Atomic orbitals modulated dual functional bimetallic phosphides derived from MOF on MOF structure for boosting high efficient overall water splitting

doi:10.1016/S1872-2067(24)60124-5

Abstract

Abstract:

The electronic modulation characteristics of efficient metal phosphide electrocatalysts can be utilized to tune the performance of oxygen evolution reaction (OER). However, improving the overall water splitting performance remains a challenging task. By building metal organic framework (MOF) on MOF heterostructures, an efficient strategy for controlling the electrical structure of MOFs was presented in this study. ZIF-67 was in-situ synthesized on MIL-88 (Fe) using a two-step self-assembly method, followed by low-temperature phosphorization to ultimately synthesize FeP-CoP₃ bimetallic phosphides. By combining atomic orbital theory and theoretical calculations (density functional theory), the results reveal the successful modulation of electronic orbitals in FeP-CoP₃ bimetallic phosphides, which are synthesized from MOF on MOF structure. The synergistic impact of the metal center Co species and the phase conjugation of both kinds of MOFs are responsible for this regulatory phenomenon. Therefore, the catalyst demonstrates excellent properties, demonstrating HER 81 mV (η10) in a 1.0 mol L^-1 KOH solution and OER 239 mV (η50) low overpotentials. The FeP-CoP₃ linked dual electrode alkaline batteries, which are bifunctional electrocatalysts, have a good electrocatalytic ability and may last for 50 h. They require just 1.49 V (η50) for total water breakdown. Through this technique, the electrical structure of electrocatalysts may be altered to increase catalytic activity.

Key words: Transition metal phosphides, MOF on MOF, Atomic orbital theory, Density functional theory calculation

Bohan An, Weilong Liu, Jipeng Dong, Ning Li, Yangqin Gao, Lei Ge. Atomic orbitals modulated dual functional bimetallic phosphides derived from MOF on MOF structure for boosting high efficient overall water splitting[J]. Chinese Journal of Catalysis, 2024, 65: 113-125.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60124-5

https://www.cjcatal.com/EN/Y2024/V65/I10/113

Figures/Tables 8

Fig. 1. (a) SEM image of FeP-CoP3. (b) TEM images of FeP-CoP3. (c-e) HRTEM images of FeP-CoP3. (f) SAED image of FeP-CoP3. (g-m) EDS elemental mapping images for Co, Fe, P, O, N, C separately.

Fig. 2. (a) Process flowchart for preparing MOF on MOF structure. XRD images of FeP-CoP3 (b), FeP and CoP3 (c), Co3O4 and Fe2O3 (d). (e) Partial enlarged XRD images of FeP-CoP3. (f) SBET image of FeP-CoP3, FeP and CoP3. (g) Raman images of FeP-CoP3, FeP and CoP3. (h) Comparison graph of Fe XPS peaks. (i) Comparison graph of Co XPS peaks. (j) Comparison graph of P XPS peaks.

Fig. 3. (a) The LSV curves of FeP-CoP3, FeP, Fe2O3, CoP3, Co3O4 and CG. (b) Tafel slops of FeP-CoP3, FeP, Fe2O3, CoP3, Co3O4 and CG. (c) Relevant overpotentials at η10, η50 and η100 of the samples. (d,e) Impedance of the prepared catalyst. (f) HER stability test of FeP-CoP3. (g) Comparison of HER performance with other catalysts. (h) Comparison of HER LSV before and after stability testing.

Fig. 4. (a) LSV curves of FeP-CoP3, FeP, Fe2O3, CoP3, Co3O4 and CG. (b) Tafel slops of FeP-CoP3, FeP, Fe2O3, CoP3, Co3O4 and CG. (c) Relevant overpotentials at η50, η100 and η150 of the samples; (d,e) Impedance of the prepared catalyst. (f) OER stability test of FeP-CoP3. (g) Comparison of OER performance with other catalysts. (h) Comparison of OER LSV before and after stability testing.

Fig. 5. (a) Overall water splitting LSV curves of as-prepared catalysts at 1 M KOH. (b) FeP-CoP3 catalytic stability. (c) XRD pattern of FeP-CoP3 recovered for OER reaction. (d) Activity comparison with other electrocatalysts.

Fig. 6. (a) Free energy diagram of HER intermediates at different U values, and bottom image is most likely OER mechanism, Gibbs free energy profiles along the reaction pathway of CoP3 (b), FeP (c), and FeP-CoP3 (d).

Fig. 7. Density of states projected on the d-states of Fe in Fe-CoP3 (a), Co in FeP-CoP3 (b), Fe in FeP (c), and Co in CoP3 (d). Dashed-dotted lines and the numbers show the position of d-band center. Eg density of states projected on the d-states of Fe in Fe-CoP3 (e), Co in FeP-CoP3 (f), Fe in FeP (g), Co in CoP3 (h). (i) The charge density difference between FeP-CoP3. Charge buildup and depletion are represented by the colors blue and yellow, respectively. (j) Schematic diagram of OER process.

Fig. 8. Schematics of d-orbital electronic configurations of central metals in single atom Fe (a), single atom Co (b), and FeP-CoP3 (c) [43].

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