Supporting Information (SI) for Structural Evolution of Co-Based Metal Organic Frameworks in Pyrolysis for Synthesis of Core-Shells on Nanosheets: Co@CoO x @Carbon-rGO 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 450001, P R China Henan Center for Disease Control and Prevention, 105 Nongyenan Road, Zhengzhou 450016, P R China Department of Chemistry, Tsinghua University, 1 Tsinghua Park, Beijing 100084, P R China * Corresponding Author. E-mail: lbjfcl@zzu.edu.cn. S-1
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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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
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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Figure S6. TEM images of (a-d) Co@CoO x @C, (e-f) Co@CoO x @CG, and (g) the lineal scanning image of Co@CoO x @CG. S-7
Figure S7. TEM images of Co@CoO x @N-C and (e-d) Co@CoO x @CG. Figure S8. Particle size distribution of (a) Co@CoOx@CG, and (b) Co@CoOx@N-CG. S-8
Figure S9. XPS fine spectra of (a, b) N1s in Co@CoO x @N-C, Co@CoO x @N-CG, (c) Co2p3 in Co@CoO x @CG and Co@CoO x @N-CG. Figure S10. TG curves of (a) Co@CoO x @C and Co@CoO x @N-C, (b) Co@CoO x @CG, and Co@CoO x @N-C G in air. Table S1. Mass ratio of N, C, H and O of the Co@CoO x @C, Co@CoO x @CG, Co@CoO x @N-C and Co@CoO x @N-CG by element analysis. Sample N C H O % Co@CoO x @C 0 2.95 0.06 8.19 Co@CoO x @CG 0.11 22.05 0.36 19.60 Co@CoO x @C-N 1.18 9.17 0 6.61 Co@CoO x @C-NG 1.33 22.56 0 12.51 S-9
Table S2. Relative atomic ratio of N, C, O and Co of the Co@CoO x @C, Co@CoO x @CG, Co@CoO x @N-C and Co@CoO x @N-CG. element C N O Co Sample % Co@CoO x @C 36.87 0 40.33 22.8 Co@CoO x @CG 74.80 0.01 18.74 6.45 Co@CoO x @N-C 68.69 2.14 22.45 6.72 Co@CoO x @N-CG 80.38 1.72 13.47 4.44 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
Figure S13. Hydrogen generation of (a) Co@CoO x @CG and (b) HG of Co@CoO x @CG, Co@CG, Co@N-CG, and Co@CoO x @N-CG different conditions under self-stirring at the same conditions (catalyst: 20 mg, : 80 mg, deionized water: 20 ml, 500 rpm). S-11
Figure S14. Hydrogen generation under self-stirring at different concentration with (a) Co@CoO x @C, (b) Co@CoO x @N-C, (c) Co@CoO x @CG, and (d) Co@CoO x @N-CG (catalyst: 20 mg, NaOH: 1 g, deionized water: 20 ml, 303 K, 500 rpm) (e) Co@CoO x @CG, (f) Co@CoO x @N-CG 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 x @CG (catalyst: 20 mg, : 80 mg, deionized water: 20 ml, self-stirring at 500 rpm, 303 K, 5wt% NaOH). S-12
Figure S15. Hydrogen generation with (a) Co@CoO x @CG, and (b) Co@CoO x @N-CG 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 303-328 K. S-13
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 S1 5670 ml min 1 g Co 1 (298 K) 58 S2 7400 ml min 1 g Co 1 (303K) 51 7900 ml min 1 g Co 1 (303K) 50 8400 ml min 1 g Co 1 (303K) 49 8300 ml min 1 g Co 1 (303K) 47 S3 S3 S3 S3 0.57 L min 1 g cat 1 (298 K) S4 0.3 L min 1 g cat 1 (298 K) S5 4200 ml min 1 g cat 1 (303 K) 44 S6 1368.2 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 1288.0 ml min 1 g Co 1 (298 K) 31 S10 CoB/Ag TiO 2 120 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 S11 1280 ml min 1 g cat 1 (298 K) 55 S12 1170 ml min 1 g cat 1 (313 K) 19 S13 2513 ml min 1 g 1 cat (313 K) 58 S14 6250 ml min 1 g cat 1 (303 K) 55 S15 5555 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
Figure S17. (a) XRD patterns of Co@CoO x @N-CG-1st and Co@CoO x @N-CG-1st after 200 C, and (b) FTIR of Co@CoO x @C and Co@CoO x @C-1st. References S1. Mahmood, J.; Jung, S. M.; Kim, S. J.; Park, J.; Yoo, J. W.; Baek, J. B. Cobalt Oxide Encapsulated in C 2 N-h2D Network Polymer as a Catalyst for Hydrogen Evolution. Chem. Mater. 2015, 27, 4860 4864. S2. Baydaroglu, F.; Ozdemir, E.; Hasimoglu, A. An Effective Synthesis Route for Improving The Catalytic Activity of Carbon-Supported Co-B Catalyst for Hydrogen Generation Through Hydrolysis of. Int. J. Hydrogen Energy 2014, 39, 1516 1522. S3. Ozdemir, E. Enhanced Catalytic Activity of Co-B/Glassy Carbon and Co-B/Graphite Catalysts for Hydrolysis of Sodium Borohydride. Int. J. Hydrogen Energy 2015, 40, 14045 14051. S4. Simagina, V. I.; Komova, O. V.; Ozerova, A. M.; Netskina, O. V.; Odegova, G. V.; Kellerman, D. G.; Bulavchenko, O. A.; Ishchenko, A. V. Cobalt Oxide Catalyst for Hydrolysis of Sodium Borohydride and Ammonia Borane. Appl. Catal. A-Gen. 2011, 394, 86 92. S5. Krishnan, P.; Hsueh, K. L.; Yim, S. D. Catalysts for the Hydrolysis of Aqueous Borohydride Solutions to Produce Hydrogen for PEM Fuel Cells. Appl. Catal. B-Environ. 2007, 77, 206 214. S6. Ke, D. D.; Tao, Y.; Li, Y.; Zhao, X.; Zhang, L.; Wang, J. D.; Han, S. M. Kinetics Study on Hydrolytic Dehydrogenation of Alkaline Sodium Borohydride Catalyzed by Mo-modified Co-B Nanoparticles. Int. J. Hydrogen Energy 2015, 40, 7308 7317. S7. Zou, Y. J.; Cheng, J.; Wang, Q. Y.; Xiang, C. L.; Chu, H. L.; Qiu, S. J.; Zhang, H. Z.; Xu, F.; Liu, S. S.; Tang, C. Y.; Sun, L. X. Cobalt-Boron/Nickel-Boron Nanocomposite with Improved Catalytic Performance for the Hydrolysis of Ammonia Borane. Int. J. Hydrogen Energy 2015, 40, 13423 13430. S-15
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