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.
†
* E-mail:
[email protected];
[email protected]
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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.
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Figure S2. Fourier transform κ3-weighted oscillation curves of N-Ni, Ni framework, Ni 3 N and Ni foil.
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Figure S3. High-resolution XPS spectra of N-Ni and Ni framework in the Ni 2p regions.
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Figure S4. (a) XRD pattern of Ni 3 N/Ni along with the standard pattern of Ni 3 N. (b) LSV curves of N-Ni, and Ni 3 N/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 3 N/Ni).
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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.
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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.
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Figure S7. (a-c) SEM images of N-Co at different magnifications. (d) High-resolution N 1s spectrum of NCo. (e) XRD patterns of N-Co and Co.
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Figure S8. (a-c) SEM images of N-Cu at different magnifications. (d) High-resolution N 1s spectrum of NCu. (e) XRD patterns of N-Cu and Cu.
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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.
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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.
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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.
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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.
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Figure S13. Comparison of the kinetic energy barrier profiles of water dissociation on Ni(111) and NNi(111). IS: initial state; TS: transition state; FS: final state.
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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
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, 17886-17892.). Color code: blue, Ni; yellow, N; white, H.
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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 N-Ni 1.0 M KPi ~10 64 18 h Co-P 0.1 M KPi >137 5h a-MoS x 2.0 M KPi 287 >290 H 2 -CoCat/FTO 0.5 M KPi ~325 40,000 s NiMoZn 0.1 M KPi ~187 NiS 1.0 M KPi 275 ~387 23 h Ni-Mo-S/C 0.5 M KPi ~125 200 30,000 s Ni-C-N NSs 1.0 M KPi 92.1 70 h Ni 3 N NSs 1.0 M KPi ~250 ~400 NiC NSs 1.0 M KPi ~100 ~200 CoP/CC 1.0 M KPi ~60 ~200 1000 cycles Co-S films 1.0 M KPi ~63 ~180 40 h Co-NRCNT 0.1 M KPi 330 540 10 h Mo 2 B 1.0 M KPi 250 45 h Mo 2 C 1.0 M KPi 200 45 h ALD-NiS x 1.0 M KPi 576 100 cycles Cu 2 MoS 4 0.1 M KPi ~200 ~350 60 min h-NiS x 1.0 M KPi 210 6h Fe 1-x S 0.1 M KPi >637 24 h Co 9 S 8 -700 1.0 M KPi ~150 370 10h 2D FeS 2 Discs 0.1 M KPi >100 >100 125h FeP/Ti 1.0 M KPi ~60 102 16h Fe x S y /C 0.1 M KPi ~280 ~557 28h h-Zn 0.3 Co 2.7 S 4 0.1 M KPi 90 60h Mo 2 C@NC 0.1 M KPi ~80 156 15h 3D ordered 1.0 M KPi >100 204 10h porous Mo 2 C Ni 3 S 2 /NF 1.0 M KPi ~50 170 1000 cycles Co/CoO x /CN 1.0 M KPi 280 NiWS x ~250 ~350 3h 1.0 M PBS NiWS x ~200 ~275 1h Co-HNP/CC 1.0 M KPi 243 20h a -2 Overpotential required to reach current densities of 1 or 10 mA cm .
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II. Supplementary References
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