Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (4): 637-647.DOI: 10.1016/S1872-2067(20)63686-5
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Chuchu Wua,b,c, Xiaoming Zhanga,b, Huanqiao Lia,b, Zhangxun Xiaa,b, Shansheng Yud, Suli Wanga,b,*(), Gongquan Suna,b,#()
Received:
2020-05-17
Accepted:
2020-06-23
Online:
2021-04-18
Published:
2021-01-22
Contact:
Suli Wang,Gongquan Sun
About author:
#Tel/Fax: +86-411-84379063; E-mail: gqsun@dicp.ac.cnSupported by:
Chuchu Wu, Xiaoming Zhang, Huanqiao Li, Zhangxun Xia, Shansheng Yu, Suli Wang, Gongquan Sun. Iron-based binary metal-organic framework nanorods as an efficient catalyst for the oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2021, 42(4): 637-647.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63686-5
Scheme 1. Scheme of the preparation and structure of Fe2M-MIL-88B (Orange, blue, gray, red, and white spheres represent Fe, M, C, O, and H atoms, respectively).
Fig. 1. SEM and TEM images of Fe2Mn-MIL-88B (a,e), Fe-MIL-88B (b,f), Fe2Co-MIL-88B (c,g), and Fe2Ni-MIL-88B (d,h) (inset: distributions of the length of the samples). TEM images of Fe2Ni-MIL-88B (i) and the corresponding elemental mapping of oxygen (j), iron (k), and nickel (l), along with the corresponding EDX spectra (m) in the selected region.
Fig. 3. OER polarization curves (a) and Tafel plots (b) calculated from the polarization curves of Fe2M-MIL-88B and 20% Ir/C in O2-saturated 0.1 M KOH; (c) EIS spectra of Fe2M-MIL-88B at an overpotential of 350 mV with an inset showing the equivalent circuit model (symbols: raw data; lines: linear fit results); (d) Chronoamperometry results of Fe2Ni-MIL-88B/CC and OER polarization curves before (dashed curve) and after (solid curve) the stability test (without iR-correction); (e) ECSA of Fe2M-MIL-88B calculated from LSV measurements performed in a non-faradaic region at different scan rates.
Catalyst | Loading (mg cm-2) | η (mV) @10 mA cm-2 | Tafel slope (mV dec-1) | Ref. |
---|---|---|---|---|
Fe2Ni-MIL-88B | 0.191 | 307 | 38 | This work |
Fe2Co-MIL-88B | 0.191 | 348 | 47 | This work |
MAF-X27-OH | 0.18 | 461 | 66 | [ |
NiFe-MOF | 0.3 | 406 | — | [ |
Ti3C2Tx-CoBDC | 0.208 | 410 | 48.2 | [ |
Fe3-Co2 | 0.2 | 283 | 43 | [ |
Fe:2D-Co-NS | 0.2 | 282 | 59 | [ |
FeCo-MNS-1.0 | 0.36 | 298 | 21.6 | [ |
CTGU-10c2 | 0.14 | 240 | 58 | [ |
Table 1 Comparison of the electrocatalytic OER performance of Fe2M-MIL-88B with that of other reported MOF electrocatalysts tested in 0.1 M KOH on a GC-RDE.
Catalyst | Loading (mg cm-2) | η (mV) @10 mA cm-2 | Tafel slope (mV dec-1) | Ref. |
---|---|---|---|---|
Fe2Ni-MIL-88B | 0.191 | 307 | 38 | This work |
Fe2Co-MIL-88B | 0.191 | 348 | 47 | This work |
MAF-X27-OH | 0.18 | 461 | 66 | [ |
NiFe-MOF | 0.3 | 406 | — | [ |
Ti3C2Tx-CoBDC | 0.208 | 410 | 48.2 | [ |
Fe3-Co2 | 0.2 | 283 | 43 | [ |
Fe:2D-Co-NS | 0.2 | 282 | 59 | [ |
FeCo-MNS-1.0 | 0.36 | 298 | 21.6 | [ |
CTGU-10c2 | 0.14 | 240 | 58 | [ |
Fig. 5. (a) LSV measurements of the catalysts in O2-purged 0.0316 M KOH (pH 12.57, ■), 0.1 M KOH (pH 13.12, ●), 0.316 M KOH (pH 13.54, ▲), and 1 M KOH (pH 13.98, ▼). OER current density at (b) 1.550 V vs. RHE and the indicated potential (c) after iR-correction at the investigated pH values.
Fig. 6. (a) XPS survey patterns of all the samples; (b) Mn 2p high-resolution spectrum of Fe2Mn-MIL-88B; (c) Fe 2p high-resolution spectra of all samples (Dashes: raw data. Gray line: fitting results); (d) Mn 3s high-resolution XPS spectrum of Fe2Mn-MIL-88B; (e) Co 2p and (f) Ni 2p high-resolution spectra of Fe2Co-MIL-88B and Fe2Ni-MIL-88B, respectively; (g) Fe3+ content calculated from the fitting results of Fe2M-MIL-88B.
Initial spin multiplicity | 1 | 2 | 3 | |
---|---|---|---|---|
Fe2Mn | Final spin | 3.82×2, -3.45Mn | -3.77, 1.52, 3.68Mn | -3.80, 3.01, 3.28Mn |
Energy (Ha) | -4887.845132 | -4887.833044 | -4887.818988 | |
Fe | Final spin | 3.83×2; 3.81 | 3.78, -3.82, 1.10 | 3.75, -3.80, 2.08 |
Energy (Ha) | -5000.539747 | -5000.531345 | -5000.533114 | |
Fe2Co | Final spin | 1.72, -1.40, 0.69Co | 1.72, -1.37, 0.70Co | 1.87, -0.70, 0.82Co |
Energy (Ha) | -5119.585567 | -5119.585562 | -5119.582236 | |
Fe2Ni | Final spin | 1.90, -1.86, 1.35Ni | 1.66, -2.13, 1.23Ni | 1.97, -1.67, 1.39Ni |
Energy (Ha) | -5245.130615 | -5245.129398 | -5245.130189 |
Table 2 Energies of Fe2M-MIL-88B with varied Mulliken spin states.
Initial spin multiplicity | 1 | 2 | 3 | |
---|---|---|---|---|
Fe2Mn | Final spin | 3.82×2, -3.45Mn | -3.77, 1.52, 3.68Mn | -3.80, 3.01, 3.28Mn |
Energy (Ha) | -4887.845132 | -4887.833044 | -4887.818988 | |
Fe | Final spin | 3.83×2; 3.81 | 3.78, -3.82, 1.10 | 3.75, -3.80, 2.08 |
Energy (Ha) | -5000.539747 | -5000.531345 | -5000.533114 | |
Fe2Co | Final spin | 1.72, -1.40, 0.69Co | 1.72, -1.37, 0.70Co | 1.87, -0.70, 0.82Co |
Energy (Ha) | -5119.585567 | -5119.585562 | -5119.582236 | |
Fe2Ni | Final spin | 1.90, -1.86, 1.35Ni | 1.66, -2.13, 1.23Ni | 1.97, -1.67, 1.39Ni |
Energy (Ha) | -5245.130615 | -5245.129398 | -5245.130189 |
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