Hierarchically porous materials: Synthesis strategies and emerging applications

Abstract

Great interests have arisen over the last decade in the development of hierarchically porous materials. The hierarchical structure enables materials to have maximum structural functions owing to enhanced accessibility and mass transport properties, leading to improved performances in various applications. Hierarchical porous materials are in high demand for applications in catalysis, adsorption, separation, energy and biochemistry. In the present review, recent advances in synthesis routes to hierarchically porous materials are reviewed together with their catalytic contributions.

Key words： hierarchically porous materials; synthesis; application

Acknowledgements

This work was carried out in the framework of a program for Changjiang Scholars and Innovative Research Team (IRT_15R52) of the Chinese Ministry of Education. B. L. Su acknowledges the Chinese Central Government for an “Expert of the State” position in the Program of the “Thousand Talents”, the Chinese Ministry of Education for a “Changjiang Chaire Professor” position and a Clare Hall Life Membership at the Clare Hall College and the financial support of the Department of Chemistry, University of Cambridge. L.H. Chen acknowledges Hubei Provincial Department of Education for the “Chutian Scholar” program. This work was also financially supported by NFSC-21301133, NFSC-51472190, ISTC-2015DFE52870, SRF for ROCS SEM ([2015]311), Hubei Provincial Natural Science Foundation (2015CFB428, 2014CFB160).

References

1 Baerlocher C, Meier W, Olson D. Atlas of Zeolite Framework Types. Elsevier, 2007, 10–45

2 Kresge C T, Leonowicz M E, Roth W J, Vrtuli J C, Beck J S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature, 1992, 359(6397): 710–712

3 Zhao D, Feng J, Huo Q, Melosh W, Fredrickson G H, Chmelka B F, Stucky G D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science, 1998, 279(5350): 548–552

4 Holland B, Blanford C, Stein A. Synthesis of macroporous minerals with highly ordered three-dimensional arrays of spheroidal voids. Science, 1998, 281(5376): 538–540

5 Sing K, Everett D, Haul R, Moscou L, Pierotti R, Rouquerol J, Siemieniewska T. Reporting physisorption data for gas solid system. Pure and Applied Chemistry, 1985, 57: 603–619

6 Su B L, Sanchez C, Yang X Y. Hierarchically structured porous materials: From nanoscience to catalysis, separation, optics, energy, and life science. Germany: Wiley-VCH, 2012, 15–45

7 Yang P, Tao D, Zhao D, Feng P, Pine D, Chmelka B, Whitesides G, Stucky G. Hierarchically ordered oxides. Science, 1998, 282(5397): 2244–2246

8 Yuan Z, Su B L. Insights into hierarchically meso-macroporous structured material. Journal of Materials Chemsitry A, 2006, 16(7): 663–677

9 Pérez Ramirez J, Christensen C, Egeblad K, Christensen H, Groen J. Hierarchical zeolites: Enhanced utilisation of microporous crystals in catalysis by advances in materials design. Chemical Society Reviews, 2008, 37: 2530–2542

10 Yang X Y, Li Y, Lemaire A, Yu J, Su B L. Hierarchically structured functional materials: Synthesis strategies for multimodal porous networks. Pure and Applied Chemistry, 2009, 81(12): 2265–2307

11 Yang X Y, Alexandre L, Arnaud L, Tian G, Su B L. Self-formation phenomenon to hierarchically structured porous materials: Design, synthesis, formation mechanism and applications, Chemical Communications, 2011, 47(10): 2763–2786

12 Jacobsen C J H, Madsen C, Houzvicka J, Schmidt I, Carlsson A. Mesoporous zeolite single crystals. Journal of the American Chemical Society, 2000, 122(29): 7116–7117

13 Schmidt I, Boisen A, Gustavsson E, Stahl K, Pehrson S, Dahl S, Carlsson A, Jacobsen C J H. Carbon nanotube templated growth of mesoporous zeolite single crystals. Chemistry of Materials, 2001, 13(12): 4416–4418

14 Cho H S, Ryoo R. Synthesis of ordered mesoporous MFI zeolite using CMK carbon templates. Microporous and Mesoporous Materials, 2012, 151: 107–112

15 Chen H, Wydra J, Zhang X, Lee P S, Wang Z, Fan W, Tsapatsis M. Hydrothermal synthesis of zeolites with three-dimensionally ordered mesoporous-imprinted structure. Journal of Materials Chemsitry A, 2011, 133: 12390–12393

16 Kustova M, Egeblad K, Zhu K, Christensen C H. Versatile route to zeolite single crystals with controlled mesoporosity: In situ sugar decomposition for templating of hierarchical zeolites. Chemistry of Materials, 2007, 19(12): 2915–2917

17 Chu N B, Wang J Q, Zhang Y, Yang J H, Lu J M, Yin D H. Nestlike hollow hierarchical MCM-22 microspheres: Synthesis and exceptional catalytic properties. Chemistry of Materials, 2010, 22(9): 2757–2763

18 Wang X D, Yang W L, Tang Y, Wang Y J, Fu S K, Gao Z. Fabrication of hollow zeolite spheres. Chemical Communications, 2000, 21: 2161–2162

19 Valtchev V. Core-shell polystyrene/zeolite A microbeads. Chemistry of Materials, 2002, 14(3): 956–958

20 Petkovich N D, Stein A. Controlling macro- and mesostructures with hierarchical porosity through combined hard and soft templating. Chemical Society reviews, 2013, 42: 3721–3739

21 Huang L, Wang Z, Sun J, Miao L, Li Q, Yan Y, Zhao D. Fabrication of ordered porous structures by self-assembly of zeolite nanocrystals. Journal of the American Chemical Society, 2000, 122(14): 3530–3531

22 Zhu G, Qiu S, Gao F, Li D, Li Y, Wang R, Terasaki O. Template-assisted self-assembly of macro-micro bifunctional porous materials. Journal of Materials Chemistry, 2001, 11(6): 1687–1693

23 Sanchez C, Arribart H, Guille M M G. Biomimetism and bioinspiration as tools for the design of innovative materials and systems. Nature Materials, 2005, 4: 277–288

24 Dong A, Wang Y, Tang Y, Zhang Y, Hong A, Ren N, Gao Z. Mechanically stable zeolite monoliths with three-dimensional ordered macropores by the transformation of mesoporous silica spheres. Advanced Materials, 2002, 14(20): 1506–1510

25 Justin Thomas K R, Lin J T, Velusamy M, Tao Y T, Chuen C H. Color tuning in benzo [1, 2, 5] thiadiazole-based small molecules by amino conjugation/deconjugation: Bright red-light-emitting diode. Advanced Functional Materials, 2004, 14(1): 83–90

26 Song W, Kanthasamy R, Grassian V H, Larsen S C. Hexagonal, hollow, aluminium-containing ZSM-5 tubes prepared from mesoporous silica templates. Chemical Communications, 2004, 17: 1920–1921

27 Ren N, Yang Y H, Zhang Y H, Wang Q R, Tang Y. Heck coupling in zeolitic microcapsular reactor: A test for encaged quasi-homogeneous catalysis. Journal of Catalysis, 2007, 246(1): 215–222

28 Machoke A G, Beltrán A M, Inayat A, Winter B, Weissenberger T, Kruse N, Güttel R, Spiecker E, Schwieger W. Micro/macroporous system: MFI-type zeolite crystals with embedded macropores. Advanced Materials, 2015, 27(6): 1066–1070

29 Zhang X, Yan W, Yang H, Liu B, Li H. Gaseous infiltration method for preparation of three-dimensionally ordered macroporous polyethylene. Polymer, 2008, 49(25): 5446–5451

30 Lodge T P, Rasdal A, Li Z, Hillmyer M A. Simultaneous, segregated storage of two agents in a multicompartment micelle. Journal of the American Chemical Society, 2005, 127(50): 17608–17609

31 Sun J H, Shan Z, Maschmeyer T, Coppens M O. Synthesis of bimodal nanostructured silicas with independently controlled small and large mesopore sizes. Langmuir, 2003, 19(20): 8395–8402

32 Antonietti M, Berton B, Göltner C, Hentze H P. Synthesis of mesoporous silica with large pores and bimodal pore size distribution by templating of polymer latices. Advanced Materials, 1998, 10(2): 154–159

33 Groenewolt M, Antonietti M, Polarz S. Mixed micellar phases of nonmiscible surfactants: Mesoporous silica with bimodal pore size distribution via the nanocasting process. Langmuir, 2004, 20(18): 7811–7819

34 Avera S, Boissiere C, Grosso D, Asakawa T, Sanchez C, Linden M. One-pot aerosol synthesis of ordered hierarchical mesoporous core-shell silica nanoparticles. Chemical Communications, 2004, 10(14): 1630–1631

35 Zhou Y, Antonietti M. A novel tailored bimodal porous silica with well-defined inverse opal microstructure and super-microporous lamellar nanostructure. Chemical Communications, 2003, 20(20): 2564–2565

36 Kuang D, Brezesinski T, Smarsly B. Hierarchical porous silica materials with a trimodal pore system using surfactant templates. Journal of the American Chemical Society, 2004, 126(34): 10534–10535

37 Liu J, Yang T Y, Wang D W, Lu G Q, Zhao D Y, Qiao S Z. A facile soft-template synthesis of mesoporous polymeric and carbonaceous nanospheres. Nature Communications, 2013, 4: 2798

38 Cao S, Gody G, Zhao W, Perrier S, Peng X Y, Ducati C, Zhao D Y, Cheetham A K. Hierarchical bicontinuous porosity in metal-organic frameworks templated from functional block co-oligomer micelles. Chemical Science (Cambridge), 2013, 4(9): 3573–3577

39 Martins L, Rosa M M A, Pulcinelli S H, Santilli C V. Preparation of hierarchically structured porous aluminas by a dual soft template method. Microporous and Mesoporous Materials, 2010, 132(1-2): 268–275

40 Choi M, Cho H S, Srivastava R, Venkatesan C, Choi D H, Ryoo R. Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity. Nature Materials, 2006, 5(9): 718–723

41 Cho K, Cho H S, De Menorval L C, Ryoo R. Generation of mesoporosity in LTA zeolites by organosilane surfactant for rapid molecular transport in catalytic application. Chemistry of Materials, 2009, 21(23): 5664–5673

42 Wang H, Pinnavaia T J. MFI zeolite with small and uniform intracrystal mesopores. Angewandte Chemie International Edition, 2006, 45(45): 7603–7606

43 Choi M, Na K, Kim J, Sakamoto Y, Terasaki O, Ryoo R. Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts. Nature, 2009, 461(7261): 246–249

44 Na K, Choi M, Park W, Sakamoto Y, Terasaki O, Ryoo R. Pillared MFI zeolite nanosheets of a single-unit-cell thickness. Journal of the American Chemical Society, 2010, 132(12): 4169–4177

45 Na K, Jo C, Kim J, Cho K, Jung J, Seo Y, Messinger R J, Chmelka B F, Ryoo R. Directing zeolite structures into hierarchically nanoporous architectures. Science, 2011, 333(6040): 328–332

46 Xiao F S, Wang L, Yin C, Lin K, Di Y, Li J, Xu R, Su D S, Schlögl R, Yokoi T, Tatsumi T. Catalytic properties of hierarchical mesoporous zeolites templated with a mixture of small organic ammonium salts and mesoscale cationic polymers. Angewandte Chemie, 2006, 118(19): 3162–3165

47 Song J, Ren L, Yin C, Ji Y, Wu Z, Li J, Xiao F S. Stable, porous, and bulky particles with high external surface and large pore volume from self-assembly of zeolite nanocrystals with cationic polymer. Journal of Physical Chemistry C, 2008, 112(23): 8609–8613

48 Zhong L S, Hu J S, Liang H P, Cao A M, Song W G, Wan L J. Self-Assembled 3D flowerlike iron oxide nanostructures and their application in water treatment. Advanced Materials, 2006, 18(18): 2426–2431

49 Xu L, Sithambaram S, Zhang Y, Chen C H, Jin L, Joesten R, Suib S L. Novel urchin-like CuO synthesized by a facile reflux method with efficient olefin epoxidation catalytic performance. Chemistry of Materials, 2009, 21(7): 1253–1259

50 Holland B T, Abrams L, Stein A. Dual templating of macroporous silicates with zeolitic microporous frameworks. Journal of the American Chemical Society, 1999, 121(17): 4308–4309

51 Bian S W, Ma Z, Zhang L S, Niu F, Song W G. Silica nanotubes with mesoporous walls and various internal morphologies using hard/soft dual templates. Chemical Communications, 2009, 10(10): 1261–1263

52 Stein A, Rudisill S G, Petkovich N D. Perspective on the influence of interactions between hard and soft templates and precursors on morphology of hierarchically structured porous materials. Chemistry of Materials, 2014, 26(1): 259–276

53 Yang R C, Ma F Y, Tang D X. Template synthesis to fabrication of 3D ordered hierarchical materials. Advanced Materials Research, 2013, 602: 1355–1358

54 Zhao Q L, Wang X Y, Liu J, Wang H, Zhang Y W, Gao J, Lu Q, Zhou H Y. Design and synthesis of three-dimensional hierarchical ordered porous carbons for supercapacitors. Electrochimica Acta, 2015, 154: 110–118

55 Gundiah G. Macroporous silica-alumina composites with mesoporous walls. Bulletin of Materials Science, 2001, 24(2): 211–214

56 Drisko G L, Zelcer A, Luca V, Caruso R A, Soler-Illia G J D A. One-pot synthesis of hierarchically structured ceramic monoliths with adjustable porosity. Chemistry of Materials, 2010, 22(15): 4379–4385

57 Mandlmeier B, Szeifert J M, Fattakhova-Rohlfing D, Amenitsch H, Bein T. Formation of interpenetrating hierarchical titania structures by confined synthesis in inverse opal. Journal of the American Chemical Society, 2011, 133(43): 17274–17282

58 Petkovich N D, Stein A. Controlling macro-and mesostructures with hierarchical porosity through combined hard and soft templating. Chemical Society Reviews, 2013, 42(9): 3721–3739

59 Danumah C, Vaudreuil S, Bonneviot L, Bousmina M, Giasson S, Kaliaguine S. Synthesis of macrostructured MCM-48 molecular sieves. Microporous and Mesoporous Materials, 2001, 44: 241–247

60 Oh C G, Baek Y, Ihm S K. Synthesis of skeletal-structured biporous silicate powders through microcolloidal crystal templating. Advanced Materials, 2005, 17(3): 270–273

61 Deng Y, Liu C, Yu T, Liu F, Zhang F, Wan Y, Zhang L, Wang C, Tu B, Webley P A, Wang H, Zhao D. Facile synthesis of hierarchically porous carbons from dual colloidal crystal/block copolymer template approach. Chemistry of Materials, 2007, 19(13): 3271–3277

62 Zhang S, Chen L, Zhou S, Zhao D, Wu L. Facile synthesis of hierarchically ordered porous carbon via in situ self-assembly of colloidal polymer and silica spheres and its use as a catalyst support. Chemistry of Materials, 2010, 22(11): 3433–3440

63 Zhang F, Wang K X, Li G D, Chen J S. Hierarchical porous carbon derived from rice straw for lithium ion batteries with high-rate performance. Electrochemistry Communications, 2009, 11(1): 130–133

64 Huang W T, Zhang H, Huang Y Q, Wang W K, Wei S H. Hierarchical porous carbon obtained from animal bone and evaluation in electric double-layer capacitors. Carbon, 2011, 49(3): 838–843

65 Smith C J, Field M, Coakley C J, Awschalom D D. Organizing nanometer-scale magnets with bacterial threads. IEEE Transactions on Magnetics, 1998, 34(4): 988–990

66 Zhi L, Zhang L, Schalchi A B , Tan X H, Xu Z W, Wang H L, Olsen B C, Holt C M B, David M. Carbonized Chicken Eggshell Membranes with 3D Architectures as High-Performance Electrode Materials for Supercapacitors. Advanced Energy Materials, 2012, 2(4): 431–437

67 Song N, Jiang H, Cui T, Chang L, Wang X. Synthesis and enhanced gas-sensing properties of mesoporous hierarchical α-Fe₂O₃ architectures from an eggshell membrane. Micro & Nano Letters, 2012, 7(9): 943–946

68 Zhang W, Zhang D, Fan T J, Gu J J, Ding J, Wang H, Guo Q X, Ogawa H. Novel photoanode structure templated from butterfly wing scales. Chemistry of Materials, 2009, 21(1): 33–40

69 Zhu W J, Huang H, Zhang W K, Tao X Y, Gan Y P, Xia Y, Yang H, Guo X Z. Synthesis of MnO/C composites derived from pollen template for advanced lithium-ion batteries. Electrochimica Acta, 2015, 152(10): 286–293

70 Kim H, Kim H J, Huh H K, Hwang H J, Lee S J. Structural design of a double-layered porous hydrogel for effective mass transport. Biomicrofluidics, 2015, 9(2): 18–24

71 Wang L Q, Shin Y, Samuels W D, Exarhos G J, Moudrakovski I L, Terskikh V V, Ripmeester J A. Magnetic resonance studies of hierarchically ordered replicas of wood cellular structures prepared by surfactant-mediated mineralization. Journal of Physical Chemistry B, 2003, 107(50): 13793–13802

72 You J, Cao G. Synthesis and characterization of hierarchical biomorphic mesoporous TiO₂ nanosheets using caltrop-stem as biotemplate. Journal of Inorganic and Organometallic Polymers and Materials, 2013, 23(6): 1417–1424

73 Yang X Y, Li Z Q, Liu B, Klein-Hofmann A, Tian G, Feng Y F, Ding Y, Su D S, Xiao F S. “Fish-in-Net” encapsulation of enzymes in macroporous cages for stable, reusable, and active heterogeneous biocatalysts. Advanced Materials, 2006, 18(4): 410–414

74 Huang L, Wang H, Hayashi C Y, Tian B, Zhao D, Yan Y. Single-strand spider silk templating for the formation of hierarchically ordered hollow mesoporous silica fibers. Journal of Materials Chemistry, 2003, 13(4): 666–668

75 Zhu S, Zhang D, Chen Z, Zhou G, Jiang H, Li J. Sonochemical fabrication of morpho-genetic TiO₂ with hierarchical structures for photocatalyst. Journal of Nanoparticle Research, 2010, 12(7): 2445–2456

76 Ogasawara W, Shenton W, Davis S A, Mann S. Template mineralization of ordered macroporous chitin-silica composites using a cuttlebone-derived organic matrix. Chemistry of Materials, 2000, 12(10): 2835–2837

77 Pedroni V, Schulz P C, Gschaider de Ferreira M E, Morini M A. A chitosan-templated monolithic siliceous mesoporous-macroporous material. Colloid & Polymer Science, 2000, 278(10): 964–971

78 Walsh D, Arcelli L, Ikoma T, Tanaka J, Mann S. Dextran templating for the synthesis of metallic and metal oxide sponges. Nature Materials, 2003, 2(6): 386–390

79 Caruso R A, Antonietti M. Silica films with bimodal pore structure prepared by using membranes as templates and amphiphiles as porogens. Advanced Functional Materials, 2002, 12(4): 307–312

80 Giunta P R, Washington R P, Campbell T D, Steinbock O, Stiegman A E. Preparation of mesoporous silica monoliths with ordered arrays of macrochannels templated from electric-field-oriented hydrogels. Angewandte Chemie International Edition, 2004, 43(12): 1505–1507

81 Zhao D, Yang P, Chmelka B, Stucky G. Multiphase assembly of mesoporous-macroporous membranes. Chemistry of Materials, 1999, 11(5): 1174–1178

82 Stubenrauch C, Tessendorf R, Strey R, Lynch I, Dawson K A. Gelled polymerizable microemulsions phase behavior. Langmuir, 2007, 23(14): 7730–7737

83 Li X, Sun G, Li Y, Yu J C, Wu J, Ma G H, Ngai T. Porous TiO₂ materials through pickering high-internal phase emulsion templating. Langmuir, 2014, 30(10): 2676–2683

84 Carn F, Colin A, Achard M F, Deleuze H, Sellier E, Birot M, Backov R, Capadona J R, Shanmuganathan K, Tyler D J, Rowan S J, Weder C. General synthesis of ordered crystallized metal oxide nanoarrays replicated by microwave-digested mesoporous silica. Journal of the American Chemical Society, 2014, 14(9): 1370–1374

85 Sen T, Tiddy G J T, Casci J L, Anderson M W. Macro-cellular silica foams: Synthesis during the natural creaming process of an oil-in-water emulsion. Chemical Communications, 2003, 17: 2182–2183

86 Zhang H F, Hardy G C, Rosseinsky M J, Cooper A I. Uniform emulsion-templated silica beads with high pore volume and hierarchical porosity. Advanced Materials, 2003, 15(1): 78–81

87 Carn F, Colin A, Achard M F, Deleuze H, Sellier E, Birot M, Backov R. Inorganic monoliths hierarchically textured via concentrated direct emulsion and micellar templates. Journal of Materials Chemistry, 2004, 14(9): 1370–1376

88 Li H, Jin J, Wu W, Chen C, Li L, Li Y, Zhao W, Gu J, Chen G, Shi J. Synthesis of a hierarchically macro-/mesoporous zeolite based on a micro-emulsion mechanism. Journal of Materials Chemistry, 2011, 21(48): 19395–19401

89 Hu X F, Cheng F Y, Han X P, Zhang T R, Chen J. Oxygen bubble-templated hierarchical porous ε-MnO₂ as a superior catalyst for rechargeable Li-O₂ batteries. Small, 2015, 11(7): 809–813

90 Bagshaw S A. Morphosynthesis of macrocellular mesoporous silicate foams. Chemical Communications, 1999, 9(9): 767–768

91 Carn F, Colin A, Achard M F, Deleuze H, Saadi Z, Backov R. Rational design of macrocellular silica scaffolds obtained by a tunable sol-gel foaming process. Advanced Materials, 2004, 16(2): 140–144

92 Carn F, Colin A, Achard M F, Deleuze H, Sanchez C, Backov R. Anatase and rutile TiO₂ macrocellular foams: Air-liquid foaming sol-gel process towards controlling cell sizes, morphologies, and topologies. Advanced Materials, 2005, 17(1): 62–66

93 Suzuki K, Ikari K, Imai H. Synthesis of mesoporous silica foams with hierarchical trimodal pore structures. Journal of Materials Chemistry, 2003, 13(7): 1812–1816

94 Wang J G, Li F, Zhou H J, Sun P C, Ding D T, Chen T H. Silica hollow spheres with ordered and radially oriented amino-functionalized mesochannels. Chemistry of Materials, 2009, 21(4): 612–620

95 Li Y, Shi J. Hollow-structured mesoporous materials: Chemical synthesis, functionalization and applications. Advanced Materials, 2014, 26(20): 3176–3205

96 Miyamoto M, Kamei T, Nishiyama N, Egashira Y, Ueyama K. Single crystals of ZSM-5/silicalite composites. Advanced Materials, 2005, 17(16): 1985–1988

97 Porcher F, Dusausoy Y, Souhassou M, Lecomte C. Epitaxial growth of zeolite X on zeolite A and twinning in zeolite A: Structural and topological analysis. Mineralogical Magazine, 2000, 64(1): 1–8

98 Thomas J M, Millward G R. Direct, real-space determination of intergrowths in ZSM-5/ZSM-11 catalysts. Journal of the Chemical Society. Chemical Communications, 1982, (24): 1380–1383

99 Goossens A M, Wouters B H, Buschmann V, Martens J A. Oriented FAU zeolite films on micrometer-sized EMT crystals. Advanced Materials, 1999, 11(7): 561–564

100 Lillerud K P, Raeder J H. On the synthesis of erionite-offretite intergrowth zeolites. Zeolites, 1986, 6(6): 474–483

101 Bouizi Y, Rouleau L, Valtchev V P. Bi-phase MOR/MFI-type zeolite core-shell composite. Microporous and Mesoporous Materials, 2006, 91(1-3): 70–77

102 Yonkeu A L, Miehe G, Fuess H, Goossens A M, Martens J A. A new overgrowth of mazzite on faujasite zeolite crystal investigated by X-ray diffraction and electron microscopy. Microporous and Mesoporous Materials, 2006, 96(1-3): 396–404

103 Wakihara T, Yamakita S, Iezumi K, Okubo T. Heteroepitaxial growth of a zeolite film with a patterned surface-texture. Journal of Americal Chemistry Society, 2003, 125(41): 12388–12389

104 Bouizi Y, Diaz I, Rouleau L, Valtchev V P. Core-shell zeolite microcomposites. Advanced Functional Materials, 2005, 15(12): 1955–1960

105 Zheng J J, Zeng Q H, Ma J H, Zhang X W, Sun W F, Li R F. Synthesis of hollow zeolite composite spheres by using. BETA zeolite crystal as template. Chemistry Letters, 2010, 39(4): 330–331

106 Tsang C, Dai P, Petty R H. Upgrading and catalytic cracking catalyst. US Patent 5888921, <Date>1999-03-30</Date>

107 Lei Q, Zhao T B, Li F, Wang Y Y, Zheng M F. Fabrication of hierarchically structured monolithic silicalite-1 through steam-assisted conversion of macroporous silica gel. Chemistry Letters, 2006, 35(5): 490–491

108 Lei Q, Zhao T L F, Li Y, Zhang L L, Wang Y. Catalytic cracking of large molecules over hierarchical zeolites. Chemical Communications, 2006, 16: 1769–1771

109 Lei Q, Zhao T, Li F, Wang Y F, Hou L. Zeolite beta monoliths with hierarchical porosity by the transformation of bimodal pore silica gel. Journal of Porous Materials, 2008, 15(6): 643–646

110 Sachse A, Galarneau A, Di Renzo F, Fajula F, Coq B. Synthesis of zeolite monoliths for flow continuous processes: The case of sodalite as a basic catalyst. Chemistry of Materials, 2010, 22(14): 4123–4125

111 Yang X Y, Tian G, Chen L H, Li Y, Rooke J C, Wei Y X, Liu Z M, Deng Z, Van Tendeloo G, SuB L. Well organized zeolite nanocrystal aggregates with interconnected hierarchically micro-meso- macropore systems showing enhanced catalytic performance. Chemistry European Journal A, 2011, 17(52): 14987–14995

112 SUN M H, Huang S Z, Chen L H, Li Y, Yang X Y, Yuan Z Y, Su B L. Applications of hierarchically structured porous materials from energy storage and conversion, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine Chemical Society reviews, 2016, 45: 3479–3563

113 Li X Y, Chen L H, Li Y, Rooke J C, Deng Z, Hu Z Y, Liu J, Krief A, Yang X Y, Su B L. Tuning the structure of a hierarchically porous ZrO₂ for dye molecule depollution. Microporous and Mesoporous Materials, 2012, 152: 110–121

114 Li X Y, Chen L H, Li Y, Rooke J C, Wang C, Lu Y, Krief A, Yang X Y, Su B L. Self-generated hierarchically porous titania with high surface area: Photocatalytic activity enhancement by macrochannel structure. Journal of Colloid and Interface Science, 2012, 368(1): 128–138

115 Chen L H, Li X Y, Tian G, Li Y, Tan H Y, Van Tendeloo G, Zhu G S, Qiu S L, Yang X Y, Su B L. Multimodal zeolite-beta-based catalysts with a hierarchical, three-level pore structure. ChemSusChem, 2011, 4(10): 1452–1456

116 Chen L H, Li X Y, Tian G, Li Y, Rooke J C, Zhu G S, Qiu S L, Yang X Y, Su B L. Highly stable and reusable multimodal zeolite TS-1 based catalysts with hierarchically interconnected three-level micro-meso-macroporous structure. Angewandte Chemie International Edition, 2011, 50(47): 11156–11161

117 Chen L H, Xu S T, Li X Y, Tian G, Li Y, Rooke J C, Su B L. Multimodal Zr-Silicalite-1 zeolite nanocrystal aggregates with interconnected hierarchically micro-meso-macroporous architecture and enhanced mass transport property. Journal of Colloid and Interface Science, 2012, 377(1): 368–374

118 Blin J L, Leonard A, Yuan Z Y, Gigot L, Vantomme A, Cheetham A K, Su B L. Hierarchically mesoporous/macroporous metal oxides templated from polyethylene oxide surfactant assemblies. Angewand Chemie International Edit ion, 2003, 42: 2872–2875

119 Li Y, Yang X Y, Tian G, Vantomme A, Yu J, Van T G, Su B L. Chemistry of trimethyl aluminum: A spontaneous route to thermally stable 3D crystalline macroporous alumina foams with a hierarchy of pore sizes. Chemistry of Materials, 2010, 22(10): 3251–3258

120 Yuan Z Y, Vantomme A, Léonard A, Su B L. Surfactant-assisted synthesis of unprecedented hierarchical meso-macrostructured zirconia. Chemical Communications, 2003, 9(13): 1558–1559

121 Deng W, Toepke M W, Shanks B H. Surfactant-assisted synthesis of alumina with hierarchical nanopores. Advanced Functional Materials, 2003, 13(1): 61–65

122 Collins A, Carriazo D, Davis S A, Mann S. Spontaneous template-free assembly of ordered macroporous titania. Chemical Communications, 2004, 5(5): 568–569

123 Léonard A, Blin J L, Su B L. One-pot surfactant assisted synthesis of aluminosilicate macrochannels with tunable micro- or mesoporous wall structure. Chemistry Communications, 2003: 2568–2569

124 Ren T Z, Yuan Z Y, Su B L. Microwave-assisted preparation of hierarchical mesoporous-macroporous boehmite AlOOH and g-Al₂O₃. Langmuir, 2004, 20(4): 1531–1534

125 Ren T Z, Yuan Z Y, Su B L. A novel macroporous structure of mesoporous titanias: Synthesis and characterisation. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2004, 241(1-3): 67–73

126 Deng W, Shanks B H. Synthesis of hierarchically structured aluminas under controlled hydrodynamic conditions. Chemistry of Materials, 2005, 17(12): 3092–3100

127 Su B L, Léonard A, Yuan Z Y. Highly ordered mesoporous CMI-n materials and hierarchically structured meso-macroporous compositions. Comptes Rendus. Chimie, 2005, 8(3-4): 713–726

128 Yuan Z Y, Ren T Z, Azioune A, Pireaux J J, Su B L. Marvelous self-assembly of hierarchically nanostructured porous zirconium phosphate solid acids with high thermal stability. Catalysis Today, 2005, 105(105): 647–654

129 Lemaire A, Wang Q Y, Wei Y X, Liu Z M, Su B L. Hierarchically structured meso-macroporous aluminosilicates with high tetrahedral aluminium content in acid catalysed esterification of fatty acids. Journal of Colloid & Interface Science, 2011, 363: 511–520

130 Vantomme A, Léonard A, Yuan Z Y, Su B L. Hierarchically nanostructured porous functional ceramics key. Engineering Materials, 2007, 336: 1933–1938

131 Lemaire A, Su B L. Tailoring the porous hierarchy and the tetrahedral aluminum content by using carboxylate ligands: hierarchically structured macro-mesoporous aluminosilicates from a single molecular source. Langmuir, 2010, 26(22): 17603–17616

132 Lemaire A, Rooke J C, Chen L H, Su B L. Direct observation of macrostructure formation of hierarchically structured meso-macroporous aluminosilicates with 3D interconnectivity by optical microscope. Langmuir, 2011, 27(6): 3030–3043

133 Zhang K B, Fu Z Y, Nakayama T, Suzuki T, Suematsu H, Niihara K. One-pot synthesis of hierarchically macro/mesoporous Al₂O₃ monoliths from a facile sol–gel process. Materials Research Bulletin, 2011, 46(11): 2155–2162

134 Yang X Y, Li Y, Van T G, Xiao F, Su B L. One-pot synthesis of catalytically stable and active nanoreactors: Encapsulation of size-controlled nanoparticles within a hierarchically macroporous core@ ordered mesoporous shell system. Advanced Materials, 2009, 21(13): 1368–1372

135 Kloestra K R, van Bekkum H, Jansen J C. Mesoporous material containing framework tectosilicate by pore-wall recrystallization. Chemical Communications, 1997, 23(23): 2281–2282

136 Hu M C, Zielke J T, Byers C H, Lin J S, Harris M T. Probing the early-stage/rapid processes in hydrolysis and condensation of metal alkoxides. Journal of Materials Science, 2000, 35(8): 1957–1971

137 Su B L, Vantomme A, Surahy L, Pirard R, Pirard J P. Hierarchical multimodal mesoporous carbon materials with parallel macrochannels. Chemistry of Materials, 2007, 19(13): 3325–3333

138 Vantomme A, Yuan Z Y, Su B L. One-pot synthesis of a high-surface-area zirconium oxide material with hierarchically three-length-scaled pore structure. New Journal of Chemistry, 2004, 28(9): 1083–1085

139 Léonard A, Su B L. Hierarchical aluminosilicate macrochannels with structured mesoporous walls: Towards a single catalyst for multistep reactions. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2007, 300(1-2): 129–135

140 Hakim S H, Shanks B H. A comparative study of macroporous metal oxides synthesized via a unified approach. Chemistry of Materials, 2009, 21(10): 2027–2038

141 Léonard A, Vantomme A, Bouvy C, Moniotte N, Mariaulle P, Su B L. Highly ordered mesoporous and hierarchically nanostructured meso-macroporous materials for nanotechnology, biotechnology, information technology and medical applications. Nanopages, 2006, 1(1): 1–44

142 Yuan Z Y, Ren T Z, Su B L. Hierarchically mesostructured titania materials with an unusual interior macroporous structure. Advanced Materials, 2003, 15(17): 1462–1465

143 Ren T Z, Yuan Z Y, Su B L. Template-free synthesis of hierarchical mesoporous alumina-based materials with uniform channel-like macrostructures. Studies in Surface Science & Catalysis, 2007, 165: 287–290

144 Yuan Z Y, Ren T Z, Vantomme A, Su B L. Facile and generalized preparation of hierarchically mesoporous-macroporous binary metal oxide materials. Chemistry of Materials, 2004, 16(24): 5096–5106

145 Ren T Z, Yuan Z Y, Su B L. Thermally stable macroporous zirconium phosphates with supermicroporous walls: A self-formation phenomenon of hierarchy. Chemical Communications, 2004, (23): 2730–2731

146 Ren T Z, Yuan Z Y, Azioun A, Pireaux J J, Su B L. Tailoring the porous hierarchy of titanium phosphates. Langmuir, 2006, 22(8): 3886–3894

147 Yuan Z Y, Ren T Z, Azioune A, Pireaux J J, Su B L. Self-assembly of hierarchically mesoporous-macroporous phosphated nanocrystalline aluminum (oxyhydr) oxide materials. Chemistry of Materials, 2006, 18(7): 1753–1767

148 Wan Y, Zhao D. On the controllable soft-templating approach to mesoporous silicates. Chemical Reviews, 2007, 107(7): 2821–2860

149 Zhao D, Huo Q, Feng J, Chmelka B F, Stucky G D. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures. Journal of the American Chemical Society, 1998, 120(24): 6024–6036

150 Ryoo R, Ko C H, Kruk M, Antochshuk V, Jaroniec M. Block-copolymer- templated ordered mesoporous silica: Array of uniform mesopores or mesopore-micropore network. Journal of Physical Chemistry B, 2000, 104(48): 11465–11471

151 Imperor-Clerc M, Davidson P, Davidson A. Existence of a microporous corona around the mesopores of silica-based SBA-15 materials templated by triblock copolymers. Journal of the American Chemical Society, 2000, 122(48): 11925–11933

152 Wang J, Feng S, Song Y, Li W, Gao W, Elzatahry A A, Aldhayan D, Xia Y, Zhao D. Elzatahry, Zhao A A. Synthesis of hierarchically porous carbon spheres with yolk-shell structure for high performance supercapacitors. Catalysis Today, 2015, 243: 199–208

153 Haskouri E I, de Zárate J, Guillem D O, Latorre C, Caldés J, Beltrán M, Beltrán A, Descalzo D, Rodríguez-López A B, Gertrudis Martínez-Máñez R. Silica-based powders and monoliths with bimodal pore systems. Chemical Communications, 2002, 4(4): 330–331

154 Kim J H, Fang B, Song M Y, Yu J S. Topological transformation of thioether-bridged organosilicas into nanostructured functional materials. Chemistry of Materials, 2012, 24(12): 2256–2264

155 Wu D, Fu R, Dresselhaus M S, Dresselhaus G. Nano-structure control of carbon aerogels via a microemulsion-templated sol-gel polymerization method. Carbon, 2006, 44(4): 675–681

156 Fu R, Zheng B, Liu J, Dresselhaus M S, Dresselhaus G, Satcher J H, Baumann T F. The fabrication and characterization of carbon aerogels by gelation and supercritical drying in isopropanol. Advanced Functional Materials, 2003, 13(7): 558–562

157 Nakanishi K, Soga N. Phase separation in gelling silica-organic polymer solution: Systems containing poly(sodium styrenesulfonate). Journal of the American Ceramic Society, 1991, 74(10): 2518–2530

158 Sun Y. Porous zirconium phosphates prepared by surfactant-assistedprecipitation. Journal of Materials Chemistry, 2000, 10(10): 2320–2324

159 Unger K K, Tanaka N, Machtejevas E. Monolithic silicas in separation science: Concepts, syntheses, characterization, modeling and applications. Germany: Wiley-VCH, 2010, 125–161

160 Inagaki S, Guan S, Fukushima Y, Ohsuna T, Terasaki O. Novel mesoporous materials with a uniform distribution of organic groups and inorganic oxide in their frameworks. Journal of the American Chemical Society, 1999, 121(41): 9611–9614

161 Sun X H, Zheng C M, Qiao M Q, Yan J L, Wang X P, Guan N J. Bioinspired synthesis of hierarchical macro-mesoporous titania with tunable macroporous morphology using cell-assemblies as macrotemplates. Chemical Communications, 2009: 4750–4752

162 Konishi J, Fujit K, Nakanishi K, Hirao K. Monolithic TiO₂ with controlled multiscale porosity via a template-free sol-gel process accompanied by phase separation. Chemistry of Materials, 2006, 18(25): 6069–6074

163 Smått J H, Schunk S, Lindén M. Versatile double-templating synthesis route to silica monoliths exhibiting a multimodal hierarchical porosity. Chemistry of Materials, 2003, 15(12): 2354–2361

164 Takahashi R, Sato S, Sodesawa T, Suzuki K, Tafu M, Nakanishi K, Soga N. Phase separation in sol-gel process of alkoxide-derived silica-zirconia in the presence of polyethylene oxide. Journal of the American Ceramic Society, 2001, 84(9): 1968–1976

165 Murai S, Fujita K, Nakanishi K, Hirao K. Morphology control of phase-separation-induced alumina-silica macroporous gels for rare-earth-doped scattering media. Journal of Physical Chemistry B, 2004, 108(43): 16670–16676

166 Nakanishi K, Kobayashi Y, Amatani T, Hirao K, Kodaira T. Spontaneous formation of hierarchical macro-mesoporous ethane-silica monolith. Chemistry of Materials, 2004, 16(19): 3652–3658

167 Amatani T, Nakanishi K, Hirao K, Kodaira T. Monolithic periodic mesoporous silica with well-defined macropores. Chemistry of Materials, 2005, 17(8): 2114–2119

168 Brandhuber D, Torma V, Raab C, Peterlik H, Kulak A, Hüsing N. Glycol-modified silanes in the synthesis of mesoscopically organized silica monoliths with hierarchical porosity. Chemistry of Materials, 2005, 17(16): 4262–4271

169 Konishi J, Fujita K, Nakanishi K, Hirao K, Komarneni S, Parker J C. Macroporous Morphology Induced by Phase Separation in Sol-Gel Systems Derived from Titania Colloid, MRS Proceedings. Cambridge: Cambridge University Press, 2003, 788: 8–11

170 Huesing N, Raab C, Torma V, Roig A, Peterlik H. Periodically mesostructured silica monoliths from diol-modified silanes. Chemistry of Materials, 2003, 15(14): 2690–2692

171 Wu Q L, Subramanian N, Rankin S E. Hierarchically porous titania thin film prepared by controlled phase separation and surfactant templating. Langmuir, 2011, 27(15): 9557–9566

172 François B, Pitois O, François J. Polymer films with a self-organized honeycomb morphology. Advanced Materials, 1995, 7(12): 1041–1044

173 Saito Y, Shimomura M, Yabu H. Dispersion of Al₂O₃ nanoparticles stabilized with mussel-inspired amphiphilic copolymers in organic solvents and formation of hierarchical porous films by the breath figure technique. Chemical Communications, 2013, 49(54): 6081–6083

174 Kon K, Brauer C N, Hidaka K, Löhmannsröben H G, Karthaus O. Preparation of patterned zinc oxide films by breath figure templating. Langmuir, 2010, 26(14): 12173–12176

175 Peng J, Han Y, Yang Y, Li B. The influencing factors on the macroporous formation in polymer films by water droplet templating. Polymer, 2004, 45(2): 447–452

176 Sel O, Laberty-Robert C, Azais T, Sanchez C. Designing meso-and macropore architectures in hybrid organic-inorganic membranes by combining surfactant and breath figure templating (BFT). Physical Chemistry Chemical Physics, 2009, 11(19): 3733–3741

177 Böker A, Lin Y, Chiapperini K, Horowitz R, Thompson M, Carreon V, Xu T, Abetz C, Skaff H, Dinsmore A D, Emrick T, RussellT P. Hierarchical nanoparticle assemblies formed by decorating breath figures. Nature Materials, 2004, 3(5): 302–306

178 Srinivasarao M, Collings D, Philips A, Patel S. Three-dimensionally ordered array of air bubbles in a polymer film. Science, 2001, 292(5514): 79–83

179 Gao Y, Hou Y, Beaujuge P M. Arrays of hollow silica half-nanospheres via the breath figure approach. Advanced Materials Interfaces, 2015, 2(9): 1500078

180 Deville S. Freeze-casting of porous ceramics: A review of current achievements and issues. Advanced Engineering Materials, 2008, 10(3): 155–169

181 Chatterji S. Aspects of the freezing process in a porous material–water system: Part 1. Freezing and the properties of water and ice. Cement and Concrete Research, 1999, 29(4): 627–630

182 DeSimone J M, Guan Z, Elsbernd C S. Synthesis of fluoropolymers in supercritical carbon dioxide. Science, 1992, 257(5072): 945–947

183 Ho M H, Kuo P Y, Hsieh H J, Hsien T Y, Hou L T, Lai J Y, Wang D M. Preparation of porous scaffolds by using freeze-extraction and freeze-gelation methods. Biomaterials, 2004, 25(1): 129–138

184 Kang H W, Tabata Y, Ikada Y. Fabrication of porous gelatin scaffolds for tissue engineering. Biomaterials, 1999, 20(14): 1339–1344

185 Hsieh C Y, Tsai S P, Ho M H, Wang D M, Liu C E, Hsieh C H, Hsieh H J. Analysis of freeze-gelation and cross-linking processes for preparing porous chitosan scaffolds. Carbohydrate Polymers, 2007, 67(1): 124–132

186 Daamen W F, Van Moerkerk H T B, Hafmans T, Buttafoco L, Poot A A, Veerkamp J H, Van Kuppevelt T H. Preparation and evaluation of molecularly-defined collagen-elastin-glycosaminoglycan scaffolds for tissue engineering. Biomaterials, 2003, 24(22): 4001–4009

187 Yannas I V, Burke J F, Gordon P L, Huang C, Rubenstein R H. Design of an artificial skin. II. Control of chemical composition. Journal of Biomedical Materials Research, 1980, 14(2): 107–132

188 Shalaby W S W, Peck G E, Park K. Release of dextromethorphan hydrobromide from freeze-dried enzyme-degradable hydrogels. Journal of Controlled Release, 1991, 16(3): 355–363

189 Mukai S R, Nishihara H, Tamon H. Formation of monolithic silica gel microhoneycombs (SMHs) using pseudosteady state growth of microstructural ice crystals. Chemical Communications, 2004, 7(7): 874–875

190 Nishihara H, Mukai S R, Yamashita D, Tamon H. Ordered macroporous silica by ice templating. Chemistry of Materials, 2005, 17(3): 683–689

191 Mahler W, Bechtold M F. Freeze-formed silica fibres. Nature, 1980, 285(5759): 27–28

192 Fukasawa T, Ando M, Ohji T, Kanzaki S. Synthesis of porous ceramics with complex pore structure by freeze-dry processing. Journal of the American Ceramic Society, 2001, 84(1): 230–232

193 Sofie S W, Dogan F. Freeze casting of aqueous alumina slurries with glycerol. Journal of the American Ceramic Society, 2001, 84(7): 1459–1464

194 Gutiérrez M C, Jobbágy M, Rapún N, Ferrer M L, del Monte F A. Biocompatible bottom-up route for the preparation of hierarchical biohybrid materials. Advanced Materials, 2006, 18(9): 1137–1140

195 Zhang H, Hussain I, Brust M, Butler M F, Rannard S P, Cooper A I. Aligned two-and three-dimensional structures by directional freezing of polymers and nanoparticles. Nature Materials, 2005, 4(10): 787–793

196 Perriman A W, Brogan A P, Cölfen H, Tsoureas N, Owen G R, Mann S. Reversible dioxygen binding in solvent-free liquid myoglobin. Nature Chemistry, 2010, 2(8): 622–626

197 Eckert C A, Knutson B L, Debenedetti P G. Supercritical fluids as solvents for chemical and materials processing. Nature, 1996, 383(6598): 313–318

198 Cooper A I. Porous materials and supercritical fluids. Advanced Materials, 2003, 15(13): 1049–1059

199 DeSimone J M, Maury E E, Menceloglu Y Z, McClain J B, Romack T J, Combes J R. Dispersion polymerizations in supercritical carbon dioxide. Science, 1994, 265(5170): 356–359

200 Kendall J L, Canelas D A, Young J L, DeSimone J M. Polymerizations in supercritical carbon dioxide. Chemical Reviews, 1999, 99(2): 543–564

201 DeSimone J M. Practical approaches to green solvents. Science, 2002, 297(5582): 799–803

202 Partap S, Rehman I, Jones J R, Darr J A. Supercritical carbon dioxide in water emulsion-templated synthesis of porous calcium alginate hydrogels. Advanced Materials, 2006, 18(4): 501–504

203 Palocci C, Barbetta A, La Grotta A, Dentini M. Porous biomaterials obtained using supercritical CO₂-water emulsions. Langmuir, 2007, 23(15): 8243–8251

204 Butler R, Hopkinson I, Cooper A I. Synthesis of porous emulsion-templated polymers using high internal phase CO₂-in-water emulsions. Journal of the American Chemical Society, 2003, 125(47): 14473–14481

205 Langer R, Vacanti J. Tissue engineering. Science, 1993, 260(5110): 920–926

206 Sui R, Charpentier P. Synthesis of metal oxide nanostructures by direct sol-gel chemistry in supercritical fluids. Chemical Reviews, 2012, 112(6): 3057–3082

207 Xu S, Yang H, Wang K, Wang B, Xu Q. Effect of supercritical CO₂ on fabrication of free-standing hierarchical graphene oxide/carbon nanofiber/polypyrrole film and its electrochemical property. Physical Chemistry Chemical Physics, 2014, 16(16): 7350–7357

208 Wang M, Zhao B, Xu S, Lin L, Liu S, He D. Synthesis of hierarchically structured ZnO nanomaterials via a supercritical assisted solvothermal process. Chemical Communications, 2014, 50(8): 930–932

209 Nugroho A, Kim S J, Chang W, Chung K Y, Kim J. Design and fabrication of hierarchically porous carbon with a template-free method. Scientific Reports, 2014, 4: 6349

210 Wang L, Zhuo L, Zhang C, Zhao F. Supercritical carbon dioxide assisted deposition of Fe₃O₄ nanoparticles on hierarchical porous carbon and their lithium-storage performance. Chemistry (Weinheim an der Bergstrasse, Germany), 2014, 20(15): 4308–4315

211 Nugroho A, Yoon D, Joo O S, Chung K Y, Kim J. Continuous synthesis of Li₄Ti₅O₁₂ nanoparticles in supercritical fluids and their electrochemical performance for anode in Li-ion batteries. Chemical Engineering Journal, 2014, 258: 357–366

212 Davis S A, Burkett S L, Mendelson N H, Mann S. Bacterial templating of ordered macrostructures in silica and silica-surfactant mesophases. Nature, 1997, 385(6615): 420–423

213 Meldrum F C, Seshadri R. Porous gold structures through templating by echinoidskeletal plates. Chemical Communications, 2000, 1(1): 29–30

214 Qi L, Li J, Ma J. Biomimetic morphogenesis of calcium carbonate in mixed solutions of surfactants and double-hydrophilic block copolymers. Advanced Materials, 2002, 14(4): 300–303

215 Cook G, Timms P L, Göltner Spickermann C. Exact replication of biological structures by chemical vapor deposition of silica. Angewandte Chemie International Edition, 2003, 42(5): 557–559

216 Hall S R, Bolger H, Mann S. Morphosynthesis of complex inorganic forms using pollen grain templates. Chemical Communications, 2003, 22(22): 2784–2785

217 Valtchev V P, Smaihi M, Faust A C, Vidal L. Biomineral-silica-induced zeolitzation of equisetum arvense. Angewandte Chemie International Edition, 2003, 42(24): 2782–2785

218 Sim K, Youn H J. Preparation of porous sheets with high mechanical strength by the addition of cellulose nanofibrils. Cellulose, 2016, 23(2): 1383–1392

219 Farin D, Peleg S, Yavin D, Avnir D. Applications and limitations of boundary-line fractal analysis of irregular surfaces: Proteins, aggregates, and porous materials. Langmuir, 1985, 1(4): 399–407

220 Shim I K, Jung M R, Kim K H, Seol Y J B, Park Y J D, Park W H, Lee S J. Novel three-dimensional scaffolds of poly(L-lactic acid) microfibers using electrospinning and mechanical expansion: Fabrication and bone regeneration. Journal of Biomedical Materials Research Part B: Applied Biomaterials, 2010, 95(1): 150–160

221 Jia Y, Han W, Xiong G, Yang W. Layer-by-layer assembly of TiO₂ colloids onto diatomite to build hierarchical porous materials. Journal of Colloid and Interface Science, 2008, 323(2): 326–331

222 Zampieri A, Mabande G T P, Selvam T, Schwieger W, Rudolph A, Hermann R, Sieber H, Greil P. Biotemplating of Luffa cylindrica sponges to self-supporting hierarchical zeolite macrostructures for bio-inspired structured catalytic reactors. Materials Science and Engineering, 2006, 26(1): 130–135

223 Holmes S M, Graniel-Garcia B E, Foran P, Hill P, Roberts E P L, Sakakini B H, Newton J M. A novel porous carbon based on diatomaceous earth. Chemical Communications, 2006, 25(25): 2662–2663

224 Vrieling E G, Beelen T P M, van Santen R A, Gieskes W W. Mesophases of (bio) polymer-silica particles inspire a model for silica biomineralization in diatoms. Angewandte Chemie International Edition, 2002, 41(9): 1543–1546

225 Wang Y, Tang Y, Dong A, Wang X, Ren N, Gao Z. Zeolitization of diatomite to prepare hierarchical porous zeolite materials through a vapor-phase transport process. Journal of Materials Chemistry, 2002, 12(6): 1812–1818

226 Yang H, Zhao D. Synthesis of replica mesostructures by the nanocasting strategy. Journal of Materials Chemistry, 2005, 15: 1217–1231

227 Polarz S, Antonietti M. Porous materials via nanocasting procedures: Innovative materials and learning about soft-matter organization. Chemical Communications, 2002, 22(22): 2593–2604

228 Kyotani T, Nagai T, Inoue S, Tomita A. Formation of new type of porous carbon by carbonization in zeolite nanochannels. Chemistry of Materials, 1997, 9(2): 609–615

229 Lu A, Schmidt W, Spliethoff B, Schüth F. Synthesis and characterization of nanocast silica NCS-1 with CMK-3 as a template. Chemistry (Weinheim an der Bergstrasse, Germany), 2004, 10(23): 6085–6092

230 Ryoo R, Joo S H, Jun S. Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation. Journal of Physical Chemistry B, 1999, 103(37): 7743–7746

231 Schüth F. Endo- und exotemplate zur erzeugung von anorganischen materialien mit großer spezifischer oberfläChe. Angewandte Chemie, 2003, 115(31): 3730–3750

232 Velev O D, Jede T A, Lobo R F, Lenhoff A M. Porous silica via colloidal crystallization. Nature, 1997, 389(6650): 447–448

233 Lu A H, Schüth F. Nanocasting: A versatile strategy for creating nanostructured porous materials. Advanced Materials, 2006, 18(14): 1793–1805

234 Jun S, Joo S H, Ryoo R, Kruk M, Jaroniec M, Liu Z, Ohsuna T, Terasaki O. Synthesis of new, nanoporous carbon with hexagonally ordered mesostructure. Journal of the American Chemical Society, 2000, 122(43): 10712–10713

235 Ryoo R, Joo S H, Kruk M, Jaroniec M. Ordered mesoporous carbons. Advanced Materials, 2001, 13(9): 677–681

236 Kang M, Kim D, Yi S H, Han J U, Yie J E, Kim J M. Preparation of stable mesoporous inorganic oxides via nano-replication technique. Catalysis Today, 2004, 93-95: 695–699

237 Marsh H, Heintz E A, Rodriguez R F. Introduction to Carbon Technologies. Spain: University of Alicante, Secretariado de Publicaciones, 1997, 151–167

238 Lee J, Kim J, Hyeon T. A facile synthesis of bimodal mesoporous silica and its replication for bimodal mesoporous carbon. Chemical Communications, 2003, 10(10): 1138–1139

239 Taguchi A, Smått J H, Lindén M. Carbon monoliths possessing a hierarchical, fully interconnected porosity. Advanced Materials, 2003, 15(14): 1209–1211

240 Lu A H, Smått J H, Lindén M. Combined surface and volume templating of highly porous nanocast carbon monoliths. Advanced Functional Materials, 2005, 15(5): 865–871

241 Chai G S, Shin I S, Yu J S. Synthesis of ordered, uniform, macroporous carbons with mesoporous walls templated by aggregates of polystyrene spheres and silica particles for use as catalyst supports in direct methanol fuel cells. Advanced Materials, 2004, 16(22): 2057–2061

242 Yoon S B, Sohn K, Kim J Y, Shin C H, Yu J S, Hyeon T. Fabrication of carbon capsules with hollow macroporous core/mesoporous shell structures. Advanced Materials, 2002, 14(1): 19–21

243 Kim M, Sohn K, Na H B, Hyeon T. Synthesis of nanorattles composed of gold nanoparticles encapsulated in mesoporous carbon and polymer shells. Nano Letters, 2002, 2(12): 1383–1387

244 Zhang X, Tu K N, Xie Y H, Tung C H, Xu S. Single-step fabrication of nickel films with arrayed macropores and nanostructured skeletons. Advanced Materials, 2006, 18(14): 1905–1909

245 Martin C R, Che G, Lakshmi B B, Fisher E R. Carbon nanotubule membranes for electrochemical energy storage and production. Nature, 1998, 393(6683): 346–349

246 Chen X, Steinhart M, Hess C, Gösele U. Ordered arrays of mesoporous microrods from recyclable macroporous silicon templates. Advanced Materials, 2006, 18(16): 2153–2156

247 Panda M, Seshadri R, Gopalakrishnan J. Preparation of PbZrO₃/AsO₄ composites (A= Ca, Sr, Ba) and PbZrO₃ by metathetic reactions in the solid state: Metathetic exchange of divalent species. Chemistry of Materials, 2003, 15(7): 1554–1559

248 Panda M, Rajamathi M, Seshadri R. A template-free, combustion-chemical route to macroporous nickel monoliths displaying a hierarchy of pore sizes. Chemistry of Materials, 2002, 14(11): 4762–4767

249 Toberer E S, Schladt T D, Seshadri R. Macroporous manganese oxides with regenerative mesopores. Journal of the American Chemical Society, 2006, 128(5): 1462–1463

250 Muir D M. A review of the selective leaching of gold from oxidised copper-gold ores with ammonia-cyanide and new insights for plant control and operation. Minerals Engineering, 2011, 24(6): 576–582

251 Zhang L, Wu H B, Liu B, Lou X W D. Formation of porous SnO₂ microboxes via selective leaching for highly reversible lithium storage. Energy & Environmental Science, 2014, 7(3): 1013–1017

252 Yuan Z Y, Blin J L, Su B L. Design of bimodal mesoporous silicas with interconnected pore systems by ammonia post-hydrothermal treatment in the mild-temperature range. Chemical Communications, 2002, 5(5): 504–505

253 Sun Z, Liu Y, Li B, Wei J, Wang M, Yue Q, Deng Y, Kaliaguine S, Zhao D. General synthesis of discrete mesoporous carbon microspheres through a confined self-assembly process in inverse opals. ACS Nano, 2013, 7(10): 8706–8714

254 Tao Y, Kanoh H, Abrams L, Kaneko K. Mesopore-modified zeolites: Preparation, characterization, and applications. Chemical Reviews, 2006, 106(3): 896–910

255 van Donk S, Janssen A H, Bitter J H, deJong K P. Generation, characterization, and impact of mesopores in zeolite catalysts. Catalysis Reviews, 2003, 45(2): 297–319

256 Mei C, Liu Z, Wen P, Xie Z, Hua W, Gao Z. Regular HZSM-5 microboxes prepared via a mild alkaline treatment. Journal of Materials Chemistry, 2008, 18(29): 3496–3500

257 Zhou J, Hua Z, Shi J, He Q, Guo L, Ruan M. Synthesis of a hierarchical micro/mesoporous structure by steam-assisted post-crystallization. Chemistry (Weinheim an der Bergstrasse, Germany), 2009, 15(47): 12949–12954

258 Groen J C, Bach T, Ziese U, Paulaime-van Donk A M, de Jong K P, Moulijn J A, Pérez-Ramírez J. Creation of hollow zeolite architectures by controlled desilication of Al-zoned ZSM-5 crystals. Journal of the American Chemical Society, 2005, 127(31): 10792–10793

259 Verboekend D, Vilé G, Pérez-Ramírez J. Hierarchical Y and USY zeolites designed by post-synthetic strategies. Advanced Functional Materials, 2012, 22(5): 916–928

260 Dähne L, Leporatti S, Donath E, Möhwald H. Fabrication of micro reaction cages with tailored properties. Journal of the American Chemical Society, 2001, 123(23): 5431–5436

261 Lin K J, Chen L J, Prasad M R, Cheng C Y. Core-shell synthesis of a novel, spherical, mesoporous silica/platinum nanocomposite: Pt/PVP@ MCM-41. Advanced Materials, 2004, 16(20): 1845–1849

262 Liu Y, Zhang W, Pinnavaia T J. Steam-stable MSU-S aluminosilicate mesostructures assembled from zeolite ZSM-5 and zeolite beta seeds. Angewandte Chemie International Edition, 2001, 40(7): 1255–1258

263 Xiao F S, Han Y, Yu Y, Meng X, Yang M, Wu S. Hydrothermally stable ordered mesoporous titanosilicates with highly active catalytic sites. Journal of the American Chemical Society, 2002, 124(6): 888–889

264 Chal R, Gerardin C, Bulut M, van Donk S. Overview and industrial assessment of synthesis strategies towards zeolites with mesopores. ChemCatChem, 2011, 3(1): 67–81

265 Möller K, Bein T. Mesoporosity—A new dimension for zeolites. Chemical Society Reviews, 2013, 42(9): 3689–3707

266 Rolison D R. Catalytic nanoarchitectures—The importance of nothing and the unimportance of periodicity. Science, 2003, 299(5613): 1698–1701

267 Wang X, Yu J C, Ho C, Hou Y, Fu X. Photocatalytic activity of a hierarchically macro/mesoporous titania. Langmuir, 2005, 21(6): 2552–2559

268 Shi J W, Zong X, Wu X, Cui H J, Xu B, Wang L Z, Fu M L. Carbon-doped titania hollow spheres with tunable hierarchical macroporous channels and enhanced visible light-induced photocatalytic activity. Chemcatchem, 2012, 4(4): 488–491

269 Yu J G, Su Y R, Cheng B. Template-free fabrication and enhanced photocatalytic activity of hierarchical macro-mesoporous titania. Advanced Functional Materials, 2007, 17(12): 1984–1990

270 Zhou H, Ding L, Fan T, Ding J, Zhang D, Guo Q. Leaf-inspired hierarchical porous CdS/Au/N-TiO₂ heterostructures for visible light photocatalytic hydrogen evolution. Applied Catalysis B: Environmental, 2014, 147: 221–228

271 Schnepp Z, Yang W, Antonietti M, Giordano C. Biotemplating of metal carbide microstructures: The magnetic leaf. Angewandte Chemie International Edition, 2010, 49(37): 6564–6566

272 Zhu J, Zhu Y, Zhu L, Rigutto M, van der Made A, Yang C, Pan S, Wang L, Zhu L, Jin Y, Sun Q, Wu Q, Meng X, Zhang D, Han Y, Li J, Chu Y, Zheng A, Qiu S, Zheng X, Xiao F S, van der Made A, Yang C, Pan S X, Xiao F S. Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template. Journal of the American Chemical Society, 2014, 136(6): 2503–2510

273 Corma A, Diaz-Cabanas M J, Martínez-Triguero J, Rey F, Rius J. A large-cavity zeolite with wide pore windows and potential as an oil refining catalyst. Nature, 2002, 418(6897): 514–517

274 Tang T, Yin C, Wang L, Ji Y, Xiao F S. Superior performance in deep saturation of bulky aromatic pyrene over acidic mesoporous beta zeolite-supported palladium catalyst. Journal of Catalysis, 2007, 249(1): 111–115

275 Serrano D P, Sanz R, Pizarro P, Moreno I, Medina S. Hierarchical TS-1 zeolite as an efficient catalyst for oxidative desulphurization of hydrocarbon fractions. Applied Catalysis B: Environmental, 2014, 146: 35–42

276 Zhang S, Xu W, Zeng M, Li J, Li J, Xu J, Wang X. Superior adsorption capacity of hierarchical iron oxide @ magnesium silicate magnetic nanorods for fast removal of organic pollutants from aqueous solution. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(38): 11691–11697

277 Ma T Y, Zhang X J, Yuan Z Y. Hierarchical meso-/macroporous aluminum phosphonate hybrid materials as multifunctional adsorbents. Journal of Physical Chemistry C, 2009, 113(29): 12854–12862

278 Xiao H, Ai Z, Zhang L. Nonaqueous sol-gel synthesized hierarchical CeO₂ nanocrystal microspheres as novel adsorbents for wastewater treatment. Journal of Physical Chemistry C, 2009, 113(38): 16625–16630

279 Han S, Sohn K, Hyeon T. Fabrication of new nanoporous carbons through silica templates and their application to the adsorption of bulky dyes. Chemistry of Materials, 2000, 12(11): 3337–3341

280 Ayad M, Zaghlol S. Nanostructured crosslinked polyaniline with high surface area: Synthesis, characterization and adsorption for organic dye. Chemical Engineering Journal, 2012, 79: 204–206

281 Iwasaki M, Miwa S, Ikegami T, Tomita M, Tanaka N, Ishihama Y. One-dimensional capillary liquid chromatographic separation coupled with tandem mass spectrometry unveils the Escherichia coli proteome on a microarray scale. Analytical Chemistry, 2010, 82(7): 2616–2620

282 Miyamoto K, Hara T, Kobayashi H, Morisaka H, Tokuda D, Horie K, Koduki K, Makino S, Núñez O, Yang C, Kawabe T, Ikegami T, Takubo H, Ishihama Y, TanakaN. High-efficiency liquid chromatographic separation utilizing long monolithic silica capillary columns. Analytical Chemistry, 2008, 80(22): 8741–8750

283 Meunier C F, Rooke J C, Léonard A, Van Cutsem P, Su B L. Design of photochemical materials for carbohydrate production via the immobilisation of whole plant cells into a porous silica matrix. Journal of Materials Chemistry, 2010, 20(5): 929–936

284 Léonard A, Rooke J C, Meunier C F, Sarmento H, Descy J P, Su B L. Cyanobacteria immobilised in porous silica gels: Exploring biocompatible synthesis routes for the development of photobioreactors. Energy & Environmental Science, 2010, 3(3): 370–377

285 Meunier C F, Rooke J C, Léonard A, Xie H, Su B L. Living hybrid materials capable of energy conversion and CO₂ assimilation. Chemical Communications, 2010, 46(22): 3843–3859

286 Rooke J C, Léonard A, Meunier C F, Sarmento H, Descy J P, Su B L. Hybrid photosynthetic materials derived from microalgae cyanidium caldarium encapsulated within silica gel. Journal of Colloid and Interface Science, 2010, 344(2): 348–352

287 Rooke J C, Meunier C, Léonard A, Su B L. Energy from photobioreactors: Bioencapsulation of photosynthetically active molecules, organelles, and whole cells within biologically inert matrices. Pure and Applied Chemistry, 2008, 80(11): 2345–2376

288 Xiong J, Das S N, Shin B, Kar J P, Choi J H, Myoung J M. Biomimetic hierarchical ZnO structure with superhydrophobic and antireflective properties. Journal of Colloid and Interface Science, 2010, 350(1): 344–347

289 Hajdu K, Gergely C, Martin M, Cloitre T, Zimányi L, Tenger K, Khoroshyy P, Palestino G, Agarwal V, Hernádi K, Németh Z, Nagy L, HernAdi K, Nemeth Z. Porous silicon/photosynthetic reaction center hybrid nanostructure. Langmuir, 2012, 28(32): 11866–11873

290 Léonard A, Dandoy P, Danloy E, Leroux G, Meunier C F, Rooke J C, Su B L. Whole-cell based hybrid materials for green energy production, environmental remediation and smart cell-therapy. Chemical Society Reviews, 2011, 40(2): 860–885

291 Rooke J C, Léonard A, Meunier C F, Su B L. Designing photobioreactors based on living cells immobilized in silica gel for carbon dioxide mitigation. ChemSusChem, 2011, 4(9): 1249–1257

292 Zhou H, Li P, Guo J, Yan R, Fan T, Zhang D, Ye J. Artificial photosynthesis on tree trunk derived alkaline tantalates with hierarchical anatomy: Towards CO₂ photo-fixation into CO and CH₄. Nanoscale, 2015, 7(1): 113–120

293 Steele B C H, Heinze A. Materials for fuel-cell technologies. Nature, 2001, 414(6861): 345–352

294 Winter M, Brodd R J. What are batteries, fuel cells, and supercapacitors? Chemical Reviews, 2004, 104(10): 4245–4270

295 Bang J H, Han K, Skrabalak S E, Kim H, Suslick K S. Porous carbon supports prepared by ultrasonic spray pyrolysis for direct methanol fuel cell electrodes. Journal of Physical Chemistry C, 2007, 111(29): 10959–10964

296 Chai G S, Yoon S B, Yu J S, Choi J H, Sung Y E. Ordered porous carbons with tunable pore sizes as catalyst supports in direct methanol fuel cell. Physical of Chemistry B, 2004, 108(22): 7074–7079

297 Walcarius A. Mesoporous materials and electrochemistry. Chemical Society Reviews, 2013, 42(9): 4098–4140

298 Jin J, Huang S Z, Li Y, Tian H, Wang H E, Yu Y, Chen L H, Hasan T, Su B L. Hierarchical nanosheet-constructed yolk-shell TiO₂ porous microspheres for lithium batteries with high capacity, superior rate and long cycle capability. Nanoscale, 2015, 7(30): 12979–12989

299 Huang S Z, Cai Y, Jin J, Liu J, Li Y, Yu Y, Wang H E, Chen L H, Su B L. Hierarchical mesoporous urchin-like Mn₃O₄/carbon microspheres with highly enhanced lithium battery performance by in-situ carbonization of new lamellar manganese alkoxide (Mn-DEG). Nano Energy, 2015, 12: 833–844

300 Jin J, Huang S Z, Liu J, Li Y, Chen L H, Yu Y, Wang H E, Grey C P, Su B L. Phases hybriding and hierarchical structuring of mesoporous TiO₂ nanowire bundles for high rate and high capacity lithium batteries. Advancement of Science, 2015, 2: 1500070

301 Huang S Z, Cai Y, Jin J, Li Y, Zheng X F, Wang H E, Wu M, Chen L H, Su B L. Annealed vanadium oxide nanowires and nanotubes as high performance cathode materials for lithium ion battery. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(34): 14099–14108

302 Jin J, Huang S Z, Liu J, Li Y, Chen D S, Wang H E, Yu Y, Chen L H, Su B L. Design of new anode material structure on the basis of hierarchically three dimensionally ordered macro-mesoporous TiO₂ for high performance lithium ion batteries. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(25): 9699–9708

303 Huang S Z, Jin J, Cai Y, Li Y, Tan H Y, Wang H E, Van Tendeloo G, Su B L. Engineering single crystalline Mn₃O₄ nano-octahedra with exposed highly active {011} facets for high performance lithium ion batteries. Nanoscale, 2014, 6(12): 6819–6827

304 Zheng X F, Shen G F, Li Y, Duan H N, Yang X Y, Huang S Z, Wang H E, Wang C, Deng Z, Su B L. Self-templated synthesis of microporous CoO nanoparticles with highly enhanced performance for both photocatalysis and lithium-ion batteries. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(4): 1394–1400

305 Wang H E, Chen D S, Cai Y, Zhang R L, Xu J M, Deng Z, Zheng X F, Li Y, Bello I, Su B L. Facile synthesis of hierarchical and porous V₂O₅ microspheres as cathode materials for lithium ion batteries. Journal of Colloid and Interface Science, 2014, 418: 74–80

306 Wang H E, Jin J, Cai Y, Xu J M, Chen D S, Zheng X F, Deng Z, Li Y, Bello I, Su B L. Facile and fast synthesis of porous TiO₂ spheres for use in lithium ion batteries. Journal of Colloid and Interface Science, 2014, 417: 144–151

307 Cai Y, Wang H E, Huang S Z, Jin J, Wang C, Yu Y, Li Y, Su B L. Hierarchical nanotube-constructed porous TiO₂-B spheres for high performance lithium ion batteries. Scientific Reports, 2015, 5: 11557

308 Zhou H, Zhu S, Hibino M, Honma I, Ichihara M. Lithium storage in ordered mesoporous carbon (CMK-3) with high reversible specific energy capacity and good cycling performance. Advanced Materials, 2003, 15(24): 2107–2111

309 Wang Z, Li F, Ergang N S, Stein A. Effects of hierarchical architecture on electronic and mechanical properties of nanocast monolithic porous carbons and carbon-carbon nanocomposites. Chemistry of Materials, 2006, 18(23): 5543–5553

310 Hu Y S, Adelhelm P, Smarsly B M, Hore S, Antonietti M, Maier J. Synthesis of hierarchically porous carbon monoliths with highly ordered microstructure and their application in rechargeable lithium batteries with high-rate capability. Advanced Functional Materials, 2007, 17(12): 1873–1878

311 Hao G P, Li W C, Qian D, Wang G H, Zhang W P, Zhang T, Wang A Q, Schüth F, Bongard H J, Lu A H. Structurally designed synthesis of mechanically stable poly (benzoxazine-co-resol)-based porous carbon monoliths and their application as high-performance CO₂ capture sorbents. Journal of the American Chemical Society, 2011, 133(29): 11378–11388

312 Xia Y, Yoshio M, Noguchi H. Improved electrochemical performance of LiFePO₄ by increasing its specific surface area. Electrochimica Acta, 2006, 52(1): 240–245

313 Doherty C M, Caruso R A, Smarsly B M, Drummond C J. Colloidal crystal templating to produce hierarchically porous LiFePO₄ electrode materials for high power lithium ion batteries. Chemistry of Materials, 2009, 21(13): 2895–2903

314 Doherty C M, Caruso R A, Smarsly B M, Adelhelm P, Drummond C J, Doherty C M, Caruso R A, Smarsly B M. Hierarchically porous monolithic LiFePO₄/carbon composite electrode materials for high power lithium ion batteries. Chemistry of Materials, 2009, 21(21): 5300–5306

315 Sinha N N, Shivakumara C, Munichandraiah N. High rate capability of a dual-porosity LiFePO₄/C composite. ACS Applied Materials & Interfaces, 2010, 2(7): 2031–2038

316 Liu J, Conry T E, Song X, Doeff M M, Richardson T J. Nanoporous spherical LiFePO₄ for high performance cathodes. Energy & Environmental Science, 2011, 4(3): 885–888

317 Jiao F, Bao J, Hill A H, Bruce P G. Synthesis of ordered mesoporous Li-Mn-O spinel as a positive electrode for rechargeable lithium batteries. Angewandte Chemie International Edition, 2008, 47(50): 9711–9716

318 Luo J, Wang Y, Xiong H, Xia Y. Ordered mesoporous spinel LiMn₂O₄ by a soft-chemical process as a cathode material for lithium-ion batteries. Chemistry of Materials, 2007, 19(19): 4791–4795

319 Xia X H, Tu J P, Wang X L, Gu C D, Zhao X B. Hierarchically porous NiO film grown by chemical bath deposition via a colloidal crystal template as an electrochemical pseudocapacitor material. Journal of Materials Chemistry, 2011, 21(3): 671–679

320 Elimelech M, Phillip W A. The future of seawater desalination: Energy, technology, and the environment. Science, 2011, 333(6043): 712–717

321 Xia X, Tu J, Xiang J, Huang X, Wang X, Zhao X. Hierarchical porous cobalt oxide array films prepared by electrodeposition through polystyrene sphere template and their applications for lithium ion batteries. Journal of Power Sources, 2010, 195(7): 2014–2022

322 Yuan Y, Xia X, Wu J, Yang J, Chen Y, Guo S. Hierarchically ordered porous nickel oxide array film with enhanced electrochemical properties for lithium ion batteries. Electrochemistry Communications, 2010, 12(7): 890–893

323 Jung H G, Oh S W, Ce J, Jayaprakash N, Sun Y K. Mesoporous TiO₂ nano networks: Anode for high power lithium battery applications. Electrochemistry Communications, 2009, 11(4): 756–759

324 Yan H, Sokolov S, Lytle J C, Stein A, Zhang F, Smyrl W H. Colloidal-crystal-templated synthesis of ordered macroporous electrode materials for lithium secondary batteries. Journal of the Electrochemical Society, 2003, 150(8): A1102–A1107

325 Jiao F, Shaju K M, Bruce P G. Synthesis of nanowire and mesoporous low-temperature LiCoO₂ by a post-templating reaction. Angewandte Chemie International Edition, 2005, 44(40): 6550–6553

326 Fan L Z, Hu Y S, Maier J, Adelhelm P, Smarsly B, Antonietti M, Fan L Z, Hu Y S, Maier J. High electroactivity of polyaniline in supercapacitors by using a hierarchically porous carbon monolith as a support. Advanced Functional Materials, 2007, 17(16): 3083–3087

327 Song H K, Jung Y H, Lee K H, Dao L H. Electrochemical impedance spectroscopy of porous electrodes: The effect of pore size distribution. Electrochimica Acta, 1999, 44(20): 3513–3519

328 Rose M, Korenblit Y, Kockrick E, Borchardt L, Oschatz M, Kaskel S, Yushin G. Hierarchical micro-and mesoporous carbide-derived carbon as a high-performance electrode material in supercapacitors. Small, 2011, 7(8): 1108–1117

329 Xia K, Gao Q, Jiang J, Hu J. Hierarchical porous carbons with controlled micropores and mesopores for supercapacitor electrode materials. Carbon, 2008, 46(13): 1718–1726

330 Eliaz N. Degradation of implant materials. Springer Science Business Media, 2012, 151–173

331 Xu M, Li H, Zhai D, Chang J, Chen S, Wu C. Hierarchically porous nagelschmidtite bioceramic-silk scaffolds for bone tissue engineering. Journal of Materials Chemistry. B, Materials for Biology and Medicine, 2015, 3(18): 3799–3809

332 Fu Q, Saiz E, Rahaman M N, Tomsia A P. Bioactive glass scaffolds for bone tissue engineering: State of the art and future perspectives. Materials Science and Engineering C, 2011, 31(7): 1245–1256

333 Manzano M, Vallet-Regí M. Revisiting bioceramics: Bone regenerative and local drug delivery systems. Progress in Solid State Chemistry, 2012, 40(3): 17–30

334 Saiz E, Zimmermann E A, Lee J S, Wegst U G, Tomsia A P. Perspectives on the role of nanotechnology in bone tissue engineering. Dental Materials, 2013, 29(1): 103–115

335 Porter J R, Ruckh T T, Popat K C. Bone tissue engineering: A review in bone biomimetics and drug delivery strategies. Biotechnology Progress, 2009, 25(6): 1539–1560

336 Hollister S J. Porous scaffold design for tissue engineering. Nature Materials, 2005, 4(7): 518–524

337 Chen Q Z, Thompson I D, Boccaccini A R. 45S5 Bioglass®-derived glass-ceramic scaffolds for bone tissue engineering. Biomaterials, 2006, 27(11): 2414–2425

338 Baino F, Vitale-Brovarone C. Three-dimensional glass-derived scaffolds for bone tissue engineering: Current trends and forecasts for the future. Journal of Biomedical Materials Research. Part A, 2011, 97(4): 514–535

339 Anselme K. Osteoblast adhesion on biomaterials. Biomaterials, 2000, 21(7): 667–681

340 Jones J R, Lee P D, Hench L L. Hierarchical porous materials for tissue engineering. Philosophical Transactions of the Royal Society of London A: Mathematical. Physical and Engineering Sciences, 1838, 2006(364): 263–281

341 Hench L L. Bioceramics: From concept to clinic. Journal of the American Ceramic Society, 1991, 74(7): 1487–1510

342 Brinker C J, Scherer G W. Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing. United States: Academic press, 2013, 130–178

343 Sepulveda P, Jones J R, Hench L L. In vitro dissolution of melt-derived 45S5 and sol-gel derived 58S bioactive glasses. Journal of Biomedical Materials Research, 2002, 61(2): 301–311

344 Yuan H, de Bruijn J D, Zhang X, Blitterswijk C A, de Groot K. Bone induction by porous glass ceramic made from Bioglassw (45S5). Journal of Biomedical Materials Research, 2001, 58(3): 270–276

345 Sepulveda P, Jones J R, Hench L L. Bioactive sol-gel foams for tissue repair. Journal of Biomedical Materials Research, 2002, 59(2): 340–348

346 Tian G, Gu Z, Liu X, Zhou L, Yin W, Yan L, Jin S, Ren W, Xing G, Li S, ZhaoY. Facile fabrication of rare-earth-doped Gd₂O₃ hollow spheres with upconversion luminescence, magnetic resonance, and drug delivery properties. Journal of Physical Chemistry C, 2011, 115(48): 23790–23796

347 Xu Z H, Ma P A, Li C X, Hou Z Y, Zhai X F, Huang S S, Lin J. Monodisperse core-shell structured up-conversion Yb (OH) CO₃@ YbPO₄: Er³⁺ hollow spheres as drug carriers. Biomaterials, 2011, 32(17): 4161–4173

348 Allen T M, Cullis P R. Drug delivery systems: Entering the mainstream. Science, 2004, 303(5665): 1818–1822

349 Ye F, Guo H, Zhang H, He X. Polymeric micelle-templated synthesis of hydroxyapatite hollow nanoparticles for a drug delivery system. Acta Biomaterialia, 2010, 6(6): 2212–2218

350 Zhang H, Sun J, Ma D, Bao X, Klein-Hoffmann A, Weinberg G, Su D, Schlögl R. Unusual mesoporous SBA-15 with parallel channels running along the short axis. Journal of the American Chemical Society, 2004, 126(24): 7440–7441

351 Liu J, Hartono S B, Jin Y G, Li Z, Lu G Q M, Qiao S Z. A facile vesicle template route to multi-shelled mesoporous silica hollow nanospheres. Journal of Materials Chemistry, 2010, 20(22): 4595–4601

352 Piao Y, Kim J, Na H B, Kim D, Baek J S, Ko M K, Lee J H, Shokouhimehr M, Hyeon T. Wrap-bake-peel process for nanostructural transformation from β-FeOOH nanorods to biocompatible iron oxide nanocapsules. Nature Materials, 2008, 7(3): 242–247

353 Son J S, Appleford M, Ong J L, Wenke J C, Kim J M, Choi S H, Oh D S. Porous hydroxyapatite scaffold with three-dimensional localized drug delivery system using biodegradable microspheres. Journal of Controlled Release, 2011, 153(2): 133–140

354 Giger E V, Puigmarti L J, Schlatter R, Castagner B, Dittrich P S, Leroux J C. Gene delivery with bisphosphonate-stabilized calcium phosphate nanoparticles. Journal of Controlled Release, 2011, 150(1): 87–93

355 Yang H, Hao L, Zhao N, Du C, Wang Y. Hierarchical porous hydroxyapatite microsphere as drug delivery carrier. CrystEngComm, 2013, 15(29): 5760–5763

356 Zhao W, Chen H, Li Y, Li L, Lang M, Shi J. Uniform rattle-type hollow magnetic mesoporous apheres as drug delivery carriers and their sustained-release property. Advanced Functional Materials, 2008, 18(18): 2780–2788

357 Wang T, Chai F, Fu Q, Zhang L, Liu H, Li L, Liao Y, Su Z, Wang C, Duan B, Ren D. Uniform hollow mesoporous silica nanocages for drug delivery in vitro and in vivo for liver cancer therapy. Journal of Materials Chemistry, 2011, 21(14): 5299–5306

358 Gai S L, Yang P, Li P, Wang C X, Dai W X, Niu Y L, Lin N. Synthesis of magnetic, up-conversion luminescent, and mesoporous core-shell-structured nanocomposites as drug carriers. Advanced Functional Materials, 2010, 20(7): 1166–1172

359 Liu J, Qiao S Z, Chen J S, Lou X W, Xing X, Lu G Q. Yolk/shell nanoparticles: New platforms for nanoreactors, drug delivery and lithium-ion batteries. Chemical Communications, 2011, 47(47): 12578–12591

360 Chen D, Li L, Tang F, Qi S. Facile and scalable synthesis of tailored silica ‘nanorattle’ structures. Advanced Materials, 2009, 21(37): 3804–3807

361 Hu S H, Chen Y Y, Liu T C, Tung T H, Liu M D, Chen S Y. Remotely nano-rupturable yolk/shell capsules for magnetically-triggered drug release. Chemical Communications, 2011, 47(6): 1776–1778

362 Chen Y, Chen H R, Zhang S J, Chen F, Zhang L X, Zhang J M, Zhu M, Wu H X, Guo L M, Feng J W, Shi J L. Multifunctional mesoporous nanoellipsoids for biological bimodal imaging and magnetically targeted delivery of anticancer drugs. Advanced Functional Materials, 2011, 21(2): 270–278

363 Wu H X, Zhang S J, Zhang J M, Liu G, Shi J L, Zhang L X, Cui X Z, Ruan M L, He Q J, Bu W B A. Hollow-core, magnetic, and mesoporous double-shell nanostructure: In situ decomposition/reduction synthesis, bioimaging, and drug-delivery properties. Advanced Functional Materials, 2011, 21(10): 1850–1862

364 Zhang X F, Clime L, Roberge H, Normandin F, Yahia L H, Sacher E, Veres T. pH-triggered doxorubicin delivery based on hollow nanoporous silica nanoparticles with free-standing superparamagnetic Fe₃O₄ cores. Journal of Physical Chemistry C, 2011, 115(5): 1436–1443

365 Lu Y, Zhao Y, Yu L, Dong L, Shi C, Hu M J, Xu Y J, Wen L P, Yu S H. Hydrophilic Co@ Au yolk/shell nanospheres: Synthesis, assembly, and application to gene delivery. Advanced Materials, 2010, 22(12): 1407–1411

366 Suh W H, Jang A R, Suh Y H, Suslick K S. Porous hollow, ball-in-ball metal oxide microspheres: Preparation, endocytosis, and cytotoxicity. Advanced Materials, 2006, 18(14): 1832–1837

367 Li L L, Tang F Q, Li Y H, Liu T L, Hao N J, Chen D, Teng X, He J Q. In vivo delivery of silica nanorattle encapsulated docetaxel for liver cancer therapy with low toxicity and high efficacy. ACS Nano, 2010, 4(11): 6874–6882

368 Chen Y, Chen H R, Guo L M, He Q J, Chen F, Zhou J, Feng J W, Shi J L. Hollow/rattle-type mesoporous nanostructures by a structural difference-based selective etching strategy. ACS Nano, 2010, 4(1): 529–539