Remarkable Adsorptive Performance of a Metal-Organic Framework, Vanadium-benzenedicarboxylate (MIL-47), for Benzothiophene

Transcription

1 This journal is (c) Th Royal Socity of Chmistry Rmarkabl Adsorptiv Prformanc of a Mtal-Organic Framwork, Vanadium-bnzndicarboxylat (), for Bnzothiophn Nazmul Abdin Khan, a Jong Won Jun, a Jong Hwa Jong a and Sung Hwa Jhung a * a Dpartmnt of Chmistry, Kyungpook National Univrsity, Dagu 7-7, Kora. Fax: ; E- mail: sung@knu.ac.kr

2 This journal is (c) Th Royal Socity of Chmistry Supplmntary Information Exprimntal procdurs: Th MOFs (MIL-53(Al), MIL-53(Cr), (V) usd in this study wr synthsizd hydrothrmally undr autognous prssur similar to th rportd mthods. -3. Howvr, instad of convntional lctric hating, microwavs (Mars-5, CEM) wr usd as a hating sourc in ordr to tak advantag of rapid synthsis of porous matrials undr microwav irradiation. For th synthsis of MIL-53(Al), aluminum chlorid hxahydrat (AlCl 3 6H O, Sigma Aldrich, 99%), trphthalic acid (TPA, C 6 H 4,4-(CO H) ; Sigma Aldrich, 98%) and dionizd watr wr mixd in th molar ratio of Al:.5TPA:8H O. Th raction mixturs containing TPA, aluminum chlorids and watr wr stirrd for 5 min, loadd into a Tflon-lind autoclav, sald and placd in th microwav ovn and finally hatd for.5 h at o C undr autognous prssur. Th MIL-53(Cr) and (V) wr synthsizd similarly from chromium (III) chlorid hxahydrat (CrCl 3 6H O, Sigma Aldrich, 96%) and vanadium (III) chlorid (VCl 3, Sigma Aldrich, 97%), rspctivly. Th raction tmpratur and tim wr changd a bit for th synthss of th two MOFs (MIL-53(Cr): o C, h; : 75 o C, h). Aftr th synthsis, th MOF sampls wr rcovrd by cooling, filtration, watr washing and drying. To rmov TPA from th as-synthsizd MOFs, purification was carrid out with sonication using an ultrasonic gnrator (VC 75, max. powr 75 W, Sonic & matrials, Inc.) in th prsnc of N,N-dimthylformamid (DMF) following th rportd purification mthod. 4 Brifly,.3 g of a MOF such as MIL-53(Al) was suspndd in ml of DMF and sonicatd for h at 7 o C. Th purifid MOFs wr collctd aftr filtration and drid at 5 C for 5 h. Th phass of purifid products wr idntifid by analysis with an X-ray diffractomtr (MO3X-HF, Modl NO. 3, Cu Ka radiation) (Supporting Fig. 6). Bfor X-ray diffraction, MOFs wr hydratd for days ovr saturatd ammonium chlorid aquous solution. Th porosity of th M-BDCs is analyzd with th nitrogn adsorption (Supporting Fig. 7). Th nitrogn sorption was carrid out using Micromritics Tristar II 3 adsorption unit at liquid nitrogn tmpratur (96 o C) aftr vacuation at 5 o C for 5 h. Surfac ara and micropor volum wr calculatd with th BET quation and t-plot, rspctivly, using th nitrogn adsorption isothrms. Bfor adsorption of bnzothiophn, th adsorbnts wr drid ovrnight undr vacuum at 5 o C and wr kpt in a dsiccator to avoid adsorption of watr vapor. Th drid adsorbnt was put in n-octan solutions having spcific BT concntrations. Aftr adsorption for a pr-dtrmind tim undr magntic stirring, th solution was sparatd from th adsorbnts with a syring filtr (PTFE, hydrophobic,.5 μm). Aftr sparation, th solutions wr analyzd for BT concntration using a GC (DS 6, DS SCIENCE INC.) quippd with a FID dtctor and DB-5 column. T. Loisau, C. Srr, C. Hugunard, G. Fink, F. Taulll, M. Hnry, T. Bataill and G. Féry, Chm. Eur. J., 4,, 373. C. Srr, F. Millang, C. Thouvnot, M. Noguès, G. Marsolir, D. Louër and G. Féry, J. Am. Chm. Soc.,, 4, K. Barthlt, J. Marrot, D. Riou and G. Féry, Angw. Chm. Int. Ed.,, 4, 8. 4 E. Haqu, N. A. Khan, J. E. L and S. H. Jhung, Chm. Eur. J., 9, 5, 73.

3 This journal is (c) Th Royal Socity of Chmistry Calculations for kintic and thrmodynamic paramtrs: Th adsorption rat constant was calculatd using psudo-scond ordr raction kintics., Namly, th changs of adsorption amount with tim ar tratd with th vrsatil psudo-scond-ordr kintic modl, bcaus th whol data during adsorption tim can b tratd succssfully: dq t or, / dt k t q t k q ( q q ) t q t [Eq.] [Eq. ] Whr, q : amount adsorbd at quilibrium (mg/g); q t : amount adsorbd at tim t (mg/g); t: adsorption tim (h). Thrfor, th scond ordr kintic constant (k ) can b calculatd by k = slop /intrcpt whn th t/q t is plottd against t. Th maximum adsorption capacity was calculatd using th Langmuir adsorption isothrm,3 aftr adsorption for 4 h. Th adsorption isothrms in various conditions hav bn plottd to follow th Langmuir quation:,3 C q C Q o Q b o [Eq.3] Whr, : quilibrium concntration of adsorbat (mg/l) q : th amount of adsorbat adsorbd (mg/g) Q : Langmuir constant (maximum adsorption capacity) (mg/g) b : Langmuir constant (L/mg or L/mol) So, th maximum adsorption capacity Q can b obtaind from th rciprocal of th slop of a plot of /q againt. To gt th thrmodynamic paramtrs of adsorption such as ΔG (fr nrgy chang), ΔH (nthalpy chang) and ΔS (ntropy chang) th adsorption was furthr carrid out at 35 and 45 o C. Th Gibbs fr nrgy chang ΔG can b calculatd by th following quation 4: 4,5 G RT ln b [Eq. 4] (whr, R is gas constant) Th Langmuir constant b (dimnsion: L/mol) can b obtaind from th slop/intrcpt of th Langmuir plot. Th nthalpy chang ΔH and ntropy chang ΔS can b obtaind by using th van t Hoff quation: 4,5 S ln b R H RT [Eq.5] Th nthalpy chang ΔH and ntropy chang ΔS wr obtaind from th (-slop x R) and (intrcpt x R), rspctivly, of th van t Hoff plot. B. H. Hamd and A. A. Rahman, J. Hazard. Matr., 8, 6, 576. Y. S. Ho and G. McKay, Procss Biochm., 999, 34, S.-H. Lin and R.-S. Juang, J. Environ. Manag., 9, 9, K. P. Singh, D. Mohan, S. Sinha, G. S Tondon and D. Gosh, Ind. Eng. Chm. Rs., 3, 4, 965;

4 This journal is (c) Th Royal Socity of Chmistry J.-H. Huang, K.-L. Huang, S.-Q. Liu, A.-T. Wang and C. Yan, Colloid Surf. A: Physicochm. Eng. Aspcts, 8, 33, Z.-M. Ni, S.-J. Xia, L.-G. Wang, F.-F. Xing and G.-X. Pan, J. Colloid Intrfac Sci., 7, 36, G. Crini and P.-M. Badot, Prog. Polym. Sci., 8, 33, 399.

5 This journal is (c) Th Royal Socity of Chmistry / mg.g / mg.g / mg.g / mg.g (c) (c) / mg.g / mg.g Supplmntary Fig.. Effct of contact tim and initial BT concntration on th adsorption of BT ovr th thr adsorbnts at 35 o C: C i = 5 ppm; C i = 5 ppm; (c) C i = ppm. Supplmntary Fig.. Effct of contact tim and initial BT concntration on th adsorption of BT ovr th thr adsorbnts at 45 o C: C i = 5 ppm; C i = 5 ppm; (c) C i = ppm.

6 This journal is (c) Th Royal Socity of Chmistry / h.g.mg t.q t / g.l.q / ppm / h.g.mg t.q t / g.l.q / ppm (c) (c) h.g.mg t.q t / g.l.q / ppm Supplmntary Fig. 3. Plots of psudo-scondordr kintics of BT adsorption ovr th thr adsorbnts at 5 o C: C i = 5 ppm; C i = 5 ppm; (c) C i = ppm. Supplmntary Fig. 4. Langmuir plots for BT adsorption ovr th thr adsorbnts at 5 o C; 35 o C and (c) 45 o C.

7 This journal is (c) Th Royal Socity of Chmistry MIL-53(Al) MIL-53(Cr) (A) ph Stirring tim / h Supplmntary Fig. 5. Changs of ph of aquous slurry (. g of M-BDCs in. ml watr) of thr adsorbnts with stirring tim. (B) Intnsity / a.u Intnsity / a.u thta / dg thta / dg (C) Intnsity / a.u thta / dg Supplmntary Fig. 6. XRD pattrns of th synthsizd (A) MIL-53(Al), (B) MIL-53(Cr), (C). Plots and in ach cas rprsnt th XRD pattrns of simulatd structur and synthsizd sampl, rspctivly. For th XRD masurmnt, th MOFs wr hydratd aftr purification.

8 This journal is (c) Th Royal Socity of Chmistry 4 35 Quantity adsorbd / cm 3.g Rlativ prssur / P.P o Supplmntary Fig. 7. Nitrogn adsorption isothrms of th thr adsorbnts.