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Enhanced electrocatalytic activity of Co@N-doped carbon nanotubes by ultrasmall defect-rich TiO2 nanoparticles for hydrogen evolution reaction

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Abstract

Despite being technically possible, splitting water to generate hydrogen is practically unfeasible, mainly because of the lack of sustainable and efficient earth-abundant catalysts for the hydrogen-evolution reaction (HER). Herein, we report a durable and highly active electrochemical HER catalyst based on defect-rich TiO2 nanoparticles loaded on Co nanoparticles@N-doped carbon nanotubes (D-TiO2/Co@NCT) synthesized by electrostatic spinning and a subsequent calcining process. The ultrasmall TiO2 nanoparticles are 1.5–2 nm in size and have a defect-rich structure of oxygen vacancies. D-TiO2/Co@NCT exhibits excellent HER catalytic activity in an acidic electrolyte (0.5 M H2SO4), with a low onset potential of −57.5 mV (1 mA·cm–2), a small Tafel slope of 73.5 mV·dec–1, and extraordinary long-term durability. X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and theoretical calculations confirm that the Ti3+ defect-rich structure can effectively regulate the catalytic activity for electrochemical water splitting.

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References

  1. Sathre, R.; Scown, C. D.; Morrow, W. R., III; Stevens, J. C.; Sharp, I. D.; Ager, J. W., III; Walczak, K.; Houle, F. A.; Greenblatt, J. B. Life-cycle net energy assessment of large-scale hydrogen production via photoelectrochemical water splitting. Energy Environ. Sci. 2014, 7, 3264–3278.

    Article  Google Scholar 

  2. Ye, G. L.; Gong, Y. J.; Lin, J. H.; Li, B.; He, Y. M.; Pantelides, S. T.; Zhou, W.; Vajtai, R.; Ajayan, P. M. Defects engineered monolayer MoS2 for improved hydrogen evolution reaction. Nano Lett. 2016, 16, 1097–1103.

    Article  Google Scholar 

  3. Sun, C. C.; Dong, Q. C.; Yang, J.; Dai, Z. Y.; Lin, J. J.; Chen, P.; Huang, W.; Dong, X. C. Metal–organic framework derived CoSe2 nanoparticles anchored on carbon fibers as bifunctional electrocatalysts for efficient overall water splitting. Nano Res. 2016, 9, 2234–2243.

    Article  Google Scholar 

  4. Bai, S.; Wang, C. M.; Deng, M. S.; Gong, M.; Bai, Y.; Jiang, J.; Xiong, Y. J. Surface polarization matters: Enhancing the hydrogen-evolution reaction by shrinking Pt shells in Pt-Pd-graphene stack structures. Angew. Chem., Int. Ed. 2014, 53, 12120–12124.

    Article  Google Scholar 

  5. Wang, C. H.; Hu, F.; Yang, H. C.; Zhang, Y. J.; Lu, H.; Wang, Q. B. 1.82 wt.% Pt/N, P co-doped carbon overwhelms 20 wt.% Pt/C as a high-efficiency electrocatalyst for hydrogen evolution reaction. Nano Res. 2017, 10, 238–246.

    Article  Google Scholar 

  6. Konkena, B.; Junge Puring, K.; Sinev, I.; Piontek, S.; Khavryuchenko, O.; Durholt, J. P.; Schmid, R.; Tüysüz, H.; Muhler, M.; Schuhmann, W. et al. Pentlandite rocks as sustainable and stable efficient electrocatalysts for hydrogen generation. Nat. Commun. 2016, 7, 12269.

    Article  Google Scholar 

  7. Wu, H. B.; Xia, B. Y.; Yu, L.; Yu, X. Y.; Lou, X. W. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production. Nat. Commun. 2015, 6, 6512.

    Article  Google Scholar 

  8. Wang, D. Y.; Gong, M.; Chou, H. L.; Pan, C. J.; Chen, H. A.; Wu, Y. P.; Lin, M. C.; Guan, M.; Yang, J.; Chen, C. W. et al. Highly active and stable hybrid catalyst of cobalt-doped FeS2 nanosheets-carbon nanotubes for hydrogen evolution reaction. J. Am. Chem. Soc. 2015, 137, 1587–1592.

    Article  Google Scholar 

  9. Zhang, X. W.; Meng, F.; Mao, S.; Ding, Q.; Shearer, M. J.; Faber, M. S.; Chen, J. H.; Hamers, R. J.; Jin, S. Amorphous MoSxCly electrocatalyst supported by vertical graphene for efficient electrochemical and photoelectrochemical hydrogen generation. Energy Environ. Sci. 2015, 8, 862–868.

    Article  Google Scholar 

  10. Yang, L. J.; Zhou, W. J.; Lu, J.; Hou, D. M.; Ke, Y. T.; Li, G. Q.; Tang, Z. H.; Kang, X. W.; Chen, S. W. Hierarchical spheres constructed by defect-rich MoS2/carbon nanosheets for efficient electrocatalytic hydrogen evolution. Nano Energy 2016, 22, 490–498.

    Article  Google Scholar 

  11. Ye, W.; Ren, C. H.; Liu, D. B.; Wang, C. M.; Zhang, N.; Yan, W. S.; Song, L.; Xiong, Y. J. Maneuvering charge polarization and transport in 2H-MoS2 for enhanced electrocatalytic hydrogen evolution reaction. Nano Res. 2016, 9, 2662–2671.

    Article  Google Scholar 

  12. Wang, S. Y.; Zhang, L.; Li, X.; Li, C. L.; Zhang, R. J.; Zhang, Y. J.; Zhu, H. W. Sponge-like nickel phosphide–carbon nanotube hybrid electrodes for efficient hydrogen evolution over a wide pH range. Nano Res. 2017, 10, 415–425.

    Article  Google Scholar 

  13. Tian, J. Q.; Liu, Q.; Asiri, A. M.; Sun, X. P. Self-supported nanoporous cobalt phosphide nanowire arrays: An efficient 3D hydrogen-evolving cathode over the wide range of pH 0–14. J. Am. Chem. Soc. 2014, 136, 7587–7590.

    Article  Google Scholar 

  14. Li, Y. J.; Zhang, H. C.; Jiang, M.; Kuang, Y.; Sun, X. M.; Duan, X. Ternary NiCoP nanosheet arrays: An excellent bifunctional catalyst for alkaline overall water splitting. Nano Res. 2016, 9, 2251–2259.

    Article  Google Scholar 

  15. Zou, X. X.; Huang, X. X.; Goswami, A.; Silva, R.; Sathe, B. R.; Mikmeková, E.; Asefa, T. Cobalt-embedded nitrogenrich carbon nanotubes efficiently catalyze hydrogen evolution reaction at all pH values. Angew. Chem., Int. Ed. 2014, 53, 4372–4376.

    Article  Google Scholar 

  16. Zhou, W. J.; Zhou, J.; Zhou, Y. C.; Lu, J.; Zhou, K.; Yang, L. J.; Tang, Z. H.; Li, L. G.; Chen, S. W. N-doped carbonwrapped cobalt nanoparticles on N-doped graphene nanosheets for high-efficiency hydrogen production. Chem. Mater. 2015, 27, 2026–2032.

    Article  Google Scholar 

  17. Tahir, M.; Mahmood, N.; Zhang, X. X.; Mahmood, T.; Butt, F. K.; Aslam, I.; Tanveer, M.; Idrees, F.; Khalid, S.; Shakir, I. et al. Bifunctional catalysts of Co3O4@GCN tubular nanostructured (TNS) hybrids for oxygen and hydrogen evolution reactions. Nano Res. 2015, 8, 3725–3736.

    Article  Google Scholar 

  18. Deng, J.; Ren, P. J.; Deng, D. H.; Bao, X. H. Enhanced electron penetration through an ultrathin graphene layer for highly efficient catalysis of the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2015, 54, 2100–2104.

    Article  Google Scholar 

  19. Zhou, W. J.; Yin, Z. Y.; Du, Y. P.; Huang, X.; Zeng, Z. Y.; Fan, Z. X.; Liu, H.; Wang, J. Y.; Zhang, H. Synthesis of few-layer MoS2 nanosheet-coated TiO2 nanobelt heterostructures for enhanced photocatalytic activities. Small 2013, 9, 140–147.

    Article  Google Scholar 

  20. Liu, B.; Liu, L.-M.; Lang, X.-F.; Wang, H.-Y.; Lou, X. W.; Aydil, E. S. Doping high-surface-area mesoporous TiO2 microspheres with carbonate for visible light hydrogen production. Energy Environ. Sci. 2014, 7, 2592–2597.

    Article  Google Scholar 

  21. Li, L. D.; Yan, J. Q.; Wang, T.; Zhao, Z. J.; Zhang, J.; Gong, J. L.; Guan, N. J. Sub-10 nm rutile titanium dioxide nanoparticles for efficient visible-light-driven photocatalytic hydrogen production. Nat. Commun. 2015, 6, 5881.

    Article  Google Scholar 

  22. Liu, P. X.; Zhao, Y.; Qin, R. X.; Mo, S. G.; Chen, G. X.; Gu, L.; Chevrier, D. M.; Zhang, P.; Guo, Q.; Zang, D. D. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 2016, 352, 797–800.

    Article  Google Scholar 

  23. Kuld, S.; Thorhauge, M.; Falsig, H.; Elkjær, C. F.; Helveg, S.; Chorkendorff, I.; Sehested, J. Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis. Science 2016, 352, 969–974.

    Article  Google Scholar 

  24. Bruix, A.; Rodriguez, J. A.; Ramírez, P. J.; Senanayake, S. D.; Evans, J.; Park, J. B.; Stacchiola, D.; Liu, P.; Hrbek, J.; Illas, F. A new type of strong metal-support interaction and the production of H2 through the transformation of water on Pt/CeO2(111) and Pt/CeOx/TiO2(110) catalysts. J. Am. Chem. Soc. 2012, 134, 8968–8974.

    Article  Google Scholar 

  25. Xu, Y. F.; Zhang, C.; Zhang, L. X.; Zhang, X. H.; Yao, H. L.; Shi, J. L. Pd-catalyzed instant hydrogenation of TiO2 with enhanced photocatalytic performance. Energy Environ. Sci. 2016, 9, 2410–2417.

    Article  Google Scholar 

  26. Chen, X. B.; Liu, L.; Yu, P. Y.; Mao, S. S. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 2011, 331, 746–750.

    Article  Google Scholar 

  27. Pei, D.-N.; Gong, L.; Zhang, A.-Y.; Zhang, X.; Chen, J.-J.; Mu, Y.; Yu, H.-Q. Defective titanium dioxide single crystals exposed by high-energy {001} facets for efficient oxygen reduction. Nat. Commun. 2015, 6, 8696.

    Article  Google Scholar 

  28. An, L.; Yan, H. J.; Chen, X.; Li, B.; Xia, Z. H.; Xia, D. G. Catalytic performance and mechanism of N-CoTi@CoTiO3 catalysts for oxygen reduction reaction. Nano Energy 2016, 20, 134–143.

    Article  Google Scholar 

  29. Swaminathan, J.; Subbiah, R.; Singaram, V. Defect-rich metallic titania (TiO1.23)—An efficient hydrogen evolution catalyst for electrochemical water splitting. ACS Catal. 2016, 6, 2222–2229.

    Article  Google Scholar 

  30. Yin, Y.; Han, J. C.; Zhang, Y. M.; Zhang, X. H.; Xu, P.; Yuan, Q.; Samad, L.; Wang, X. J.; Wang, Y.; Zhang, Z. H. et al. Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets. J. Am. Chem. Soc. 2016, 138, 7965–7972.

    Article  Google Scholar 

  31. Zhou, W. J.; Lu, J.; Zhou, K.; Yang, L. J.; Ke, Y. T.; Tang, Z. H.; Chen, S. W. CoSe2 nanoparticles embedded defective carbon nanotubes derived from MOFs as efficient electrocatalyst for hydrogen evolution reaction. Nano Energy 2016, 28, 143–150.

    Article  Google Scholar 

  32. Xie, J. F.; Zhang, J. J.; Li, S.; Grote, F.; Zhang, X. D.; Zhang, H.; Wang, R. X.; Lei, Y.; Pan, B. C.; Xie, Y. Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. J. Am. Chem. Soc. 2013, 135, 17881–17888.

    Article  Google Scholar 

  33. Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 1996, 6, 15–50.

    Article  Google Scholar 

  34. Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.

    Article  Google Scholar 

  35. Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.

    Article  Google Scholar 

  36. Nørskov, J. K.; Bligaard, T.; Logadottir, A.; Kitchin, J. R.; Chen, J. G.; Pandelov, S.; Stimming, U. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 2005, 152, J23–J26.

    Article  Google Scholar 

  37. Deng, J.; Ren, P. J.; Deng, D. H.; Yu, L.; Yang, F.; Bao, X. H. Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction. Energy Environ. Sci. 2014, 7, 1919–1923.

    Article  Google Scholar 

  38. Xia, B. Y.; Yan, Y.; Li, N.; Wu, H. B.; Lou, X. W.; Wang, X. A metal–organic framework-derived bifunctional oxygen electrocatalyst. Nat. Energy 2016, 1, 15006.

    Article  Google Scholar 

  39. Wu, Q. P.; Huang, F.; Zhao, M. S.; Xu, J.; Zhou, J. C.; Wang, Y. D. Ultra-small yellow defective TiO2 nanoparticles for co-catalyst free photocatalytic hydrogen production. Nano Energy 2016, 24, 63–71.

    Article  Google Scholar 

  40. Zuo, F.; Wang, L.; Wu, T.; Zhang, Z. Y.; Borchardt, D.; Feng, P. Y. Self-doped Ti3+ enhanced photocatalyst for hydrogen production under visible light. J. Am. Chem. Soc. 2010, 132, 11856–11857.

    Article  Google Scholar 

  41. Zuo, F.; Bozhilov, K.; Dillon, R. J.; Wang, L.; Smith, P.; Zhao, X.; Bardeen, C.; Feng, P. Y. Active facets on titanium(III)- doped TiO2: An effective strategy to improve the visiblelight photocatalytic activity. Angew. Chem., Int. Ed. 2012, 51, 6223–6226.

    Article  Google Scholar 

  42. Zhou, W. J.; Xiong, T. L.; Shi, C. H.; Zhou, J.; Zhou, K.; Zhu, N. W.; Li, L. G.; Tang, Z. H.; Chen, S. W. Bioreduction of precious metals by microorganism: Efficient gold@N-doped carbon electrocatalysts for the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2016, 55, 8416–8420.

    Article  Google Scholar 

  43. Wang, Z.-L.; Hao, X.-F.; Jiang, Z.; Sun, X.-P.; Xu, D.; Wang, J.; Zhong, H.-X.; Meng, F.-L.; Zhang, X.-B. C and N hybrid coordination derived Co–C–N complex as a highly efficient electrocatalyst for hydrogen evolution reaction. J. Am. Chem. Soc. 2015, 137, 15070–15073.

    Article  Google Scholar 

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Acknowledgements

We thank the Fundamental Research Funds for the Central Universities (No. D2153880), Project of Public Interest Research and Capacity Building of Guangdong Province (No. 2014A010106005) and the National Natural Science Foundation of China (No. 51502096).

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Authors and Affiliations

  1. School of Environment and Energy, Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou, 510006, China

    Jiayuan Yu, Weijia Zhou, Tanli Xiong, Aili Wang & Shaowei Chen

  2. School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou Higher Education Mega Center, Guangzhou, 510006, China

    Jiayuan Yu, Aili Wang & Benli Chu

  3. Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, CA, 95064, USA

    Shaowei Chen

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  1. Jiayuan Yu
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Correspondence to Weijia Zhou.

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Enhanced electrocatalytic activity of Co@N-doped carbon nanotubes by ultrasmall defect-rich TiO2 nanoparticles for hydrogen evolution reaction

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Yu, J., Zhou, W., Xiong, T. et al. Enhanced electrocatalytic activity of Co@N-doped carbon nanotubes by ultrasmall defect-rich TiO2 nanoparticles for hydrogen evolution reaction. Nano Res. 10, 2599–2609 (2017). https://doi.org/10.1007/s12274-017-1462-1

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