Abstract
Heterogeneous single-atom spin catalysts combined with magnetic fields provide a powerful means for accelerating chemical reactions with enhanced metal utilization and reaction efficiency. However, designing these catalysts remains challenging due to the need for a high density of atomically dispersed active sites with a short-range quantum spin exchange interaction and long-range ferromagnetic ordering. Here, we devised a scalable hydrothermal approach involving an operando acidic environment for synthesizing various single-atom spin catalysts with widely tunable substitutional magnetic atoms (M1) in a MoS2 host. Among all the M1/MoS2 species, Ni1/MoS2 adopts a distorted tetragonal structure that prompts both ferromagnetic coupling to nearby S atoms as well as adjacent Ni1 sites, resulting in global room-temperature ferromagnetism. Such coupling benefits spin-selective charge transfer in oxygen evolution reactions to produce triplet O2. Furthermore, a mild magnetic field of ~0.5 T enhances the oxygen evolution reaction magnetocurrent by ~2,880% over Ni1/MoS2, leading to excellent activity and stability in both seawater and pure water splitting cells. As supported by operando characterizations and theoretical calculations, a great magnetic-field-enhanced oxygen evolution reaction performance over Ni1/MoS2 is attributed to a field-induced spin alignment and spin density optimization over S active sites arising from field-regulated S(p)–Ni(d) hybridization, which in turn optimizes the adsorption energies for radical intermediates to reduce overall reaction barriers.
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Acknowledgements
J. Lu acknowledges the support from the Singapore Ministry of Education Tier 2 (MOE2019-T2-2-044 and MOE-T2EP50121-0008) and from the Singapore Ministry of Education through the Research Centre of Excellence programme (grant EDUN C-33-18-279-V12, I-FIM). X.L. acknowledges the support from the National Natural Science Foundation of China (12172386 and 12132020), National Natural Science Foundation of Guangdong Province, China (2021B1515020021) and the Guangdong Provincial Key Laboratory of Magnetoelectric Physics and Devices (LaMPad) (Grant No. 2022B1212010008). Q.H. acknowledges the support by the National Research Foundation (NRF) Singapore, under its NRF Fellowship (NRF-NRFF11-2019-0002). T.S. acknowledges the support from the Qin Chuangyuan project of Shaanxi Province (QCYRCXM-2022-213). A portion of this work was performed on the Steady High Magnetic Field Facilities, High Magnetic Field Laboratory, Chinese Academy of Sciences. The computational work for this article was partially performed on resources of the National Supercomputing Centre, Singapore. W. J. Zang is working at Department of Materials Science and Engineering, University of California, Irvine, Irvine 92617, and acknowledges the support from University of California to perform some STEM images. C.H. Chuang acknowledges the financial grants from MOST 110-2112-M-032-015 and MOST 110-2112-M-032-001.
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Contributions
T.S. and J. Lu conceived and designed the experiments. W.Z., H.X. and Q.H. performed the electron microscopy experiments and data analysis. T.S. performed the materials synthesis and OER test. Z.J.L., Z.H.L. and L.C. performed the electron spin resonance spectroscopy and analysis. J.S.D.R., C.O.M.M. and Y.-R.L. performed the S K-edge XANES spectra under magnetic field. C.-H.C. and S.X. analysed the data of the S K-edge XANES spectra. J. Li, X.H. and P.L. performed the Raman spectra and X-ray absorption spectroscopy analysis. J.S. and H.L. took the photos of the large cell. S.X. performed the XAFS measurement and XANES simulations. H.L. and X.S. performed the X-ray diffraction measurement. Z.J.L., Y.Z., J.C. and K.S.N. participated in the discussion and analysis. Z.T. and X.L. carried out theoretical calculations. T.S., Z.T., X.L. and J. Lu wrote the manuscript. All authors discussed and commented on the manuscript.
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Extended data
Extended Data Fig. 1 Structural characterization of Ni1/MoS2 with different metal loading.
a, HRTEM image of Ni1/MoS2 (14:100). b, HAADF-STEM image and corresponding EDS maps of Ni1/MoS2 (14:100). c, XRD patterns of Ni1/MoS2 with different Ni contents. d, The experimental (green) linear intensity profile of STEM (Fig. 1h) and the calculated data (Fig. 1i) (yellow) of Ni1/MoS2. e, The experimental (solid line) and simulation (dotted line) curves of Ni K-edge XANES spectra. f, Comparison of the experimental (solid line) FT-EXAFS curves with the calculated data (dotted line).
Extended Data Fig. 2 Characterization and the origin of ferromagnetism in Ni1/MoS2.
a, The peak separation of ESR spectra for Ni1/MoS2 (14:100) under different temperatures. b, c, Comparison of the Ni K-edge XANES (b) and FT-EXAFS (c) spectra for Ni1/MoS2 (14:100) with and without magnetic field. d, d-orbital splitting of a NiMo site for six (left, Es = 0.461 eV, C3h) and four (right, Es = 1.129 eV, C2v) coordination numbers. e, The energy localized function (ELF) of one Ni dopant-substituted Mo site in MoS2. f, Total and projected DOS of individual NiMo site with neighbouring six S and Mo atoms in antiferromagnetic Ni1/MoS2 as shown in Fig. 4c. Yellow, blue and green spheres are S, Mo and Ni atoms, respectively.
Extended Data Fig. 3 MFE of Ni1/MoS2 for OER and the comparison with commercial IrO2 catalysts.
a, Overpotentials of Ni1/MoS2 (14:100) at current density of 40 mA cm−2 and Tafel slopes. The averaged value in (a) together with the error bar is obtained from the analysis of five sets of experimental results. b, EIS spectra of MoS2 and Co1/MoS2 with and without magnetic field. c, LSV curves of Ni1/MoS2 (0.8:100). d, I-T curves of Ni1/MoS2 upon switching on and switching off different magnetic fields at 1.6 V vs. RHE. e, I-T curves of Ni1/MoS2 after switching off magnetic fields at 1.6 V vs. RHE. f, I-T curves of Ni1/MoS2 at different voltages upon switching on and switching off the magnetic field at 502 mT. g, I-T curves of Ni1/MoS2 under 502 mT and IrO2 catalyst at 1.6 V vs. RHE.
Extended Data Fig. 4 The origin of giant MFE of ferromagnetic Ni1/MoS2.
a, The second possible free energy profile of OER with the corresponding adsorption configurations of reaction intermediates over ferromagnetic (cyan) and antiferromagnetic (dark red) Ni1/MoS2. b, c, The spin density plot of *OOH on S site over ferromagnetic (b) and antiferromagnetic (c) Ni1/MoS2 model towards the transition from *OOH to O2. Yellow, blue, green, red and light blue spheres are S, Mo, Ni, O and H atoms, respectively. The light blue and purple isosurfaces represent the spin-up and spin-down density, respectively.
Extended Data Fig. 5 Probe the catalytic OER site and the origin of giant MFE for ferromagnetic Ni1/MoS2.
a, b, The first derivative curves of operando S K-edge XANES at different potentials under 0 mT (a) and 112 mT (b). c, d, PDOS of O species over AFM (c) and FM (d) coupled counterparts of Ni1/MoS2.
Extended Data Fig. 6 Giant MFE of 2.4 inch-sized ferromagnetic Ni1/MoS2 (14:100) electrode for a large water splitting cell.
a, Photograph of the inch-sized Ni1/MoS2 and Pt/C electrodes. b–c, inch-sized Ni1/MoS2 as anode (b) for magnetic-field enhanced water splitting (c).
Supplementary information
Supplementary Information
Supplementary Figs. 1–53, Tables 1–12 and Discussion.
Supplementary Video 1
The giant MFE for water splitting over Ni1/MoS2 SASCs under a magnetic field.
Source data
Source Data Fig. 1
Synthesis and characterization of a series of M1/MoS2 SASCs.
Source Data Fig. 2
Ferromagnetism of Ni1/MoS2.
Source Data Fig. 3
Giant MFE of ferromagnetic Ni1/MoS2 for the OER and water splitting.
Source Data Fig. 4
The origin of ferromagnetic Ni1/MoS2.
Source Data Fig. 5
The origin of the giant MFE of ferromagnetic Ni1/MoS2.
Source Data Extended Data Fig. 1
Structural characterization of Ni1/MoS2 with different metal loadings.
Source Data Extended Data Fig. 2
Characterization and origin of ferromagnetism in Ni1/MoS2.
Source Data Extended Data Fig. 3
MFE of Ni1/MoS2 for the OER and the comparison with commercial IrO2 catalysts.
Source Data Extended Data Fig. 4
The origin of the giant MFE of ferromagnetic Ni1/MoS2.
Source Data Extended Data Fig. 5
Probe of the catalytic OER site and the origin of the giant MFE for ferromagnetic Ni1/MoS2.
Source Data Extended Data Fig. 6
Giant MFE of 2.4 inch ferromagnetic Ni1/MoS2 (14:100) electrode for a large water splitting cell.
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Sun, T., Tang, Z., Zang, W. et al. Ferromagnetic single-atom spin catalyst for boosting water splitting. Nat. Nanotechnol. 18, 763–771 (2023). https://doi.org/10.1038/s41565-023-01407-1
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DOI: https://doi.org/10.1038/s41565-023-01407-1
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