the Cale paatetr ws held constant during fing Bers wee calcite frm the ada devatin nthe pacametrclelted Gig ting PIOS ESDSINAATTEOS FIORESDSINGFEOS ‘onlaion leah (AD tas? ee amet spacing (A) nes imsa Bilayer Tics (A) ais? siea Palyanpersty of layer thckness 20 005, 0248006 Contam berween amelae (A) 535006 «10-* Number of lel plates 3 314004 10° "The conan s aay om the saterng length density of he diferent lets athe aeliaeFPO[SDS and FEO/amerphous liae/D026 1. Yang ea /Miroporeus an Mesoporous Materials 1212010) 21-27, “gs sps ” — NaF 108 micelle ananonst Reet Ronoeann cont ioe tifccoreces revmnanncet eet foeee Stretched pearlnecklace-ike complex. Silica vesicle ‘Bl: PPO wih SDS i an pa freue af the SDS). ‘Green: PEO ith plymertzing TEOS Cc. PEO PPO PEO. scheme 1 Scheme & On SSDS micelles Polymcrizing TEOS cpost structures and mechanism fo he frmatin of MSV. PPO and SDS ae in the blue layer. the PEO chan are re. with polymerizing sate Species and region contaiing these species shown in aren (Fr inrpetation ofthe elezencsC elu this gue legen the eader is efered to he Web version of this aie) soluble via salting out effects, inducing the formation of vesicles. These vesicles consist of a PPO/SDS inner layer surrounded by PEO layers on both sides, with a water pool enclosed inside. The stability ofthese vesicles was greatly improved by converting the terminal hydroxyl groups of the block copolymer into aldehydes [29]. In this current work. introducing the silicate precursor also appeared to stabilize the P103-SDS vesicles, ‘According to the modeled scattering length densities from the SSANS experiment, the added SDS segregates into the hydrophobic PPO region. Increasing the amount of SDS increases the degree of hydration ofthe copolymer micelles and partially destroys the mi- celles. After the silicate precursor is added, the modeled scattering, length densities in the SANS data show that the lamellar structure is made up of larger regions of these hydrophobic PPO and SDS ‘complexes sandwiched between a silica/PEO region, but with sil ‘ate partially aso intruding into the PPO(SDS region, around the hydrophilic head groups of the SDS. The silica content in the two-phase region of the lameliae helps to explain why these lamel- le remain stable after calcination, as this silica can act as pillars holding the lamellae apart after the surfactant is removed. Based on the above experimental results, we propose a mecha- nism for the formation of mesoporous silica vesicles (MSV), as shown in Scheme 1, The P103/SDS[NaF acidic solution forms mixed micelles which only rearrange into vesicles upon the addition of the silica precursor and these vesicles act as the template for the silica mineralization. When the silicate precutsor TEOS is added Ingo the solution, it polymerizes around the hydrophilic PEO groups forming a silica layer, The silicate precursor will also poly= ‘merize around the head groups of the SDS because of their hydro philicity. Polymerization and condensation of this inorganic precursor therefore play a significant role in obtaining the vesicle structure. It not only acts as a crosslinker to stabilize the poly- ‘mer/SDS vesicle but also alters the micellar curvature to help form the vesicle. The TEOS increases the volume of both the PEO filled regions and, to a lesser extent, the areas of the PPO/SDS region ‘where the polar SDS headgroups can interact with the positively charged silica intermediates generated in acidic solutions such as used here. These effects increase the packing parameter of the sur- factant system leading to vesicle formation, ‘Ta some extent, the vesicle size was able to be varied by chang- ing the molar ratio of the nonionic and anionic co-surfactants ‘When SDS is introduced into the P103 solutions i€ binds to the PPO regions in the triblock copolymer chains, The ionic repulsion between SDS micelles causes the PPO chains to become stretched, Which results in the formation of a “complex ionie surfactant ‘Addition of fluoride salt then leads to the screening of the electro static repulsion between SDS head groups inducing the formation ‘of vesicles [29]. Ifthe amount of SDS is increased then the PPO re- ‘sions will try Co accommodate the SDS binding by increasing the amount of stretching to incorporate more SDS into the structure, but this will be balanced by the entropic penalties resulting from this stretching of the PPO chain. The width of the PPO|SDS region is thus restricted by the physical length ofthe PPO section, and this entropic force. Thus further addition of SDS above the amount ‘which can be accommodated by stretching the PPO chain, will re sult in an expansion ofthe vesicle radius to allow more material © ‘be incorporated in each vesicle, resulting in the increase of vesicle ‘eavity sizes from nanometers to micrometers. Pluronic P103 has moderately short EO chains, so multilamellar vesicle structures will therefore preferentially form as the system becomes more hydrophobic. Kipkemboi synthesized multilamellar silica vesicles templated by Pluronic P103 by increasing the syn- thesis temperature, which increased the hydrophobic character ‘of the EO segment (similar to the role of salt here) and pushed the Pluronic P103 system into the multilameliar vesicle phase [26]. Recently, Zhou also found that adding the hydrophobic spe- ces TIPB increased the average packing parameter of Pluronic sur- factants P123 and ultimately transformed a cylindrical micelle phase into multilamellar vesicle phase (12). In our case, in @ strongly acidic medium, the presence of SDS increases the hydro- phobic volume, and increasing the inorganic salt concentration en- larges the effective hydrophobic/hydrophilc ratio, These changes15 Yang el /zoporous ond Mesoporous Mates 181 (2010) 21-27, 2 result in an increase of the average packing parameter of P103, ultimately inducing a phase transformation to form multilamellar vesicles. The subsequent calcination removes the organic compo- nent, leading to the formation of multlamellar vesice-like silica, 5. Conclusion Mesoporous silica vesicle materials with a hierarchical struc- cure were synthesized using a nonionic-anionic co-surfactant in the presence of an inorganic salt. These materials have a mesopor- ‘ous wall structure, large surface area, large pore volume, and high chermal stability; moreover, the hierarchical morphologies can be varied by adjusting the molar ratio of SDS/Pluronic P103 and the salt concentration. These materials are expected to have potential practical applications for drug delivery, bimolecular, encapsulation and catalysis Acknowledgments This work is financially supported by the National Natural Sci- fence Foundation of China (No. 20273075, 20221603 and 20480200) and the Scientific Research Foundation forthe Returned (Overseas Chinese Scholars, State Education Ministry. 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