DOI QR코드

DOI QR Code

POSS/Polyurethane Hybrids and Nanocomposites: A Review on Preparation, Structure and Performance

  • Diao, Shuo (Key Laboratory of Beijing City for Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology) ;
  • Mao, Lixin (Key Laboratory of Beijing City for Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology) ;
  • Zhang, Liqun (Key Laboratory of Beijing City for Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology) ;
  • Wang, Yiqing (Key Laboratory of Beijing City for Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology)
  • Received : 2015.02.03
  • Accepted : 2015.03.03
  • Published : 2015.03.31

Abstract

Polyhedral oligomeric silsesquioxane (POSS) is an important inorganic-organic hybrid material with a three-dimensional structure. Polyurethane (PU) is a widely applied polymer that has versatile properties with the change of two phase structure. When POSS is incorporated into PU by physical or chemical methods, many properties can be greatly improved, such as mechanical properties, thermal stability, biodegradation resistance, and water resistance. This paper reviews the recent progress in preparation, structure, and performance of POSS-modified polyurethane from the viewpoint of physical blending and chemical modification.

References

  1. R. Hernandez, J. Weksler, A. Padsalgikar, T. Choi, et al., "A comparison of phase organization of model segmented polyurethanes with different intersegment compatibilities", Macromolecules, 41, 9767 (2008). https://doi.org/10.1021/ma8014454
  2. A. M. Castagna, A. Pangon, T. Choi, G. P. Dillon, and J. Runt, "The role of soft segment molecular weight on microphase separation and dynamics of bulk polymerized polyureas", Macromolecules, 45, 8438 (2012). https://doi.org/10.1021/ma3016568
  3. Z. S. Petrovic and J. Ferguson, "Polyurethane elastomers", Prog. Polym. Sci., 16, 695 (1991). https://doi.org/10.1016/0079-6700(91)90011-9
  4. R. Udagama, E. Degrandi-Contraires, C. Creton, C. Graillat, T. F. McKenna, and E. Bourgeat-Lami, "Synthesis of Acrylic-Polyurethane Hybrid Latexes by Miniemulsion Polymerization and Their Pressure-Sensitive Adhesive Applications", Macromolecules, 48, 2632 (2011).
  5. A. Samimi and S. Zarinabadi, "Application Polyurethane as Coating in Oil and Gas Pipelines", Int. J. Sci. Invest., 43 (2012).
  6. L. F. Cabeza, A. Castell, M. Medrano, I. Martorell, G. Perez, and I. Fernande, "Experimental study on the performance of insulation materials in Mediterranean construction", Energ. Buildings, 42, 630 (2010). https://doi.org/10.1016/j.enbuild.2009.10.033
  7. M. S. El-Shahawi, A. S. Bashammakh, A. A. Al-Sibaai, M. I. Orief, and F. M. Al-Shareef, "Solid phase preconcentration and determination of trace concentrations of total gold (I) and/or (III) in sea and wastewater by ion pairing impregnated polyurethane foam packed column prior flame atomic absorption spectrometry", Miner. Process, 100, 110 (2011). https://doi.org/10.1016/j.minpro.2011.05.004
  8. D. W. Scott, "Thermal Rearrangement of Branched-Chain Methylpolysiloxanes1", Am. Chem. Soc., 68, 356 (1946). https://doi.org/10.1021/ja01207a003
  9. F. J. Feher, D. A. Newman, and J. F. Walzer, "Silsesquioxanes as models for silica surfaces", J. Am. Chem. Soc., 111, 1741 (1989). https://doi.org/10.1021/ja00187a028
  10. J. D. Lichtenhan, Y. A. Otonari, and M. J. Carr, "Linear hybrid polymer building blocks: methacrylate-functionalized polyhedral oligomeric silsesquioxane monomers and polymers", Macromolecules, 28, 8435 (1995). https://doi.org/10.1021/ma00128a067
  11. P. D. Lickiss and F. Rataboul, "Fully condensed polyhedral oligosilsesquioxanes (POSS): from synthesis to application", Adv. Organomet. Chem., 57, 1 (2008).
  12. R. H. Baney and X. Cao, "Polysilsesquioxanes", Silicon-Containing Polymers, 157 (2000).
  13. G. Li, L. Wang, H. Ni, and C. U. Pittman Jr, "Polyhedral oligomeric silsesquioxane (POSS) polymers and copolymers: a review", J. Inorg. Organomet. Polym., 11, 123 (2001). https://doi.org/10.1023/A:1015287910502
  14. Y. Liu, X. Yang, W. Zhang, and S, Zheng, "Star-shaped poly (${\varepsilon}$-caprolactone) with polyhedral oligomeric silsesquioxane core", Polymer, 47, 6814 (2006). https://doi.org/10.1016/j.polymer.2006.07.050
  15. M. A. Hoque, Y. H. Cho, and Y. Kawakami, "High performance holographic gratings formed with novel photopolymer films containing hyper-branched silsesquioxane", React. Funct. Polym, 67, 1192 (2007). https://doi.org/10.1016/j.reactfunctpolym.2007.07.016
  16. Y. Ni, S. Zheng, and K. Nie, "Morphology and thermal properties of inorganic-organic hybrids involving epoxy resin and polyhedral oligomeric silsesquioxanes", Polymer, 45, 5557 (2004). https://doi.org/10.1016/j.polymer.2004.06.008
  17. B. H. Tan, H. Hussain, and C. B. He, "Tailoring Micelle Formation and Gelation in (PEG-P (MA-POSS)) Amphiphilic Hybrid Block Copolymers", Macromolecules, 44, 622 (2011). https://doi.org/10.1021/ma102510u
  18. F. Mammeri, C. Bonhomme, F. Ribot, and S. Dire, "New monofunctional POSS and its utilization as dewetting additive in methacrylate based free-standing films", J. Chem. Mater., 21, 4163 (2009). https://doi.org/10.1021/cm900339h
  19. N. Fritz, H. C. Koo, Z. Wilson, E. Uzunlar, and Z. Wen, "Electroless deposition of copper on organic and inorganic substrates using a Sn/Ag catalyst", J. Electrochem. Soc., 111, 1741 (1989).
  20. J. Wei, B. H. Tan, Y. Bai, J. Ma, and X. Lu, "Self-assembly behaviors of telechelic poly (styrene-Ran-sodium styrenesulfonate) with polyhedral oligomeric silsesquioxane as End groups", J. Phys. Chem. B, 115, 1929 (2011). https://doi.org/10.1021/jp1078168
  21. S. Sulaiman, A. Bhaskar, J. Zhang, R. Guda, T. Goodson Iii, and R. M. Laine, "Molecules with perfect cubic symmetry as nanobuilding blocks for 3-D assemblies. Elaboration of octavinylsilsesquioxane. Unusual luminescence shifts may indicate extended conjugation involving the silsesquioxane core", Chem. Mater., 20, 5563 (2008). https://doi.org/10.1021/cm801017e
  22. E. Kharlampieva, V. Kozlovskaya, B. Wallet, et al., "Cocross-linking silk matrices with silica nanostructures for robust ultrathin nanocomposites", ACS nano, 2, 7053 (2010).
  23. K. Koh, S. Sugiyama, T. Morinaga, K. Ohno, Y. Tsujii, et al., "Precision synthesis of a fluorinated polyhedral oligomeric silsesquioxane-terminated polymer and surface characterization of its blend film with poly (methyl methacrylate)", Macromolecules, 38, 1264 (2005). https://doi.org/10.1021/ma047636l
  24. S. C. Chan, S. W. Kuo, H. S. She, H. M. Lin, H. F. Lee, and F. C. Chang, "Supramolecular aggregations through the inclusion complexation of cyclodextrins and polymers with bulky end groupss", J. Polym. Sci. Polym. Chem., 45, 125 (2007). https://doi.org/10.1002/pola.21820
  25. R. H. Baney, M. Itoh, A. Sakakibara, and T. Suzuki, "Silsesquioxanes", Chem. Rev., 95, 1409 (1995). https://doi.org/10.1021/cr00037a012
  26. G. Li, L. Wang, H. Ni, and C. U. Pittman Jr, "Polyhedral oligomeric silsesquioxane (POSS) polymers and copolymers: a review", J. Inorg. Organomet. Polym., 11, 123 (2001). https://doi.org/10.1023/A:1015287910502
  27. K. Xie, Y. Zhang, and Y. Yu, "Preparation and characterization of cellulose hybrids grafted with the polyhedral oligomeric silsesquioxanes (POSS)", Carbohyd. Polym., 77, 858 (2009). https://doi.org/10.1016/j.carbpol.2009.03.010
  28. W. Zhang, B. Fang, A. Walther, and A. H. Muuller, "Synthesis via RAFT polymerization of tadpole-shaped organic/inorganic hybrid poly (acrylic acid) containing polyhedral oligomeric silsesquioxane (POSS) and their self-assembly in water", Macromolecules, 42, 2563 (2009). https://doi.org/10.1021/ma802803d
  29. J. Y. Lee, Y. M. Lee, B. Bhattacharya, Y. C. Nho, and J. K. Park, "Solid polymer electrolytes based on crosslinkable polyoctahedral silsesquioxanes (POSS) for room temperature lithium polymer batteries", J. Solid. State. Electr., 14, 1445 (2010). https://doi.org/10.1007/s10008-009-0968-1
  30. S. A. Madbouly and J. U. Otaigbe, "Recent advances in synthesis, characterization and rheological properties of polyurethanes and POSS/polyurethane nanocomposites dispersions and films", Prog. Polym. Sci., 43, 1283 (2009).
  31. M. Xue, X. Zhang, Z. Wu, H. Wang, X. Ding, and X. Y Tian, "Preparation and Flame Retardancy of Polyurethane/POSS Nanocomposites", Chin. J. Chem. Phys., 26, 445 (2013). https://doi.org/10.1063/1674-0068/26/04/445-450
  32. H. J. Kim, C. K. Kim, and Y. Kwon, "Ablation and fire-retardant properties of hydroxyl-terminated polybutadiene-based polyurethane-g-polyhedral oligomeric silsesquioxane composites", High Perform Polym., (2014).
  33. W. Hao, C. Fang, J. Yu, L. Zhang, and T. Xue, "Polyurethane electrospun mats strengthened and toughened by physically blended polyhedral oligomeric silsesquioxane", J. Appl. Polym. Sci., 131, 20 (2014).
  34. S. Bourbigot, T. Turf, S. Bellayer, and S. Duquesne, "Polyhedral oligomeric silsesquioxane as flame retardant for thermoplastic polyurethane", Polym. Degrad. Stabil., 94, 1230 (2009). https://doi.org/10.1016/j.polymdegradstab.2009.04.016
  35. E. Ayandele, B. Sarkar, and P. Alexandridis, "Polyhedral oligomeric silsesquioxane (POSS)-containing polymer nanocomposites", Nanomaterials, 2, 445 (2012). https://doi.org/10.3390/nano2040445
  36. X. Gu, J. Wu, and P. T. Mather, "Polyhedral oligomeric silsesquioxane (POSS) suppresses enzymatic degradation of PCLbased polyurethanes", Biomacromolecules, 12, 3066 (2011). https://doi.org/10.1021/bm2006938
  37. G. Pan, "Polyhedral oligomeric silsesquioxane (POSS)", Physical Properties of Polymers Handbook, 577 (2007).
  38. D. B. Cordes, P. D. Lickiss, and F. Rataboul, "Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes", Chem. Rev., 110, 2081 (2010). https://doi.org/10.1021/cr900201r
  39. J. D. Lichtenhan, "Polyhedral oligomeric silsesquioxanes: building blocks for silsesquioxane-based polymers and hybrid materials", Comment Inorg. Chem., 17, 115 (1995). https://doi.org/10.1080/02603599508035785
  40. A. K. Nanda, D. A. Wicks, S. A. Madbouly, and J. U. Otaigbe, "Nanostructured polyurethane/POSS hybrid aqueous dispersions prepared by homogeneous solution polymerization", Macromolecules, 39, 7037 (2006). https://doi.org/10.1021/ma060809h
  41. S. A. Madbouly, J. U. Otaigbe, A. K. Nanda, and D. A. Wicks, "Rheological behavior of POSS/polyurethane-urea nanocomposite films prepared by homogeneous solution polymerization in aqueous dispersions", Macromolecules, 40, 4982 (2007). https://doi.org/10.1021/ma070186n
  42. S. Turri and M. Levi, "Structure, dynamic properties, and surface behavior of nanostructured ionomeric polyurethanes from reactive polyhedral oligomeric silsesquioxanes", Macromolecules, 38, 5569 (2005). https://doi.org/10.1021/ma047304g
  43. K. N. Raftopoulos, C. Pandis, L. Apekis, P. Pissis, B. Janowski, K. Pielichowski, and J. Jaczewska, "Polyurethane-POSS hybrids: Molecular dynamics studies", Polymer, 5, 709 (2010).
  44. K. N. Raftopoulos, M. Jancia, D. Aravopoulou, E. Hebda, K. Pielichowski, and P. Pissis, "POSS along the Hard Segments of Polyurethane. Phase Separation and Molecular Dynamics", Macromolecules, 46, 7378 (2013). https://doi.org/10.1021/ma401417t
  45. J. P. Lewicki, S. J. Harley, A. Loui, K. Pielichowski, B. P. Mayer, B. Janowski, and R. S. Maxwell, "The influence of polyhedral oligomeric silsequioxanes on domain microstructure in polyurethane elastomers", Silicon, 5, 205 (2013). https://doi.org/10.1007/s12633-013-9147-1
  46. S. Zhang, Q. Zou, and L. Wu, "Preparation and characterization of polyurethane hybrids from reactive polyhedral oligomeric silsesquioxanes", Macromol. Mater. Eng., 291, 895 (2006). https://doi.org/10.1002/mame.200600144
  47. B. Janowski and K. Pielichowski, "Thermo (oxidative) stability of novel polyurethane/POSS nanohybrid elastomers", Thermochim. Acta, 478, 51 (2008). https://doi.org/10.1016/j.tca.2008.08.015
  48. B. Janowski and K. Pielichowski, "A Kinetic Analysis of the Thermo-Oxidative Degradation of PU/POSS nanohybrid Elastomers", Silicon, 1, (2014).
  49. J. P. Lewicki, K. Pielichowski, P. T. De La Croix, B. Janowski, D. Todd, and J. J. Liggat, "Thermal degradation studies of polyurethane/POSS nanohybrid elastomers", Polym. Degrad. Stabil., 95, 1099 (2010). https://doi.org/10.1016/j.polymdegradstab.2010.02.021
  50. J. P. Lewicki, K. Pielichowski, M. Jancia, E. Hebda, R. L. Albo, and R. S. Maxwell, "Degradative and morphological characterization of POSS modified nanohybrid polyurethane elastomers", Polym. Degrad. Stabil., 104, 50 (2014). https://doi.org/10.1016/j.polymdegradstab.2014.03.025
  51. B. X. Fu, B. S. Hsiao, S. Pagola, P. Stephens, H. White, et al., "Structural development during deformation of polyurethane containing polyhedral oligomeric silsesquioxanes (POSS) molecules", Polymer, 42, 599 (2001). https://doi.org/10.1016/S0032-3861(00)00389-X
  52. B. X. Fu, B. S. Hsiao, H. White, M. Rafailovich, et al., "Nanoscale reinforcement of polyhedral oligomeric silsesquioxane (POSS) in polyurethane elastomer", Polymer, 49, 437 (2000).
  53. P. T. Knight, K. M. Lee, H. Qin, and P. T. Mather, "Biodegradable thermoplastic polyurethanes incorporating polyhedral oligosilsesquioxane", Biomacromolecules, 9, 2458 (2008). https://doi.org/10.1021/bm8004935
  54. Q. Guo, P. T. Knight, J. Wu, and P. T. Mather, "Blends of paclitaxel with POSS-based biodegradable polyurethanes: morphology, miscibility, and specific interactions", Macromolecules, 43, 4991 (2010). https://doi.org/10.1021/ma100662x
  55. D. Neumann, M. Fisher, L. Tran, and J. G. Matisons, "Synthesis and characterization of an isocyanate functionalized polyhedral oligosilsesquioxane and the subsequent formation of an organic-inorganic hybrid polyurethane", J. Am. Chem. Soc., 124, 13998 (2002). https://doi.org/10.1021/ja0275921
  56. E. Markovic, K. Nguyen, S. Clarke, K. Constantopoulos, J. Matisons, and G. P. Simon, "Synthesis of POSS-polyurethane hybrids using octakis (m-isoprenyl-${\alpha}$, ${\alpha}^{\prime}$-dimethylbenzylisocyanato dimethylsiloxy) octasilsesquioxane (Q8M8TMI) as a crosslinking agent", J. Polym. Sci., Polym. Chem., 51, 5038 (2013). https://doi.org/10.1002/pola.26934
  57. Y. Ti and D. Chen, "Temperature dependence of hydrogen bond in Fe-OCAP/polyurethane blends", J. Appl. Polym. Sci., 130, 2265 (2013). https://doi.org/10.1002/app.39414
  58. L. Verdolotti, S. Colini, G. Porta, and S. Iannace, "Effects of the addition of LiCl, $LiClO_4$, and $LiCF_3SO_3$ salts on the chemical structure, density, electrical, and mechanical properties of rigid polyurethane foam composite", Polym. Eng. Sci., 51, 1137 (2011). https://doi.org/10.1002/pen.21846
  59. J. Zhang and C. P. Hu, "Synthesis, characterization and mechanical properties of polyester-based aliphatic polyurethane elastomers containing hyperbranched polyester segments", J. Am. Chem. Soc., 44, 3708 (2008).
  60. D. Przadka, J. Jeczalik, E. Andrzejewska, B. Marciniec, M. Dutkiewicz, and M. Szlapka, "Novel hybrid polyurethane/POSS materials via bulk polymerization", React. Funct. Polym., 73, 114 (2013). https://doi.org/10.1016/j.reactfunctpolym.2012.09.006
  61. Y. Wei, F. Cheng, H. Li, and J. Yu, "Synthesis and properties of polyurethane resins based on liquefied wood", J. Appl. Polym. Sci., 92, 351 (2004). https://doi.org/10.1002/app.20023
  62. S. Vlad, D. Filip, D. Macocinschi, I. Spiridon, A. Nistor, L. M. Gradinaru, and V. E. Musteata, ""New polyetherurethanes based on cellulose derivative for biomedical applications", Optoelectron. Adv. Mater., 4, 407 (2010).
  63. K. Y. Mya, Y. Wang, L. Shen, J. Xu, Y. Wu, X. Lu, and C. He, "Star-like polyurethane hybrids with functional cubic silsesquioxanes: Preparation, morphology, and thermomechanical properties", J. Polym. Sci., Polym. Chem., 47, 4602 (2009). https://doi.org/10.1002/pola.23512
  64. Y. Liu, Y. Ni, and S. Zheng, "Polyurethane networks modified with octa (propylglycidyl ether) polyhedral oligomeric silsesquioxane", Macromol. Chem. Phys., 207, 1842 (2006). https://doi.org/10.1002/macp.200600241
  65. Q. Zhang, H. He, K. Xi, X. Huang, X. Yu, and X. Jia, "Synthesis of N-Phenylaminomethyl POSS and its utilization in polyurethane", Macromolecules, 44, 550 (2011). https://doi.org/10.1021/ma101825j
  66. Q. Zhang, X. Huang, X. Wang, X. Jia, and K. Xi, "Rheological study of the gelation of cross-linking polyhedral oligomeric silsesquioxanes (POSS)/PU composites", Polymer, 55, 1282 (2014). https://doi.org/10.1016/j.polymer.2014.01.040
  67. Q. Zhang, X. Huang, Z. Meng, X. Jia, and K. Xi, "N-Phenylaminomethyl hybrid silica, a better alternative to achieve reinforced PU nanocomposites", RSC Adv., 4, 18146 (2014). https://doi.org/10.1039/c4ra01419g
  68. G Markevicius, S Chaudhuri, C Bajracharya, R. Rastogi, J. Xiao, C. Burnett, and T. Q. Chastek, "Polyoligomeric silsesquioxane (POSS)-hydrogenated polybutadiene polyurethane coatings for corrosion inhibition of AA2024", Prog. Org. Coat., 75, 319 (2012). https://doi.org/10.1016/j.porgcoat.2012.08.001
  69. H. Liu and S. Zheng, "Polyurethane networks nanoreinforced by polyhedral oligomeric silsesquioxane", Macromol. Rapid Commun., 26, 196 (2005). https://doi.org/10.1002/marc.200400465
  70. K. Madhavan, D. Gnanasekaran, and B. S. R. Reddy, "Poly (dimethylsiloxane-urethane) membranes: effect of linear siloxane chain and caged silsesquioxane on gas transport properties", J. Polym. Res., 18, 1851 (2011). https://doi.org/10.1007/s10965-011-9592-8
  71. K. Madhavan and B. S. R. Reddy, "Synthesis and characterization of polyurethane hybrids: Influence of the polydimethylsiloxane linear chain and silsesquioxane cubic structure on the thermal and mechanical properties of polyurethane hybrids", J. Appl. Polym. Sci., 113, 4052 (2009). https://doi.org/10.1002/app.30494
  72. G. H. Lopes, J. Junges, R. Fiorio, M. Zeni, and A. J. Zattera, "Thermoplastic polyurethane synthesis using POSS as a chain modifier", Mater. Res., 15, 698 (2012). https://doi.org/10.1590/S1516-14392012005000085
  73. M. Oaten and N. R. Choudhury, "Silsesquioxane-urethane hybrid for thin film applications", Macromolecules, 38, 6392 (2005). https://doi.org/10.1021/ma0476543
  74. R. Pan, R. Shanks, and L. L. Wang, "Crystallite Cluster Structure Formation Resulting from Semi-Enclosed Cage Interaction in TSI-POSS/PU Hybrid Composites", Advanced Materials Research, 1091, 19 (2015). https://doi.org/10.4028/www.scientific.net/AMR.1091.19
  75. R. Pan, R. Shanks, and L. Wang, "Trisilanolisobutyl POSS/polyurethane hybrid composites: preparation, WAXS and thermal properties", Polym. Bull., 71, 2453 (2014). https://doi.org/10.1007/s00289-014-1201-7
  76. L. Zheng, S. Hong, G. Cardoen, E. Burgaz, S. P. Gido, and E. B. Coughlin, "Polymer nanocomposites through controlled self-assembly of cubic silsesquioxane scaffolds", Macromolecules, 37, 8606 (2004). https://doi.org/10.1021/ma048557c
  77. K. Madhavan and B. S. R. Reddy, "Synthesis and characterization of poly (dimethylsiloxane-urethane) elastomers: Effect of hard segments of polyurethane on morphological and mechanical properties", J. Polym. Sci., Polym. Chem., 44, 2980 (2006).
  78. K. Madhavan and B. S. R. Reddy, "Structure-gas transport property relationships of poly(dimethylsiloxane-urethane) nanocomposite membranes", J. Membrane Sci., 342, 291 (2009). https://doi.org/10.1016/j.memsci.2009.07.002
  79. V. N. Bliznyuk, T. A. Tereshchenko, M. A. Gumenna, Y. P. Gomza, A. V. Shevchuk, N. S. Klimenko, and V. V. Shevchenko, "Structure of segmented poly(ether urethane)s containing amino and hydroxyl functionalized polyhedral oligomeric silsesquioxanes (POSS)", Polymer, 49, 2298 (2008). https://doi.org/10.1016/j.polymer.2008.02.044
  80. K. N. Raftopoulos, S. Koutsoumpis, M. Jancia, et al., "Reduced Phase Separation and Slowing of Dynamics in Polyurethanes with Three-Dimensional POSS-Based Cross-Linking Moieties", Macromolecules, (2015).
  81. X. Wang, Y. Hu, L. Song, W. Xing, H. Lu, P. Lv, and G. Jie, "UV-curable waterborne polyurethane acrylate modified with octavinyl POSS for weatherable coating applications", J. Polym. Res., 18, 721 (2011). https://doi.org/10.1007/s10965-010-9468-3
  82. E. H. Kim, S. W. Myoung, Y. G. Jung, and U. Paik, "Polyhedral oligomeric silsesquioxane-reinforced polyurethane acrylate", Prog. Org. Coat., 64, 205 (2009). https://doi.org/10.1016/j.porgcoat.2008.07.026

Cited by

  1. Development of Biodegradable Poly(citrate)-Polyhedral Oligomeric Silsesquioxanes Hybrid Elastomers with High Mechanical Properties and Osteogenic Differentiation Activity vol.8, pp.5, 2016, https://doi.org/10.1021/acsami.5b10378