One-pot synthesis and shape control of metal selenides, sulfides and oxides with oxalic acid as the reducing reagent

  • Hua LinEmail author
  • Shijie He
  • Dingyu Liu
  • Jian Zou
  • Lu Li
  • Yanlong Ma
  • Qing Li
Original Article


One specific method is often limited within the synthesis of one specific material like metal chalcogenides, the hot topics in nanomaterials since decades ago, which raises the cost of production if manufactured in industry. Here 23 compounds, including individual components and composites, have been synthesized through the same hydrothermal method with oxalic acid as the reducing reagent. What is more, shape-/composition-controlled synthesis of CdSe, vanadium oxides, and nickel sulfides have also been realized by simply controlling the amount of oxalic acid used in each synthesis. The method developed here is inspiring for the synthesis of other nanomaterials and the shape-/composition-controlled synthesis provides a simple strategy for the surfactant-free shape engineering of nanomaterials and enriches the knowledge about crystal growth.


Metal chalcogenides One-pot synthesis Hydrothermal method Shape control 



This work was supported by the Fundamental Research Funds for the Central Universities Key Project (Grant No. XDJK2017B062) and the National Science Foundation for Young Scientists of China (Grant No.51605392).

Supplementary material

13204_2019_954_MOESM1_ESM.docx (3.4 mb)
Supplementary material 1 (DOCX 3441 KB)


  1. Bilde M, Barsanti K, Booth M et al (2015) Saturation vapor pressures and transition enthalpies of low-volatility organic molecules of atmospheric relevance_ from dicarboxylic acids to complex mixtures. Chem Rev 115:4115–4156CrossRefGoogle Scholar
  2. Chen M, Gao L (2005) Synthesis and characterization of cadmium selenide nanorods via surfactant-assisted hydrothermal method. J Am Ceram Soc 88:1643–1646CrossRefGoogle Scholar
  3. Chirayil T, Zavalij PY, Whittingham MS (1998) Hydrothermal synthesis of vanadium oxides. Chem Mater 10:2629–2640CrossRefGoogle Scholar
  4. Comini E, Baratto C, Faglia G et al (2009) Quasi-one dimensional metal oxide semiconductors: Preparation, characterization and application as chemical sensors. Prog Mater Sci 54:1–67CrossRefGoogle Scholar
  5. Darr JA, Zhang J, Makwana NM et al (2017) Continuous hydrothermal synthesis of inorganic nanoparticles: applications and future directions. Chem Rev 117:11125–11238CrossRefGoogle Scholar
  6. Feng S, Xu R (2001) New materials in hydrothermal synthesis. Acc Chem Res 34:239–247CrossRefGoogle Scholar
  7. Gerdes F, Navío C, Juárez BH et al (2017) Size, shape, and phase control in ultrathin CdSe nanosheets. Nano Lett 17:4165–4171CrossRefGoogle Scholar
  8. Guiton BS, Gu Q, Prieto AL et al (2005) Single-crystalline vanadium dioxide nanowires with rectangular cross sections. J Am Chem Soc 127:498–499CrossRefGoogle Scholar
  9. He J, Chen Y, Manthirama A (2018) Vertical Co9S8 hollow nanowall arrays grown on Celgard separator as a multifunctional polysulfide barrier for high-performance Li-S batteries. Energ Environ Sci 11:2560–2568CrossRefGoogle Scholar
  10. Jang SY, Song YM, Kim HS et al (2010) Three synthetic routes to single-crystalline PbS nanowires with controlled growth direction and their electrical transport properties. ACS Nano 4:2391–2401CrossRefGoogle Scholar
  11. Kim F, Kwan S, Akana J et al (2001) Langmuir-Blodgett nanorod assembly. J Am Chem Soc 123:4360–4361CrossRefGoogle Scholar
  12. Kim MS, Lee S, Koo JH et al (2012) Induced transition of CdSe nanoparticle superstructures by controlling the internal flow of colloidal solution. ACS Appl Mater Interfaces 4:5162–5168CrossRefGoogle Scholar
  13. Li Y, Chen G, Wang Q et al (2010) Hierarchical ZnS–In2S3–CuS nanospheres with nanoporous structure: facile synthesis, growth mechanism, and excellent photocatalytic activity. Adv Funct Mater 20:3390–3398CrossRefGoogle Scholar
  14. Lin X, Liang Y, Lu Z et al (2017) Mechanochemistry: a green, activation-free and top-down strategy to high-surface-area carbon materials. ACS Sustainable Chem Eng 5:8535–8540CrossRefGoogle Scholar
  15. Mclaren A, Valdes-Solis T, Li G et al (2009) Shape and size effects of ZnO nanocrystals on photocatalytic activity. J Am Chem Soc 131:12540–12541CrossRefGoogle Scholar
  16. Pan Q, Xie J, Zhu T et al (2014) Reduced graphene oxide-induced recrystallization of NiS nanorods to nanosheets and the improved Na-storage properties. Inorg Chem 53:3511–3518CrossRefGoogle Scholar
  17. Rabenau A (1985) The role of hydrothermal synthesis in preparative chemistry. Angew Chem Int Ed 24:1026–1040CrossRefGoogle Scholar
  18. Rice KP, Saunders AE, Stoykovich MP (2013) Seed-Mediated growth of shape-controlled wurtzite CdSe nanocrystals_ platelets, cubes, and rods. J Am Chem Soc 135:6669–6676CrossRefGoogle Scholar
  19. Roffey A, Hollingsworth N, Islam H-U et al (2016) Phase control during the synthesis of nickel sulfide nanoparticles from dithiocarbamate precursors. Nanoscale 8:11067–11075CrossRefGoogle Scholar
  20. Sapsford KE, Algar WR, Berti L et al (2013) Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology. Chem Rev 113:1904–2074CrossRefGoogle Scholar
  21. Seh ZW, Kibsgaard J, Dickens CF et al (2017) Combining theory and experiment in electrocatalysis: insights into materials design. Science 355:eaad4998CrossRefGoogle Scholar
  22. Sivanantham A, Ganesan P, Shanmugam S (2016) Hierarchical NiCo2S4 nanowire arrays supported on Ni foam: an efficient and durable bifunctional electrocatalyst for oxygen and hydrogen evolution reactions. Adv Funct Mater 26:4661–4672CrossRefGoogle Scholar
  23. Sohn JI, Joo HJ, Porter AE et al (2007) Direct observation of the structural component of the metal—insulator phase transition and growth habits of epitaxially grown VO2 Nanowires. Nano Lett 7:1570–1574CrossRefGoogle Scholar
  24. Sounart TL, Liu J, Voigt JA et al (2007) Secondary nucleation and growth of ZnO. J Am Chem Soc 129:15786–15793CrossRefGoogle Scholar
  25. Strelcov E, Lilach Y, Kolmakov A (2009) Gas sensor based on metal—insulator transition in VO2 nanowire thermistor. Nano Lett 9:2322–2326CrossRefGoogle Scholar
  26. Tong Y, Bohn BJ, Bladt E et al (2017) From precursor powders to CsPbX3 perovskite nanowires: one-pot synthesis, growth mechanism, and oriented self-assembly. Angew Chem Int Ed 56:13887–13892CrossRefGoogle Scholar
  27. Wang QH, Kalantar-Zadeh K, Kis A et al (2012) Electronics and optoelectronics of two-dimensional transition metal dichalcogenidesColeman. Nat Nanotechnol 7:699–712CrossRefGoogle Scholar
  28. Yang S, Gao L (2006) Controlled synthesis and aelf-assembly of CeO2 nanocubes. J Am Chem Soc 128:9330–9331CrossRefGoogle Scholar
  29. Yuwono VM, Burrows ND, Soltis JA et al (2010) Oriented aggregation: formation and transformation of mesocrystal intermediates revealed. J Am Chem Soc 132:2163–2165CrossRefGoogle Scholar
  30. Zhang T, Dong W, Keeter-Brewer M et al (2006) Site-specific nucleation and growth kinetics in hierarchical nanosyntheses of branched ZnO crystallites. J Am Chem Soc 128:10960–10968CrossRefGoogle Scholar
  31. Zhou L, Shao M, Zhang C et al (2017) Hierarchical CoNi-sulfide nanosheet arrays derived from layered double hydroxides toward efficient hydrazine electrooxidation. Adv Mater 29:1604080CrossRefGoogle Scholar
  32. Zhou J, Lin J, Huang X et al (2018) A library of atomically thin metal chalcogenides. Nature 556:355–359CrossRefGoogle Scholar

Copyright information

© King Abdulaziz City for Science and Technology 2019

Authors and Affiliations

  1. 1.Faculty of Materials and EnergySouthwest UniversityChongqingChina
  2. 2.School of Chemistry and Chemical EngineeringSouthwest UniversityChongqingChina
  3. 3.College of Materials Science and EngineeringChongqing University of TechnologyChongqingChina

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