Electronic supporting information

for paper

Tuning the gate-opening pressure and particle size distribution of the switchable metal-organic framework DUT-8(Ni) by controlled nucleation in a

micromixer

H. Miura,a,b V. Bon,*a I. Senkovska,a S. Ehrling,a S. Watanabe,c M. Ohbab and S. Kaskela

Table of content

1. Schemes and photos of the experimental setup 22. Characterization of the micromixer by Villermaux-Dushman method 33. PXRD patterns 44. Nitrogen physisorption isotherms 65. Scanning electron microscopy 86. DRIFT spectra 107. TG curves 13

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017

1. Schemes and photos of the experimental setup.

Figure S1. Photograph of experimental system using micromixer for the synthesis of samples: (a) m1, (b) m2 and (c) m3-m8.

Figure S2. Schematic representation of the micromixer

(b)

(c)

(a)

2. Villermaux-Dushman method

Figure S3. UV-Vis spectra for resulting solution of the (a) set 1, (b) set 2 and (c) set 3 by Villermaux-Dushman reaction

Figure S4. Dependence of the characteristic mixing time tm on the flow rate for the micromixer.

Table S1. Concentration sets for Villermaux-Dushman reactionC

(mol/L) [H+] [KI] [KIO3] [NaOH] [H3BO3]Set 1 0.02 0.032 0.006 0.09 0.09Set 2 0.015 0.016 0.003 0.045 0.045Set 3 0.015 0.032 0.006 0.09 0.09

(a) (b) (c)

3. PXRD patterns

Figure S5. PXRD patterns for activated DUT-8(Ni) samples, synthesized in batch using different ratio of reactants and the order of mixing (b1, b2, b3, b4, b5 and b6).

Simulated pattern of open phase DUT-8(Ni)

b1

b2

b3

b5

b6

b4

2Ɵ / °

Intensity / a.u

.

Figure S6. PXRD patterns for activated DUT-8(Ni) samples, synthesized by batch synthesis procedures at different temperatures (b7, b8, b9, b10, b11, b12, b13, b14 and b15).

Simulated pattern of open phase DUT-8(Ni)

b7

b8

b9

b11

b12

b10

2Ɵ / °

Intensity / a.u

.

b13

b14

b15

Simulated pattern of close phase DUT-8(Ni)

4. Nitrogen physisorption isotherms

Figure S7. Nitrogen physisorption isotherms for samples b1 – b6 measured at 77 K.

(a) (b)

(c)

Figure S8. Nitrogen physisorption isotherms for (a) b7 – b9, (b) b10 – b12 and (a) b13 – b15 measured at 77 K.

5. Scanning electron microscopy

(a) b1 (b) b2 (c) b3

(d) b4 (e) b5 (f) b6

Figure S9. SEM images for samples b1-b6.

(a) b7 (b) b8 (c) b9

(d) b10 (e) b11 (f) b12

(g) b13 (h) b14 (i) b15

Figure S10. SEM images for samples b7-b15.

6. DRIFT spectra

Figure S11. DRIFT spectra for samples b1- b6.

b1

b2

b3

b5

b6

b4

Figure S12. DRIFT spectra for samples b7- b15.

b7

b8

b9

b11

b12

b10

b13

b14

b15

Figure S13. DRIFT spectra for samples m1, m2 and m3.

Figure S14. DRIFT spectra for samples m3- m8.

m4

m5

m6

m7

m8

m3

m1

m2

m3

7. TG curves

Figure S15. TG curves for samples m3-m8.

0 100 200 300 400 500 600 700 800 900 10000

20

40

60

80

100

m3m4m5m6Weight

loss/%

T /