Abstract
In this work, a unique Cu2O hexapod microcrystal with {100} facets etched concave structure has been successfully synthesized by a facile oxide etching method. Air and chloride ion were employed as etchant and shape controller agent, respectively. For the facet-selective adsorption of chloride ions on {110} and {111} planes, the oxide molecules may prefer to act on {100} facets and induced the concave structure formation, along the [100] zone axis. The {100} facets selectively etched Cu2O concave hexapod microcrystal exhibited highly improved photocatalytic activities (2.2 times) than that of basic structure, and displayed facet-dependent characteristics, which made them promising candidates for photocatalysts and sensing materials.
Similar content being viewed by others
References
Heo H, Lee MH, Yang J, Wee HS, Lim J, Hahm D, Yu JW, Bae WK, Lee WB, Kang MS, Char K (2017) Assemblies of colloidal CdSe tetrapod nanocrystals with lengthy arms for flexible thin-film transistors. Nano Lett 17(4):2433–2439
Fiore A, Mastria R, Lupo MG, Lanzani G, Giannini C, Carlino E, Morello G, De Giorgi M, Li Y, Cingolani R, Manna L (2009) Tetrapod-shaped colloidal nanocrystals of II-VI semiconductors prepared by seeded growth. J Am Chem Soc 131(6):2274–2282
Liu HN, Xu YL, Qin Y, Sanderson W, Crowley D, Turner CH, Bao YP (2013) Ligand-directed formation of gold tetrapod nanostructures. J Phys Chem C 117(33):17143–17150
Wang JJ, Singh A, Liu P, Singh S, Coughlan C, Guo YN, Ryan KM (2013) Colloidal synthesis of Cu2SnSe3 tetrapod nanocrystals. J Am Chem Soc 135(21):7835–7838
Wang H, He L, Wang LH, Hu PF, Guo L, Han XD, Li JH (2012) Facile synthesis of Ag3PO4 tetrapod microcrystals with an increased percentage of exposed 110 facets and highly efficient photocatalytic properties. CrystEngComm 14(24):8342–8344
Kim DY, Yu T, Cho EC, Ma YY, Park OO, Xia YN (2011) Synthesis of gold nano-hexapods with controllable arm lengths and their tunable optical properties. Angewandte Chemie Int Edition 50(28):6328–6331
Cho YS, Huh YD (2013) Preparation of uniform hexapod Cu2O and hollow hexapod CuO. Bull Korean Chem Soc 34(10):3101–3104
Xiong YL, Ma YL, Li JJ, Huang JB, Yan YC, Zhang H, Wu JB, Yang DR (2017) Strain-induced Stranski-Krastanov growth of Pd@Pt core-shell hexapods and octapods as electrocatalysts for methanol oxidation. Nanoscale 9(31):11077–11084
Wang LM, Liu B, Ran SH, Huang HT, Wang XF, Liang B, Chen D, Shen GZ (2012) Nanorod-assembled Co3O4 hexapods with enhanced electrochemical performance for lithium-ion batteries. J Mater Chem 22(44):23541–23546
Zheng XZ, Han J, Fu Y, Deng Y, Liu YY, Yang Y, Wang T, Zhang LW (2018) Highly efficient CO2 reduction on ordered porous Cu electrode derived from Cu2O inverse opals. Nano Energy 48:93–100
Li L, Zhang R, Vinson J, Shirley EL, Greeley JP, Guest JR, Chan MKY (2018) Imaging catalytic activation of CO2 on Cu2O (110): a first-principles study. Chem Mater 30(6):1912–1923
Sun Y, Yu X, Jin ZS, Liu JW, Li ZH (2018) Synthesis of mix-faceted Cu2O nanoparticles with tunable 111 and 100 facet ratios for enhanced photocatalytic activity. Micro Nano Lett 13(1):135–137
Zhang AY, He YY, Lin T, Huang NH, Xu Q, Feng JW (2017) A simple strategy to refine Cu2O photocatalytic capacity for refractory pollutants removal: roles of oxygen reduction and Fe(II) chemistry. J Hazard Mater 330:9–17
Su Y, Li HF, Ma HB, Robertson J, Nathan A (2017) Controlling surface termination and facet orientation in Cu2O nanoparticles for high photocatalytic activity: a combined experimental and density functional theory study. ACS Appl Mater Interfaces 9(9):8100–8106
Tan YB, Jia ZQ, Sun JY, Wang YZ, Cui ZH, Guo XX (2017) Controllable synthesis of hollow copper oxide encapsulated into N-doped carbon nanosheets as high-stability anodes for lithium-ion batteries. J Mater Chem A 5(46):24139–24144
Wang LL, Zhang R, Zhou TT, Lou Z, Deng JN, Zhang T (2017) P-type octahedral Cu2O particles with exposed 111 facets and superior CO sensing properties. Sens Actuators B Chem 239:211–217
Wozniak-Budych MJ, Przysiecka L, Maciejewska BM, Wieczorek D, Staszak K, Jarek M, Jesionowski T, Jurga S (2017) Facile synthesis of sulfobetaine-stabilized Cu2O nanoparticles and their biomedical potential. ACS Biomater Sci Eng 3(12):3183–3194
Ghosh S, Das R, Naskar MK (2016) Morphological evolution of hexapod Cu2O microcrystals by a rapid template-free autoclaving technique. Mater Lett 183:325–328
Yang LF, Chu DQ, Wang LM (2015) Porous hexapod CuO nanostructures: precursor-mediated fabrication, characterization, and visible-light induced photocatalytic degradation of phenol. Mater Lett 160:246–249
Kang WP, Liu FL, Su YL, Wang DJ, Shen Q (2011) The catanionic surfactant-assisted syntheses of 26-faceted and hexapod-shaped Cu2O and their electrochemical performances. CrystEngComm 13(12):4174–4180
Ho JY, Huang MH (2009) Synthesis of submicrometer-sized Cu2O crystals with morphological evolution from cubic to hexapod structures and their comparative photocatalytic activity. J Phys Chem C 113(32):14159–14164
Zhao ZL, Wang X, Si JQ, Yue CT, Xia CG, Li FW (2018) Truncated concave octahedral Cu2O nanocrystals with hkk high-index facets for enhanced activity and stability in heterogeneous catalytic azide-alkyne cycloaddition. Green Chem 20(4):832–837
Liu C, Chang YH, Chen JN, Feng SP (2017) Electrochemical synthesis of Cu2O concave octahedrons with high-index facets and enhanced photoelectrochemical activity. ACS Appl Mater Interfaces 9(44):39027–39033
Wang X, Liu C, Zheng BJ, Jiang YQ, Zhang L, Xie ZX, Zheng LS (2013) Controlled synthesis of concave Cu2O microcrystals enclosed by hhl high-index facets and enhanced catalytic activity. J Mater Chem A 1(2):282–287
Shi J, Li J, Huang XJ, Tan YW (2011) Synthesis and enhanced photocatalytic activity of regularly shaped Cu2O nanowire polyhedra. Nano Res 4(5):448–459
Han L, Yu XY, Lou XW (2016) Formation of prussian-blue-analog nanocages via a direct etching method and their conversion into Ni-Co-mixed oxide for enhanced oxygen evolution. Adv Mater 28(23):4601–4605
Kuo C-H, Huang MH (2008) Fabrication of truncated rhombic dodecahedral Cu2O nanocages and nanoframes by particle aggregation and acidic etching. J Am Chem Soc 130(38):12815–12820
Chen L, Ji F, Xu Y, He L, Mi YF, Bao F, Sun BQ, Zhang XH, Zhang Q (2014) High-yield seedless synthesis of triangular gold nanoplates through oxidative etching. Nano Lett 14(12):7201–7206
Sui YM, Fu WY, Zeng Y, Yang HB, Zhang YY, Chen H, Li YX, Li MH, Zou GT (2010) Synthesis of Cu2O nanoframes and nanocages by selective oxidative etching at room temperature. Angew Chemie Int Edition 49(25):4282–4285
Shang Y, Sun D, Shao Y, Zhang D, Guo L, Yang S (2012) A facile top-down etching to create a Cu2O jagged polyhedron covered with numerous 110 edges and 111 corners with enhanced photocatalytic activity. Chem a Eur J 18(45):14261–14266
Xie SF, Zhang H, Lu N, Jin MS, Wang JG, Kim MJ, Xie ZX, Xia YN (2013) Synthesis of rhodium concave tetrahedrons by collectively manipulating the reduction kinetics, facet-selective capping, and surface diffusion. Nano Lett 13(12):6262–6268
Chen K, Xue D (2011) Nanoscale surface engineering of cuprous oxide crystals: the function of chloride. Nanosci Nanotechnol Lett 3(3):383–388
Kim MH, Lim B, Lee EP (2008) Polyol synthesis of Cu2O nanoparticles: use of chloride to promote the formation of a cubic morphology. J Mater Chem 18(34):4069–4073
Pradhan D, Leung KT (2008) Controlled growth of two-dimensional and one-dimensional ZnO nanostructures on indium tin oxide coated glass by direct electrodeposition. Langmuir 24(17):9707–9716
Pradhan D, Sindhwani S, Leung KT (2010) Parametric study on dimensional control of ZnO nanowalls and nanowires by electrochemical deposition. Nanoscale Res Lett 5(11):1727–1736
Li H, Yu K, Li C, Guo B, Lei X, Fu H, Zhu Z (2015) Novel dual-petal nanostructured WS2@MoS2 with enhanced photocatalytic performance and a comprehensive first-principles investigation. J Mater Chem A 3(40):20225–20235
Liu J, Yang SL, Wu W, Tian QY, Cui SY, Dai ZG, Ren F, Xiao XH, Jiang CZ (2015) 3D flowerlike alpha-Fe2O3@TiO2 core-shell nanostructures: general synthesis and enhanced photocatalytic performance. ACS Sustain Chem Eng 3(11):2975–2984
Manna G, Bose R, Pradhan N (2014) Photocatalytic Au-Bi2S3 heteronanostructures. Angewandte Chemie-International Edition 53(26):6743–6746
Guo YN, Li H, Chen J, Wu XJ, Zhou L (2014) TiO2 mesocrystals built of nanocrystals with exposed 001 facets: facile synthesis and superior photocatalytic ability. J Mater Chem 2(46):19589–19593
Niu P, Zhang LL, Liu G, Cheng HM (2012) Graphene-like carbon nitride nanosheets for improved photocatalytic activities. Adv Funct Mater 22(22):4763–4770
Mishra AK, Pradhan D (2016) Morphology controlled solution-based synthesis of Cu2O crystals for the facets-dependent catalytic reduction of highly toxic aqueous Cr(VI). Cryst Growth Des 16(7):3688–3698
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant No. 11602159, 51205276, and 61474079), the Special Talents in Shanxi Province (Grant No. 201605D211020), the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (Grant No. 2016136) and the 2018 Study Abroad Program for the University-Sponsored Young Teachers.
Author information
Authors and Affiliations
Contributions
Pengwei Li: Conceived and designed the study, revised and rewrote the paper. Lina Liu: Performed most of the experiments, wrote the manuscript. Dongjie Qin: Assisted in synthesis of Cu2O materials. Cuixian Luo: Reviewed and edited the manuscript. Gang Li: Reviewed and edited the manuscript. Jie Hu: Reviewed and edited the manuscript. Huabei Jiang: Reviewed and edited the manuscript. Wendong Zhang: Reviewed and edited the manuscript. All authors read and approved the manuscript.
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interests.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Li, P., Liu, L., Qin, D. et al. Cu2O concave hexapod microcrystals: selective facet etching and highly improved photocatalytic performance. J Mater Sci 54, 2876–2884 (2019). https://doi.org/10.1007/s10853-018-3031-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-018-3031-8