, Volume 81, Issue 2, pp 247–256 | Cite as

C18-Free Organic–Inorganic Hybrid Silica Particles Derived from Sole Silsesquioxane for Reversed-Phase HPLC

  • Shi-Hao Peng
  • Xiu-Yun Yue
  • Ya-Li Wang
  • Qi Wei
  • Su-Ping Cui
  • Zuo-Ren Nie
  • Qun-Yan Li


Ethyl-bridged organic–inorganic hybrid silica particles were prepared via a sol–gel and hydrothermal synthesis approach using 1,2-bis(triethoxysilyl)ethane (BTESE) as the sole precursor, and triblock copolymer poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (P123) and dodecyltrimethylammonium bromide (DTAB) as combined templates. The morphology, pore structure, chemical composition and liquid chromatographic performance of the obtained materials were investigated in detail. The particles exhibit a high surface area of 1136.40 m2/g, together with a pore volume of 0.39 cm3/g and an average pore size of 2.30 nm. Used as stationary phase for high-performance liquid chromatography (HPLC), the particles without extra bonding either C18 or C8 can successfully separate a mixture of uracil, phenol, pyridine, methylbenzene, ethylbenzene and tert-butylbenzene. The obtained materials also show practical application in the separation of phthalate acid esters (PAEs), which are harmful to environment and human health. Although the columns packed with ethyl-bridged organic–inorganic hybrid silica show lower column efficiency and peak symmetry compared to commercial column, they have considerably higher chemical stability in alkaline mobile phase. The HSS column also possesses high mechanical stability which is similar to that of the commercial column.


Organic–inorganic hybrid silica particle Stationary phase High-performance liquid chromatography Hydrophobic Chemical stability 



This research was financially supported by Scientific Research Common Program of the Beijing Municipal Commission of Education (Grant No. KZ201410005006), National Natural Science Foundation of China (Grant Nos. 21171014, 50502002, 51402007), Beijing Natural Science Foundation of China (Grant No. 2141001), State Key Laboratory of Solid Waste Reuse for Building Materials (Grant No. SWR-2014-010), and Funding Project for Academic Human Resources Development in Institutions of Higher Learning Under the Jurisdiction of Beijing Municipality.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Nawrocki J, Dunlap C, Mccormick A (2004) Part I, Chromatography using ultra-stable metal oxide-based stationary phases for HPLC. J Chromatogr A 1028:1–30CrossRefGoogle Scholar
  2. 2.
    Poole CF, Kiridena W, Dekay C (2006) Insights into the retention mechanism on an octadecylsiloxane-bonded silica stationary phase (HyPURITY C18) in reversed-phase liquid chromatography. J Chromatogr A 1115:133–141CrossRefGoogle Scholar
  3. 3.
    Zhang Y, Jin Y, Yu H (2010) Pore expansion of highly monodisperse phenylene-bridged organosilica spheres for chromatographic application. Talanta 81:824–830CrossRefGoogle Scholar
  4. 4.
    Mccalley DV (1999) Comparison of the performance of conventional C18 phases with others of alternative functionality for the analysis of basic compounds by reversed-phase high-performance liquid chromatography. J Chromatogr A 844:23–38CrossRefGoogle Scholar
  5. 5.
    Kirkland JJ, Glajch JL, Farlee RD (1989) Synthesis and characterization of highly stable bonded phases for HPLC column packings. Anal Chem 61:2–11CrossRefGoogle Scholar
  6. 6.
    Floyd TR, Hartwick RA, Dibussolo JM (1988) Studies on the stabilization of reversed phases for liquid chromatography. J Chromatogr A 443:155–172CrossRefGoogle Scholar
  7. 7.
    Kirkland JJ, Henderson JW, Destefano JJ (1997) Stability of silica-based, endcapped columns with pH 7 and 11 mobile phases for reversed-phase high-performance liquid chromatography. J Chromatogr A 762:97–112CrossRefGoogle Scholar
  8. 8.
    Kirkland JJ, van Straten MA (1995) High pH mobile phase effects on silica-based reversed-phase high-performance liquid chromatographic columns. J Chromatogr A 691:3–19CrossRefGoogle Scholar
  9. 9.
    Mandal M, Manchanda AS, Zhuang J (2012) Face-centered-cubic large-pore periodic mesoporous organosilicas with unsaturated and aromatic bridging groups. Langmuir 28:8737–8745CrossRefGoogle Scholar
  10. 10.
    Nohair B, Thao PTH, Nguyen VTH (2012) Hybrid periodic mesoporous organosilicas (PMO-SBA-16): a support for immobilization of d-amino acid oxidase and glutaryl-7-amino cephalosporanic acid acylase enzymes. J Phys Chem C 116:10904–10912CrossRefGoogle Scholar
  11. 11.
    Wang W, Grozea D, Kohli S (2011) Water repellent periodic mesoporous organosilicas. ACS Nano 5:1267–1275CrossRefGoogle Scholar
  12. 12.
    Mandal M, Kruk M (2010) Large-pore ethylene-bridged periodic mesoporous organosilicas with face-centered cubic structure. J Phys Chem C 114:20091–20099CrossRefGoogle Scholar
  13. 13.
    Castricum HL, Sah A, Kreiter R (2008) Hydrothermally stable molecular separation membranes from organically linked silica. J Mater Chem 18:2150–2158CrossRefGoogle Scholar
  14. 14.
    Claessens HA, van Straten MA (2004) Review on the chemical and thermal stability of stationary phases for reversed-phase liquid chromatography. J Chromatogr A 1060:23–41CrossRefGoogle Scholar
  15. 15.
    Yoshina-Ishii C, Asefa T (1999) Periodic mesoporous organosilicas, PMOs: fusion of organic and inorganic chemistry ‘inside’ the channel walls of hexagonal mesoporous silica. Chem Commun 24:2539–2540CrossRefGoogle Scholar
  16. 16.
    Huang L, Lu J, Di B (2011) Self-assembled highly ordered ethane-bridged periodic mesoporous organosilica and its application in HPLC. J Sep Sci 34:2523–2527CrossRefGoogle Scholar
  17. 17.
    Neue UD, Walter TH, Alden BA (1999) Use of high-performance LC packings from ph1 to ph 12. Am Lab 31:36–39Google Scholar
  18. 18.
    Liu Y, Grinberg N, Thompson KC (2005) Evaluation of a C18 hybrid stationary phase using high-temperature chromatography. Anal Chim Acta 554:144–151CrossRefGoogle Scholar
  19. 19.
    Wei Q, Wang F, Nie ZR (2008) Highly hydrothermally stable microporous silica membranes for hydrogen separation. J Phys Chem B 112:9354–9359CrossRefGoogle Scholar
  20. 20.
    Mesa M, Sierra L, López B (2003) Preparation of micron-sized spherical particles of mesoporous silica from a triblock copolymer surfactant, usable as a stationary phase for liquid chromatography. Solid State Sci 5:1303–1308CrossRefGoogle Scholar
  21. 21.
    Shu L, Chen S, Zhao WW (2016) High-performance liquid chromatography separation of phthalate acid esters with mil-53(al) packed column. J Sep Sci 39:3163–3170CrossRefGoogle Scholar
  22. 22.
    Jiang DD, Wei Q, Cui SP (2006) Controllable morphology and pore structure of micron-sized organic–inorganic hybrid silica spheres derived from silsesquioxane. J Sol Gel Sci Technol 78:40–49CrossRefGoogle Scholar
  23. 23.
    Wyndham KD, O’Gara JE, Walter TH (2003) Characterization and evaluation of C18 HPLC stationary phases based on ethyl-bridged hybrid organic/inorganic particles. Anal Chem 75:6781–6788CrossRefGoogle Scholar
  24. 24.
    Yu H, Jia C, Wu H (2012) Highly stable high performance liquid chromatography stationary phase based on direct chemical modification of organic bridges in hybrid silica. J Chromatogr A 1247:63–70CrossRefGoogle Scholar
  25. 25.
    Chen WY, Wei Q, Liu YJ (2014) The particle size control of organic–inorganic hybrid silica by surfactant-mediated assembly of silsesquioxane. Adv Mater Res 1058:30–34CrossRefGoogle Scholar
  26. 26.
    Lu J, Huang L, Di B (2011) Spherical periodic mesoporous organosilicas bearing camphorsulfonamide substructures for HPLC. Chromatographia 74:515–521CrossRefGoogle Scholar
  27. 27.
    Cai H, Zhao D (2009) A mild method to remove organic templates in periodic mesoporous organosilicas by the oxidation of perchlorates. Micropor Mesopor Mater 118:513–517CrossRefGoogle Scholar
  28. 28.
    Yue XY, Jiang DD, Shu L (2016) Mesoporous C18-bonded ethyl-bridged organic–inorganic hybrid silica: a facile one-pot synthesis and liquid chromatographic performance. Micropor Mesopor Mater 236:277–283CrossRefGoogle Scholar
  29. 29.
    Canivet J, Fateeva A (2014) Water adsorption in MOFs: fundamentals and applications. Chem Soc Rev 43:5594–5617CrossRefGoogle Scholar
  30. 30.
    Canivet J, Bonnefoy J, Daniel C (2014) Structure–property relationships of water adsorption in metal-organic frameworks. N J Chem 38:3102–3111CrossRefGoogle Scholar
  31. 31.
    Khutia A, Rammelberg HU, Schmidt T (2013) Water sorption cycle measurements on functionalized mil-101Cr for heat transformation application. Chem Mater 25:790–798CrossRefGoogle Scholar
  32. 32.
    Schoenecker PM, Carson CG, Jasuja H (2012) Effect of water adsorption on retention of structure and surface area of metal–organic frameworks. Ind Eng Chem Res 51:6513–6519CrossRefGoogle Scholar
  33. 33.
    Liu J, Wang Y, Benin AI (2010) CO2/H2O adsorption equilibrium and rates on metal–organic frameworks: HKUST-1 and Ni/DOBDC. Langmuir 26:14301–14307CrossRefGoogle Scholar
  34. 34.
    Na W, Wei Q, Lan JN (2010) Effective immobilization of enzyme in glycidoxypropyl-functionalized periodic mesoporous organosilicas (PMOs). Micropor Mesopor Mater 134:72–78CrossRefGoogle Scholar
  35. 35.
    Jang HR, Oh HJ, Kim JH (2013) Synthesis of mesoporous spherical silica via spray pyrolysis: pore size control and evaluation of performance in paclitaxel pre-purification. Micropor Mesopor Mater 165:219–227CrossRefGoogle Scholar
  36. 36.
    Borges EM, Volmer DA (2015) Silica, hybrid silica, hydride silica and non-silica stationary phases for liquid chromatography. Part II: chemical and thermal stability. J Chromatogr Sci 53:1107–1122CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.College of Materials Science and EngineeringBeijing University of TechnologyBeijingPeople’s Republic of China

Personalised recommendations