Supporting Information (SI) for

Transcription

1 Supporting Information (SI) for Structural Evolution of Co-Based Metal Organic Frameworks in Pyrolysis for Synthesis of Core-Shells on Nanosheets: Composites for Enhanced Hydrogen Generation Activity Congcong Xing, Yanyan Liu, Yongheng Su, Yinghao Chen, Shuo Hao, Xianli Wu, Xiangyu Wang, Huaqiang Cao and Baojun Li *,, College of Chemistry and Molecular Engineering, Zhengzhou University, 100 Science Road, Zhengzhou , P R China Henan Center for Disease Control and Prevention, 105 Nongyenan Road, Zhengzhou , P R China Department of Chemistry, Tsinghua University, 1 Tsinghua Park, Beijing , P R China * Corresponding Author. lbjfcl@zzu.edu.cn. S-1

2 Figure S1. Photographs of Co-MOF, Co-MOF-GO, Co-MOF-PVP and Co-MOF-PVP-GO powders. Figure S2. Equipment for hydrogen generation. S-2

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4 Figure S3. TEM images of (a, b) Co-MOF (c, d) Co-MOF-GO, (e, f) Co-MOF-PVP, and (g, h) Co-MOF-PVP-GO. S-4

5 Figure S4. Hydrogen generation performances with (a) Co-MOFs composites under same condition (catalyst: 20 mg, : 80 mg, deionized water: 20 ml, NaOH: 5wt%, 303 K), (b) Co-MOF-GO and Co-MOF-PVP-GO (c) three repeatable Co-MOF-GO at the same conditions (catalyst: 20 mg, : 80 mg, deionized water: 20 ml, self-stirring at 500 rpm, 303 K), and (d) XRD patterns of Co-MOF-GO after hydrogen generation. Figure S5. Hydrogen generation with Co@C, Co@N-C, Co@CG, and Co@N-CG at the same conditions (catalyst: 20 mg, : 80 mg, deionized water: 20 ml, self-stirring at 500 rpm, 303 K, 5wt% NaOH). S-5

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7 Figure S6. TEM images of (a-d) (e-f) and (g) the lineal scanning image of S-7

8 Figure S7. TEM images of and (e-d) Figure S8. Particle size distribution of (a) and (b) S-8

9 Figure S9. XPS fine spectra of (a, b) N1s in (c) Co2p3 in and Figure S10. TG curves of (a) and (b) and G in air. Table S1. Mass ratio of N, C, H and O of the Co@CoO Co@CoO Co@CoO and Co@CoO by element analysis. Sample N C H O % Co@CoO Co@CoO Co@CoO Co@CoO S-9

10 Table S2. Relative atomic ratio of N, C, O and Co of the Co@CoO Co@CoO Co@CoO and Co@CoO element C N O Co Sample % Co@CoO Co@CoO Co@CoO Co@CoO Figure S11. View of the magnetism of four composites in the absence of water. Figure S12. View of the magnetism of four composites in water. S-10

11 Figure S13. Hydrogen generation of (a) and (b) HG of Co@N-CG, and different conditions under self-stirring at the same conditions (catalyst: 20 mg, : 80 mg, deionized water: 20 ml, 500 rpm). S-11

12 Figure S14. Hydrogen generation under self-stirring at different concentration with (a) (b) (c) and (d) (catalyst: 20 mg, NaOH: 1 g, deionized water: 20 ml, 303 K, 500 rpm) (e) Co@CoO (f) Co@CoO at different rotate rate with (catalyst: 20 mg, : 80 mg, NaOH: 1 g, deionized water: 20 ml, 303 K), and (g) Hydrogen generation three repeatable Co@CoO (catalyst: 20 mg, : 80 mg, deionized water: 20 ml, self-stirring at 500 rpm, 303 K, 5wt% NaOH). S-12

13 Figure S15. Hydrogen generation with (a) and (b) at different rotate rate with magneton (catalyst: 20 mg, : 80 mg, NaOH: 1 g, deionized water: 20 ml, 303 K). Figure S16. The corresponding Arrhenius plots of lnk versus reciprocal absolute temperature 1/T in the temperature range of K. S-13

14 Table S3. The H 2 generation specific rates and activation energies with various catalysts. Catalyst Catalyst weight (mg) Hydride Maximum H 2 generation specific rate Activation energy (kj mol 1 ) Refere nce Co@C 2 N 50 Co B 125 Co B/G 50 Co B/GC 50 Co B/G 50 Co B/GC 50 Co 3 O 4 12 LiCoO 2 12 Co Mo B 10 Co-B/Ni-B 50 p(spm)-co 150 Co x B/CHM 10 wt. % 0.12M 5 wt.% 0.05 M 10M 3.44 M 8903 ml min 1 g cat 1 (303 K) 66 S ml min 1 g Co 1 (298 K) 58 S ml min 1 g Co 1 (303K) ml min 1 g Co 1 (303K) ml min 1 g Co 1 (303K) ml min 1 g Co 1 (303K) 47 S3 S3 S3 S L min 1 g cat 1 (298 K) S4 0.3 L min 1 g cat 1 (298 K) S ml min 1 g cat 1 (303 K) 44 S ml min 1 g 1 cat (298 K) 1000 ± 53 ml min 1 g 1 Co (303 K) 34 S7 41 S8 7.2 L min 1 g Co 1 (323 K) _ S9 p(spm)-co 0.05 M ml min 1 g Co 1 (298 K) 31 S10 CoB/Ag TiO Ni-Co/r-GO 100 Ni/Au/Co Co/SiO 2 -LP h-coo nanoplates h-coo nanorods 1 wt.% 16.5 mm 5 wt.% 6294 ml min 1 g Co 1 (303 K) 44 S ml min 1 g cat 1 (298 K) 55 S ml min 1 g cat 1 (313 K) 19 S ml min 1 g 1 cat (313 K) 58 S ml min 1 g cat 1 (303 K) 55 S ml min 1 g cat 1 (303 K) 53 S15 h-coo long nanorods 3665 ml min 1 g cat 1 (303 K) 43 S15 S-14

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