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Supporting Information

Nickel-Substituted Zeolitic Imidazolate Frameworks for

Time-Resolved Alcohol Sensing and Photo Catalysis under

Visible Light

Rui Li,[a]

Xiaoqian Ren,[a]

Hongwei Ma,[a]

Xiao Feng,[a]

Zhengguo Lin,[a]

Xingguo Li,

[b] and Changwen Hu,*

, [a] Bo Wang*

,[a]

aKey Laboratory of Cluster Science, Ministry of Education of China, School of

Chemistry, Beijing Institute of Technology, P.R. China

bCollege of Chemistry and Molecular Engineering, Peking University, P.R. China

Table of Contents

S-1. Synthetic materials and measurements…………………………………….S2

Materials……………………………………………………………………….S2

Measurements……………………………………………………..…………...S3

S-2. Synthetic methods………………………………………………….….…….S3

S-3. X-ray crystal dada for BIT-12.………………………..….…..…….……....S3

S-4. The powder X-ray diffraction (PXRD) patterns of samples...……………S5

S-5. SEM and FT-IR spectroscopy of samples…………………………..….…..S6

S-6. Elemental analyses, XPS and TGA……………….…………………………S7

S-7. Gas adsorption analyses……………………….………………………….....S9

S-8. The diffuse reflectance UV-vis spectroscopy.…………….………….…….S10

S-9. Solvatochromic and vapochromism effects experiments………………....S10

S-10. Photodegradation of MB on samples under visible-light………………..S13

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2014

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S-1. Synthetic materials and measurements.

Materials.

All chemicals were obtained commercially and used without additional

purification. Zinc oxide (ZnO), nickel acetate tetrahydrate (Ni(OAc)2•4H2O), ethanol

(EtOH), methanol (MeOH), isopropanol (iPrOH), and benzyl alcohol (BnOH) were

obtained from Sinopharm Chemical Reagent Co., Ltd, 2-methylimidazole (HMeIM)

was purchased from J＆K Scientific Company. Methylene blue (MB) was purchased

from TCI Tokyo Chemical Industry Co., Ltd.

Measurements.

Mechanochemical synthetic reactions were carried out in a ball mill (QM-3B,

Nanjing University Instrument Factory, China). Powder X-ray diffraction (PXRD)

patterns of the samples were analyzed with monochromatized Cu-Kα (λ = 1.54178 Å)

incident radiation by a Shimadzu XRD-6000 instrument operating at 40 kV voltage

and 50 mA current. PXRD patterns were recorded from 5° to 40° (2θ) at 298 K. The

morphology and size of as-obtained products were investigated using emission

scanning electron microscope (SEM, JSM 7500 F). Elemental analyses (C, H, and N)

were conducted on Perkin-Elmer 2400 CHN elemental analyzer, Zn and Ni were

determined by a JY-ULTIMA2 ICP atomic emission spectrometer. The FT-IR spectra

were recorded from KBr pellets in the range 400-4000 cm-1

on Nicolet 170 SXFT/IR

spectrometer. The thermogravimetric analysis (TGA) was carried out using a TA

Instruments SDTQ600 apparatus in the temperature range of 30 °C to 900 °C under

N2 flow at a heating rate of 10 °C/min. A diffuse reflectance UV-vis spectrum (BaSO4

pellets) was obtained from the solid state with a Varian Cary 500 UV-vis-NIR

spectrometer. N2 isotherm was measured using a Builder SSA-4200 automatic

volumetric gas adsorption analyzer. The samples were activated at 180 °C for 12 h

prior to analysis. Crystal data for BIT-12 was collected at 296(2) K on Bruker

APEX–II CCD detector with graphite monochromatic Mo Kα radiation (λ=0.71073Å).

Photodegradation under visible-light was carried out using a 300 W xenon lamp

( CEL-HXF300, jin yuan).

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S-2. Synthetic methods.

Mechanochemical synthetic reactions were carried out in a ball mill using a 50

mL stainless steel grinding jar and 5 steel balls with 10 mm diameter. Zinc oxide (5

mmol), 2-methyl imidazole (20 mmol), and nickel acetate tetrahydrate (5 mmol) were

added into the jar, along with 1 mL ethanol. Then the mixture was ground for 30

minutes at 40 Hz. The solids were collected and green powders BIT-11 were obtained.

The powders were washed with large amounts of methanol and violet powders

BIT-11b were obtained. The solids were dried at 120 °C for 12 hours. The Ni-HMeIM

clusters were ball milled using the same method with 2-methyl imidazole (10 mmol),

and nickel acetate tetrahydrate (5 mmol), along with 1 mL ethanol.

Violet sample BIT-11b can also be accessed by stirring the mixtures of Zn(NO3)2•

6H2O (0.988 mmol), Ni(NO3)2•6H2O (0.988 mmol), and HMeIM ( 15.808 mmol) in

methanol (60 mL) for 24 hours. After washed with methanol (30 mL) for three times,

violet powders were obtained.

ZIF-8 was synthesized according to the literature.[1]

Ni-Substituted ZIF-8 single

crystal BIT-12 was solvothermally synthesized using Zn(NO3)2•6H2O (0.6 mmol),

Ni(NO3)2•6H2O (0.6 mmol) and HMeIM (2.4 mmol) dissolved in 15 mL DMF and

three drops HNO3, then heated at 120 °C for 24 hours. After washed with methanol

(15 mL) for three times, crystals were obtained. ICP-MAS and elemental analysis for

C96H120N48Ni0.48Zn11.52: Calculated: C% 42.18, H% 4.39, N% 24.61, Ni% 1.03, Zn%

27.42; Found: C% 42.38, H% 4.66, N% 23.90, Ni% 1.17, Zn% 28.80.

S-3. X-ray crystal dada for BIT-12.

Crystal data for BIT-12 was collected at 296(2) K on Bruker APEX–II CCD

detector with graphite monochromatic Mo Kα radiation (λ=0.71073Å). The structure

was solved by direct methods and refined by full-matrix least-squares against Fo2 by

the SHELXTL program package (Bruker). [2-4]

All the active hydrogen atoms were not

incorporated in the refinement and all atoms were refined anisotropically.

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Table S1. Crystallographic Data for BIT-12

Compounds BIT-12

Formula C96 H120 N48 Ni0.48 Zn11.52

Mr 2731.08

Crystal system Cubic

Space group I 3m

Temperature 296(2) K

a (Å) 16.992(4)

b (Å) 16.992(4)

c (Å) 16.992(4)

α (deg) 90

β (deg) 90

γ (deg) 90

V (Å3) 4906 (2)

Z 1

Dcalc. (g cm-3

) 0.924

F(000) 1391

R1[I>2σ(I)] 0.0558

wR2[I>2σ(I)] 0.1650

R1(all data) 0.0618

wR2(all data) 0.1667

GOOF 1.158

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Figure S1. PXRD patterns of as-synthesized single crystals of BIT-12.

S-4. The powder X-ray diffraction (PXRD) patterns of samples.

Figure S2. PXRD patterns of BIT-11, -11b, and other comparable samples as control

experiments. ZIF-8 with Ni(OAc)2•4H2O, and HMeIM with Ni(OAc)2•4H2O were

ball milled respectively.

The X-Ray powder diffraction pattern of the Ni-HMeIM cluster was indexed with

a=26.1799 Å, b=7.7014 Å， c=7.5304 Å, α =90°, β =90°, γ =90°, space group

P212121. Pawley fitting of the experimental data against above unit cell parameters

converges with Rwp=3.74%, indicating that the calculated peak positions are in good

agreement with the observed ones, and that the sample is pure-phase.

The positions of 4 Ni atoms were located by charge flipping methods implemented

in the TOPAS software. The coordinates of the independent Ni are (0.37314, 0.65446

0.37812 Å). The other 3 Ni atoms are located at positions in accordance with space

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group P212121.

Based on the cell volume (V=1518.29), the space group and the distribution of Ni

atoms, there are 4 Ni-HMeIM-acetate clusters in the unit cell.

Figure S3. The X-Ray powder diffraction pattern of the Ni-HMeIM cluster was

indexed with space group P212121. Pawley fitting of the experimental data (grey)

against above unit cell parameters converges with Rwp=3.74%. The insert pictures

highlight the transformation of Ni-HMeIM clusters and BIT-11 in MeOH.

S-5. SEM and FT-IR spectroscopy of samples.

Figure S4. SEM images of BIT-11b.

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Figure S5. FT-IR spectra of BIT-11 and BIT-11b. Dark green, for BIT-11; Light green,

for sample obtained by ball milled HMeIM and Ni(OAc)2•4H2O; Purple, for BIT-11b.

S-6. Elemental analyses, XPS and TGA.

Table S2. The results of different Ni loadings by controlling the amount of starting

Ni(OAc)2•4H2O Mechanochemically.

entry

starting materials

ratio

n(Zn)/

n(Ni(OAc)2•4H2O)

experimental

results

n(Zn)/n(Ni)

products

1

2

3

4

1:1

1:1

1:2

1:2

48: 52[a]

24:1[b]

32:68[a]

16:1[b]

(Zn0.48+Ni0.52)(C4.65N1.9H6.8)2

(Zn0.96+Ni0.04)(C3.6N1.75H5.2)2

(Zn0.32+Ni0.68)(C4.67N1.74H6.9)2

(Zn0.94+Ni0.06)(C3.87N1.86H5)2

5 2:1 65:35[a]

(Zn0.65+Ni0.35)(C4.25N1.74H5.87)2

6 2:1 24:1[b]

(Zn0.96+Ni0.04)(C5.57N2.68H7.2)2

[a] unwashed; [b] washed with MeOH.

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Table S3. The results of ICP of BIT-11 and BIT-11b, starting materials ratio

n(Zn)/ n(Ni(OAc)2•4H2O) = 1:1.

Zn% Ni%

BIT-11 11.57 11.21

BIT-11b 30.38 1.16

Figure S6. X-ray photoelectron spectroscopy (XPS) for BIT-11. Starting materials

ratio n(Zn)/ n(Ni(OAc)2•4H2O) = 1:1.

Figure S7. X-ray photoelectron spectroscopy (XPS) for BIT-11b. Starting materials

ratio n(Zn)/ n(Ni(OAc)2•4H2O) = 1:1..

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Figure S8. The TGA diagrams of samples.

S-7. Gas adsorption analyses.

Figure S9. Carbon dioxide (CO2) adsorption isotherms of BIT-11 and BIT-11b

collected at 273 K.

Figure S10. N2 adsorption isotherms of BIT-12 collected at 77 K. The

Brunauer-Emmett-Teller (BET) surface area of BIT-12 is 1510 m2/g (P/P0 = 0.05-0.30,

linearity = 0.996).

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S-8. The diffuse reflectance UV-vis spectroscopy.

Figure S11. The diffuse reflectance UV-vis spectra of samples. Light green (solid

line), for sample obtained by ball milled HMeIM and Ni(OAc)2•4H2O; Light green

(dotted line), for commercial Ni(OAc)2•4H2O; Dark green (solid line), for BIT-11.

S-9. Solvatochromic and vapochromism effects experiments.

Solvatochromic effects.

Green BIT-11 (150 mg) was immersed in 4 mL MeOH, EtOH, iPrOH, and BnOH,

respectively. At certain time intervals, the samples were filtered and dried, then

measured by diffuse-reflectance UV-Vis-NIR spectroscopy and PXRD.

Figure S12. Pictures of the color changes soaked in different alcohols at certain time

intervals for BIT-11. The solvents in bottles from left to right: MeOH, EtOH, iPrOH,

and BnOH. The middle pictures highlight the difference between in MeOH and in

EtOH. The right pictures focus on the color of the samples in EtOH.

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Figure S13. The diffuse reflectance UV-vis spectra of BIT-11 soaked in different

alcohols at certain time intervals.

Figure S14. PXRD patterns of as-synthesized BIT-11 soaked in (a) MeOH, (b) EtOH,

(c) iPrOH, (d) BnOH at different periods of time.

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Figure S15. PXRD patterns of as-synthesized BIT-11 soaked in different alcohols for

(a) 2 min, (b) 2 days, (c) 6 days (d) 12 days.

Vapochromism effects.

BIT-11 (25 mg) was placed on the pavilion over liquid inside a closed jar filled

with MeOH (1 mL) and EtOH (1 mL), respectively. The jar was kept under 25 °C for

24 h.

Figure S16. (a) Schematic representation of the vapochromism experiments. (b) The

pictures of the vapochromism phenomena upon exposing to the vapor of EtOH and

MeOH.

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Figure S17. Representation of solvatochromic effects for different alcohols.

Table S4. The steric energy of some alcohols.

alcohol molecular

formula

Space filling The steric energy

(Kcal/mol)

MeOH CH3OH

3.361

EtOH C2H5OH

4.183

iPrOH (CH3)2CHOH

4.888

BnOH C6H5CH2OH

8.402

S-10. Photodegradation of MB on samples under visible-light.

Photocatalytic experiments in aqueous solutions were performed in a 500 mL

water-cooled quartz cylindrical vessel. BIT-11b (50 mg) was suspended in 100 mL

methylene blue (MB) aqueous solution (10 mg/L). The suspension was ultrasonicated

for 10 min and stirred in the dark for 30 min to ensure adsorption equilibrium of MB

onto the samples was established. A 300 W xenon lamp with a filter of 420 nm was

used as a light source. The suspension was vigorously stirred during the whole

process. Visible light irradiated the solution for 0, 5, 10, 15, 20, and 25 minutes, and

the corresponding solutions were filtered. The absorbance of MB aqueous solutions

was then measured by a UV-vis spectrometer. The photodegradation of MB on

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Ni(OAc)2, ZIF-8, as well as the mixture of Ni(OAc)2 and ZIF-8 were tested under the

same conditions.

Figure S18. The UV-vis spectra of MB solution after photodegradation using ZIF-8

and BIT-11b. a) 0 min; b) 15min; c) 30 min. The insert pictures highlight the

experiment results of photodegradation, left: ZIF-8; right: BIT-11b. (C0=10 mg/L, 100

mL; the weight of catalyst = 20 mg).

Figure S19. PXRD patterns of BIT-11b before and after catalysis.

References

[1] O. Karagiaridi, M. B. Lalonde, W. Bury, A. A. Sarjeant, O. K. Farha,

J. T. Hupp, J. Am. Chem. Soc. 2012, 134, 18790–18796.

[2] Sheldrick, G. M, SHELXL 97, Program for the Refinement of Crystal Structure,

University of Göttingen, Germany, 1997.

[3] Sheldrick, G. M. SHELXL 97, Program for Crystal Structure Refinement,

University of Göttingen, Göttingen, Germany, 1997.

[4] Sheldrick ,G. M. SHELXTL NT/2000, v6.12; Bruker Analytical X-ray Systems.