Surfactant-directed assembly of mesoporous metal-organic framework nanoplates in ionic liquid

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1 Electronic supplementry informtion for: Surfctnt-directed ssemly of mesoporous metl-orgnic frmework nnopltes in ionic liquid Li Peng, Jinling Zhng*, Jinshen Li, Buxing Hn*, Zhimin Xue nd Gunying Yng Beijing Ntionl Lortory for Moleculr Sciences, CAS Key Lortory of Colloid nd Interfce nd Thermodynmics, Institute of Chemistry, Chinese Acdemy of Sciences E-mil: 1. Experimentl Mterils. N-EtFOSA (>95%) ws purchsed from Gungzhou Leelchem Corportion without ny further purifiction. 1,1,3,3-Tetrmethylgunidine (TMG) ws produced y Alf Aesr. Trifluorocette nd triethylmine were provided y Beijing Chemicl Regent Compny. Copper(II) cette monohydrte (Cu(OAc) 2 H 2 O) (A. R. Grde) ws purchsed from Alf Aesr. H 3 BTC (purity 95%) ws provided y Aldrich. N-EtFOSA TMGT Fig. S1 Moleculr structures of N-EtFOSA nd TMGT. 1

2 Synthesis of TMGT The ionic liquid (IL) TMGT ws prepred ccording to the literture method. 1 In typicl experiment, 100 ml ethnol nd 23 g TMG (0.2 mol) were loded into 250 ml flsk in wter th of 15 o C. Then 0.2 mol CF 3 COOH in 35 ml ethnol ws chrged into the flsk under stirring. The rection lsted for 2 hours. The rection mixture ws evported under reduced pressure. Then, the IL ws dried under vcuum t 100 o C for 48 hours, nd product ws otined. Synthesis of Cu-BTC MOFs The MOFs were synthesized using similr synthetic protocol reported y Yghi nd coworkers. 2 In typicl experiment, H 3 BTC (0.3 mmol) nd Cu(OAc) 2 H 2 O (0.54 mmol) were dded into N-EtFOSA/TMGT solution (5 g), which ws loded in n Teflon-lined stinless-steel utoclve. Then 0.5 ml triethylmine ws dded into the utoclve to deprotonte the linker. The mixture ws stirred t 30 o C for 23 hours, nd then the lue product ws wshed with ethnol repetedly using Soxhlet extrctor. The finl product ws otined fter eing dried t 60 o C under vcuum for 24 hours. Chrcteriztion of Cu-BTC MOFs The resulting products were chrcterized y wide-ngle XRD (Model D/MAX2500, Rigk) with Cu Kα rdition t scnning rte of 2 min -1 nd smll-ngle XRD on X'Pert PRO MPD with 0.02 o min -1. The morphologies of the MOF were chrcterized y HITACHI S-4800 scnning electron microscope equipped with EDX nd JeoL-1010 trnsmission electron microscope t 100 kv. The porosity properties of the MOFs were determined y nitrogen dsorptiondesorption isotherms using Micromeritics ASAP 2020M system. FT-IR spectr were determined using Bruker Tensor 27 spectrometer, nd the smples were prepred y the KBr pellet method. The TG mesurement ws crried out using TA Q50 with N 2 flow of 40 ml/min. X-ry photoelectron spectroscopy dt were otined with n ESCAL220i-XL electron spectrometer from VG Scientific using 300W AlKα rdition. The se pressure ws out mr. The inding energies were referenced to the C1s line t ev from dventitious cron. The surfce tension of the surfctnt/il solutions ws performed on Kyow Cvp Surfce Tensionmeter A3. The elementl nlysis of S ws performed on CS-344 element nlysis instrument. The element S ws undetectle, indicting tht the surfctnt cn e removed y repeted wshing. The elementl nlysis of N ws performed on FLASH EA1112 elementl nlysis instrument, which shows content of 0.21 wt%, indicting tht smll mount of IL (1.1 wt%) ws present in smple. 2. Results 2

3 (2,2,2) intensity/.u. (2,0,0) (2,2,0) (4,4,0) (4,0,0) (5,1,1) (3,3,1) (6,0,0) (7,3,1) (7,1,1) (7,5,1) c (7,7,3) (9,7,1) d Thet/degree Fig. S2 Wide-ngle XRD ptterns of the MOFs synthesized in 0.05 wt% (), 2 wt% (), nd 5 wt% (c) N-EtFOSA/TMGT solutions nd the simulted XRD pttern of HKUST-1 (d). The XRD pttern of the MOF is in nice greement with the reported nd simulted XRD ptterns of HKUST-1. 3 The rod diffrction peks indicte tht the smples re constructed with smll nnocrystls. It is notle tht reflections ttriuted y CuO (2θ=35.5 nd 38.7 ) or Cu 2 O (2θ=36.43 ) re sent from the XRD pttern, indicting the high qulity of the smples prepred under mient conditions. 3

4 d Trnsmittnce c Wvenumer/cm -1 Fig. S3 FTIR spectr of MOFs synthesized in 0.05 wt% (), 2 wt% (), nd 5 wt% (c) N- EtFOSA/TMGT solutions nd H 3 BTC (d). The FT-IR spectr of the three MOFs (curves,, nd c) disply the chrcteristic symmetric (1630 cm -1, 1562 cm -1 ) nd symmetric virtion (1443 cm -1, 1373 cm -1 ) of croxylte nions in deprotonted H 3 BTC, which is consistent with tht in literture. 4 In comprison with the IR spectrum of H 3 BTC (curve d), the wvenumer difference of symmetric nd symmetric virtion of croxylte nions is nrrowed. This indictes tht croxylte groups of BTC re coordinted to Cu (II) ions. 5 4

5 Mss/% Temperture/ o C Fig. S4 Thermogrvimetric curve of MOF synthesized in 2 wt% N-EtFOSA/TMGT solution. In the temperture rnge elow 170 C, the weight loss (out 25 wt%) is ssigned to the desorption of wter nd ethnol oth dsored on surfce nd locted inside the pores of MOF. A sudden weight loss of out 40% tkes plce fter 300 C, corresponding to the decomposition of HKUST-1 to CuO nd voltile compounds. 3,3c,6 A Cu 2p 3/2,934.6eV Cu 2p 1/2,954.4eV Counts/.u Binding Energy/eV 5

6 B C 1S, 284.8eV Counts/.u Binding Energy/eV C O 1S,954.4eV Counts/.u Binding Energy/eV Fig. S5 X-ry photoelectron spectroscopy (XPS) of MOF synthesized in 2 wt% N-EtFOSA/TMGT solution. The inding energies of copper element re 934 ev nd 954 ev, chrcteristic of Cu 2p 3/2 nd Cu 2p 1/2 of Cu 2+, respectively. The inding energies of cron element nd oxygen element re ev nd ev respectively. The tom percentges in MOF gined from the res of peks for copper element, cron element nd oxygen element re 7.86%, 59.99% nd 25.56%. Thus the tomic rtio of C to Cu is 7.63, higher thn the clculted vlue 6 of Cu 3 (BTC) 2. This cn e ttriuted to the existence of ethnol dsored in MOF, which ws reveled y TG determintion. 6

7 Pt C Cu O Pt Pt Pt Cu Pt kev Fig. S6 Energy dispersive X-ry (EDX) spectrum of the MOF synthesized in 2 wt% N-EtFOSA/TMGT solution. It demonstrtes the presence of copper, oxygen nd cron in the prepred MOF. The Pt results from smple sprying for etter conductivity, in order to gin etter SEM imges. 2.0 dv/dw/cm 3 g -1 nm Pore width/nm Fig. S7 The micropore size distriution of MOF synthesized in 2 wt % N-EtFOSA/TMGT solution. 7

8 2-Thet d(nm) intensity/.u c d Thet/degree Fig. S8 Smll-ngle X-ry diffrction ptterns of the MOFs synthesized in 5 wt% (), 2 wt% (), 0.05 wt% (c) N-EtFOSA/TMGT solution nd MOF synthesized in pure TMGT (d). A Volume Adsored/cm 3 g Reltive Pressure(P/P o ) 8

9 B Volume dsored/cm 3 g Pore dimeter/nm C dv/dw/cm 3 g -1 nm Pore dimeter/nm Fig. S9 N 2 dsorption desorption isotherms (A), mesopore size distriution curves (B), nd micropore size distriution curves (C) for MOFs synthesized in 0.05 wt% () nd 5 wt% () N-EtFOSA/TMGT solutions. 9

10 Fig. S10 SEM nd TEM imges of MOF synthesized in pure TMGT. Surfce tension/dyne cm Concentrtion of surfctnt/wt% Fig. S11 Surfce tensions of N-EtFOSA/TMGT solutions with different surfctnt weight frctions. References 1 H. X. Go, B. X. Hn, J. C. Li, T. Jing, Z. M. Liu, W. Z. Wu, Y. H. Chng nd J. M. Zhng, Synth. Commun., 2004, 34, D. J. Trnchemontgne, J. R. Hunt nd O. M. Yghi, Tetrhedron, 2008, 64, () M. Hrtmnn, S. Kunz, D. Himsl, nd O. Tngermnn, Lngmuir, 2008, 24, 8634; () S. Diring, S. Furukw, Y. Tkshim, T. Tsuruok nd S. Kitgw, Chem. Mter., 2010, 22, 4531; (c) H. Q. Du, J. F. Bi, C. Y. Zuo, Z. F. Xin nd J. B. Hu, CrystEngComm, 2011, 13, 3314; (d) S. S. -Y. Chui, S. M. -F. Lo, J. P. H. Chrmnt, A. G. Orpen nd I. D. Willims, Science, 1999, 283,

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