Supporting Information Coordination-enabled one-step assembly of ultrathin, hybrid microcapsules with weak ph-response Chen Yang,, Hong Wu,, Xiao Yang,, Jiafu Shi*,,, Xiaoli Wang,, Shaohua Zhang, and Zhongyi Jiang*,, Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China; School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China; Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China. *Corresponding author: Prof. Zhongyi Jiang (zhyjiang@tju.edu.cn) Prof. Jiafu Shi (shijiafu@tju.edu.cn) S1
Table S1 The effect of charge and radius of the metal ions on the stability of the coordination compound Notes: Atomic number Element Coordination Ionic radius (nm) 2 Ch arg e radius 12 Mg (II) 4 0.57 7.018 13 Al (III) 6 0.535 16.822 20 Ca (II) 4 1 4.000 21 Sc (III) 6 0.745 12.081 22 Ti (IV) 6 0.605 26.446 23 V (III) 6 0.64 14.063 24 Cr (III) 6 0.615 14.634 25 Mn (II) 4 0.66(hs) 6.061 26 Fe (III) 6 0.645(hs) 13.953 26 Fe (II) 4 0.63(hs) 6.349 26 Co (II) 4 0.58(hs) 6.897 27 Co (III) 6 0.61(hs) 14.754 28 Ni (II) 4 0.55 7.273 29 Cu (II) 4 0.57 7.018 30 Zn (II) 4 0.6 6.667 31 Ga (III) 6 0.62 14.516 33 As (III) 6 0.58 15.517 38 Sr (II) 4 1.18 3.390 39 Y (III) 6 0.9 10.000 40 Zr (IV) 6 0.72 22.222 49 In (III) 6 0.8 11.250 a. The data of ionic radius came from website (http://abulafia.mt.ic.ac.uk/shannon/ptable.php) that was hosted by the Atomistic Simulation Group in the Materials Department of Imperial College. b. hs represents high spin. c. Metal ions with stable high oxidation state (i.e., Ti IV, Fe III, Cr III ) could coordinate with catechol primarily through tris- coordination state. The divalent metal ions (i.e., Cu II, Ni II, Cr II ) could coordinate with catechol only through mono- and bis- coordination state. 1-2 S2
Table S2 Ti and TA concentrations in the feeds and in the products Molar ratio of Molar ratio of Molar ratio of Final c TA /(mm) Final c Ti /(mm) TA to Ti (in the feed) C (inta) to Ti (in the product) TA to Ti (in the product) Note 0.240 i 1.440 1:6 - - 0.240 i 2.400 ii 1:10 iii 12.29:1 1:6.18 0.240 i 12.000 1:50 1.70:1 1:44.7 0.024 2.400 ii 1:100 - - 2.400 2.400 ii 1:1 5.51:1 1:13.79 0.024 0.240 1:10 iii - - 2.400 24.000 1:10 iii 3.13:1 1:24.28 Cannot obain microcapsules Can obtain microcapsules as shown in Figure S3a-b Can obtain microcapsules as shown in Figure S3c-d Cannot obain microcapsules Can obtain microcapsules as shown in Figure S3e-f Cannot obain microcapsules Can form precipitates as shown in Figure S3g-h Can form numerous 12.000 120.000 1:10 iii 3.49:1 1:21.78 precipitates as shown in Figure S3i-j i. Superscript i denoted as group "i" that has the same concentration of TA in the feed. ii. Superscript ii denoted as group "ii" that has the same concentration of Ti-BALDH in the feed. iii. Superscript iii denoted as group "iii" that has the same molar ratio of TA and Ti-BALDH in the feed. S3
Figure S1 The EDS result of the TA-Ti IV microcapsules. S4
100 Weight remain 80 60 40 71.96% 20 0 200 400 600 800 1000 Temperature ( o C) Figure S2 The TGA curve of the TA-Ti IV microcapsules. S5
a) c) e) g) i) b) d) f) h) j) Figure S3 The SEM imgages of the TA-Ti IV product (microcapsule/precipitate) by changing the concentrations of TA and Ti. (a, b) c TA =0.240 mm, c Ti =2.400 mm. (c, d) c TA =2.400 mm, c Ti =2.400 mm. (e, f) c TA =0.240 mm c Ti =12.000 mm. (g, h) c TA = 2.400 mm c Ti =24.000 mm. (I, j) c TA =12.000 mm c Ti =120.000 mm. S6
PSS- CaC 3 Ti IV TA EDTA - - H + H + ph < 3 3 ph 11 ph > 11 vs. - H + 3 < ph < 6 7 < ph < 9 Figure S4 The fabrication process of the TA-Ti IV microcapsules and the probable structure of TA-Ti IV and TA-Fe III coordination states at different ph values. Ti,, C, H, Fe atoms are represented by blue, red, gray, white, purple spheres, respectively. The remainder of TA molecule is represented by yellow sticks. S7
H Ti Ti H Figure S5 Probable chemical structure of TA-Ti IV cooridination compounds under alkaline condition. S8
Ti Figure S6 Probable chemical structure of TA-Ti IV cooridination compounds under neutral condition. S9
H H H H Ti Ti Figure S7 Probable chemical structure of TA-Ti IV cooridination compounds under acid condition. S10
H H H-bond H H H -H +,-e or -H. -H + H 1 1 1 -e H 1 1 Figure S8 eaction scheme of the auto-oxidation of catechol to quinone. 3 S11
H 1 2 -NH 2 Michael Addition Shif f Bases H H N- 2 1 NH- 2 Figure S9. Probable reaction scheme of the Michael addition and Schiff base reaction. 4-6 1 S12
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