logo

Cobalt-vanadium bimetal-based nanoplates for efficient overall water splitting

More info
  • ReceivedAug 15, 2017
  • AcceptedSep 7, 2017
  • PublishedNov 7, 2017

Abstract

The development of effective and low-cost catalysts for overall water splitting is essential for clean production of hydrogen from water. In this paper, we report the synthesis of cobalt-vanadium (Co-V) bimetal-based catalysts for the effective water splitting. The Co2V2O7·xH2O nanoplates containing both Co and V elements were selected as the precursors. After the calcination under NH3 atmosphere, the Co2VO4 and Co/VN could be obtained just by tuning the calcination temperature. Electrochemical tests indicated that the Co-V bimetal-based materials could be used as active hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalyst by regulating their structure. The Co/VN showed good performance for HER with the onset potential of 68 mV and can achieve a current density of 10 mA cm−2 at an overpotential of 92 mV. Meanwhile, the Co2VO4 exhibited the obvious OER performance with overpotential of 300 mV to achieve a current density of 10 mA cm−2. When the Co2VO4 and Co/VN were used as the anode and cathode in a two-electrode system, respectively, the cell needed a voltage of 1.65 V to achieve 10 mA cm−2 together with good stability. This work would be indicative to constructing Co-V bimetal-based catalysts for the catalytic application.


Funded by

the Key Program Projects of the National Natural Science Foundation of China(21631004)

the National Natural Science Foundation of China(21601055,21571054,21401048)

the Natural Science Foundation of Heilongjiang Province(B2017008)

and Heilongjiang University Excellent Youth Foundation.


Acknowledgment

This work was supported by the Key Program Projects of the National Natural Science Foundation of China (21631004), the National Natural Science Foundation of China (21601055, 21571054 and 21401048), the Natural Science Foundation of Heilongjiang Province (B2017008), and Heilongjiang University Excellent Youth Foundation.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Fu H and Tian C designed and engineered this work; Xiao Y carried out the experiments. Tian C, Xiao Y and Fu H wrote this paper. All authors contributed to the general discussion.


Author information

Yinglu Xiao received her BSc degree from Harbin University in 2015. She is currently a master candidate at Heilongjiang University under the guidance of Profs. Chungui Tian and Honggang Fu. Her research is focused on the design and synthesis of vanadium-based catalysts for HER and OER.


Chungui Tian received his BSc degree in 1997 from Inner Mongolia University for Nationalities. In 2004 and 2007, he received his MSc and PhD degrees both from Northeast Normal University under the guidance of Prof. Enbo Wang. Then, he joined Heilongjiang University as a lecturer. He became an assistant professor and a full professor in 2009 and 2014, respectively. His research interests focus on designed synthanis and electrocatalytic application of W (Mo,V)-based materials.


Honggang Fu received his BSc degree in 1984 and MSc degree in 1987 from Jilin University, China. He joined Heilongjiang University as an assistant professor in 1988. In 1999, he received his PhD degree from Harbin Institute of Technology, China. He became a full professor in 2000. Currently, he is Cheung Kong Scholar Professor. His interests focus on the oxide-based nanomaterials for solar energy conversion and photocatalysis, the carbon-based nanomaterials for energy conversion and storage, and electrocatalysis.


Supplement

Supplementary information

Experimental details and supporting data are available in the online version of the paper.


References

[1] Mendoza-Sánchez B, Gogotsi Y. Synthesis of two-dimensional materials for capacitive energy storage. Adv Mater, 2016, 28: 6104-6135 CrossRef PubMed Google Scholar

[2] Morales-Guio CG, Stern LA, Hu X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem Soc Rev, 2014, 43: 6555-6569 CrossRef PubMed Google Scholar

[3] Lu S, Zhuang Z. Electrocatalysts for hydrogen oxidation and evolution reactions. Sci China Mater, 2016, 59: 217-238 CrossRef Google Scholar

[4] Luo J, Im JH, Mayer MT, et al. Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts. Science, 2014, 345: 1593-1596 CrossRef PubMed ADS Google Scholar

[5] Zhang Y, Shao Q, Pi Y, et al. A cost-efficient bifunctional ultrathin nanosheets array for electrochemical overall water splitting. Small, 2017, 13: 1700355 CrossRef PubMed Google Scholar

[6] Tahir M, Pan L, Idrees F, et al. Electrocatalytic oxygen evolution reaction for energy conversion and storage: a comprehensive review. Nano Energ, 2017, 37: 136-157 CrossRef Google Scholar

[7] Jiao Y, Zheng Y, Jaroniec M, et al. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem Soc Rev, 2015, 44: 2060-2086 CrossRef PubMed Google Scholar

[8] Ou G, Fan P, Zhang H, et al. Large-scale hierarchical oxide nanostructures for high-performance electrocatalytic water splitting. Nano Energ, 2017, 35: 207-214 CrossRef Google Scholar

[9] Kuai L, Geng J, Chen C, et al. A reliable aerosol-spray-assisted approach to produce and optimize amorphous metal oxide catalysts for electrochemical water splitting. Angew Chem Int Ed, 2014, 53: 7547-7551 CrossRef PubMed Google Scholar

[10] Li X, Zhang L, Huang M, et al. Cobalt and nickel selenide nanowalls anchored on graphene as bifunctional electrocatalysts for overall water splitting. J Mater Chem A, 2016, 4: 14789-14795 CrossRef Google Scholar

[11] Zhang J, Zhao Z, Xia Z, et al. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat Nanotech, 2015, 10: 444-452 CrossRef PubMed ADS Google Scholar

[12] Tang C, Gan L, Zhang R, et al. Ternary FexCo1–xP nanowire array as a robust hydrogen evolution reaction electrocatalyst with Pt-like activity: experimental and theoretical insight. Nano Lett, 2016, 16: 6617-6621 CrossRef PubMed ADS Google Scholar

[13] Zhang YX, Chang C, Teng F, et al. Defect-engineered ultrathin δ-MnO2 nanosheet arrays as bifunctional electrodes for efficient overall water splitting. Adv Energy Mater, 2017, 7: 1700005 CrossRef Google Scholar

[14] Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chem Soc Rev, 2015, 44: 5148-5180 CrossRef PubMed Google Scholar

[15] Yan Y, Xia BY, Zhao B, et al. A review on noble-metal-free bifunctional heterogeneous catalysts for overall electrochemical water splitting. J Mater Chem A, 2016, 4: 17587-17603 CrossRef Google Scholar

[16] Qu Y, Shao M, Shao Y, et al. Ultra-high electrocatalytic activity of VS2 nanoflowers for efficient hydrogen evolution reaction. J Mater Chem A, 2017, 5: 15080-15086 CrossRef Google Scholar

[17] Wu A, Tian C, Yan H, et al. Hierarchical MoS2@MoP core-shell heterojunction electrocatalysts for efficient hydrogen evolution reaction over a broad pH range. Nanoscale, 2016, 8: 11052-11059 CrossRef PubMed ADS Google Scholar

[18] Liu T, Liu D, Qu F, et al. Enhanced electrocatalysis for energy-efficient hydrogen production over cop catalyst with nonelectroactive Zn as a promoter. Adv Energ Mater, 2017, 7: 1700020 CrossRef Google Scholar

[19] Zeng M, Wang H, Zhao C, et al. 3D graphene foam-supported cobalt phosphate and borate electrocatalysts for high-efficiency water oxidation. Sci Bull, 2015, 60: 1426-1433 CrossRef Google Scholar

[20] Tang C, Zhang R, Lu W, et al. Fe-doped CoP nanoarray: a monolithic multifunctional catalyst for highly efficient hydrogen generation. Adv Mater, 2017, 29: 1602441 CrossRef PubMed Google Scholar

[21] Ma M, Zhu G, Xie F, et al. Homologous catalysts based on fe-doped cop nanoarrays for high-performance full water splitting under benign conditions. ChemSusChem, 2017, 10: 3188-3192 CrossRef PubMed Google Scholar

[22] Zhang X, Gu W, Wang E. Wire-on-flake heterostructured ternary Co0.5Ni0.5P/CC: an efficient hydrogen evolution electrocatalyst. J Mater Chem A, 2017, 5: 982-987 CrossRef Google Scholar

[23] Tang C, Cheng N, Pu Z, et al. NiSe nanowire film supported on nickel foam: an efficient and stable 3D bifunctional electrode for full water splitting. Angew Chem Int Ed, 2015, 54: 9351-9355 CrossRef PubMed Google Scholar

[24] Jia X, Zhao Y, Chen G, et al. Ni3FeN nanoparticles derived from ultrathin NiFe-layered double hydroxide nanosheets: an efficient overall water splitting electrocatalyst. Adv Energ Mater, 2016, 6: 1502585 CrossRef Google Scholar

[25] Yan H, Tian C, Wang L, et al. Phosphorus-modified tungsten nitride/reduced graphene oxide as a high-performance, non-noble-metal electrocatalyst for the hydrogen evolution reaction. Angew Chem Int Ed, 2015, 54: 6325-6329 CrossRef PubMed Google Scholar

[26] Zhang L, Xie L, Ma M, et al. Co-based nanowire films as complementary hydrogen- and oxygen-evolving electrocatalysts in neutral electrolyte. Catal Sci Technol, 2017, 7: 2689-2694 CrossRef Google Scholar

[27] Liao L, Wang S, Xiao J, et al. A nanoporous molybdenum carbide nanowire as an electrocatalyst for hydrogen evolution reaction. Energ Environ Sci, 2014, 7: 387-392 CrossRef Google Scholar

[28] Zhang F, Shi Y, Xue T, et al. In situ electrochemically converting Fe2O3-Ni(OH)2 to NiFe2O4-NiOOH: a highly efficient electrocatalyst towards water oxidation. Sci China Mater, 2017, 60: 324-334 CrossRef Google Scholar

[29] Zhao Y, Jia X, Chen G, et al. Ultrafine NiO nanosheets stabilized by TiO2 from monolayer NiTi-LDH precursors: an active water oxidation electrocatalyst. J Am Chem Soc, 2016, 138: 6517-6524 CrossRef PubMed Google Scholar

[30] Wang J, Cui W, Liu Q, et al. Recent progress in cobalt-based heterogeneous catalysts for electrochemical water splitting. Adv Mater, 2016, 28: 215-230 CrossRef PubMed Google Scholar

[31] Chen Z, Zhao H, Zhang J, et al. IrNi nanoparticle-decorated flower-shaped NiCo2O4 nanostructures: controllable synthesis and enhanced electrochemical activity for oxygen evolution reaction. Sci China Mater, 2017, 60: 119-130 CrossRef Google Scholar

[32] Hang L, Sun Y, Men D, et al. Hierarchical micro/nanostructured C doped Co/Co3O4 hollow spheres derived from PS@Co(OH)2 for the oxygen evolution reaction. J Mater Chem A, 2017, 5: 11163-11170 CrossRef Google Scholar

[33] Artero V, Chavarot-Kerlidou M, Fontecave M. Splitting water with cobalt. Angew Chem Int Ed, 2011, 50: 7238-7266 CrossRef PubMed Google Scholar

[34] Lin Y, Pan Y, Zhang J. CoP nanorods decorated biomass derived N, P co-doped carbon flakes as an efficient hybrid catalyst for electrochemical hydrogen evolution. Electrochim Acta, 2017, 232: 561-569 CrossRef Google Scholar

[35] Yang L, Yu J, Wei Z, et al. Co-N-doped MoO2 nanowires as efficient electrocatalysts for the oxygen reduction reaction and hydrogen evolution reaction. Nano Energ, 2017, CrossRef Google Scholar

[36] Tabassum H, Guo W, Meng W, et al. Hydrogen evolution: metal-organic frameworks derived cobalt phosphide architecture encapsulated into B/N Co-doped graphene nanotubes for all pH value electrochemical hydrogen evolution. Adv Energ Mater, 2017, CrossRef Google Scholar

[37] Feng JX, Xu H, Dong YT, et al. Efficient hydrogen evolution electrocatalysis using cobalt nanotubes decorated with titanium dioxide nanodots. Angew Chem Int Ed, 2017, 56: 2960-2964 CrossRef PubMed Google Scholar

[38] Peng X, Hu L, Wang L, et al. Vanadium carbide nanoparticles encapsulated in graphitic carbon network nanosheets: a high-efficiency electrocatalyst for hydrogen evolution reaction. Nano Energ, 2016, 26: 603-609 CrossRef Google Scholar

[39] Shi H, Liang H, Ming F, et al. Efficient overall water-splitting electrocatalysis using lepidocrocite VOOH hollow nanospheres. Angew Chem Int Ed, 2017, 56: 573-577 CrossRef PubMed Google Scholar

[40] Xing M, Kong LB, Liu MC, et al. Cobalt vanadate as highly active, stable, noble metal-free oxygen evolution electrocatalyst. J Mater Chem A, 2014, 2: 18435-18443 CrossRef Google Scholar

[41] Zhang J, Yuan B, Cui S, et al. Facile synthesis of 3D porous Co3-V2O8 nanoroses and 2D NiCo2V2O8 nanoplates for high performance supercapacitors and their electrocatalytic oxygen evolution reaction properties. Dalton Trans, 2017, 46: 3295-3302 CrossRef PubMed Google Scholar

[42] Shen FC, Wang Y, Tang YJ, et al. CoV2O6-V2O5 coupled with porous N-doped reduced graphene oxide composite as a highly efficient electrocatalyst for oxygen evolution. ACS Energ Lett, 2017, 2: 1327-1333 CrossRef Google Scholar

[43] Hyun S, Ahilan V, Kim H, et al. The influence of Co3V2O8 morphology on the oxygen evolution reaction activity and stability. Electrochem Commun, 2016, 63: 44-47 CrossRef Google Scholar

[44] Shang X, Yan KL, Rao Y, et al. In situ cathodic activation of V-incorporated NixSy nanowires for enhanced hydrogen evolution. Nanoscale, 2017, 9: 12353-12363 CrossRef PubMed Google Scholar

[45] Fan K, Chen H, Ji Y, et al. Nickel-vanadium monolayer double hydroxide for efficient electrochemical water oxidation. Nat Commun, 2016, 7: 11981 CrossRef PubMed ADS Google Scholar

[46] Lettenmeier P, Wang L, Golla-Schindler U, et al. Nanosized IrOx-Ir catalyst with relevant activity for anodes of proton exchange membrane electrolysis produced by a cost-effective procedure. Angew Chem Int Ed, 2016, 55: 742-746 CrossRef PubMed Google Scholar

[47] Baudrin E. Synthesis and electrochemical properties of cobalt vanadates vs. lithium. Solid State Ion, 1999, 123: 139-153 CrossRef Google Scholar

[48] Wu F, Yu C, Liu W, et al. Large-scale synthesis of Co2V2O7 hexagonal microplatelets under ambient conditions for highly reversible lithium storage. J Mater Chem A, 2015, 3: 16728-16736 CrossRef Google Scholar

[49] Peng X, Wang L, Hu L, et al. In situ segregation of cobalt nanoparticles on VN nanosheets via nitriding of Co2V2O7 nanosheets as efficient oxygen evolution reaction electrocatalysts. Nano Energ, 2017, 34: 1-7 CrossRef Google Scholar

[50] Huang K, Bi K, Liang C, et al. Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte. Sci Rep, 2015, 5: 11351 CrossRef PubMed ADS Google Scholar

[51] Zhao D, Cui Z, Wang S, et al. VN hollow spheres assembled from porous nanosheets for high-performance lithium storage and the oxygen reduction reaction. J Mater Chem A, 2016, 4: 7914-7923 CrossRef Google Scholar

[52] Zhu C, Liu Z, Wang J, et al. Novel Co2VO4 anodes using ultralight 3D metallic current collector and carbon sandwiched structures for high-performance Li-ion batteries. Small, 2017, 13: 1701260 CrossRef PubMed Google Scholar

[53] Zhang S, Ni B, Li H, et al. Cobalt carbonate hydroxide superstructures for oxygen evolution reactions. Chem Commun, 2017, 53: 8010-8013 CrossRef PubMed Google Scholar

[54] Zhao Y, Liu J, Liu C, et al. Amorphous CuPt alloy nanotubes induced by Na2S2O3 as efficient catalysts for the methanol oxidation reaction. ACS Catal, 2016, 6: 4127-4134 CrossRef Google Scholar

[55] García-Contreras MA, Fernández-Valverde SM, Vargas-García JR. Pt, PtCo and PtNi electrocatalysts prepared by mechanical alloying for the oxygen reduction reaction in 0.5 M H2SO4. Int J Hydrogen Energy, 2008, 33: 6672-6680 CrossRef Google Scholar

[56] Liu YR, Shang X, Gao WK, et al. Ternary CoS2/MoS2/RGO electrocatalyst with CoMoS phase for efficient hydrogen evolution. Appl Surf Sci, 2017, 412: 138-145 CrossRef ADS Google Scholar

[57] Yang Y, Xu X, Wang X. Synthesis of Mo-based nanostructures from organic-inorganic hybrid with enhanced electrochemical for water splitting. Sci China Mater, 2015, 58: 775-784 CrossRef Google Scholar

[58] Kibsgaard J, Jaramillo TF, Besenbacher F. Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13](2−) clusters. Nat Chem, 2014, 6: 248-253 CrossRef PubMed ADS Google Scholar

[59] Chen P, Xu K, Fang Z, et al. Metallic Co4N porous nanowire arrays activated by surface oxidation as electrocatalysts for the oxygen evolution reaction. Angew Chem Int Ed, 2015, 54: 14710-14714 CrossRef PubMed Google Scholar

[60] Yan KL, Shang X, Li Z, et al. Ternary mixed metal Fe-doped NiCo2O4 nanowires as efficient electrocatalysts for oxygen evolution reaction. Appl Surf Sci, 2017, 416: 371-378 CrossRef ADS Google Scholar

[61] Yan KL, Shang X, Gao WK, et al. Ternary MnO2/NiCo2O4/NF with hierarchical structure and synergistic interaction as efficient electrocatalysts for oxygen evolution reaction. J Alloys Compd, 2017, 719: 314-321 CrossRef Google Scholar

  • Scheme 1

    Schematic illustration for the formation of Co-V bimetal-based catalysts.

  • Figure 1

    (a) XRD pattern; (b) SEM image; (c–f) TEM images of the Co2V2O7·xH2O precursor nanoplates. The inset in (f) is the HRTEM image of the selected area.

  • Figure 2

    (a) XRD pattern; (b) SEM image; (c–f) TEM images of Co/VN. The inset in (f) is an HRTEM image.

  • Figure 3

    (a) The XPS survey spectrum; (b–d) high resolution spectra of Co 2p, V 2p and N 1s of Co/VN hybrid.

  • Figure 4

    (a) Linear sweep voltammetry (LSV) curves for Co2VO4, Co/VN, Co3V/VN and commercial Pt/C with iR compensation; (b) Tafel plots for Co2VO4, Co/VN, Co3V/VN and Pt/C; (c) the capacitive current at 0.15 V of Co2VO4, Co/VN and Co3V/VN; (d) polarization data for the Co/VN sample initially and after 5000 CV. The inset in (d) is the dependence of the current density for Co/VN at overpotential of 92 mV for 20 h.

  • Figure 5

    (a) LSV curves for Co2VO4, Co/VN, Co3V/VN and commercial RuO2 with iR compensation; (b) iR compensation Tafel plots for Co2VO4, Co/VN, Co3V/VN and RuO2; (c) the capacitive current at 1.30 V of Co2VO4, Co/VN and Co3V/VN; (d) polarization data for the Co/VN sample initially and after 5000 CV. The inset in (d) is the dependence of the current density for Co2VO4 at 1.55 V for 12 h.

  • Figure 6

    (a) LSV curves of the Co2VO4||Co/VN water splitting system in 1 mol L−1 KOH. The inset in (a) is a photograph of the two electrode device. (b) Chronoamperometry of water electrolysis using the Co2VO4||Co/VN two electrode water splitting system at 1.653 V.

Copyright 2019 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有

京ICP备18024590号-1