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Tetrafunctional Cu2S thin layers on Cu2O nanowires for efficient photoelectrochemical water splitting

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Abstract

Photoelectrochemical (PEC) water splitting by photocathodes based on p-type semiconductors is a promising process for direct and efficient hydrogen generation. The identification of ideal photocathode materials with a high photoconversion efficiency and long-term stability is still a significant challenge. Herein, we propose a new photocathode consisting of Cu2S-coated Cu2O nanowires (NWs) supported on a three-dimensional porous copper foam. The Cu2S thin layer is generated in situ on the surface of the Cu2O NWs and has four functions: (1) Sensitizer, with a band gap of 1.2 eV, for extending the range of optical absorption into the near-infrared region; (2) electron trapper, with appropriate energy level alignment to Cu2O, for achieving effective electron transfer and trapping; (3) electrocatalyst, with excellent electrocatalytic activity for the hydrogen evolution reaction; and (4) protector, preventing direct contact between Cu2O and the electrolyte in order to significantly increase the stability. A photocathode based on the tetrafunctional Cu2S-coated Cu2O NWs exhibits significantly enhanced PEC performance and remarkably improved long-term stability under illumination. The present strategy, based on the in situ generation of multifunctional layers, opens a new avenue for the rational design of photocathodes for PEC water reduction.

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References

  1. Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q. X.; Santori, E. A.; Lewis, N. S. Solar water splitting cells. Chem. Rev. 2010, 110, 6446–6473.

    Article  Google Scholar 

  2. Zhang, Z. H.; Dua, R.; Zhang, L. B.; Zhu, H. B.; Zhang, H. N.; Wang, P. Carbon-layer-protected cuprous oxide nanowire arrays for efficient water reduction. ACS Nano 2013, 7, 1709–1717.

    Article  Google Scholar 

  3. Li, Z. Z.; Xin, Y. M.; Zhang, Z. H. New photocathodic analysis platform with quasi-core/shell-structured TiO2@ Cu2O for sensitive detection of H2O2 release from living cells. Anal. Chem. 2015, 87, 10491–10497.

    Article  Google Scholar 

  4. Zhang, R.; Yang, L.; Huang, X. N.; Chen, T.; Qu, F. L.; Liu, Z. A.; Du, G.; Asiri, A. M.; Sun, X. P. Se doping: An effective strategy toward Fe2O3 nanorod arrays for greatly enhanced solar water oxidation. J. Mater. Chem. A 2017, 5, 12086–12090.

    Article  Google Scholar 

  5. Paracchino, A.; Laporte, V.; Sivula, K.; Grätzel, M.; Thimsen, E. Highly active oxide photocathode for photoelectrochemical water reduction. Nat. Mater. 2011, 10, 456–461.

    Article  Google Scholar 

  6. Paracchino, A.; Mathews, N.; Hisatomi, T.; Stefik, M.; Tilley, S. D.; Grätzel, M. Ultrathin films on copper(I) oxide water splitting photocathodes: A study on performance and stability. Energy Environ. Sci. 2012, 5, 8673–8681.

    Article  Google Scholar 

  7. Morales-Guio, C. G.; Tilley, S. D.; Vrubel, H.; Grätzel, M.; Hu, X. L. Hydrogen evolution from a copper(I) oxide photocathode coated with an amorphous molybdenum sulphide catalyst. Nat. Commun. 2014, 5, 3059.

    Article  Google Scholar 

  8. Schreier, M.; Luo, J. S.; Gao, P.; Moehl, T.; Mayer, M. T.; Grätzel, M. Covalent immobilization of a molecular catalyst on Cu2O photocathodes for CO2 reduction. J. Am. Chem. Soc. 2016, 138, 1938–1946.

    Article  Google Scholar 

  9. Zhang, L. Z.; Jing, D. W.; Guo, L. J.; Yao, X. D. In situ photochemical synthesis of Zn-doped Cu2O hollow microcubes for high efficient photocatalytic H2 production. ACS Sustainable Chem. Eng. 2014, 2, 1446–1452.

    Article  Google Scholar 

  10. Tian, J. Q.; Li, H. Y.; Xing, Z. C.; Wang, L.; Luo, Y. L.; Asiri, A. M.; Al-Youbi, A. O.; Sun, X. P. One-pot green hydrothermal synthesis of CuO-Cu2O-Cu nanorod-decorated reduced graphene oxide composites and their application in photocurrent generation. Catal. Sci. Technol., 2012, 2, 2227–2230.

    Article  Google Scholar 

  11. Ho-Kimura, S.; Moniz, S. J. A.; Tang, J.; Parkin, I. P. A method for synthesis of renewable Cu2O junction composite electrodes and their photoelectrochemical properties. ACS Sustainable Chem. Eng. 2015, 3, 710–717.

    Article  Google Scholar 

  12. Shi, J.; Li, J.; Huang, X. J.; Tan, Y. W. Synthesis and enhanced photocatalytic activity of regularly shaped Cu2O nanowire polyhedra. Nano Res. 2011, 4, 448–459.

    Article  Google Scholar 

  13. Zhang, Z. H.; Wang, P. Highly stable copper oxide composite as an effective photocathode for water splitting via a facile electrochemical synthesis strategy. J. Mater. Chem. 2012, 22, 2456–2464.

    Article  Google Scholar 

  14. Zhuang, T. T.; Liu, Y.; Li, Y.; Zhao, Y.; Wu, L.; Jiang, J.; Yu, S. H. Integration of semiconducting sulfides for fullspectrum solar energy absorption and efficient charge separation. Angew. Chem., Int. Ed. 2016, 55, 6396–6400.

    Article  Google Scholar 

  15. Minguez-Bacho, I.; Courté, M.; Fan, H. J.; Fichou, D. Conformal Cu2S-Coated Cu2O nanostructures grown by ion exchange reaction and their photoelectrochemical properties. Nanotechnology 2015, 26, 185401.

    Article  Google Scholar 

  16. Gao, M. R.; Xu, Y. F.; Jiang, J.; Yu, S. H. Nanostructured metal chalcogenides: Synthesis, modification, and applications in energy conversion and storage devices. Chem. Soc. Rev. 2013, 42, 2986–3017.

    Article  Google Scholar 

  17. Kim, Y.; Park, K. Y.; Jang, D. M.; Song, Y. M.; Kim, H. S.; Cho, Y. J.; Myung, Y.; Park, J. Synthesis of Au-Cu2S coreshell nanocrystals and their photocatalytic and electrocatalytic activity. J. Phys. Chem. C 2010, 114, 22141–22146.

    Article  Google Scholar 

  18. Xie, L.; Asiri, A. M.; Sun, X. P. Monolithically integrated copper phosphide nanowire: An efficient electrocatalyst for sensitive and selective nonenzymatic glucose detection. Sens. Actuators. B: Chem. 2017, 244, 11–16.

    Article  Google Scholar 

  19. Liu, M.; Zhang, R.; Zhang, L. X.; Liu, D. N.; Hao, S.; Du, G.; Asiri, M. A.; Kong, R.; Sun, X. P. Energy-efficient electrolytic hydrogen generation using a Cu3P nanoarray as a bifunctional catalyst for hydrazine oxidation and water reduction. Inorg. Chem. Front. 2017, 4, 420–423.

    Article  Google Scholar 

  20. Alam, R.; Labine, M.; Karwacki, J. C.; Kamat, P. V. Modulation of Cu2–xS nanocrystal plasmon resonance through reversible photoinduced electron transfer. ACS Nano 2016, 10, 2880–2886.

    Article  Google Scholar 

  21. Georgieva, Z. N.; Tomat, M. A.; Kim, C.; Plass, K. E. Stabilization of Plasmon resonance in Cu2−xS semiconductor nanoparticles. Chem. Commun. 2016, 52, 9082–9085.

    Article  Google Scholar 

  22. Wang, S. H.; Riedinger, A.; Li, H. B.; Fu, C. H.; Liu, H. Y.; Li, L. L.; Liu, T. L.; Tan, L. F.; Barthel, M. J.; Pugliese, G. et al. Plasmonic copper sulfide nanocrystals exhibiting nearinfrared photothermal and photodynamic therapeutic effects. ACS Nano 2015, 9, 1788–1800.

    Article  Google Scholar 

  23. Li, M.; Zhao, R. J.; Su, Y. J.; Hu, J.; Yang, Z.; Zhang, Y. F. Synthesis of CuInS2 nanowire arrays via solution transformation of Cu2S self-template for enhanced photoelectrochemical performance. Appl. Catal. B: Environ. 2017, 203, 715–724.

    Article  Google Scholar 

  24. Tian, J. Q.; Liu, Q.; Cheng, N. Y.; Asiri, A. M.; Sun, X. P. Self-supported Cu3P nanowire arrays as an integrated high-performance three-dimensional cathode for generating hydrogen from water. Angew. Chem., Int. Ed. 2014, 53, 9577–9581.

    Article  Google Scholar 

  25. Xie, L. S.; Tang, C.; Wang, K. Y.; Du, R.; Asiri, A. M.; Sun, X. P. Cu(OH)2@CoCO3(OH)2·nH2O core-shell heterostructure nanowire array: an efficient 3D anodic catalyst for oxygen evolution and methanol electrooxidation. Small 2017, 13, 1602755.

    Article  Google Scholar 

  26. Zhao, Y.; Wang, C. Y.; Wallace, G. G. Tin nanoparticles decorated copper oxide nanowires for selective electrochemical reduction of aqueous CO2 to CO.J. Mater. Chem. A 2016, 4, 10710–10718.

    Article  Google Scholar 

  27. Wu, G. J.; Guan, N. J.; Li, L. D. Low temperature CO oxidation on Cu-Cu2O/TiO2 catalyst prepared by photodeposition. Catal. Sci. Technol. 2011, 1, 601–608.

    Article  Google Scholar 

  28. Meng, C. H.; Liu, Z. Y.; Zhang, T. R.; Zhai, J. Layered MoS2 nanoparticles on TiO2 nanotubes by a photocatalytic strategy for use as high-performance electrocatalysts in hydrogen evolution reactions. Green Chem. 2015, 17, 2764–2768.

    Article  Google Scholar 

  29. Nakamura, S.; Yamamoto, A. Electrodeposition of pyrite(FeS2) thin films for photovoltaic cells. Sol. Energy Mater. Sol. Cells 2001, 65, 79–85.

    Article  Google Scholar 

  30. Du, J. K.; Bao, J. G.; Fu, X. Y.; Lu, C. H.; Kim, S. H. Mesoporous sulfur-modified iron oxide as an effective fenton-like catalyst for degradation of bisphenol A. Appl. Catal. B 2016, 184, 132–141.

    Article  Google Scholar 

  31. Amorousse, R.; Fujisato, K.; Habu, H.; Bachar, A.; Follet-Houttemane, C.; Hori, K. Catalytic decomposition of ammonium dinitramide (ADN) as high energetic material over CuO-based catalysts. Catal. Sci. Technol. 2013, 3, 2614–2619.

    Article  Google Scholar 

  32. An, L.; Huang, L.; Zhou, P. P.; Yin, J.; Liu, H. Y.; Xi, P. X. A self-standing high-performance hydrogen evolution electrode with nanostructured NiCo2O4/CuS heterostructures. Adv. Funct. Mater. 2015, 25, 6814–6822.

    Google Scholar 

  33. Zhang, Z. H.; Yang, X. L.; Hedhili, M. N.; Ahmed, E.; Shi, L.; Wang, P. Microwave-assisted self-doping of TiO2 photonic crystals for efficient photoelectrochemical water splitting. ACS Appl. Mater. Interface 2014, 6, 691–696.

    Article  Google Scholar 

  34. Wang, P.; Ng, Y. H.; Amal, R. Embedment of anodized p-type Cu2O thin films with CuO nanowires for improvement in photoelectrochemical stability. Nanoscale 2013, 5, 2952–2958.

    Article  Google Scholar 

  35. Huang, Q.; Kang, F.; Liu, H.; Li, Q.; Xiao, X. D. Highly aligned Cu2O/CuO/TiO2 core/shell nanowire arrays as photocathodes for water photoelectrolysis. J. Mater. Chem. A, 2013, 1, 2418–2425.

    Article  Google Scholar 

  36. Kargar, A.; Partokia, S. S.; Niu, M. T.; Allameh, P.; Yang, M. C.; May, S.; Cheung, J. S.; Sun, K.; Xu, K.; Wang, D. Solution-grown 3D Cu2O networks for efficient solar water splitting. Nanotechnology 2014, 25, 205401.

    Article  Google Scholar 

  37. Dubale, A. A.; Pan, C. J.; Tamirat, A. G.; Chen, H. M.; Su, W. N.; Chen, C. H.; Rick, J.; Ayele, D. W.; Aragaw, B. A.; Lee, J. F. et al. Heterostructured Cu2O/CuO decorated with nickel as a highly efficient photocathode for photoelectrochemical water reduction. J. Mater. Chem. A 2015, 3, 12482–12499.

    Article  Google Scholar 

  38. Dubale, A. A.; Su, W. N.; Tamirat, A. G.; Pan, C. J.; Aragaw, B. A.; Chen, H. M.; Chen, C. H.; Hwang, B. J. The Nano Res. 11 synergetic effect of graphene on Cu2O nanowire arrays as a highly efficient hydrogen evolution photocathode in water splitting. J. Mater. Chem. A 2014, 2, 18383–18397.

    Article  Google Scholar 

  39. Dubale, A. A.; Tamirat, A. G.; Chen, H. M.; Berhe, T. A.; Pan, C. J.; Su, W. N.; Hwang, B. J. A highly stable CuS and CuS–Pt modified Cu2O/CuO heterostructure as an efficient photocathode for the hydrogen evolution reaction. J. Mater. Chem. A 2016, 4, 2205–2216.

    Article  Google Scholar 

  40. Jin, Z. X.; Hu, Z. F.; Yu, J. C.; Wang, J. F. Room temperature synthesis of a highly active Cu/Cu2O photocathode for photoelectrochemical water splitting. J. Mater. Chem. A, 2016, 4, 13736–13741.

    Article  Google Scholar 

  41. Ye, M. D.; Gong, J. J.; Lai, Y. K.; Lin, C. J.; Lin, Z. Q. High-efficiency photoelectrocatalytic hydrogen generation enabled by palladium quantum dots-sensitized TiO2 nanotube arrays. J. Am. Chem. Soc. 2012, 134, 15720–15723.

    Article  Google Scholar 

  42. Savchenko, N. D.; Shchurova, T. N.; Popovych, K. O.; Rubish, I. D.; Leising, G. Simulation of electronic states in the band gap of ZnS:Cu, Cl crystallophosphors. Semicond. Phys., Quantum Electron. Optoelectron. 2004, 7, 133–137.

    Google Scholar 

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Acknowledgements

Z.H.Z. thanks to the support from “Yingcai” program of ECNU and the National Natural Science Foundation of China (NSFC) (No. 21405046).

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  1. School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, China

    Zhenzhen Li & Zhonghai Zhang

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  1. Zhenzhen Li
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Correspondence to Zhonghai Zhang.

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Li, Z., Zhang, Z. Tetrafunctional Cu2S thin layers on Cu2O nanowires for efficient photoelectrochemical water splitting. Nano Res. 11, 1530–1540 (2018). https://doi.org/10.1007/s12274-017-1769-y

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