Supporting information

Transcription

1 a Supporting information Core-Shell Nanocomposites Based on Gold Embedded Porous Carbons Derived from Metal Organic Frameworks as Efficient Dual Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions Jia Lu a, Weijia Zhou a *, Likai Wang a, Jin Jia a, Yunting Ke a, Linjing Yang a, Kai Zhou a, Xiaojun Liu a, Zhenghua Tang a, Ligui Li a, Shaowei Chen a,b * New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou, Guangdong , China b Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064, United States * s: eszhouwj@scut.edu.cn (W. J. Z.); shaowei@ucsc.edu (S. W. C.) Table S1. Elemental compositions of Au@Zn-Fe-C hybrids prepared at different Au/Fe molar ratios Au/Fe molar ratio C (at.%) Au (at.%) Fe (at.%) Zn (at.%) 1: : : Table S2. Comparison of the ORR catalytic performance of Au@Zn-Fe-C with other catalysts derived from MOFs (at the electrode rotation rate of 1600 rpm) Catalysts Onset potential Current density at +0.4 V (ma n Electrolyte Ref. (V vs. RHE) cm -2 ) Au@Zn-Fe-C M KOH this work N,S-porous carbon M KOH 1 N-graphene/Co-embedded porous carbon M KOH 2 N-doped porous carbon M KOH 3 N-doped porous carbon nanopolyhrdra M KOH 4 N-doped carbon nanotubes M KOH 5 N-decorated nanoporous carbon M KOH 6 SI-1

2 Table S3. Comparison of the HER activity of in 0.5 M H 2 SO 4 with results of relevant HER catalysts reported in recent literature Catalysts Onset j = 10 Tafel slope potential ma cm -2 (mv dec -1 ) (V vs. RHE) (V vs. RHE) Ref. Au@Zn-Fe-C this work MOFs-derived MoC X octahedrons N-graphene/Co-embedded porous carbon derived from MOFs GO/Cu-MOF Co embedded N-rich CNTs FeCo@NCNTs Single-shell carbon encapsulated Fe nanoparticles N-doped hexagonal carbon N,S-graphene N,P-graphene MoS 2 /RGO SI-2

3 Figure S1. TGA curves of (a) Zn-Fe-MOF and (b) Figure S2. (a) SEM image and (b) XRD patterns of Zn-Fe-MOF. Zn-Fe-MOF possessed a regular octahedral morphology, with an average length of ca. 200 nm, and the XRD patterns of Zn-Fe-MOF were consistent with the results of Wang et al. 16 Figure S3. Particle size distributions of (a) Au nanoparticle cores and (b) Au@Zn-Fe-C core-shell hybrids. Data were obtained from TEM measurements as shown in Figure 2. Figure S4. (a) Nitrogen adsorption/desorption isotherms and (b) pore size distributions of Zn-Fe-C and Au@Zn-Fe-C. The corresponding BET values are 19.4 and 8.7 m 2 /g, respectively. SI-3

4 Figure S5. a) RRDE voltammograms of Zn-Fe-MOF pyrolyzed at different temperatures at a rotation rate of 1600 rpm in an O 2 -saturated 0.1 M KOH solution at 10 mv s 1. (b) Polarization curves of Zn- Fe-MOF pyrolyzed at different temperature at 5 mv s 1 in a 0.5 M H 2 SO 4 solution (ir-corrected). Figure S6. (a) RRDE voltammograms of Au@Zn-Fe-C and 20 wt% Pt/C at a rotation rate of 1600 rpm in O 2 -saturated 0.1 M KOH solution at 10 mv s 1. (b) Corresponding number of electron transfer (n). Figure S7. Cyclic voltammograms of (a) Zn-Fe-C and (b) Au@Zn-Fe-C in N 2 and O 2 -saturated 0.1 M KOH at 50 mv s 1. It can be seen that the reduction peak of Au@Zn-Fe-C (+0.67 V vs. RHE) was more positive that that of Zn-Fe-C (+0.55 V vs. RHE), suggesting a higher ORR activity. Figure S8. TEM images of Au nanoparticles. SI-4

5 Figure S9. (a) RDE voltammograms of Zn-C, at a rotation rate of 1600 rpm in an O 2 -saturated 0.1 M KOH solution at 10 mv s 1. (b) Polarization curves of Zn-C, Au@ Zn-C, and Au@Zn-Fe-C at 5 mv s 1 in a 0.5 M H 2 SO 4 solution (ir-corrected). Figure S10. (a) RRDE voltammograms of Au@Zn-Fe-C with different Au/Fe ratios at a rotation rate of 1600 rpm in O 2 -saturated 0.1 M KOH solution at 10 mv s -1. (b) Corresponding number of electron transfer (n). Figure S11. Time dependence of the HER current density of Au@Zn-Fe-C loaded on glass carbon electrode at 0.15 V vs. RHE (ir-uncorrected). Inset is the photo image of H 2 bubbles formed on the electrode surface. Figure S12. (a) RRDE voltammograms of Au/Zn-Fe-C and Au@Zn-Fe-C at a rotation rate of 1600 rpm in an O 2 -saturated 0.1 M KOH solution at 10 mv s 1. (b) Polarization curves of Au/Zn-Fe-C and Au@Zn-Fe-C at 5 mv s 1 in a 0.5 M H 2 SO 4 solution (ir-corrected) SI-5

6 Figure S13. (a) RRDE voltammograms of pure Pt nanoparticles and at a rotation rate of 1600 rpm in an O 2 -saturated 0.1 M KOH solution at 10 mv s 1. (b) Polarization curves of pure Pt nanoparticles and Pt@Zn-Fe-C at 5 mv s 1 in a 0.5 M H 2 SO 4 solution. References 1. Li, J.; Chen, Y.; Tang, Y.; Li, S.; Dong, H.; Li, K.; Han, M.; Lan, Y.-Q.; Bao, J.; Dai, Z., J. Mater. Chem. A 2014, 2, Hou, Y.; Wen, Z.; Cui, S.; Ci, S.; Mao, S.; Chen, J., Adv. Funct. Mater. 2015, 25, Zhang, P.; Sun, F.; Xiang, Z.; Shen, Z.; Yun, J.; Cao, D., Energy Environ. Sci. 2014, 7, Zhang, L.; Su, Z.; Jiang, F.; Yang, L.; Qian, J.; Zhou, Y.; Li, W.; Hong, M., Nanoscale 2014, 6, Su, P.; Xiao, H.; Zhao, J.; Yao, Y.; Shao, Z.; Li, C.; Yang, Q., Chem. Sci. 2013, 4, Aijaz, A.; Fujiwara, N.; Xu, Q., J. Am. Chem. Soc. 2014, 136, Wu, H. B.; Xia, B. Y.; Yu, L.; Yu, X.-Y.; Lou, X. W., Nat. Commun. 2015, 6, Jahan, M.; Liu, Z.; Loh, K. P., Adv. Funct. Mater. 2013, 23, Zou, X.; Huang, X.; Goswami, A.; Silva, R.; Sathe, B. R.; Mikmeková, E.; Asefa, T., Angew. Chem. 2014, 126, Deng, J.; Ren, P.; Deng, D.; Yu, L.; Yang, F.; Bao, X., Energy Environ. Sci. 2014, 7, Tavakkoli, M.; Kallio, T.; Reynaud, O.; Nasibulin, A. G.; Johans, C.; Sainio, J.; Jiang, H.; Kauppinen, E. I.; Laasonen, K., Angew. Chem. 2015, 127, Liu, Y.; Yu, H.; Quan, X.; Chen, S.; Zhao, H.; Zhang, Y., Sci. Rep. 2014, 4, Ito, Y.; Cong, W.; Fujita, T.; Tang, Z.; Chen, M., Angew. Chem. Int. Ed. 2015, 54, Zheng, Y.; Jiao, Y.; Li, L. H.; Xing, T.; Chen, Y.; Jaroniec, M.; Qiao, S. Z., ACS Nano 2014, 8, Li, Y.; Wang, H.; Xie, L.; Liang, Y.; Hong, G.; Dai, H., J. Am. Chem. Soc. 2011, 133, Zhang, Z. C.; Chen, Y. F.; Xu, X. B.; Zhang, J. C.; Xiang, G. L.; He, W.; Wang, X. Angew. Chem. Int. Ed. 2014, 53, SI-6