Supporting Information Investigation on Hydrogenation of Metal ...
Supporting Information
Investigation on Hydrogenation of Metal Organic Frameworks HKUST-1, MIL-53 and ZIF-8 by Hydrogen Spillover
Hao Chen1, Lifeng Wang1, Jun Yang2 and Ralph T. Yang1,*
1
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109
2
Research and Advanced Engineering, Ford Motor Company, MD1170/RIC, Dearborn,
Michigan 48121
* Corresponding author. Email: [email protected] Telephone: (734) 936-0771; Fax: (734) 764-7453
Synthesis of Zn-MOF-74 The synthesis procedure is summarized here, which is similar to previous reports.1-3 2,5-Dihydroxybenzene-1,4-dicarboxylic acid (0.2g, Sigma-Aldrich) and zinc nitrate hexahydrate (0.91g, Sigma-Aldrich) were dissolved in 40 mL of N,Ndimethylformamide (Sigma-Aldrich) with stirring in a 80 ml wide mouth glass jar. After dissolution of the reagents, 2 mL of deionized water was added. The jar was tightly capped and placed in an 100 °C oven for 20 h to yield trigonal block crystals. After decanting the hot mother liquor and rinsing with DMF, the product was immersed in methanol (Sigma-Aldrich) for 6 d, during which the activation solvent was decanted and freshly replenished three times. The solvent was removed under vacuum at 270 °C, yielding the porous material. Pt doped Zn-MOF-74 was synthesized by the similar procedure with other Pt doped MOFs described in the manuscript.
Figure S1. TEM image of Pt doped HKUST-1. The Pt particle sizes are estimated to range from slightly below 1 nm to approximately 10 nm.
Intensity (a.u.)
(A) (B) (C) (D) (E)
5
10 15 20 25 30 35 40 45 50 55 60 2Theta (degree)
Figure S2. XRD patterns ranged from 5-60° in 2θ for (A) Pt-HKUST-1, (B) Pt-HKUST100, (C) Pt-HKU-75, (D) Pt-HKU-50 and (E) Pt-HKU-25.
Intensity (a.u.)
(A)
(B)
5
10 15 20 25 30 35 40 45 50 55 60 2Theta (degree)
Figure S3. XRD patterns ranged from 5-60° in 2θ for (A) Pt-HKUST-1, (B) Pt-HKUST-1 after N2 treatment at 150°C for 16 hours.
2600 2400
(A)
2200
Intensity (a.u.)
2000 1800 1600 1400
(B)
1200 1000 800 600
925
930
935
940
945
950
955
960
965
Binding Energy (eV)
Figure S4. Cu 2p XPS spectra of (A) pristine HKUST-1 and (B) Pt-HKUST-1 after N2 treatment at 150°C for 16 hours.
14000
12000
Intensity (a.u.)
10000
8000
6000
4000
(A) (B) (C)
2000
0
5
10
15
20
25
30
35
40
45
50
2Theta (degee)
Figure S5. XRD patterns ranged from 5-60° in 2θ for (A) pristine Zn-MOF-74, in good agreement with literature 2-4 ; (B) Pt doped Zn-MOF-74 before H2 treatment at 150°C for 16 hours; (C) Pt doped Zn-MOF-74 after H2 treatment at 150°C for 16 hours. No peak change was observed on Zn-MOF-74 after Pt-doping procedure and H2 treatment.
3000 (A)
2500 (B)
2000
Intensity (a.u.)
980
500
988
992
996
1000
Kinetic Energy (eV)
1500
1000
984
(A) (B)
0
1015 1020 1025 1030 1035 1040 1045 1050 Binding Energy (eV)
Figure S6. Zn 2p XPS spectra of (A) pristine Zn-MOF-74, (B) Pt doped Zn-MOF-74 after H2 treatment at 150°C for 16 hours; inset figure shows Zn LMM spectra of (A) pristine Zn-MOF-74, (B) Pt doped Zn-MOF-74 after H2 treatment at 150°C for 16 hours. No peak shift was observed in Zn 2p XPS spectra and Zn LMM spectra for Pt doped ZnMOF-74 after H2 treatment at 150°C for 16 hours compared with pristine Zn-MOF-74, which indicates that Zn2+ in Zn-MOF-74 was not reduced by H2 at 150°C for 16 hours.
2.0
H2 amount (cc/g STP)
1.8 (A)
1.6 1.4
(B)
1.2 1.0 0.8
(C)
0.6 0.4 0.2 0.0 0
100 200 300 400 500 600 700 800 Pressure (mmHg)
Figure S7: H2 isotherms at 298K for (A) untreated Pt-HKUST-1 (never contacted with hydrogen before the measurement), (B) treated Pt-HKUST-1 (treated in H2 at 150°C for 16 h), (C) Pristine HKUST-1.
References: (1) Rowsell, J. L. C.; Yaghi, O. M. Journal of the American Chemical Society 2006, 128, 1304. (2) Grant Glover, T.; Peterson, G. W.; Schindler, B. J.; Britt, D.; Yaghi, O. Chemical Engineering Science 2011, 66, 163. (3)
Tranchemontagne, D. J.; Hunt, J. R.; Yaghi, O. M. Tetrahedron 2008, 64, 8553.
(4) Sanz, R.; Martinez, F.; Orcajo, G.; Wojtas, L.; Briones, D. Dalton Transactions 2013, 42, 2392.
Investigation on Hydrogenation of Metal Organic Frameworks HKUST-1, MIL-53 and ZIF-8 by Hydrogen Spillover
Hao Chen1, Lifeng Wang1, Jun Yang2 and Ralph T. Yang1,*
1
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109
2
Research and Advanced Engineering, Ford Motor Company, MD1170/RIC, Dearborn,
Michigan 48121
* Corresponding author. Email: [email protected] Telephone: (734) 936-0771; Fax: (734) 764-7453
Synthesis of Zn-MOF-74 The synthesis procedure is summarized here, which is similar to previous reports.1-3 2,5-Dihydroxybenzene-1,4-dicarboxylic acid (0.2g, Sigma-Aldrich) and zinc nitrate hexahydrate (0.91g, Sigma-Aldrich) were dissolved in 40 mL of N,Ndimethylformamide (Sigma-Aldrich) with stirring in a 80 ml wide mouth glass jar. After dissolution of the reagents, 2 mL of deionized water was added. The jar was tightly capped and placed in an 100 °C oven for 20 h to yield trigonal block crystals. After decanting the hot mother liquor and rinsing with DMF, the product was immersed in methanol (Sigma-Aldrich) for 6 d, during which the activation solvent was decanted and freshly replenished three times. The solvent was removed under vacuum at 270 °C, yielding the porous material. Pt doped Zn-MOF-74 was synthesized by the similar procedure with other Pt doped MOFs described in the manuscript.
Figure S1. TEM image of Pt doped HKUST-1. The Pt particle sizes are estimated to range from slightly below 1 nm to approximately 10 nm.
Intensity (a.u.)
(A) (B) (C) (D) (E)
5
10 15 20 25 30 35 40 45 50 55 60 2Theta (degree)
Figure S2. XRD patterns ranged from 5-60° in 2θ for (A) Pt-HKUST-1, (B) Pt-HKUST100, (C) Pt-HKU-75, (D) Pt-HKU-50 and (E) Pt-HKU-25.
Intensity (a.u.)
(A)
(B)
5
10 15 20 25 30 35 40 45 50 55 60 2Theta (degree)
Figure S3. XRD patterns ranged from 5-60° in 2θ for (A) Pt-HKUST-1, (B) Pt-HKUST-1 after N2 treatment at 150°C for 16 hours.
2600 2400
(A)
2200
Intensity (a.u.)
2000 1800 1600 1400
(B)
1200 1000 800 600
925
930
935
940
945
950
955
960
965
Binding Energy (eV)
Figure S4. Cu 2p XPS spectra of (A) pristine HKUST-1 and (B) Pt-HKUST-1 after N2 treatment at 150°C for 16 hours.
14000
12000
Intensity (a.u.)
10000
8000
6000
4000
(A) (B) (C)
2000
0
5
10
15
20
25
30
35
40
45
50
2Theta (degee)
Figure S5. XRD patterns ranged from 5-60° in 2θ for (A) pristine Zn-MOF-74, in good agreement with literature 2-4 ; (B) Pt doped Zn-MOF-74 before H2 treatment at 150°C for 16 hours; (C) Pt doped Zn-MOF-74 after H2 treatment at 150°C for 16 hours. No peak change was observed on Zn-MOF-74 after Pt-doping procedure and H2 treatment.
3000 (A)
2500 (B)
2000
Intensity (a.u.)
980
500
988
992
996
1000
Kinetic Energy (eV)
1500
1000
984
(A) (B)
0
1015 1020 1025 1030 1035 1040 1045 1050 Binding Energy (eV)
Figure S6. Zn 2p XPS spectra of (A) pristine Zn-MOF-74, (B) Pt doped Zn-MOF-74 after H2 treatment at 150°C for 16 hours; inset figure shows Zn LMM spectra of (A) pristine Zn-MOF-74, (B) Pt doped Zn-MOF-74 after H2 treatment at 150°C for 16 hours. No peak shift was observed in Zn 2p XPS spectra and Zn LMM spectra for Pt doped ZnMOF-74 after H2 treatment at 150°C for 16 hours compared with pristine Zn-MOF-74, which indicates that Zn2+ in Zn-MOF-74 was not reduced by H2 at 150°C for 16 hours.
2.0
H2 amount (cc/g STP)
1.8 (A)
1.6 1.4
(B)
1.2 1.0 0.8
(C)
0.6 0.4 0.2 0.0 0
100 200 300 400 500 600 700 800 Pressure (mmHg)
Figure S7: H2 isotherms at 298K for (A) untreated Pt-HKUST-1 (never contacted with hydrogen before the measurement), (B) treated Pt-HKUST-1 (treated in H2 at 150°C for 16 h), (C) Pristine HKUST-1.
References: (1) Rowsell, J. L. C.; Yaghi, O. M. Journal of the American Chemical Society 2006, 128, 1304. (2) Grant Glover, T.; Peterson, G. W.; Schindler, B. J.; Britt, D.; Yaghi, O. Chemical Engineering Science 2011, 66, 163. (3)
Tranchemontagne, D. J.; Hunt, J. R.; Yaghi, O. M. Tetrahedron 2008, 64, 8553.
(4) Sanz, R.; Martinez, F.; Orcajo, G.; Wojtas, L.; Briones, D. Dalton Transactions 2013, 42, 2392.
