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SCIENCE CHINA Materials, Volume 64 , Issue 9 : 2337-2347(2021) https://doi.org/10.1007/s40843-020-1611-9

A shape memory porous sponge with tunability in both surface wettability and pore size for smart molecule release

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  • ReceivedNov 23, 2020
  • AcceptedJan 7, 2021
  • PublishedMar 26, 2021

Abstract


Funded by

the National Natural Science Foundation of China(22075061,21674030,51790502)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (22075061, 21674030 and 51790502).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Liu P and Lai H carried out the investigation and wrote the paper; Xia Q and Zhang D carried out the mechanical measurements and theoretical analysis; Cheng Z, Liu Y and Jiang L contributed to the conceptualization, supervision and valuable discussion.


Author information

Pengchang Liu received his Bachelor’s degree from Harbin University of Science and Technology in 2012, and his Master’s degree at Jilin University in 2015. He is currently a PhD student at the School of Chemistry and Chemical Engineering, Harbin Institute of Technology, China. His present research interest focuses on porous shape memory polymers with liquid permeation.


Zhongjun Cheng obtained his BSc (2003) and MSc (2006) degrees in chemistry at Jilin University, China, and his PhD degree (2009) at the Institute of Chemistry, Chinese Academy of Sciences, under the supervision of Professor Lei Jiang. He is currently an associate professor at Harbin Institute of Technology, Heilongjiang, China. His scientific interest is in the design and fabrication of superwetting materials with dynamic tunable micro-/nanostructures, and related applications.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


References

[1] Yao X, Hu Y, Grinthal A, et al. Adaptive fluid-infused porous films with tunable transparency and wettability. Nat Mater, 2013, 12: 529-534 CrossRef PubMed ADS Google Scholar

[2] Wang S, Liu K, Yao X, et al. Bioinspired surfaces with superwettability: New insight on theory, design, and applications. Chem Rev, 2015, 115: 8230-8293 CrossRef PubMed Google Scholar

[3] Gao X, Xu LP, Xue Z, et al. Dual-scaled porous nitrocellulose membranes with underwater superoleophobicity for highly efficient oil/water separation. Adv Mater, 2014, 26: 1771-1775 CrossRef PubMed Google Scholar

[4] Lv W, Mei Q, Xiao J, et al. 3D multiscale superhydrophilic sponges with delicately designed pore size for ultrafast oil/water separation. Adv Funct Mater, 2017, 27: 1704293 CrossRef Google Scholar

[5] Chu Z, Feng Y, Seeger S. Oil/water separation with selective super-antiwetting/superwetting surface materials. Angew Chem Int Ed, 2015, 54: 2328-2338 CrossRef PubMed Google Scholar

[6] Yu C, Zhang P, Wang J, et al. Superwettability of gas bubbles and its application: From bioinspiration to advanced materials. Adv Mater, 2017, 29: 1703053 CrossRef PubMed Google Scholar

[7] Chen C, Huang Z, Shi L, et al. Remote photothermal actuation of underwater bubble toward arbitrary direction on planar slippery Fe3O4-doped surfaces. Adv Funct Mater, 2019, 29: 1904766 CrossRef Google Scholar

[8] Ning Y, Zhang D, Ben S, et al. An innovative design by single-layer superaerophobic mesh: Continuous underwater bubble antibuoyancy collection and transportation. Adv Funct Mater, 2020, 30: 1907027 CrossRef Google Scholar

[9] Song Y, Roy P, Paramasivam I, et al. Voltage-induced payload release and wettability control on TiO2 and TiO2 nanotubes. Angew Chem, 2010, 122: 361-364 CrossRef Google Scholar

[10] Zhang Q, Kang J, Xie Z, et al. Highly efficient gating of electrically actuated nanochannels for pulsatile drug delivery stemming from a reversible wettability switch. Adv Mater, 2018, 30: 1703323 CrossRef PubMed Google Scholar

[11] Cai Q, Qiao C, Ning J, et al. A polysaccharide-based hydrogel and PLGA microspheres for sustained P24 peptide delivery: An in vitro and in vivo study based on osteogenic capability. Chem Res Chin Univ, 2019, 35: 908-915 CrossRef Google Scholar

[12] Hu Q, Li G, Liu X, et al. Superhydrophilic phytic-acid-doped conductive hydrogels as metal-free and binder-free electrocatalysts for efficient water oxidation. Angew Chem, 2019, 131: 4362-4366 CrossRef Google Scholar

[13] Li J, Gao X, Li Z, et al. Superhydrophilic graphdiyne accelerates interfacial mass/electron transportation to boost electrocatalytic and photoelectrocatalytic water oxidation activity. Adv Funct Mater, 2019, 29: 1808079 CrossRef Google Scholar

[14] Yu X, Wang Z, Jiang Y, et al. Reversible pH-responsive surface: From superhydrophobicity to superhydrophilicity. Adv Mater, 2005, 17: 1289-1293 CrossRef Google Scholar

[15] Xu L, Chen W, Mulchandani A, et al. Reversible conversion of conducting polymer films from superhydrophobic to superhydrophilic. Angew Chem Int Ed, 2005, 44: 6009-6012 CrossRef PubMed Google Scholar

[16] Lim HS, Kwak D, Lee DY, et al. UV-driven reversible switching of a roselike vanadium oxide film between superhydrophobicity and superhydrophilicity. J Am Chem Soc, 2007, 129: 4128-4129 CrossRef PubMed Google Scholar

[17] Pan Z, Cao S, Li J, et al. Anti-fouling TiO2 nanowires membrane for oil/water separation: Synergetic effects of wettability and pore size. J Membrane Sci, 2019, 572: 596-606 CrossRef Google Scholar

[18] Ou R, Wei J, Jiang L, et al. Robust thermoresponsive polymer composite membrane with switchable superhydrophilicity and superhydrophobicity for efficient oil-water separation. Environ Sci Technol, 2016, 50: 906-914 CrossRef PubMed ADS Google Scholar

[19] Zhang W, Liu N, Zhang Q, et al. Thermo-driven controllable emulsion separation by a polymer-decorated membrane with switchable wettability. Angew Chem Int Ed, 2018, 57: 5740-5745 CrossRef PubMed Google Scholar

[20] Chen L, Wang W, Su B, et al. A light-responsive release platform by controlling the wetting behavior of hydrophobic surface. ACS Nano, 2014, 8: 744-751 CrossRef PubMed Google Scholar

[21] Yan T, Chen X, Zhang T, et al. A magnetic pH-induced textile fabric with switchable wettability for intelligent oil/water separation. Chem Eng J, 2018, 347: 52-63 CrossRef Google Scholar

[22] Xu Y, Zhang Z, Geng X, et al. Smart carbon foams with switchable wettability for fast oil recovery. Carbon, 2019, 149: 242-247 CrossRef Google Scholar

[23] Cheng M, Liu Q, Ju G, et al. Bell-shaped superhydrophilic-super-hydrophobic-superhydrophilic double transformation on a pH-responsive smart surface. Adv Mater, 2014, 26: 306-310 CrossRef PubMed Google Scholar

[24] Wang J, Sun L, Zou M, et al. Bioinspired shape-memory graphene film with tunable wettability. Sci Adv, 2017, 3: e1700004 CrossRef PubMed ADS Google Scholar

[25] Gao W, Wang J, Zhang X, et al. Electric-tunable wettability on a paraffin-infused slippery pattern surface. Chem Eng J, 2020, 381: 122612 CrossRef Google Scholar

[26] MacDiarmid AG. “Synthetic metals”: A novel role for organic polymers. Angew Chem Int Ed, 2001, 40: 2581-2590 CrossRef Google Scholar

[27] Lim HS, Lee SG, Lee DH, et al. Superhydrophobic to superhydrophilic wetting transition with programmable ion-pairing interaction. Adv Mater, 2008, 20: 4438-4441 CrossRef Google Scholar

[28] Sheng Z, Wang H, Tang Y, et al. Liquid gating elastomeric porous system with dynamically controllable gas/liquid transport. Sci Adv, 2018, 4: eaao6724 CrossRef PubMed ADS Google Scholar

[29] Zhao Y, Wang H, Zhou H, et al. Directional fluid transport in thin porous materials and its functional applications. Small, 2017, 13: 1601070 CrossRef PubMed Google Scholar

[30] Cai Y, Lin L, Xue Z, et al. Filefish-inspired surface design for anisotropic underwater oleophobicity. Adv Funct Mater, 2014, 24: 809-816 CrossRef Google Scholar

[31] Liu Y, Su Y, Guan J, et al. 2D heterostructure membranes with sunlight-driven self-cleaning ability for highly efficient oil-water separation. Adv Funct Mater, 2018, 28: 1706545 CrossRef Google Scholar

[32] Li F, Wang Z, Huang S, et al. Flexible, durable, and unconditioned superoleophobic/superhydrophilic surfaces for controllable transport and oil-water separation. Adv Funct Mater, 2018, 28: 1706867 CrossRef Google Scholar

[33] Gu J, Fan H, Li C, et al. Robust superhydrophobic/superoleophilic wrinkled microspherical MOF@rGO composites for efficient oil-water separation. Angew Chem, 2019, 131: 5351-5355 CrossRef Google Scholar

[34] Yohe ST, Colson YL, Grinstaff MW. Superhydrophobic materials for tunable drug release: Using displacement of air to control delivery rates. J Am Chem Soc, 2012, 134: 2016-2019 CrossRef PubMed Google Scholar

[35] Wang D, Guo Z, Chen Y, et al. In situ hydrothermal synthesis of nanolamellate CaTiO3 with controllable structures and wettability. Inorg Chem, 2007, 46: 7707-7709 CrossRef PubMed Google Scholar

[36] Xu YF, Ma DK, Chen XA, et al. Bisurfactant-controlled synthesis of three-dimensional YBO3/Eu3+ architectures with tunable wettability. Langmuir, 2009, 25: 7103-7108 CrossRef PubMed Google Scholar

[37] Liu P, Lai H, Luo X, et al. Superlyophilic shape memory porous sponge for smart liquid permeation. ACS Nano, 2020, 14: 14047-14056 CrossRef PubMed Google Scholar

[38] Zhang D, Cheng Z, Kang H, et al. A smart superwetting surface with responsivity in both surface chemistry and microstructure. Angew Chem, 2018, 130: 3763-3767 CrossRef Google Scholar

[39] Cheng Z, Zhang D, Lv T, et al. Superhydrophobic shape memory polymer arrays with switchable isotropic/anisotropic wetting. Adv Funct Mater, 2018, 28: 1705002 CrossRef Google Scholar

[40] Cheng Z, Zhang D, Luo X, et al. Superwetting shape memory microstructure: Smart wetting control and practical application. Adv Mater, 2021, 33: 2001718 CrossRef PubMed Google Scholar

[41] Lin C, Lv J, Li Y, et al. 4D-printed biodegradable and remotely controllable shape memory occlusion devices. Adv Funct Mater, 2019, 29: 1906569 CrossRef Google Scholar

[42] Lendlein A, Langer R. Biodegradable, elastic shape-memory polymers for potential biomedical applications. Science, 2002, 296: 1673-1676 CrossRef PubMed ADS Google Scholar

[43] Chan BQY, Low ZWK, Heng SJW, et al. Recent advances in shape memory soft materials for biomedical applications. ACS Appl Mater Interfaces, 2016, 8: 10070-10087 CrossRef PubMed Google Scholar

[44] Fang Y, Ni Y, Choi B, et al. Chromogenic photonic crystals enabled by novel vapor-responsive shape-memory polymers. Adv Mater, 2015, 27: 3696-3704 CrossRef PubMed Google Scholar

[45] Wang W, Shen D, Li X, et al. Light-driven shape-memory porous films with precisely controlled dimensions. Angew Chem, 2018, 130: 2161-2165 CrossRef Google Scholar

[46] Jiang S, Hu Y, Wu H, et al. Multifunctional Janus microplates arrays actuated by magnetic fields for water/light switches and bio-inspired assimilatory coloration. Adv Mater, 2019, 31: 1807507 CrossRef PubMed Google Scholar

[47] Chen CM, Yang S. Directed water shedding on high-aspect-ratio shape memory polymer micropillar arrays. Adv Mater, 2014, 26: 1283-1288 CrossRef PubMed Google Scholar

[48] Yao X, Dunn SS, Kim P, et al. Fluorogel elastomers with tunable transparency, elasticity, shape-memory, and antifouling properties. Angew Chem Int Ed, 2014, 53: 4418-4422 CrossRef PubMed Google Scholar

[49] Song J, Gao M, Zhao C, et al. Large-area fabrication of droplet pancake bouncing surface and control of bouncing state. ACS Nano, 2017, 11: 9259-9267 CrossRef PubMed Google Scholar

[50] Bai X, Yang Q, Fang Y, et al. Anisotropic, adhesion-switchable, and thermal-responsive superhydrophobicity on the femtosecond laser-structured shape-memory polymer for droplet manipulation. Chem Eng J, 2020, 400: 125930 CrossRef Google Scholar

[51] Lv T, Cheng Z, Zhang D, et al. Superhydrophobic surface with shape memory micro/nanostructure and its application in rewritable chip for droplet storage. ACS Nano, 2016, 10: 9379-9386 CrossRef PubMed Google Scholar

[52] Gui X, Wei J, Wang K, et al. Carbon nanotube sponges. Adv Mater, 2010, 22: 617-621 CrossRef PubMed Google Scholar

[53] Cui Y, Wang Y, Shao Z, et al. Smart sponge for fast liquid absorption and thermal responsive self-squeezing. Adv Mater, 2020, 32: 1908249 CrossRef PubMed Google Scholar

[54] Barrett EP, Joyner LG, Halenda PP. The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J Am Chem Soc, 1951, 73: 373-380 CrossRef Google Scholar

[55] Xia L, Wu H, Qiu G. Shape memory behavior of carbon nanotube-reinforced trans-1,4-polyisoprene and low-density polyethylene composites. Polym Adv Technol, 2020, 31: 107-113 CrossRef Google Scholar

[56] Tsujimoto T, Toshimitsu K, Uyama H, et al. Maleated trans-1,4-polyisoprene from Eucommia ulmoides Oliver with dynamic network structure and its shape memory property. Polymer, 2014, 55: 6488-6493 CrossRef Google Scholar

[57] Su B, Tian Y, Jiang L. Bioinspired interfaces with superwettability: From materials to chemistry. J Am Chem Soc, 2016, 138: 1727-1748 CrossRef PubMed Google Scholar

[58] Min WL, Jiang B, Jiang P. Bioinspired self-cleaning antireflection coatings. Adv Mater, 2008, 20: 3914-3918 CrossRef Google Scholar

[59] Karan S, Samitsu S, Peng X, et al. Ultrafast viscous permeation of organic solvents through diamond-like carbon nanosheets. Science, 2012, 335: 444-447 CrossRef PubMed ADS Google Scholar

[60] Dong Z, Sun Y, Chu J, et al. Multivariate metal-organic frameworks for dialing-in the binding and programming the release of drug molecules. J Am Chem Soc, 2017, 139: 14209-14216 CrossRef PubMed Google Scholar

[61] Tokarev I, Minko S. Stimuli-responsive porous hydrogels at interfaces for molecular filtration, separation, controlled release, and gating in capsules and membranes. Adv Mater, 2010, 22: 3446-3462 CrossRef PubMed Google Scholar

[62] Carrillo-Carrión C, Martínez R, Navarro Poupard MF, et al. Aqueous stable gold nanostar/ZIF-8 nanocomposites for light-triggered release of active cargo inside living cells. Angew Chem, 2019, 131: 7152-7156 CrossRef Google Scholar

[63] Nagata S, Kokado K, Sada K. Metal-organic framework tethering PNIPAM for ON-OFF controlled release in solution. Chem Commun, 2015, 51: 8614-8617 CrossRef PubMed Google Scholar

[64] Mal NK, Fujiwara M, Tanaka Y. Photocontrolled reversible release of guest molecules from coumarin-modified mesoporous silica. Nature, 2003, 421: 350-353 CrossRef PubMed ADS Google Scholar

[65] Ogoshi T, Takashima S, Yamagishi TA. Photocontrolled reversible guest uptake, storage, and release by azobenzene-modified micro-porous multilayer films of pillar[5]arenes. J Am Chem Soc, 2018, 140: 1544-1548 CrossRef PubMed Google Scholar

  • Figure 1

    Schematic illustration of the design principle and smart control of the sponge. (a) PFOS ion-doped PPy that can transit between hydrophobicity/hydrophilicity was used to coat the top surface of the sponge to provide switchable wetting performance. (b) Shape memory polymer TPI-coated sponge was used as the substrate to offer the tunable pore size. By synergistically adjusting both the surface wettability and pore size, the sponge can be smartly controlled between multiple states: (c) large pores with hydrophobic surface; (d) large pores with hydrophilic surface; (e) small pores with hydrophobic surface; and (f) small pores with hydrophilic surface, respectively.

  • Figure 2

    Photos of the as-prepared sponge at initial state (a), the pressed state (b), and the recovered state (c), respectively. (d–f) SEM images of the obtained sponge viewed from top, bottom and side, respectively. Insets are amplified images of the surface corresponding to (d) and (e), respectively. (g–i) SEM images of the sponge at the pressed state viewed from top, bottom, and side, respectively. Insets are magnified surface images corresponding to (g) and (h), respectively. (j, k) Shapes of a water droplet on the top surface when the PPy was alternately changed between the oxidation/reduction states, indicating superhydrophobicity/superhydrophilicity switching can be achieved. (l) The top surface wetting performance can be repeatedly regulated. (m) Nitrogen adsorption-desorption isotherms of the SMS at the pressed state. (n) Statistic of the average pore size for the SMS in different states. (o) The pore size can be repeatedly tuned by alternately pressing/recovering the SMS’s shape. The results confirm that the as-prepared sponge has a good SME, and both surface wettability and pore size can be smartly controlled.

  • Figure 3

    Typical 3D-reconstructed Micro-XCT images of SMS at different states: (a) initial, (b) after pressing, (c–f) corresponding to the different Rs. (g) Statistic of the pore size of the SMS as the Rs is increased, indicating that the pore size can be accurately regulated. (h) Statistic of the top surface WCA on the sponge with different pore sizes, meaning that the switchable superhydrophobicity/superhydrophilicity can be always observed regardless of the variation of pore size. (i) Statistic of the water permeation flux when the sponge shows different wettabilities and pore sizes, demonstrating that not only ON/OFF water permeation, but also precise permeation flux can be controlled.

  • Figure 4

    Application of the sponge in controlling the molecule release: cumulative release of Rh B when the sponge shows the superhydrophilicity with different pore sizes (a–c), the superhydrophobicity with different pore sizes (d–f), and the switching superhydrophobicity/superhydrophilicity with different pore sizes (g–h). These results demonstrate that through regulating surface wettability and pore size, diverse release manners with controlled release velocity can be achieved.

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