Supporting information for

Transcription

1 Supporting information for An effiient route to highly-organized, tunale maroporous-mesoporous alumina Jean-Philippe Daquin, Jérémy Dhainaut, Daniel Duprez, Séastien Royer, Adam F. Lee * and Karen Wilson * Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK and Université de Poitiers, LACCO UMR 6503 CNRS, 40 Avenue du Reteur Pineau, Poitiers Cedex, Frane Present address : Shool of Chemistry, Cardiff University, Cardiff CF10 3AT, UK S1

2 1. Experimental Setion 1.1 Synthesis of monodispersed polystyrene eads Latex spheres were prepared from a similar proedure reported y Vaudreuil et al. S1, namely the emulsifier-free emulsion polymerisation method. Polymerization of styrene was arried out in a three nek ottom flask in the presene of potassium persulfate as initiator and water. Divinylenzene has een added to otain rosslinked spheres. Herein, eads of 300 nm are ahieved at 70 C for a polymerisation time of 15 h with stirring at 250 rpm and eads of 400 nm are otained at 70 C for a polymerisation time of 28 h with stirring at 250 rpm. The eads reovered y filtration and washed out with methanol and dried at 80 C for 24 h. 1.2 Synthesis of ordered mesoporous alumina. Mesoporous alumina phases were synthesized at room temperature y using a nonioni surfatant as the struturing-direting agent. In a typial preparation, 3.0 g of (EO) 20 (PO) 70 (EO) 20 trilok opolymer (pluroni P123), 4.5 ml of HNO 3 (65 wt.%) and 6.12g of aluminum isopropoxide were dissolved in 60 ml of anhydrous ethanol under vigorous stirring. After five hours of onstant stirring, the solution is aged at 60 C during 4 days under stati onditions efore alination under pure oxygen at 600 C (0.4 C min -1 with a dwell of 3 hours). 1.3 Synthesis of ordered maro-mesoporous alumina. The details of the preparation, involving lok opolymers and latex spheres as templates, are as follows: 3g of (EO) 20 (PO) 70 (EO) 20 trilok opolymer (pluroni P123), 4.5 ml of HNO 3 (65 wt.%) and 6.12g of aluminum isopropoxide are respetively added to 60 ml of anhydrous ethanol under vigorous stirring. After ageing (5 hours), 3.06g of monodispersed polystyren eads is added to the solution. The omined solution ontinued to stirring during 5 minutes and then S2

3 dried at 60 C during 4 days under stati onditions efore alination under pure oxygen at 600 C during 3 hours. 1.4 Charaterization Powder X-ray diffration patterns were olleted on a Bruker D8 advaned X-Ray diffratometer fitted with a Lynx eye high-speed strip detetor and a Cu K a radiation soure. Small-angle X-ray diffration patterns were from 0.65 to 4 with a 0.02 step size (step time = 10 s). Diffration patterns in the region are reorded with a 0.1 step size (step time = 5 s). Nitrogen porosimetry was performed on a Quantasor Nova 1200 instrument, after treatment of the samples under vaum at 200 C for four hours. Surfae areas were alulated using the Brunauer Emmet Teller (BET) method over the range P/P 0 = , where a linear relationship was maintained. Pore size distriutions were alulated using the Barrett-Joyner- Halenda (BJH) model applied to the desorption ranh of the isotherm. Mesopore volumes were evaluated on the volume adsored at P/P 0 = Sanning eletron mirographs were reorded on a JEOL JSM 7500F. Prior analysis, a thin oating of gold was performed on the samples. High-resolution transmission eletron mirosopy (HRTEM) was arried out y using a JEOL 2010 operating at 200 kv. Samples were prepared y depositing a drop of solution ontaining the sample in ethanol on a holey-aron filmed opper grid. Thermogravimetri analysis was performed using a Stanton Redroft STA 780 thermal analyser. Samples were mounted in an alumina ruile and heated at 5 C min -1 to 900 C under flowing O 2 gas (20 ml min -1 ). (S1) Vaudreuil S.; Bousmina M.; Kaliaguine S.; Bonneviot L. Adv. Mat., 2001, 13, S3

4 Figure S1. Representative SEM images of polystyrene eads of 300 nm (a) and 400 nm () average diameter. S4

5 Aluminum Isopropoxide Pluroni P123 HNO3 Polystyrene eads Ethanol Ageing (5 hours) Stati onditions at 60 C Sedimentation of PS eads Evaporation of the supernatant solution Highly-organized maro-mesoporous alumina Preursor infiltration Calination under O2 at 600 C Hyrid maro-mesophase formation Figure S2. Route of preparing organized maroporous-mesoporous alumina aording to the Evaporation Indued Self Assemly proedure. S5

6 Figure S3. TEM image of Al-M showing long-range mesopore ordering. S6

7 a Figure S4. TEM images of Al-M300-M (a,), Al-M400-M () show interpenetrating maroporemesopore networks. S7

8 Intensity (a.u.) a θ ( ) gamma-al 2 O 3 Figure S5. Wide angle powder XRD of Al-M (a), Al-M300-M (), Al-M400-M () showing transitional nature and non-math to γ-al 2 O 3. S8

9 N 2 adsored volume (m 3 /g STP) A P/P 0 a B a Pore diameter (nm) dv/dd (a.u.) Figure S6. Textural properties of Al-M (a), Al-M300-M (), Al-M400-M (). (A) Nitrogen adsorption-desorption isotherms (respetively offset y 300 m 3 /g STP) and (B) BJH pore size distriution (dedued from desorption ranhes). S9

10 A % Mass loss (a.u.) DSC (a.u.) a B a Temperature ( o C) Figure S7 : DSC (A) and TGA (B) measurements showing high thermal staility aove 600 C: a, Al-M;, Al-M300-M;, Al-M400-M. S10