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Topotactic reduction of layered double hydroxides for atomically thick two-dimensional non-noble-metal alloy

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Abstract

Layered double hydroxides (LDHs) have been widely used as catalysts owing to their tunable structure and atomic dispersion of high-valence metal ions; however, limited tunability of electronic structure and valence states have hindered further improvement in their catalytic performance. Herein, we reduced ultrathin LDH precursors in situ and topotactically converted them to atomically thick (~2 nm) two-dimensional (2D) multi-metallic, single crystalline alloy nanosheets with highly tunable metallic compositions. The as-obtained alloy nanosheets not only maintained the vertically aligned ultrathin 2D structure, but also inherited the atomic dispersion of the minor metallic compositions of the LDH precursors, even though the atomic percentage was higher than 20%, which is far beyond the reported percentages for single-atom dispersions (usually less than 0.1%). Besides, surface engineering of the alloy nanosheets can finely tune the surface electronic structure for catalytic applications. Such in situ topotactic conversion strategy has introduced a novel approach for atomically dispersed alloy nanostructures and reinforced the synthetic methodology for ultrathin 2D metal-based catalysts.

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References

  1. Geim, A. K.; Novoselov, K. S. The rise of graphene. Nat. Mater. 2007, 6, 183–191.

    Article  Google Scholar 

  2. Mannix, A. J.; Zhou, X. F.; Kiraly, B.; Wood, J. D.; Alducin, D.; Myers, B. D.; Liu, X.; Fisher, B. L.; Santiago, U.; Guest, J. R. et al. Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs. Science 2015, 350, 1513–1516.

    Article  Google Scholar 

  3. Jin, R. C.; Cao, Y. W.; Mirkin, C. A.; Kelly, K. L.; Schatz, G. C.; Zheng, J. G. Photoinduced conversion of silver nanospheres to nanoprisms. Science 2001, 294, 1901–1903.

    Article  Google Scholar 

  4. Duan, H. H.; Yan, N.; Yu, R.; Chang, C. R.; Zhou, G.; Hu, H. S.; Rong, H. P.; Niu, Z. Q.; Mao, J. J.; Asakura, H. et al. Ultrathin rhodium nanosheets. Nat. Commun. 2014, 5, 3093.

    Google Scholar 

  5. Hu, S.; Wang, X. Ultrathin nanostructures: Smaller size with new phenomena. Chem. Soc. Rev. 2013, 42, 5577–5594.

    Article  Google Scholar 

  6. Butler, S. Z.; Hollen, S. M.; Cao, L. Y.; Cui, Y.; Gupta, J. A.; Gutiérrez, H. R.; Heinz, T. F.; Hong, S. S.; Huang, J. X.; Ismach, A. F. et al. Progress, challenges, and opportunities in two-dimensional materials beyond graphene. ACS Nano 2013, 7, 2898–2926.

    Article  Google Scholar 

  7. Liu, K. K.; Zhang, W. J.; Lee, Y. H.; Lin, Y. C.; Chang, M. T.; Su, C. Y.; Chang, C. S.; Li, H.; Shi, Y. M.; Zhang, H. et al. Growth of large-area and highly crystalline MoS2 thin layers on insulating substrates. Nano Lett. 2012, 12, 1538–1544.

    Article  Google Scholar 

  8. Sun, Y. F.; Cheng, H.; Gao, S.; Liu, Q. H.; Sun, Z. H.; Xiao, C.; Wu, C. Z.; Wei, S. Q.; Xie, Y. Atomically thick bismuth selenide freestanding single layers achieving enhanced thermoelectric energy harvesting. J. Am. Chem. Soc. 2012, 134, 20294–20297.

    Article  Google Scholar 

  9. Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L. J.; Loh, K. P.; Zhang, H. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 2013, 5, 263–275.

    Article  Google Scholar 

  10. Sun, Y. F.; Gao, S.; Lei, F. C.; Xie, Y. Atomically-thin two-dimensional sheets for understanding active sites in catalysis. Chem. Soc. Rev. 2015, 44, 623–636.

    Article  Google Scholar 

  11. Huang, X. Q.; Tang, S. H.; Mu, X. L.; Dai, Y.; Chen, G. X.; Zhou, Z. Y.; Ruan, F. X.; Yang, Z. L.; Zheng, N. F. Freestanding palladium nanosheets with plasmonic and catalytic properties. Nat. Nanotechnol. 2011, 6, 28–32.

    Article  Google Scholar 

  12. Gao, S.; Lin, Y.; Jiao, X. C.; Sun, Y. F.; Luo, Q. Q.; Zhang, W. H.; Li, D. Q.; Yang, J. L.; Xie, Y. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel. Nature 2016, 529, 68–71.

    Article  Google Scholar 

  13. Xu, M. S.; Liang, T.; Shi, M. M.; Chen, H. Z. Graphenelike two-dimensional materials. Chem. Rev. 2013, 113, 3766–3798.

    Article  Google Scholar 

  14. Voiry, D.; Salehi, M.; Silva, R.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G.; Chhowalla, M. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 2013, 13, 6222–6227.

    Article  Google Scholar 

  15. Luo, J. S.; Im, J. H.; Mayer, M. T.; Schreier, M.; Nazeeruddin, M. K.; Park, N. G.; Tilley, S. D.; Fan, H. J.; Grätzel, M. Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts. Science 2014, 345, 1593–1596.

    Article  Google Scholar 

  16. Song, F.; Hu, X. L. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis. Nat. Commun. 2014, 5, 4477.

    Google Scholar 

  17. Gong, M.; Li, Y. G.; Wang, H. L.; Liang, Y. Y.; Wu, J. Z.; Zhou, J. G.; Wang, J.; Regier, T.; Wei, F.; Dai, H. J. An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation. J. Am. Chem. Soc. 2013, 135, 8452–8455.

    Article  Google Scholar 

  18. Hogeboom, G. H.; Schneider, W. C.; Pallade, G. E. Cytochemical studies of mammalian tissues I. Isolation of intact mitochondria from rat liver; some biochemical properties of mitochondria and submicroscopic particulate material. J. Biol. Chem. 1948, 172, 619–635.

    Google Scholar 

  19. Sels, B.; de Vos, D.; Buntinx, M.; Pierard, F.; Kirsch-De Mesmaeker, A.; Jacobs, P. Layered double hydroxides exchanged with tungstate as biomimetic catalysts for mild oxidative bromination. Nature 1999, 400, 855–857.

    Article  Google Scholar 

  20. Heitbaum, M.; Glorius, F.; Escher, I. Asymmetric heterogeneous catalysis. Angew. Chem., Int. Ed. 2006, 45, 4732–4762.

    Article  Google Scholar 

  21. Fan, G. L.; Li, F.; Evans, D. G.; Duan, X. Catalytic applications of layered double hydroxides: Recent advances and perspectives. Chem. Soc. Rev. 2014, 43, 7040–7066.

    Article  Google Scholar 

  22. Sideris, P. J.; Nielsen, U. G.; Gan, Z. H.; Grey, C. P. Mg/Al ordering in layered double hydroxides revealed by multinuclear NMR spectroscopy. Science 2008, 321, 113–117.

    Article  Google Scholar 

  23. Evans, D. G.; Slade, R. C. T. Structural aspects of layered double hydroxides. In Layered Double Hydroxides; Duan, X.; Evans, D. G., Eds.; Springer: Berlin Heidelberg, 2006; pp 1–87.

    Google Scholar 

  24. Wang, Q.; O'Hare, D. Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets. Chem. Rev. 2012, 112, 4124–4155.

    Article  Google Scholar 

  25. Song, F.; Hu, X. L. Ultrathin cobalt-manganese layered double hydroxide is an efficient oxygen evolution catalyst. J. Am. Chem. Soc. 2014, 136, 16481–16484.

    Article  Google Scholar 

  26. Trotochaud, L.; Young, S. L.; Ranney, J. K.; Boettcher, S. W. Nickel-iron oxyhydroxide oxygen-evolution electrocatalysts: The role of intentional and incidental iron incorporation. J. Am. Chem. Soc. 2014, 136, 6744–6753.

    Article  Google Scholar 

  27. Schneider, W. Methods for the isolation of particulate components of the cell. In Manometric Techniques; Burgess: Minneapolis, Minnesota, 1957; pp 188–201.

    Google Scholar 

  28. Gong, M.; Dai, H. J. A mini review of NiFe-based materials as highly active oxygen evolution reaction electrocatalysts. Nano Res. 2015, 8, 23–39.

    Article  Google Scholar 

  29. Morales-Guio, C. G.; Liardet, L.; Hu, X. L. Oxidatively electrodeposited thin-film transition metal (oxy)hydroxides as oxygen evolution catalysts. J. Am. Chem. Soc. 2016, 138, 8946–8957.

    Article  Google Scholar 

  30. Jiao, Y.; Zheng, Y.; Jaroniec, M.; Qiao, S. Z. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem. Soc. Rev. 2015, 44, 2060–2086.

    Article  Google Scholar 

  31. Xia, Y. N.; Xiong, Y. J.; Lim, B.; Skrabalak, S. E. Shapecontrolled synthesis of metal nanocrystals: Simple chemistry meets complex physics? Angew. Chem., Int. Ed. 2009, 48, 60–103.

    Article  Google Scholar 

  32. Washio, I.; Xiong, Y.; Yin, Y.; Xia, Y. Reduction by the end groups of poly(vinyl pyrrolidone): A new and versatile route to the kinetically controlled synthesis of Ag triangular nanoplates. Adv. Mater. 2006, 18, 1745–1749.

    Article  Google Scholar 

  33. Li, C. C.; Cai, W. P.; Cao, B. Q.; Sun, F. Q.; Li, Y.; Kan, C. X.; Zhang, L. D. Mass synthesis of large, single-crystal Au nanosheets based on a polyol process. Adv. Funct. Mater. 2006, 16, 83–90.

    Article  Google Scholar 

  34. Tangeysh, B.; Moore Tibbetts, K.; Odhner, J. H.; Wayland, B. B.; Levis, R. J. Triangular gold nanoplate growth by oriented attachment of Au seeds generated by strong field laser reduction. Nano Lett. 2015, 15, 3377–3382.

    Article  Google Scholar 

  35. Huang, X.; Zeng, Z. Y.; Bao, S. Y.; Wang, M. F.; Qi, X. Y.; Fan, Z. X.; Zhang, H. Solution-phase epitaxial growth of noble metal nanostructures on dispersible single-layer molybdenum disulfide nanosheets. Nat. Commun. 2013, 4, 1444.

    Article  Google Scholar 

  36. Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. T.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 2011, 3, 634–641.

    Article  Google Scholar 

  37. Thomas, J. M. Catalysis: Tens of thousands of atoms replaced by one. Nature 2015, 525, 325–326.

    Article  Google Scholar 

  38. Tamura, K.; Kimura, Y.; Suzuki, H.; Kido, O.; Sato, T.; Tanigaki, T.; Kurumada, M.; Saito, Y.; Kaito, C. Structure and thickness of natural oxide layer on ultrafine particle. Jpn. J. Appl. Phys. 2003, 42, 7489–7492.

    Article  Google Scholar 

  39. Knight, M. W.; King, N. S.; Liu, L. F.; Everitt, H. O.; Nordlander, P.; Halas, N. J. Aluminum for plasmonics. ACS Nano 2014, 8, 834–840.

    Article  Google Scholar 

  40. Haber, J. A.; Buhro, W. E. Kinetic instability of nanocrystalline aluminum prepared by chemical synthesis; facile room-temperature grain growth. J. Am. Chem. Soc. 1998, 120, 10847–10855.

    Article  Google Scholar 

  41. Meselson, M.; Stahl, F. W.; Vinograd, J. Equilibrium sedimentation of macromolecules in density gradients. Proc. Natl. Acad. Sci. USA 1957, 43, 581–588.

    Article  Google Scholar 

  42. Qian, L.; Lu, Z. Y.; Xu, T. H.; Wu, X. C.; Tian, Y.; Li, Y. P.; Huo, Z. Y.; Sun, X. M.; Duan, X. Trinary layered double hydroxides as high-performance bifunctional materials for oxygen electrocatalysis. Adv. Energy Mater. 2015, 5, 1500245.

    Article  Google Scholar 

  43. Brakke, M. K. Density gradient centrifugation: A new separation technique. J. Am. Chem. Soc. 1951, 73, 1847–1848.

    Article  Google Scholar 

  44. Cobo, S.; Heidkamp, J.; Jacques, P. A.; Fize, J.; Fourmond, V.; Guetaz, L.; Jousselme, B.; Ivanova, V.; Dau, H.; Palacin, S. et al. A Janus cobalt-based catalytic material for electrosplitting of water. Nat. Mater. 2012, 11, 802–807.

    Article  Google Scholar 

  45. Funke, H.; Scheinost, A. C.; Chukalina, M. Wavelet analysis of extended X-ray absorption fine structure data. Phys. Rev. B 2005, 71, 094110.

    Article  Google Scholar 

  46. Wang, H. T.; Lee, H. W.; Deng, Y.; Lu, Z. Y.; Hsu, P. C.; Liu, Y. Y.; Lin, D. C.; Cui, Y. Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting. Nat. Commun. 2015, 6, 7261.

    Article  Google Scholar 

  47. Jin, H. Y.; Wang, J.; Su, D. F.; Wei, Z. Z.; Pang, Z. F.; Wang, Y. In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution. J. Am. Chem. Soc. 2015, 137, 2688–2694.

    Article  Google Scholar 

  48. Zhang, J.; Wang, T.; Pohl, D.; Rellinghaus, B.; Dong, R. H.; Liu, S. H.; Zhuang, X. D.; Feng, X. L. Interface engineering of MoS2/Ni3S2 heterostructures for highly enhanced electrochemical overall-water-splitting activity. Angew. Chem., Int. Ed. 2016, 55, 6702–6707.

    Article  Google Scholar 

  49. Jin, Y. S.; Wang, H. T.; Li, J. J.; Yue, X.; Han, Y. J.; Shen, P. K.; Cui, Y. Porous MoO2 nanosheets as non-noble bifunctional electrocatalysts for overall water splitting. Adv. Mater. 2016, 28, 3785–3790.

    Article  Google Scholar 

  50. Gong, M.; Zhou, W.; Tsai, M.-C.; Zhou, J. G.; Guan, M. Y.; Lin, M.-C.; Zhang, B.; Hu, Y. F.; Wang, D.-Y.; Yang, J. et al. Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis. Nat. Commun. 2014, 5, 4695.

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China, the National Key Research and Development Program of China (No. 2016YFF0204402), the Program for Changjiang Scholars and Innovative Research Team in the University, the Fundamental Research Funds for the Central Universities, and the Long Term Subsidy Mechanism from the Ministry of Finance and the Ministry of Education of PRC.

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Correspondence to Yun Kuang or Xiaoming Sun.

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Li, P., Xie, Q., Zheng, L. et al. Topotactic reduction of layered double hydroxides for atomically thick two-dimensional non-noble-metal alloy. Nano Res. 10, 2988–2997 (2017). https://doi.org/10.1007/s12274-017-1509-3

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