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1 Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2016 Electronic supplementary information Three dimensional metal-organic framework derived porous CoP 3 concave polyhedrons as superior bifunctional electrocatalysts for the evolution of hydrogen and oxygen Tianli Wu, a Mingyu Pi, a Xiaodeng Wang, a Dingke Zhang b and Shijian Chen a, * a School of Physics, Chongqing University, Chongqing, , China b College of Physics and Electronic Engineering, Chongqing Normal University, Chongqing, , China *Corresponding author: Dr. Shijian Chen, sjchen@cqu.edu.cn, Tel:

2 Fig. S1 Crystal structure of CoP 3. The cobalt and phosphorus atoms are represented by blue and red, respectively.

3 Fig. S2 Low- and high- magnification SEM images of CoP 3 NPs.

4 Fig. S3 SAED pattern of CoP 3 CPs.

5 Fig. S4 EDX spectrum of CoP 3 CPs.

6 Fig. S5 (a) Nitrogen adsorption/desorption isotherm and (b) the BJH pore-size distribution curve of CoP 3 NPs and CoP 3 CPs.

7 Fig. S6 Calculated exchange current density of the CoP 3 CPs and CoP 3 NPs by applying extrapolation method to the Tafel plot.

8 Table S1. Comparison of HER performance in acid media for CoP 3 Catalyst FeP nanosheets FeP NWs/Ti CPs/CFP with other TMPs HER electrocatalysts. Onset η (mv) Current density (j, ma cm -2 ) η at the corresponding j (mv) Exchange current density (ma cm -2 ) FeP NWs FeP NPs FeP NAs FeP 2 /C *10-3 Ref. Chem. Commun., 2013, 49, 6656 Ed., 2014, 53, Chem. Commun., 2016, 52, Nanoscale, 2015, 7, 4400 J. Mater. Chem. A, 2014, 2, J. Mater. Chem. A, 2015, 3, 499 Ni 2 P NPs *10-3 J. Am. Chem. Soc., 2013, 135, 9267 Ni 2 P/graph ene Ni 2 P/CNs NiP 2 /CC Se doped NiP Cu 3 P NWs MoP Bulk MoP NPs MoP 2 NPs/Mo MoP 2 nanosheets WP J. Power Sources, 2015, 297, 45 J. Power Sources, 2015, 285, 169 Nanoscale, 2014, 6, ACS Catal., 2015, 5, 6355 Ed., 2014, 53, 9577 Energy Environ. Sci., 2014, 7, 2624 Adv. Mater., 2014, 26, 5702 Nanoscale, 2016, 8, 8500 J. Mater. Chem. A, 2016, 4, 7169 Chem. Commun., 2014, 50, 11026

9 α-wp β-wp Co2P CoP/CC CoP NPs CoP/CNs CoP 3 CPs ACS Catal., 2015, 5, 145 J. Power Sources, 2015, 278, 540 Chem. Mater., 2015, 27, 3769 J. Am. Chem. Soc., 2014, 136, 7587 Ed., 2014, 53, 5427 Ed., 2014, 53, This work NPs (Nanoparticles); CNs (Carbon Nanotubes); CC (Carbon Cloth); NWs (Nanowires); NAs (Nanoneedle Arrays); CPs (Concave Polyhedrons)

10 Table S2. Comparison of HER performance in neutral media for CoP 3 CPs/CFP with other HER electrocatalysts. Catalyst Current density (j, ma cm -2 ) Potential at the corresponding j (mv) Ref. Mo 2 B Mo 2 C H2-CoCat/FTO Co-S/FTO 2 83 CuMoS WP WP MoP 2 NPs/Mo MoP 2 nanosheets CoP NWs 2 65 Ed., 2012, 51, Ed., 2012, 51, Nat. Mater., 2012, 11, 802 J. Am. Chem. Soc., 2013, 135, Energy Environ. Sci., 2012, 5, 8912 ACS Appl. Mater. Interfaces, 2014, 6, J. Power Sources, 2015, 278, 540 Nanoscale, 2016, 8, 8500 J. Mater. Chem. A, 2016, 4, 7169 J. Am. Chem. Soc., 2014, 136, 7587 CoP 3 CPs This work

11 Table S3. Comparison of HER performance in alkaline media for CoP 3 /CFP with other HER electrocatalysts. Catalyst Potential at the Current density (j, corresponding j ma cm -2 ) (mv) Ni wire MoB NiP WP WP MoP 2 nanosheets MoP 2 NPs/Mo CoP nanowires Ref. ACS Catal., 2013, 3, 166 Ed, 2012, 51, Nanoscale, 2014, 6, ACS Appl. Mater. Interfaces, 2014, 6, J. Power Sources, 2014, 136, 7587 J. Mater. Chem. A, 2016, 4, 7169 Nanoscale, 2016, 8, 8500 J. Am. Chem. Soc., 2014, 136, 7587 CoP 3 CPs This work

12 Fig. S7 The amount of H 2 theoretically calculated (solid) and experimentally measured (red sphere) versus time for CoP 3 CPs at (a) ph 0 under an overpotential of 127 mv (50 ma cm -2 ) for 60 min, (b) ph 6.8 under overpotentials of 223 mv (20 ma cm -2 ) for 60 min. and (c) ph 14 under overpotentials of 173 mv (30 ma cm -2 ) for 60 min.

13 Fig. S8 (a) XRD patterns of CoP 3 CPs and (b), (c), (d) the XRD patterns of CoP 3 CPs/CFP electrode after 3000 cycles CV scanning at ph 0, ph 6.8, and ph 14, respectively.

14 Table S4. Comparison of OER performance in alkaline media for CoP 3 /CFP with other OER electrocatalysts. Catalyst Potential at the Current density corresponding j (j ma cm -2 ) (mv) NiOOH/Ni 5 P Ni-P/CF Co-P film CoP NPs CoP nanorods CoP hollow CoP 2 /RGO CoP 3 NAs/CFP Ref Ed, 2015, 54, J. Power Sources, 2015, 299, 342 Ed, 2015, 54, 6251 ACS Catal., 2015, 5, 4066 ACS Catal., 2015, 5, 6874 ACS Appl. Mater. Interfaces, 2016, 8, 2158 J. Mater. Chem. A, 2016, 4, 4686 This work

15 Fig. S9 The amount of O 2 theoretically calculated (solid) and experimentally measured (red sphere) versus time for the CoP 3 CPs at ph 14 under overpotentials of 420 mv (50 ma cm -2 ) for 60 min. Fig. S10 (a) XRD patterns of CoP 3 CPs and (b) the XRD patterns of CoP 3

16 CPs/CFP electrode after 3000 cycles CV scanning at ph 14.