Supporting Information

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1 Supporting Information Universal Surface Engineering of Transition Metals for Superior Electrocatalytic Hydrogen Evolution in Neutral Water Bo You, Xuan Liu, Guoxiang Hu, Sheraz Gul, Junko Yano, De-en Jiang*, and Yujie Sun*, Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322, United States Department of Chemistry, University of California, Riverside, California 92521, United States. Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States. * djiang@ucr.edu; yujie.sun@usu.edu S1

2 I. Supplementary Results Figure S1. SEM images of (a, b) pristine nickel foam and (c, d) Ni framework. The insets in (b) and (d) are the corresponding high-magnified SEM images. S2

3 Figure S2. Fourier transform κ 3 -weighted oscillation curves of N-Ni, Ni framework, Ni 3N and Ni foil. S3

4 Figure S3. High-resolution XPS spectra of N-Ni and Ni framework in the Ni 2p regions. S4

5 Figure S4. (a) XRD pattern of Ni 3N/Ni along with the standard pattern of Ni 3N. (b) LSV curves of N-Ni, and Ni 3N/Ni in 1.0 M ph= 7 phosphate buffer. The peaks in Figure S4a marked with stars are ascribed to Ni. As shown in Figure S4b, the HER activity of our N-Ni is also much higher than that of nickel nitride supported on Ni foam (Ni 3N/Ni). S5

6 Figure S5. Nyquist plots of Ni framework and N-Ni measured at an overpotential of 60 mv. The inset shows the high-frequency region of the plots. S6

7 Figure S6. (a-d) SEM images of N-Fe at different magnifications. (e) High-resolution N 1s spectrum of NFe. (f) XRD patterns of N-Fe and Fe together with the standard XRD pattern of Fe. S7

8 Figure S7. (a-c) SEM images of N-Co at different magnifications. (d) High-resolution N 1s spectrum of N- Co. (e) XRD patterns of N-Co and Co. S8

9 Figure S8. (a-c) SEM images of N-Cu at different magnifications. (d) High-resolution N 1s spectrum of N- Cu. (e) XRD patterns of N-Cu and Cu. S9

10 Figure S9. (a-c) SEM images of N-NiCo at different magnifications. (d) SEM and the corresponding elemental mapping images of N-NiCo. (e) Energy-dispersive X-ray spectra of N-NiCo. (f) XRD patterns of N-NiCo and NiCo together with the standard XRD patterns of Ni and Co. S10

11 Figure S10. LSV curves of porous (a) Fe, (b) Co, (b) Cu, and (c) NiCo alloy before (black) and after (red) ammonium carbonate treatment in 1.0 M phosphate buffer of ph 7. S11

12 Figure S11. (a) DFT-optimized structure of water adsorption on Ni(111); (b) DFT-optimized structure of water adsorption on N-Ni(111). Color code: blue, Ni; yellow, N; red, O; white, H. S12

13 Figure S12. (a) Initial (IS), transition (TS), and final (FS) states of water dissociation on Ni(111); (b) Initial (IS), transition (TS), and final (FS) states of water dissociation on N-Ni(111). Color code: blue, Ni; yellow, N; red, O; white, H. S13

14 Figure S13. Comparison of the kinetic energy barrier profiles of water dissociation on Ni(111) and N- Ni(111). IS: initial state; TS: transition state; FS: final state. S14

15 Figure S14. LSV curves of porous (a) Fe, (b) Co, (c) Cu in 1.0 M KOH before (black) and after (red) ammonium carbonate treatment. S15

16 Figure S15. (a) DFT-optimized structure of hydrogen adsorption on Ni(111); (b) DFT-optimized structure of hydrogen adsorption on N-Ni(111); (c) DFT-derived hydrogen adsorption free energy (ΔG H) on Ni(111) and N-Ni(111), relative to the computational hydrogen electrode (Nørskov et al., J. Phys. Chem. B, 2004, 108, ). Color code: blue, Ni; yellow, N; white, H. S16

17 Table S1. Comparison of HER performance in neutral media for N-Ni with other HER electrocatalysts. Catalysts Electrolyte η 1 a (mv) η 10 a (mv) Durability References N-Ni 1.0 M KPi ~ h This work Co-P 0.1 M KPi - >137 5 h S1 a-mos x 2.0 M KPi 287 >290 - S2 H 2-CoCat/FTO 0.5 M KPi ~325-40,000 s S3 NiMoZn 0.1 M KPi - ~187 - S4 NiS 1.0 M KPi 275 ~ h S5 Ni-Mo-S/C 0.5 M KPi ~ ,000 s S6 Ni-C-N NSs 1.0 M KPi h S7 Ni 3N NSs 1.0 M KPi ~250 ~400 - S7 NiC NSs 1.0 M KPi ~100 ~200 - S7 CoP/CC 1.0 M KPi ~60 ~ cycles S8 Co-S films 1.0 M KPi ~63 ~ h S9 Co-NRCNT 0.1 M KPi h S10 Mo 2B 1.0 M KPi h S11 Mo 2C 1.0 M KPi h S11 ALD-NiS x 1.0 M KPi cycles S12 Cu 2MoS M KPi ~200 ~ min S13 h-nis x 1.0 M KPi h S14 Fe 1-xS 0.1 M KPi > h S15 Co 9S M KPi ~ h S16 2D FeS 2 Discs 0.1 M KPi >100 > h S17 FeP/Ti 1.0 M KPi ~ h S18 Fe xs y/c 0.1 M KPi ~280 ~557 28h S19 h-zn 0.3Co 2.7S M KPi h S20 Mo 2C@NC 0.1 M KPi ~ h S21 3D ordered porous Mo 2C 1.0 M KPi > h S22 Ni 3S 2/NF 1.0 M KPi ~ cycles S23 Co/CoO x/cn 1.0 M KPi S24 NiWS x NiWS x 1.0 M PBS ~250 ~200 ~350 ~275 Co-HNP/CC 1.0 M KPi h S26 a Overpotential required to reach current densities of 1 or 10 ma cm -2. 3h 1h S25 S17

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