Improvement of oxygen evolution activity on isolated Mn sites by dual-heteroatom coordination

doi:10.1016/S1872-2067(23)64525-5

Abstract

Abstract:

The coordination of dual-heteroatom is an effective strategy to enhance the performance of oxygen evolution reaction (OER) of single-atom catalysts. Here, we synthesize Mn-SG-500 with isolated Mn sites coordinated with two sulfur and two oxygen atoms on graphene, and perform in-depth research on the structure-activity relationship for the OER. Under alkaline conditions, the Mn-SG-500 displays higher OER activity than commercial RuO₂. Combining in-situ structure analysis and theoretical calculations, we identify Mn-S₂O₂ as the catalytic active center, on which the oxidation of *O to *OOH is the rate-control step. The improved OER activity is attributed to the redistribution and optimization of Mn charges caused by the co-coordination of S and O. This work is helpful for further structure design and performance management of single-atom catalysts with dual-heteroatom doping.

Key words: Dual-heteroatom ligand, In-situ Raman, Oxygen evolution reaction, Single atom catalyst, Theoretical calculation

Xue Bai, Jingyi Han, Siyu Chen, Xiaodi Niu, Jingqi Guan. Improvement of oxygen evolution activity on isolated Mn sites by dual-heteroatom coordination[J]. Chinese Journal of Catalysis, 2023, 54: 212-219.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64525-5

https://www.cjcatal.com/EN/Y2023/V54/I11/212

Figures/Tables 5

Fig. 1. (a) Synthetic illustration of Mn-SG. (b) TEM image of Mn-SG-500. (c) HAADF-STEM image of Mn-SG-500. STEM image (d) and EDS elemental mappings (e) of Mn-SG-500.

Fig. 2. (a) XANES spectra at Mn K-edges of the Mn-SG-500 and referred samples. (b) FT-EXAFS spectra. (c) FT-EXAFS fitting spectrum. (d) Mn-S2O2 configuration.

Fig. 3. OER polarization curves (a) of G-500, SG-500, Mn-G-500, Mn-SG-500 and RuO2, and the corresponding Tafel slopes (b). (c) Activation energy of G-500, SG-500, Mn-G-500, and Mn-SG-500. (d) DPV curves of Mn-G-500 and Mn-SG-500. (e) Nyquist plots of the EIS test for the G-500, SG-500, Mn-G-500, and Mn-SG-500 (inset: the equivalent circuit used for fitting the Nyquist plots). (f) Chronoamperometry test for the Mn-SG-500.

Fig. 4. Ex-situ Mn 2p (a), S 2s (b), and O 1s (c) XPS spectra of fresh Mn-SG-500 and Mn-SG-500 after OER at overpotentials of 0.25, 0.35, 0.45 and 0.55 V, respectively.

Fig. 5. Population distributions for the DFT-calculated representative models: (a) Mn-S4G, (b) Mn-S3OG, (c) Mn-S2O2G para-position (d) Mn-S2O2G ortho-position, (e) Mn-SO3G, (f) Mn-S3G, (g) Mn-O3G and (h) Mn-O4G. (i) The optimized structures of three reaction intermediates of Mn-S2O2G and the reaction paths of free energy diagram for the OER on Mn-S4G, Mn-S3OG, Mn-S2O2G, Mn-SO3G, and Mn-S3G, Mn-O3G and Mn-O4G. (j) OER volcano plot of the overpotential η vs. the difference between the adsorption free energy of *O and *OOH for the seven models. (k) The projected DOS for the Mn-S2O2G. (l) The charge density differences of Mn in Mn-S2O2G. Yellow and blue areas represent charge density accumulation and depletion in the 3D map, respectively.

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