Mild metal-organic-gel route for synthesis of stable sub-5-nm metal-organic framework nanocrystals

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1 Elctronic Supplmntary Matrial Mild mtal-organic-gl rout for synthsis of stabl sub-5-nm mtal-organic framwork nanocrystals Yu Qi, Chun-Ting H, Juntao Lin, Shuping Lin, Jin Liu, Jinghong Huang, Wi Xu, Guichng Yu, Hsiu-Yi Chao, Yxiang Tong, and Zhngping Qiao ( ) MOE Ky Laboratory of Bioinorganic and Synthtic Chmistry, School of Chmistry, Sun Yat-Sn Univrsity, Guangzhou , China Yu Qi and Chun-Ting H contributd qually to this work. Supporting information to DOI /s x S1 Prparation of sampls S1.1 Ragnts and instrumnt S1.2 HKUST-1 microparticls (μps) S1.3 HKUST-1 gl (MOG) S1.4 HKUST-1 nanoparticls (NPs) S1.5 Study on th formation of MOG (Figs. S1 S6) S2 Th kintics study of dy adsorption S2.1 Dy adsorption on MOFs S2.2 Th study of adsorption kintics (Fig. S7) S2.3 Th study of adsorption isothrms (Fig. S8 and Tabl S1) S3 Discussion of adsorption mchanism (Fig. S9 and Tabl S2) S1 Prparation of sampls S1.1 Ragnts and instrumnt All ragnts wr purchasd from commrcial sourcs and usd without furthr purification. Th prparation of HKUST-1 gl (MOG) was usd ultrasonic washing machin (Auto Scinc AS3120A). Powdr X-ray diffraction (PXRD) data wr takn with a Brukr D8 ADVANCE powdr X-ray diffractomtr with (Cu Kα). Raman spctroscopy was prformd on a Lasr Micro-Raman Spctromtr (Rnishaw invia). 1 H NMR spctra wr obtaind on a Varian Mrcury-Plus 300 spctromtr. Scanning lctron micrographs (SEM) wr takn with a JSM-6330F microscop. Th crystals absorbd with dy wr photographd with a Ziss LSM 710 confocal microscop. Th zta potntial was masurd by a Zta potntial analyzr (Zta PALS, Ztasizr Nano zs90). Th concntration of rsidual of CV or MB was analyzd by a UV-Vis Spctrophotomtr (Varian Cary 300). Addrss corrspondnc to csqzp@mail.sysu.du.cn

2 S1.2 HKUST-1 microparticls (μps) Th sampl of HKUST-1 microparticls was synthsizd according to th rportd mthod with som modifications. Th powdr of Cu(NO 3 ) 2 (0.3 mmol) and 1,3,5-bnzntricarboxylic acid (0.2 mmol) wr dissolvd in 10 ml of 8:2 (v/v) dimthyl formamid:thanol (DMF:EtOH) and thn hatd in watr bath at 80 C for 24 h. Th rsulting solid was collctd by cntrifugation and washd four tims by thanol. Th gust molculs wr rmovd by hating at 200 C for 12 h in a N 2 atmosphr. S1.3 HKUST-1 gl (MOG) HKUST-1 gl was synthsizd by th following stps: 1,3,5-bnzntricarboxylic acid/anhydrous thanol solution (0.02 mol/l, 10 ml) was addd slowly into a 50 ml bakr containing of Cu(CH 3 COO) 2 /anhydrous thanol solution (0.01 mol/l, 10 ml) undr ultrasonic for about 10 min. And th ultrasonic was kpt for 2 min at 25 C. Aftr cntrifugation, th uppr liquid was discardd and th lowr sdimnt was washd by thanol for four tims, rsulting HKUST-1 gl. S1.4 HKUST-1 nanoparticls (NPs) Th HKUST-1 nanoparticls wr obtaind by hating th HKUST-1 gl at 200 C for 12 h undr N 2 atmosphr. Products obtaind on this condition wr usd for studying th proprtis. S1.5 Study on th formation of MOG (Figs. S1 S6) Som basic paramtrs for th formation of MOG wr studid, i.., coppr sourc, solvnt, rlativ quantity of ractants, ultrasonic tim and tmpratur. W changd on of th paramtrs with othr paramtrs fixd to s th ffct of this paramtr. Figurs S1 and S2 showd that coppr sourc (coppr actat or coppr nitrat) and solvnt (V watr :V thanol = 1:19 18:2, V DMF :V thanol = 1:19 18:2 (ml:ml)) wr crucial to th morphology of th product. Th products synthsizd by coppr actat ar nano-scald, whil th ons synthsizd by coppr nitrat ar micro-scald octahdral crystal. On th othr hand, th products synthsizd in absolut thanol or mixtur of thanol and DMF ar nanoparticls, but microparticls if H 2 O xcdd 4 ml in th solution. In addition, whn th solvnt changd to dimthyl dulphoxid (DMSO) and actonitril, th products wr NPs too. Figur S1 Th ffct of diffrnt coppr sourc: PXRD pattrns (a) and TEM imags (b) and (c) of products that synthsizd with Cu(CH 3 COO) 2 or Cu(NO 3 ) 2 as ractants.

3 Figur S2 Th ffct of solvnt: (a) PXRD pattrns and (b) TEM imags of HKUST-1 particls synthsizd in diffrnt solvnts. Figurs S3 S5 showd that th tim of ultrasonic (from 1 to 90 min), tmpratur of raction (25 or 50 C) and th rlativ quantity of Cu 2+ and 1, 3, 5-bnzntricarboxylic acid (mol/mol: 1/3, 1/2, 1/1, 3/2, 2/1, 5/2) ar not dcisiv to th siz of th products. Thrfor, thr s no nd to kp ths paramtrs vry strictly. Thy can vary in a broad rang. Nano Rsarch

4 Figur S3 Th ffct of raction tim: PXRD pattrns (a) and TEM imags (b) (g) of HKUST-1 nanoparticls synthsizd for diffrnt raction tim (1 90 min). Figur S4 Th ffct of raction tmpratur: PXRD pattrns of HKUST-1 nanoparticls synthsizd at diffrnt tmpraturs (25 and 50 C) Figur S5 Th ffct of rlativ quantity of ractants: PXRD pattrns of HKUST-1 nanoparticls synthsizd by diffrnt ratio of Cu 2+ and BTC.

5 Figur S6 MOG rout to [Co 3 (BDC) 3 (DMF) 2 (H 2 O) 2 ] 2 nanorods, [Ni 3 (BDC) 3 (DMF) 2 (H 2 O) 2 ] 2 and [Zn 4 O(BDC) 3 (DMF) 8 ] (BDC = 1,4-dicarboxylbnzn) nanocrystal. (a) PXRD of as-prpard sampls and simulatd PXRD pattrn from singl crystal. (b) (d) From lft to right: th transformations of mtal-organic colloid/mtal-organic gl, powdr of nanocrystals, TEM imags of nanocrystals and suspnsion of nanocrystals. Tyndall ffct of MOC and suspnsion wr shown in first and last column. (1) Cntrifugation, (2) dilution, (3) 90 C undr vacuum, (4) ultrasonic disprsion, (5) cntrifugation and drying. S2 Th kintics study of dy adsorption S2.1 Dy adsorption on MOFs A stock solution of 1.00 mmol/l CV or MB was prpard by dissolving solid CV or MB in dionizd watr. Diffrnt concntrations of CV or MB solutions wr prpard by stp-by-stp dilution of th stock solution with dionizd watr. S2.2 Th study of adsorption kintics (Fig. S7) Th kintic data ar tratd with both psudo-first ordr kintic modl of Lagrgrn and psudo-scond ordr kintic modl. Th intgral quations of ths two kintic modls ar Eqs. (S1) and (S2) Psudo-first ordr kintic modl ln (Q Q t ) = lnq k 1 t (S1) t 1 t Psudo-scond ordr kintic modl (S2) 2 Qt k2q Q Whr t (min) is tim of adsorption; k 1 (min 1 ) is th rat constant of th psudo-first ordr kintic adsorption; k Nano Rsarch

6 (g/(mg min)) is th rat constant of th psudo-scond ordr kintic adsorption; Q t (mg/g) is th amount of dy adsorbd at tim t (min); Q (mg/g) is th amount of dy adsorbd at quilibrium. Psudo-first ordr kintic modl and psudo-scond ordr on ar both classical modls to study th kintics of adsorption. Th psudo-first ordr kintic modl is applicabl to physical adsorption, whil th psudo-scond ordr kintic modl considrs both physical and chmical intraction btwn adsorbnt and adsorbat. Figur S7 shows th plots of psudo-scond ordr kintic quation. Th plots of t/q t vrsus t hav a corrlation cofficint (R 2 ), which shows that th adsorption obys psudo-scond ordr kintics. Figur S7 N 2 sorption isothrm and por siz distribution (insrt) of NPs. Figur S8 Th psudo-scond-ordr plots of dy (CV or MB) adsorption onto HKUST-1 (nanoparticls or microparticls).

7 S2.3 Th study of adsorption isothrms (Fig. S8 and Tabl S1) Langmuir modl quation and Frundlich modl quation ar most widly usd to dscrib th adsorption isothrms. Th Langmuir isothrm is givn by Eq. (S3) Q = Q K c 1 Kc max L L (S3) It can b xprssd in a linar form as Eq. (S4) c c Q = Qmax + 1 Q K max L (S4) Whr c (mmol/l) is th quilibrium concntration of dy; Q (mg/g) is th amount of adsorbd dy at quilibrium; Q max (mg/g) is th thortical maximum amount of th monolayr; K L is th Langmuir constant. Th Frundlich isothrm is givn by Eq. (S5) Q = K F c 1/n (S5) Or in a linar form as Eq. (S6) lnq = 1 n lnc + lnk F (S6) Whr K F and n ar th Frundlich constants that dscrib th adsorption capacity of th adsorbnt. Th Langmuir plots and Frundlich plots ar shown in Fig. S8. Figur S9 Langmuir and Frundlich plots of th isothrms for dy (CV or MB) adsorption onto HKUST-1 (nanoparticls or microparticls). Nano Rsarch

8 Tabl S1 Rat constant and saturatd amount of dy adsorption onto HKUST-1 nanoparticls and microparticls at diffrnt initial concntration of dy C initial (dy) (mmol/l) k 2 (g/(mg min)) Q (mg/g) NPs-CV Th numbr of dy molculs in ach unit cll of HKUST-1 Th numbr of cag ndd to catch on dy molcul k 2 (g/(mg min)) Q (mg/g) NPs-MB Th numbr of dy molculs in ach unit cll of HKUST-1 Th numbr of cag ndd to catch on dy molcul Ps-CV Ps-MB C initial (dy) k Th numbr of dy Th numbr of cag (mmol/l) 2 Q k Th numbr of dy Th numbr of cag 2 Q molculs in ach unit ndd to catch on molculs in ach unit ndd to catch on (g/(mg min)) (mg/g) cll of HKUST-1 dy molcul (g/(mg min)) (mg/g) cll of HKUST-1 dy molcul S3 Discussion of adsorption mchanism (Fig. S9 and Tabl S2) Figur S10 XRD of HKUST-1 aftr dy adsorption: (a) nanoparticls with CV adsorbd; (b) microparticls with CV adsorbd; (c) nanoparticls with MB adsorbd; (d) microparticls with MB adsorbd (pak with * in (d) wr unidntifid paks in μps-mb).

9 Figur S11 (a) CV rcycling sorption xprimnts and (b) thir corrsponding PXRD pattrns of NPs (dsorption and rgnration of th adsorbnt was achivd using mthanol, thanol, glycol, and acton, and thn dsiccatd at 200 C in N 2 for 12 h). Th initial adsorption sits for MB or watr molculs wr sarch through grand canonical Mont Carlo (GCMC) simulations by using th Fixd Loading task in th Sorption modul of MS modling 5.5 packag. Th Mtropolis Mont Carlo mthod and th univrsal forcfild (UFF) wr usd. Th modl of both framwork and th gust molculs wr rgardd as rigid and th QEq partial chargs wr mployd to th atoms of th framwork whil that of th MB and watr wr adoptd th ESP chargs. Thn, th low nrgy host gust systms obtaind from th abov adsorption simulations wr prformd gomtry optimization (th symmtry was st to P1 and just fixing th lattic angls) with th priodic boundary using molcular mchanics in th Forcit modul. Th smart algorithm basd on UFF and Ewald summation mthod for both lctrostatic and van dr Waals trms. Th convrgnc tolrancs wr st as nrgy: kcal/mol; forc: kcal/(mol Å); displacmnt: Å. Tabl S2 Lattic paramtrs of HKUST-1 without or with diffrnt gust molculs from computational simulations Sampl a (Å) b (Å) c (Å) Avrag lngth V (Å 3 ) 1 a ,529 1_H 2 O b ,401 1_1MB c ,517 1_5MB d ,505 1_5MB_H 2 O ,369 a 1: mpty framwork (with coordinatd H 2 O). b 1_H 2 O: framwork with H 2 O. c 1_1MB: framwork with 1 molcular MB in ach unit cll of HKUST-1. d 1_5MB: framwork with 5 molcular MB. 1_5MB_H 2 O: framwork with 5 molcular MB and H 2 O that filld all th spar room in ach unit cll of HKUST Nano Rsarch