b Supplementry Figure 1 Morphology chrcteriztion. (), SEM imge of PS templte nnospheres showing mono-dispersed sphericl shpe with pproximtely 200 nm in dimeter. The scle br is 500 nm. (b), SEM imge of PS-SO 3 H@mesosilics DSNs showing sphericl shpe with pproximtely 340 nm in dimeter. The scle br is 1 µm. S1
142 b 250 200 150 100 50 0-50 Chemicl shift (ppm) Supplementry Figure 2 13 C NMR spectr spectr of PS@mesosilics YSNs () nd PS-SO 3 H@mesosilics DSNs (b). S2
T b Q 200 100 0-100 -200-300 -400 Chemicl shift (ppm) Supplementry Figure 3 29 Si NMR spectr of PS@mesosilics YSNs () nd PS-SO 3 H@mesosilics DSNs (b). S3
A B c c b b 0.0 0.2 0.4 0.6 0.8 1.0 Reltive pressure (p/p 0 ) 0 20 40 60 80 Pore dimeter(nm) Supplementry Figure 4 Texturl chrcteriztion. (A) Nitrogen dsorption- desorption isotherms nd (B) Pore size distribution of PS@mesosilics YSNs (), PS-SO 3 H@mesosilics DSNs (b) nd PS-SO 3 H@mesosilics DSNs fter used in the esterifiction rection for 8 th cycles (c). S4
b c d e f Supplementry Figure 5 Stbility in different solvents. TEM imges of PS-SO 3 H@mesosilics DSNs fter tretment in different solvents: methnol (); wter (b); dioxne (c); THF (d); pentne (e) nd pyridine (f). The scle br is 200 nm. S5
b c d e d e d Supplementry Figure 6 Reversible morphology trnsformtion. TEM imges of DMF treted PS-SO 3 H@mesosilics DSNs fter tretment with trifluorocetic cid (), p-toluene sulfonic cid (b) nd chlorosulfonic cid (c); TEM imges for showing the reversible trnsformtion between DSNs nd HNs during the successive DMF (d) nd ClSO 3 H tretment (e). The scle br is 200 nm. S6
2.7 1.2 7.4 13.5 b 30 20 10 0-10 -20-30 Chemicl shift (ppm) Supplementry Figure 7 1 H MAS NMR spectr of PS-SO 3 H@mesosilics DSNs before () nd fter DMF tretment (b). S7
100 80 60 40 b 20 0 0 200 400 600 800 1000 Temperture ( o C) Supplementry Figure 8 Thermogrvimetric (TG) curves. () PS-SO 3 H@mesosilics DSNs. (b) PS-SO 3 H@mesosilics DSNs fter tretment in DMF. (c) PS-SO 3 H HNs. c S8
160 120 b c d ΔH 0 ds/kjmol -1 80 40 0 0 1 2 3 4 5 6 NH 3 coverge/mmolg -1 Supplementry Figure 9 - Δ H 0 ds/dsorbed NH 3 profiles. () Amberlyst R -15. (b) PS-SO 3 H@mesosilics DSNs. (c) PS-SO 3 H@mesosilics DSNs fter tretment in DMF. (d) PS-SO 3 H@mesosilics HNs. S9
(), Benzyl lcohol A b u n d n c e 7 0 0 0 0 0 S c n 2 5 6 ( 7. 1 9 2 m i n ) : 2 0 1 3 0 6 2 0 5 0 6-1. D \ d t. m s 7 9. 0 6 5 0 0 0 0 1 0 8. 0 6 0 0 0 0 0 5 5 0 0 0 0 5 0 0 0 0 0 4 5 0 0 0 0 4 0 0 0 0 0 3 5 0 0 0 0 3 0 0 0 0 0 2 5 0 0 0 0 2 0 0 0 0 0 1 5 0 0 0 0 5 1. 0 1 0 0 0 0 0 m / z - - > 5 0 0 0 0 0 3 1. 0 2 0 6. 8 2 8 1. 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0 2 4 0 2 6 0 2 8 0 (b), Tetrdecne A b u n d n c e S c n 1 4 7 6 ( 1 2. 4 8 1 m i n ) : 2 0 1 3 0 6 2 0 5 0 6-1. D \ d t. m s 5 7. 1 3 0 0 0 0 0 2 8 0 0 0 0 2 6 0 0 0 0 2 4 0 0 0 0 7 1. 1 2 2 0 0 0 0 4 3. 0 2 0 0 0 0 0 1 8 0 0 0 0 8 5. 1 1 6 0 0 0 0 1 4 0 0 0 0 1 2 0 0 0 0 1 0 0 0 0 0 8 0 0 0 0 m / z - - > 6 0 0 0 0 4 0 0 0 0 2 0 0 0 0 0 9 9. 1 1 9 8. 2 1 1 3. 1 1 2 7. 1 1 4 1. 1 1 5 5. 1 1 6 9. 1 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 S10
(c), 1-methyl-3-(phenylmethyl)benzene A b u n d n c e 6 0 0 0 0 S c n 1 8 8 3 ( 1 4. 2 4 6 m i n ) : 2 0 1 3 0 6 2 0 5 0 6-1. D \ d t. m s 1 6 7. 0 5 5 0 0 0 5 0 0 0 0 4 5 0 0 0 4 0 0 0 0 1 8 2. 0 3 5 0 0 0 3 0 0 0 0 2 5 0 0 0 2 0 0 0 0 1 5 0 0 0 1 0 0 0 0 5 0 0 0 0 1 5 2. 0 8 9. 0 6 5. 0 1 0 4. 0 3 2. 0 5 1. 0 1 2 8. 0 2 0 6. 9 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 m / z - - > (d), 1-methyl-2-(phenylmethyl)benzene A b u n d n c e 3 8 0 0 0 0 S c n 1 8 9 9 ( 1 4. 3 1 5 m i n ) : 2 0 1 3 0 6 2 0 5 0 6-1. D \ d t. m s 1 6 7. 0 3 6 0 0 0 0 3 4 0 0 0 0 3 2 0 0 0 0 3 0 0 0 0 0 2 8 0 0 0 0 2 6 0 0 0 0 2 4 0 0 0 0 2 2 0 0 0 0 2 0 0 0 0 0 1 8 0 0 0 0 1 6 0 0 0 0 1 4 0 0 0 0 1 2 0 0 0 0 1 0 0 0 0 0 8 0 0 0 0 1 0 4. 0 6 0 0 0 0 4 0 0 0 0 2 0 0 0 0 5 1. 0 7 7. 0 1 2 8. 0 0 3 1. 9 1 4 9. 0 2 0 6. 9 1 8 4. 9 2 8 1. 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0 2 4 0 2 6 0 2 8 0 m / z - - > S11
(e), 1-methyl-4-(phenylmethyl)benzene A b u n d n c e 6 0 0 0 0 0 S c n 1 9 1 9 ( 1 4. 4 0 2 m i n ) : 2 0 1 3 0 6 2 0 5 0 6-1. D \ d t. m s 1 6 7. 0 5 5 0 0 0 0 5 0 0 0 0 0 4 5 0 0 0 0 4 0 0 0 0 0 1 8 2. 1 3 5 0 0 0 0 3 0 0 0 0 0 2 5 0 0 0 0 2 0 0 0 0 0 1 5 0 0 0 0 1 0 0 0 0 0 1 5 2. 0 m / z - - > 5 0 0 0 0 0 8 9. 0 1 0 4. 0 6 5. 0 5 1. 0 1 2 8. 0 3 8. 0 2 0 7. 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 (f), 1,1 [oxybis(methylene)]bis-benzene A b u n d n c e 4 0 0 0 0 0 S c n 2 2 2 3 ( 1 5. 7 2 0 m i n ) : 2 0 1 3 0 6 2 0 5 0 6-1. D \ d t. m s 9 2. 0 3 8 0 0 0 0 3 6 0 0 0 0 3 4 0 0 0 0 3 2 0 0 0 0 3 0 0 0 0 0 2 8 0 0 0 0 2 6 0 0 0 0 2 4 0 0 0 0 2 2 0 0 0 0 2 0 0 0 0 0 1 8 0 0 0 0 1 6 0 0 0 0 1 4 0 0 0 0 1 2 0 0 0 0 1 0 0 0 0 0 8 0 0 0 0 6 0 0 0 0 6 5. 0 4 0 0 0 0 2 0 0 0 0 0 3 9. 0 1 1 9. 0 1 6 5. 0 1 4 1. 0 2 0 7. 0 2 8 0. 9 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0 2 4 0 2 6 0 2 8 0 m / z - - > Supplementry Figure 10 GC-MS spectr of the rection mixture of Friedel-Crfts lkyltion. () benzyl lcohol is the lkyltion gent; (b) tetrdecne is the internl stndrd. (c) 1-methyl-3-(phenylmethyl)benzene is the lkyltion product with met substitution. (d) 1-methyl-2-(phenylmethyl)benzene is the lkyltion product with ortho substitution.(e) 1-methyl-4-(phenylmethyl)benzene is the lkyltion product with pr substitution. (f) 1,1 -[oxybis(methylene)]bis-benzene is the side product of this rection. S12
Yield (%) 100 80 60 40 20 0 1 2 3 4 5 6 7 8 Recycling times Supplementry Figure 11 Ctlytic recycle bility of PS-SO 3 H@mesosilics DSNs in the esterifiction of luric cid with ethnol. Ech circulr rection ws performed t 80 o C for 6 h under the conditions of 0.10 g of PS-SO 3 H@mesosilics DSNs, 2 mmol of luric cid nd 10 mmol of ethnol. S13
b c d Supplementry Figure 12 TEM imges of the used PS-SO 3 H@mesosilics DSNs. () After the 1 st cycle for CHP clevge. (b) After the 1 st cycle for F-C lkyltion rection. (c) After the 1 st cycle for esterifiction. (d) After the 8 th cycle for the esterifiction rection. The scle br is 200 nm. S14
Supplementry Tble 1 Physicochemicl prmeters of PS@mesosilics YSNs nd PS-SO 3 H@mesosilics DSNs before nd fter reuse in ctlytic rection. Smple S BET (m 2 g -1 ) V b t (cm 3 g -1 ) c D BJH (nm) Amberlyst R -15 45 0.31 40 PS@mesosilics YSNs 416 0.19 2.1 PS-SO 3 H@mesosilics DSNs 412 0.42 2.1 Used-PS-SO 3 H@mesosilics DSNs d 234 0.21 2.2 S BET is the BET specific surfce re. b V t is the totl pore volume determined t the reltive pressure of 0.98. c D BJH is BJH pore dimeter clculted by the desorption brnches of the nitrogen sorption isotherms. d After 8 th cycle in the estrifiction rection. S15
Supplementry Methods Chrcteriztion. The nitrogen sorption experiments were performed t 77 K using Micromeritrics ASAP 2020. BET surfce re ws clculted from the dsorption dt in the reltive pressure P/P 0 in the rnge of 0.04 to 0.2. Pore size distributions were determined from the dsorption brnches using the Brret-Joyner-Hlend (BJH) method. Pore volume ws estimted t the reltive pressure P/P 0 of 0.99. Trnsmission electron microscopy (TEM) ws performed on HITACHI 7700 t n ccelertion voltge of 100 kv. High resolution trnsmission electron microscope (HR-TEM) ws performed on FEI Tecni G 2 F30 S-Twin t n ccelertion voltge of 300 kv. Scnning electron microscope (SEM) ws undertken on FEI Qunt 200F operting t n ccelerting voltge of 0.5-30 kv. FT-IR spectr were collected with Nicolet Nexus 470 IR spectrometer (KBr pellets) in the rnge of 400-4000 cm -1. S elementl nlyses were determined by mens of n Elementry Vrio EL III nlyzer. 29 Si (79.4 MHz) cross-polriztion mgic-ngle-spinning (CP-MAS) NMR ws mesured on Bruker DRX-400 spectrometer equipped with mgic-ngle-spin probe in 4-mm ZrO 2 rotor using tetrmethylsilne s reference. The experimentl prmeters re s follows: 4-kHz spin rte, 3-s pulse dely, nd 500 scns. The 1 H MAS NMR experiments were performed on Bruker AvnceIII 600 spectrometer equipped with 14.1 T wide-bore mgnet. A rotor-synchronized Hhn-echo pulse sequence ws employed to record ll 1 H MAS NMR spectr with the smples spun t 25 khz using 2.5 mm probe. The selective π/2 nd π pulse widths were 1.6 nd 3.2 μs, nd the recycle dely ws 10 s. A 32 scns were ccumulted for ech spectrum nd chemicl shifts were referenced to dmntne t 1.74 ppm. Before 1 H MAS NMR experiment, the smples were dehydrted t 423 K under pressure below 10-3 P for 10 h. The MAS 13 C NMR spectr were recorded on Bruker DRX-400. The experimentl prmeters re s S16
follows: 8 khz spin rte, 3 s pulse dely, 4 min contct time, nd 1000 scns. Acidic property of the solid mterils ws monitored by reference to the 31 P NMR chemicl shift of triethylphosphine oxide (TEPO) chemiclly dsorbed on the solid cid ctlysts. In typicl mesurement, 0.02 g of TEPO ws dissolved in 20 ml of nhydrous pentne, nd the resulting solution ws mixed with 0.05 g of solid cids which were subjected to thorough dehydrtion tretment t 120 o C for 12 hours under vcuum, nd llowed to equilibrte under stirring for 20 min before drying t 50 o C under vcuum. 31 P NMR spectr were performed on Bruker Avnce III 600 spectrometer operting t frequency of 242.9 MHz using 4 mm MAS probe. 31 P MAS NMR spectr were recorded using high-power proton decoupling with spinning rte of 12 khz. 100 scns were ccumulted with π/4 pulse width of 2.25 μs nd 30 s recycle dely. The chemicl shifts spectr were referenced to 85 wt% phosphoric cid externl stndrd. Ammoni dsorption clorimetry ws mesured with n HT-1000 clorimeter (Setrm, Frnce) under flow conditions. Before mesurement, 20 mg of smple ws purged in flowing He gs t 393 K for 12 h. After the smple pretretment, the clorimetric cell ws immersed in the isotherml clorimetric block t 393 K. After the system reched equilibrium, pulses of NH 3 were consecutively dmitted to the smple every 30 min. The net mount of mmoni irreversibly dsorbed from ech pulse ws determined by compring the mss spectrometer signl during ech pulse with signl recorded during control experiment through blnk smple tube. Net het relesed for ech pulse ws clculted from the DSC therml curve. From this the molr enthlpy of mmoni dsorption (H 0 ds) ws obtined for the mmoni dsorbed from ech pulse. Dt ws plotted s profile of H 0 ds vs. mount of mmoni irreversibly dsorbed. The cid exchnge cpcity of the ctlysts ws determined by cid-bse titrtion with stndrd NOH solution. In typicl procedure, smples were degssed t 120 o C for 3 h prior to the mesurements. S17
Then 0.05 g of solid smples ws suspended in 25 ml of 2 M queous NCl solution. The resulting suspension ws stirred t room temperture for 24 h until equilibrium ws reched, nd subsequently titrted with stndrd NOH solution. S18