noble-metal-free hetero-structural photocatalyst for efficient H 2

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Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 2017 Ni 12 P 5 nanoparticles embedded into porous g-c 3 N 4 nanosheets as a noble-metal-free hetero-structural photocatalyst for efficient H 2 production under visible light Deqian Zeng, ab Wee-Jun Ong,* a Hongfei Zheng, b Mingda Wu, c Yuanzhi Chen, b Dong-Liang Peng* b and Ming-Yong Han* a a Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR), 2 Fusionopolis Way, Innovis, Singapore 138634, Singapore. E-mail: ongwj@imre.a-star.edu.sg; ongweejun@gmail.com; my-han@imre.a-star.edu.sg b Department of Materials Science and Engineering, Collaborative Innovation Center of Chemistry for Energy Materials, College of Materials, Xiamen University, Xiamen 361005, China. E-mail: dlpeng@xmu.edu.cn c School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore. 1

Fig. S1 TEM images of 1NP-CN (a), 3NP-CN (b), 7NP-CN (c) and 10NP-CN (d) samples. 2

Fig. S2 EDX spectrum of the 5NP-CN sample. Fig. S3 Nitrogen isotherms of pure g-c 3 N 4 and the representative 5NP-CN samples. 3

Fig. S4 High resolution XPS results of the 5NP-CN sample. (a) Ni 2p, (b) P 2p, (c) C 1s, (d) N 1s and (e) O 1s. 4

Table S1 Comparison of the photocatalytic H 2 evolution reaction of the g-c 3 N 4 -based systems loaded with non-noble-metal co-catalysts. Catalyst Synthetic method Sacrificial Activity AQY (%) Ref. reagent (µmol h -1 g -1 ) (Wavelength) g-c 3 N 4 /WS 2 gas solid reaction strategy Methanol 101 --- S1 g-c 3 N 4 /WS 2 impregnation-sulfidation method Lactic 240 --- S2 acid g-c 3 N 4 /Ni 12 P 5 nanopowder was ground together TEOA 126.61 --- S3 in an agate mortar g-c 3 N 4 /WC heating a mixture of thiourea and TEOA 146.1 --- S4 commercial WC g-c 3 N 4 /Ni 2 P mix suspension under stirring TEOA 183.6 1.2 (420 nm) S5 g-c 3 N 4 /Ni 2 P gas solid reaction strategy TEOA 644 4.8 (440 nm) S6 g-c 3 N 4 /Ni 2 P gas solid reaction strategy TEOA 82.5 --- S7 g-c 3 N 4 /NiS in situ ion-exchange method TEOA 447.7 --- S8 g-c 3 N 4 /NiS hydrothermal method TEOA 482 1.9 (440 nm) S9 g-c 3 N 4 /Ni(OH) 2 precipitation method TEOA 152 1.1 (420 nm) S10 g-c 3 N 4 /Ni/NiO in situ immersion method TEOA 200 --- S11 g-c 3 N 4 /Cu H 2 reduction Methanol 20.5 0.35 (420 nm) S12 g-c 3 N 4 /MoS 2 in situ light-assisted method TEOA 252 --- S13 Ni 12 P 5 /g-c 3 N 4 Solution-phase self-assembly method TEOA 535.7 4.67 (420 nm) Our work 5

Fig. S5 TRPL decay curves of pure g-c 3 N 4 and 5NP-CN samples. References [S1] M. S. Akple, J. Low, S. Wageh, A. A. Al-Ghamdi, J. Yu and J. Zhang, Appl. Surf. Sci., 2015, 358, 196 203. [S2] Y. Hou, Y. Zhu, Y. Xu and X. Wang, Appl. Catal. B Environ., 2014, 156, 122 127. [S3] J. Wen, J. Xie, R. Shen, X. Li, X. Y. Luo, H. Zhang, A. Zhang and G. Bi, Dalton Trans., 2017, 46, 1794 1802. [S4] K. He, J. Xie, Z. Yang, R. Shen, Y. Fang, S. Ma, X. Chen and X. Li, Catal. Sci. Technol., 2017, 7, 1193 1202. [S5] Y. Chen and Z. Qin, Catal. Sci. Technol., 2016, 6, 8212 8221. [S6] A. Indra, A. Acharjya, P. W. Menezes, C. Merschjann, D. Hollmann, M. Schwarze,M. Aktas, A. Friedrich, S. Lochbrunner, A. Thomas and M. Driess, Angew. Chem., 2017, 129, 1675 1679. [S7] P. Ye, X. Liu, J. Locozzia, Y. Yuan, L. Gu, G. Xu and Z. Lin, J. Mater. Chem. A, 2017, 5, 8493 8498. [S8] Z. Chen, P. Sun, B. Fan, Z. Zhang and X. Fang, J. Phys. Chem. C, 2014, 118, 7801 7807. [S9] J. Hong, Y. Wang, Y. Wang, W. Zhang and R. Xu, ChemSusChem, 2013, 6, 2263 2268. 6

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