Supporting Information

Transcription

1 Supporting Information An In Situ One-Pot Synthetic Approach towards Multivariate Zirconium MOFs Yujia Sun, Lixian Sun, Dawei Feng,* and Hong-Cai Zhou* anie_ _sm_miscellaneous_information.pdf

2 Contents Section S1. Materials and Instrumentation.. S3 Section S2. MOF Synthesis..... S5 Section S3. Powder X-ray Diffraction... S17 Section S4. IR Spectra.. S21 Section S5. N 2 Uptake...S28 Section S6. Thermal Stability Analyses....S33 Section S7. Chemical Stability Measurements.....S35 Section S8. Controllable Incorporation of NiTCPP into UiO-66...S38 Section S9. SEM Images... S40 Section S10. SEM/EDS Analyses.....S43 Section S11. 1 H NMR Spectra...S45 Section S12. Control Experiments...S47 Section S13. Comparison of X UiO-66 and X UiO-66-NH 2...S52 Section S14. Porphyrin UiO-66 Systems with Incorporation of Multiple Functionalities....S54 Section S15. Catalytic Activity Test.....S55 Section S16. Thermodynamics behind Our Strategy S59 Section S17. Calculation of the plausible chemical formula..s60 S2

3 Section S1. Materials and Instrumentation. Methyl 4-formylbenzoate was purchased from Oakwood Products, Inc. Pyrrole, propionic acid, N,N-dimethylformamide (DMF), benzoic acid, acetone, zirconium(iv) chloride, iron(ii) chloride tetrahydrate (FeCl2 4H2O), manganese(ii) chloride tetrahydrate (MnCl2 4H2O), nickel(ii) chloride hexahydrate (NiCl2 6H2O), cobalt(ii) chloride hexahydrate (CoCl2 6H2O), copper(ii) chloride tetrahydrate (CuCl2 4 H2O), and zinc(ii) chloride (ZnCl2, anhydrous) were purchased from Alfa Aesar. Terephthalic acid (BDC), 2-aminoterephthalic acid (NH2-BDC), 2,5-dihydroxyterephthalic acid (DOBDC), 1,2,4,5-benzenetetracarboxylic acid (H4BTeC) were purchased from Sigma-Aldrich. Tetrakis(4-carboxyphenyl)porphyrin (H2TCPP), Tetrakis(4- methylphenyl)porphyrin, [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Mn(III) Chloride (MnTCPPCl), [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Fe(III) Chloride (FeTCPPCl), [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Zn(II) (ZnTCPP), [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Ni(II) (NiTCPP), [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Co(II) (CoTCPP), [5,10,15,20- Tetrakis(4-carboxyphenyl)porphyrinato]-Cu(II) (CuTCPP) were synthesized according to the procedure in previous reports with slight modifications. 1 2-Azido terephthalic acid was synthesized according to the procedure in the literature. 2 All commercial chemicals were used without further purification unless otherwise mentioned. Powder X-ray diffraction (PXRD) was carried out with a BRUKER D8-Focus Bragg Brentano X-ray powder diffractometer equipped with a Cu-sealed tube (λ = ) at 40 kv and 40 ma. Thermogravimetric analysis (TGA) were conducted on S3

4 a Shimadzu TGA-50 thermogravimetric analyzer from room temperature to 700 C at a ramp rate of 2 C/min in a flowing nitrogen atmosphere. Nuclear magnetic resonance (NMR) spectra were collected on a Mercury 300 spectrometer. The UV-vis absorption spectra were recorded on a Shimadzu UV-2450 spectrophotometer. N2 adsorptiondesorption isotherms were measured by using a Micrometritics ASAP 2420 system at 77 K. Sample was activated by solvent exchange (in several cycles using fresh acetone), followed by degassing at elevated temperature (100 C) for 3 h. Elemental microanalyses (EA) were performed on vario EL cube Elementar. Scanning electron microscope (SEM) was performed on QUANTA 450 FEG and energy dispersive X-ray spectroscopy (EDS) was carried out by X-Max20 with Oxford EDS system equipped with X-ray mapping. S4

5 Section S2. MOF Synthesis. Synthesis of NiTCPP UiO-66 ZrCl4 (30 mg, mmol), BDC (20 mg, mmol), NiTCPP (10 mg, mmol) and benzoic acid (600 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solventexchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of UiO-66 ZrCl4 (30 mg, mmol), BDC (20 mg, mmol) and benzoic acid (600 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, white precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting white powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of NiTCPP UiO-66-NH2 ZrCl4 (30 mg, mmol), NH2-BDC (20 mg, mmol), NiTCPP (10 mg, mmol) and benzoic acid (600 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After S5

6 cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of UiO-66-NH2-S1 ZrCl4 (30 mg, mmol), NH2-BDC (20 mg, mmol) and benzoic acid (600 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, white precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting white powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-NH2 ZrCl4 (30 mg, mmol), NH2-BDC (20 mg, mmol), FeTCPPCl (10 mg, mmol) and benzoic acid (600 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, brown precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting brown powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of MnTCPP UiO-66-NH2 ZrCl4 (30 mg, mmol), NH2-BDC (30 mg, mmol), MnTCPPCl (10 mg, S6

7 0.011 mmol) and benzoic acid (500 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, dark green precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting dark green powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of CuTCPP UiO-66-NH2 The same reaction conditions as synthesis of MnTCPP UiO-66-NH2, except that 10 mg CuTCPP (0.012 mmol)was used. Synthesis of ZnTCPP UiO-66-NH2 The same reaction conditions as synthesis of MnTCPP UiO-66-NH2, except that 10 mg ZnTCPP (0.012 mmol) was used. Synthesis of H2TCPP UiO-66-NH2 The same reaction conditions as synthesis of MnTCPP UiO-66-NH2, except that 10 mg H2TCPP (0.013 mmol)was used. Synthesis of CoTCPP UiO-66-NH2 The same reaction conditions as synthesis of MnTCPP UiO-66-NH2, except that 10 mg CoTCPP (0.012 mmol)was used. Synthesis of FeTCPP UiO-66 ZrCl4 (30 mg, mmol), BDC (30 mg, mmol), FeTCPPCl (10 mg, mmol) and benzoic acid (500 mg, mmol) in 2 ml of DMF were ultrasonically S7

8 dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, brown precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting brown powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of MnTCPP UiO-66 ZrCl4 (30 mg, mmol), BDC (50 mg, mmol), MnTCPPCl (10 mg, mmol) and benzoic acid (500 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, dark green precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting dark green powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of CuTCPP UiO-66 The same reaction conditions as synthesis of FeTCPP UiO-66, except that 10 mg CuTCPP (0.012 mmol) was used. Synthesis of ZnTCPP UiO-66 The same reaction conditions as synthesis of FeTCPP UiO-66, except that 10 mg ZnTCPP (0.012 mmol) was used. Synthesis of H2TCPP UiO-66 The same reaction conditions as synthesis of FeTCPP UiO-66, except that 10 mg H2TCPP (0.013 mmol) was used. S8

9 Synthesis of CoTCPP UiO-66 The same reaction conditions as synthesis of FeTCPP UiO-66, except that 10 mg CoTCPP (0.012 mmol) was used. Synthesis of NiTCPP UiO-66-2,5-(OH)2 ZrCl4 (30 mg, mmol), DOBDC (60 mg, mmol), NiTCPP (10 mg, mmol) and benzoic acid (320 mg, mmol) in 2 ml of DMF and 1 d H2O were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 105 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg MnTCPPCl (0.011 mmol) was used. Synthesis of CuTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg CuTCPP (0.012 mmol)was used. Synthesis of H2TCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that S9

10 10 mg H2TCPP (0.013 mmol) was used. Synthesis of ZnTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg ZnTCPP (0.012 mmol)was used. Synthesis of CoTCPP UiO-66-2,5-(OH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(OH)2, except that 10 mg CoTCPP (0.012 mmol)was used. Synthesis of NiTCPP UiO-66-2,5-(CH3)2 ZrCl4 (20 mg, mmol), 2,5-dimethylterephthalic acid (50 mg, mmol), NiTCPP (10 mg, mmol) and benzoic acid (250 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 135 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg MnTCPPCl (0.011 mmol) was used. Synthesis of CuTCPP UiO-66-2,5-(CH3)2 S10

11 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg CuTCPP (0.012 mmol) was used. Synthesis of H2TCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg H2TCPP (0.013 mmol) was used. Synthesis of ZnTCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg ZnTCPP (0.012 mmol) was used. Synthesis of CoTCPP UiO-66-2,5-(CH3)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(CH3)2, except that 10 mg CoTCPP (0.012 mmol) was used. Synthesis of NiTCPP UiO-66-SO3H ZrCl4 (20 mg, mmol), monosodium salt of 2-sulfonyl terephthalic acid (60 mg, mmol) and NiTCPP (10 mg, mmol) in 0.7 ml of acetic acid and 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, washed with H2O twice to remove salts, and then solventexchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-SO3H The same reaction conditions as synthesis of NiTCPP UiO-66-SO3H, except that 10 S11

12 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-SO3H ZrCl4 (30 mg, mmol), monosodium salt of 2-sulfonyl terephthalic acid (80 mg, mmol) and MnTCPPCl (5 mg, mmol) in 0.7 ml of acetic acid and 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, dark green precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, washed with H2O twice to remove salts, and then solventexchanged with acetone three times. The resulting dark green powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of CuTCPP UiO-66-SO3H The same reaction conditions as synthesis of MnTCPP UiO-66-SO3H, except that 5 mg CuTCPP (0.006 mmol) was used. Synthesis of H2CPP UiO-66-SO3H The same reaction conditions as synthesis of MnTCPP UiO-66-SO3H, except that 5 mg H2TCPP (0.006 mmol) was used. Synthesis of ZnTCPP UiO-66-SO3H The same reaction conditions as synthesis of MnTCPP UiO-66-SO3H, except that 5 mg ZnTCPP (0.006 mmol) was used. Synthesis of CoTCPP UiO-66-SO3H The same reaction conditions as synthesis of MnTCPP UiO-66-SO3H, except that 5 mg CoTCPP (0.006 mmol) was used. S12

13 Synthesis of NiTCPP UiO-66-2,5-(COOH)2 ZrCl4 (100 mg, mmol), H4BTeC (120 mg, mmol) and NiTCPP (10 mg, mmol) in 0.3 ml of TFA, 0.1 ml of H2O and 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 135 C for 10 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 10 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 5 mg MnTCPPCl (0.006 mmol) was used. Synthesis of CuTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 5 mg CuTCPP (0.006 mmol) was used. Synthesis of H2TCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 5 mg H2TCPP (0.006 mmol) was used. Synthesis of ZnTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except S13

14 that 5 mg ZnTCPP (0.006 mmol) was used. Synthesis of CoTCPP UiO-66-2,5-(COOH)2 The same reaction conditions as synthesis of NiTCPP UiO-66-2,5-(COOH)2, except that 10 mg CoTCPP (0.012 mmol) was used. Synthesis of NiTCPP UiO-66-N3 ZrCl4 (20 mg, mmol), 2-azido terephthalic acid (40 mg, mmol), NiTCPP (10 mg, mmol) and benzoic acid (320 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 120 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Synthesis of FeTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg FeTCPPCl (0.011 mmol) was used. Synthesis of MnTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg MnTCPPCl (0.011 mmol) was used. Synthesis of CuTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg CuTCPP (0.012 mmol) was used. Synthesis of H2TCPP UiO-66-N3 S14

15 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg H2TCPP (0.013 mmol) was used. Synthesis of ZnTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg ZnTCPP (0.012 mmol) was used. Synthesis of CoTCPP UiO-66-N3 The same reaction conditions as synthesis of NiTCPP UiO-66-N3, except that 10 mg CoTCPP (0.012 mmol) was used. Synthesis of TBPP UiO-66 The same reaction conditions as synthesis of NiTCPP UiO-66-1, except that 10 mg TBPP (0.010 mmol) was used. Synthesis of PP UiO-66 The same reaction conditions as synthesis of NiTCPP UiO-66-1, except that 15 mg protoporphyrin IX (PP) (0.027 mmol) was used. Synthesis of CoTCP UiO-66 ZrCl4 (30 mg, mmol), BDC (30 mg, mmol), CoTCP (5 mg, mmol) and benzoic acid (500 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 135 C for 20 h. After cooling down to room temperature, the precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solventexchanged with acetone three times. The resulting light yellow powder was obtained by centrifugation, and dried in an oven at 80 C. S15

16 Synthesis of BBA UiO-66 ZrCl4 (30 mg, mmol), BDC (20 mg, mmol), 4-bromobenzoic acid (BBA, 10 mg, mmol) and benzoic acid (500 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 135 C for 20 h. After cooling down to room temperature, the precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solvent-exchanged with acetone three times. The resulting white powder was obtained by centrifugation, and dried in an oven at 80 C. S16

17 Section S3. Powder X-ray Diffraction. Figure S1. PXRD profiles for X UiO-66 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). Figure S2. PXRD profiles for X UiO-66-NH2 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). S17

18 Figure S3. PXRD profiles for X UiO-66-2,5-(OH)2 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). Figure S4. PXRD profiles for X UiO-66-2,5-(CH3)2 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). S18

19 Figure S5. PXRD profiles for X UiO-66-SO3H (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). Figure S6. PXRD profiles for X UiO-66-2,5-(COOH)2 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). S19

20 Figure S7. PXRD profiles for X UiO-66-N3 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP). S20

21 Section S4. IR Spectra. Figure S8. IR spectrum of NiTCPP UiO-66. Figure S9. IR spectrum of FeTCPPCl UiO-66. S21

22 Figure S10. IR spectrum of MnTCPPCl UiO-66. Figure S11. IR spectrum of CuTCPP UiO-66. S22

23 Figure S12. IR spectrum of H2TCPP UiO-66. Figure S13. IR spectrum of ZnTCPP UiO-66. S23

24 Figure S14. IR spectrum of CoTCPP UiO-66. Figure S15. IR spectrum of NiTCPP UiO-66-NH2. S24

25 Figure S16. IR spectrum of NiTCPP UiO-66-2,5-(OH)2. Figure S17. IR spectrum of NiTCPP UiO-66-2,5-(CH3)2. S25

26 Figure S18. IR spectrum of NiTCPP UiO-66-SO3H. Figure S19. IR spectrum of CuTCPP UiO-66-2,5-(COOH)2. S26

27 Figure S20. IR spectrum of NiTCPP UiO-66-N3. S27

28 Section S5. N2 Uptake. Before the N2 uptake experiment, 120 mg samples were activated using the outgas function of the adsorption instrument at 100 C for 3 h prior to gas adsorption/desorption measurement. Figure S21. N2 adsorption/desorption isotherms of UiO-66 and NiTCPP UiO-66 at 77 K, 1 atm. S28

29 Figure S22. N2 adsorption/desorption isotherms of UiO-66 and NiTCPP UiO-66 at 77 K, 1 atm, presented in semi-logarithmic scale. Figure S23. DFT pore size distribution of UiO-66 using data measured with N2 at 77 K. S29

30 Figure S24. DFT pore size distribution of NiTCPP UiO-66 using data measured with N2 at 77 K. Figure S25. N2 adsorption/desorption isotherms of UiO-66-NH2 and NiTCPP UiO- 66-NH2 at 77 K, 1 atm. S30

31 Figure S26. N2 adsorption/desorption isotherms of UiO-66-NH2 and NiTCPP UiO- 66-NH2 at 77 K, 1 atm, presented in semi-logarithmic scale. Figure S27. DFT pore size distribution of UiO-66-NH2 using data measured with N2 at 77 K. S31

32 Figure S28. DFT pore size distribution of NiTCPP UiO-66-NH2 using data measured with N2 at 77 K. S32

33 Section S6. Thermal Stability Analyses mg of fresh as-synthesized MOF samples were heated on the TGA-50 (Shimadzu) thermogravimetric analyzer from room temperature to 700 C at a ramp rate of 2 C/min under N2 flow of 25 ml/min. The observed decomposition temperature is around 400 C for NiTCPP UiO-66 and 350 C for NiTCPP UiO-66-NH2, suggesting the excellent thermal stability of MOF samples. Figure S29. Thermogravimetric analysis of NiTCPP UiO-66. S33

34 Figure S30. Thermogravimetric analysis of NiTCPP UiO-66-NH2. S34

35 Section S7. Chemical Stability Measurements. NiTCPP UiO-66 and NiTCPP UiO-66-NH2 samples were selected as examples for chemical stability measurements. First, 1 M HCl, 2 M HCl, 6 M HCl, 1 mm NaOH and 10 mm NaOH aqueous solutions were prepared. Then, 100 mg of sample was immersed in 50 ml of each aqueous solution and water for 12 h. After that, all the samples were centrifuged and the solids were washed with water, DMF and acetone three times in turn and dried in the oven. These samples were characterized by powder X-ray diffraction. Then, all the samples were degassed on ASAP 2420 adsorption system at 100 C for 3 h prior to N2 adsorption measurement at 77 K. Figure S31. Powder X-ray diffraction (PXRD) profiles for NiTCPP UiO-66 without treatment of any aqueous solutions and the samples treated with water, 1 M HCl, 2 M HCl, 6 M HCl, and 1 mm NaOH aqueous solutions for 12 h. S35

36 Figure S32. Powder X-ray diffraction (PXRD) profiles for NiTCPP UiO-66-NH2 without treatment of any aqueous solutions and the samples treated with water, 1 M HCl, 2 M HCl, 6 M HCl, 1 mm NaOH and 10 mm NaOH aqueous solutions for 12 h. Figure S33. N2 adsorption isotherms of NiTCPP UiO-66 at 77 K, 1 atm after treatment with aqueous solutions with different ph. S36

37 Figure S34. N2 adsorption isotherms of NiTCPP UiO-66-NH2 at 77 K, 1 atm after treatment with aqueous solutions with different ph. Figure S35. The PXRD patterns for PCN-222(Ni) and PPF-5 before and after treatment in the stability test. S37

38 Section S8. Controllable Incorporation of NiTCPP into UiO- 66. To carry out the experiment, different amount of NiTCPP was used (3 mg, mmol; 6 mg, mmol; 9 mg, mmol; 12 mg, mmol; 15 mg, mmol; 18 mg, mmol). ZrCl4 (30 mg, mmol), BDC (20 mg, mmol), NiTCPP and benzoic acid (600 mg, mmol) in 2 ml of DMF were ultrasonically dissolved in a Pyrex vial. The mixture was heated in an oven at 130 C for 12 h. After cooling down to room temperature, red precipitates were collected by centrifugation. The solids were washed with DMF three times to remove unreacted precursors, and then solventexchanged with acetone three times. The resulting red powder was obtained by centrifugation, and dried in an oven at 80 C. Figure S36. Ni to Zr atomic ratio in NiTCPP UiO-66 with different amounts of NiTCPP ligand used in the synthesis. S38

39 Figure S37. The PXRD patterns for UiO-66 and NiTCPP UiO-66 with different amounts of NiTCPP used in the synthesis. S39

40 Section S9. SEM Images. Figure S38. Representative SEM images of NiTCPP UiO-66-NH2. S40

41 Figure S39. Representative SEM image of NiTCPP UiO-66-NH2 single crystal and corresponding EDS-mappings of Ni, Zr, C, N, O from left to right. Figure S40. Representative SEM image of NiTCPP UiO-66. Figure S41. Representative SEM image of NiTCPP UiO-66 single crystal and corresponding EDS-mappings of Ni, Zr, C, N, O from left to right. S41

42 Figure S42. Representative SEM image of FeTCPPCl UiO-66. Figure S43. Representative SEM image of FeTCPPCl UiO-66-NH2. S42

43 Section S10. SEM/EDS Analyses. Figure S44. SEM/EDS analysis for NiTCPP UiO-66. Table S1. Atomic ratio in NiTCPP UiO-66 Trial 1 Trial 2 Trial 3 Element Weight% Atomic% Weight% Atomic% Weight% Atomic% Ni Zr Average Ni: Zr ratio: 0.046: 1 S43

44 Figure S45. SEM/EDS analysis for NiTCPP UiO-66-NH2. Table S2. Atomic ratio in NiTCPP UiO-66-NH2 Trial 1 Trial 2 Trial 3 Element Weight% Atomic% Weight% Atomic% Weight% Atomic% Ni Zr Average Ni: Zr ratio: 0.051: 1 S44

45 Section S11. 1 H NMR Spectra. Approximately 15 mg of dried MOF sample was digested in 5 ml 16% HF solution. The tube was them immersed in boiling water to evaporate HF. The dried product was dissolved in DMSO-d6 for 1 H NMR test. Figure S46. Solution 1 H NMR spectrum used to determine the ratio of (a) NiTCPP and (b) BDC in NiTCPP UiO H NMR of digested NiTCPP UiO-66 (300 MHz, DMSO-d6). BDC δ: 8.00 (s, 4H). NiTCPP δ: 8.13 (d, J = 7.8 Hz, 8H), 8.30 (d, J = 8.2 Hz, 8H), 8.75 (s, 8H). Molar ratio based on integration of the peaks: NiTCPP: BDC = 0.075: 1. S45

46 Figure S47. Solution 1 H NMR spectrum used to determine the ratio of (a) NiTCPP and (b) NH2-BDC in NiTCPP UiO-66-NH2. 1 H NMR of digested NiTCPP UiO-66-NH2 (300 MHz, DMSO-d6). NH2-BDC δ: 6.99 (d, J = 8.3 Hz, 1H), 7.36 (s, 1H), 7.75 (d, J = 8.3 Hz, 1H). NiTCPP δ: 8.13 (d, J = 8.2 Hz, 8H), 8.30 (d, J = 8.0 Hz, 8H), 8.75 (s, 8H). Molar ratio based on integration of the peaks: NiTCPP: NH2-BDC = 0.071: 1. S46

47 Section S12. Control Experiments Figure S48. The product obtained after stirring UiO-66 and NiTCPP in DMF for 12 h (a) at room temperature; (b) at 85 C. (c) NiTCPP UiO-66. (d) The PXRD patterns of UiO-66 and products obtained after stirring UiO-66 and NiTCPP in DMF for 12 h at different temperatures. S47

48 Figure S49. Solution 1 H NMR spectrum of the product dissolved in DMSO-d6. The product was obtained after stirring UiO-66 and NiTCPP in DMF for 12 h at room temperature or at 85 C. No peaks of NiTCPP were observed. Figure S50. (i) Tetrahedral pore in UiO-66 with a diameter of 7.5 Å. (ii) Octahedral pore in UiO-66 with a diameter of 12 Å. (iii) NiTCPP. S48

49 Figure S51. (a) Photographs of (i) NiTCPP UiO-66, (ii) TBPP UiO-66, and (iii) PP UiO-66 samples. (b) The PXRD patterns for these samples. S49

50 Figure S52. IR spectrum of TBPP UiO-66. Figure S53. Photographs of (i) BBA UiO-66 and (ii) CoTCP UiO-66. S50

51 Figure S54. The PXRD patterns for CoTCP UiO-66 and BBA UiO-66. Table S3. Atomic ratio in BBA UiO-66 Trial 1 Trial 2 Trial 3 Element Weight% Atomic% Weight% Atomic% Weight% Atomic% Br Zr Average Br: Zr ratio: 0.011: 1 Table S4. Atomic ratio in CoTCP UiO-66 Trial 1 Trial 2 Trial 3 Element Weight% Atomic% Weight% Atomic% Weight% Atomic% Co Zr Average Co: Zr ratio: 0.018: 1 Since the size of CoTCP ligand is larger than TCPP ligand, the amount of CoTCP used in the synthesis was one third of NiTCPP in order to guarantee the formation of phasepure products. S51

52 Section S13. Comparison of X UiO-66 and X UiO-66-NH2. Figure S55. X UiO-66 samples in DMF after shaking to make the color better observed. From left to right were NiTCPP UiO-66, FeTCPPCl UiO-66, MnTCPPCl UiO-66, CuTCPP UiO-66, H2TCPP UiO-66 and ZnTCPP UiO-66. Figure S56. X UiO-66 samples in DMF with final powders attached on the bottom. From left to right were NiTCPP UiO-66, FeTCPPCl UiO-66, MnTCPPCl UiO-66, CuTCPP UiO-66, H2TCPP UiO-66 and ZnTCPP UiO-66. S52

53 Figure S57. X UiO-66-NH2 samples in DMF after shaking to make the color better observed. From left to right were NiTCPP UiO-66-NH2, FeTCPPCl UiO-66-NH2, MnTCPPCl UiO-66-NH2, CuTCPP UiO-66-NH2, H2TCPP UiO-66-NH2 and ZnTCPP UiO-66-NH2. Figure S58. X UiO-66-NH2 samples in DMF with final powders attached on the bottom. From left to right were NiTCPP UiO-66-NH2, FeTCPPCl UiO-66-NH2, MnTCPPCl UiO-66-NH2, CuTCPP UiO-66-NH2, H2TCPP UiO-66-NH2 and ZnTCPP UiO-66-NH2. S53

54 Section S14. Porphyrin UiO-66 Systems with Incorporation of Multiple Functionalities. Figure S59. Photographs of (a) X UiO-66, (b) X UiO-66-NH2, (c) X UiO-66-2,5- (OH)2, (d) X UiO-66-2,5-(CH3)2, (e) X UiO-66-SO3H, (f) X UiO-66-2,5-(COOH)2, and (g) X UiO-66-N3 (X = NiTCPP, FeTCPPCl, MnTCPPCl, CuTCPP, H2TCPP, ZnTCPP, and CoTCPP from left to right). S54

55 Section S15. Catalytic Activity Test. In order to show the preservation of the functionality of TCPP species after applying our strategy, we took FeTCPPCl UiO-66 and FeTCPPCl UiO-66-NH2 as examples for the oxidation reaction of 2,2 -azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) in the presence of H2O2 to test the catalytic activity of these MOFs. First, 50 mm ABTS, 10 mm H2O2, and 1g/L MOF solution were prepared. To carry out the experiment, 200 μl ABTS, 80 μl MOF solution, 250 μl H2O2 and 2.47 ml deionized water were added into a Pyrex vial. The addition of FeTCPPCl UiO-66 or FeTCPPCl UiO-66-NH2 and H2O2 to the substrate solution led to the appearance of green color and gave a maximum absorbance at 418 nm, which originated from the formation of oxidized ABTS product (Scheme 1). The increased intensity of the maximum absorbance (Figure S52 and S54) as well as the color change over time (Figure S53, S55 and S57) demonstrated the biomimetic catalytic activity of FeTCPP UiO-66 and FeTCPP UiO-66-NH2 compared to UiO-66. Scheme 1. Reaction catalyzed by FeTCPPCl UiO-66 Figure S60. UV-Vis absorbance changes over time for oxidation reaction of ABTS catalyzed by FeTCPPCl UiO-66. S55

56 Figure S61. From left to right were the color changes of solution using FeTCPPCl UiO-66 as the catalyst after 1 min, 3 min, 5 min, 7 min, 10 min, 15 min and 20 min. Figure S62. UV-Vis absorbance changes over time for oxidation reaction of ABTS catalyzed by FeTCPPCl UiO-66-NH2. S56

57 Figure S63. From left to right were the color changes of solution using FeTCPPCl UiO-66-NH2 as the catalyst after 1 min, 3 min, 5 min, 7 min, 10 min, 15 min and 20 min. Figure S64. UV-Vis absorbance after 20 min when using UiO-66. S57

58 Figure S65. From left to right were the photographs of the solutions after 20 min when using FeTCPPCl UiO-66, FeTCPPCl UiO-66-NH2 and UiO-66, respectively. S58

59 Section S16. Thermodynamics behind Our Strategy. Figure S66. (a) Equilibrium in formation of the MOF. (b) Expression of Gibbs free energy of the reaction. S59

60 Section S17. Calculation of the plausible chemical formula. In order to further understand the defect-related problems in our TCPP UiO-66 system, we choose NiTCPP UiO-66 as an example to figure out the plausible chemical formula of the material. According to TGA data (Figure S29), 64.3% of the weight was lost after TGA test for NiTCPP UiO-66. First, we calculate the total amount of Zr and Ni in the material according to TGA data, given that the products remained after TGA analysis were ZrO2 and NiO. Then, we calculate the ratio of Zr to Ni as well as NiTCPP to BDC from EDS data (Table S1) and 1 H NMR data (Figure S46), respectively. After combining all of these results, the preliminary chemical formula of the material can be written as Zr6O4(OH)4(BDC)3.73(NiTCPP)0.28. In order to keep the charge balance, additional hydroxide anions are added. The presence of hydroxide anions to achieve the charge balance in UiO-66 containing defects has been reported by Yaghi group. 3 Finally, the plausible chemical formula of the material can be written as Zr6O4(OH)8(BDC)3.73(NiTCPP)0.28. (C: 32.6%, H: 1.9%, N: 1.0% were calculated from the chemical formula while C: 32.6%, H: 2.0%, N: 1.2% were obtained from the elemental analysis.) Reference (1) Feng, D.; Gu, Z.-Y.; Li, J.-R.; Jiang, H.-L.; Wei, Z.; Zhou, H.-C. Angew. Chem. Int. Ed. 2012, 51, (2) Kim, M.; Cahill, J. F.; Su, Y.; Prather, K. A.; Cohen, S. M. Chem. Sci. 2012, 3, 126. (3) Trickett, C. A.; Gagnon, K. J.; Lee, S.; Gándara, F.; Bürgi, H.-B.; Yaghi, O. M. Angew. Chem. Int. Ed. 2015, 54, S60