preparation and applications of hybrid organic–inorganic monoliths: a review

1294 J. Sep. Sci. 2012, 35, 1294–1302

Tao ZhuKyung Ho Row

Department of ChemicalEngineering, Inha University,Incheon, Korea

Received January 25, 2012Revised February 05, 2012Accepted February 24, 2012

Review Article

Preparation and applications of hybridorganic–inorganic monoliths: A review

This review presents an overview of the properties of hybrid organic–inorganic monolithicmaterials and summarizes the recent developments in the preparation and applicationsof these hybrid monolithic materials. Hybrid monolithic materials with porosities, surfacefunctionalities, and fast dynamic transport have developed rapidly, and have been used in awide range of applications owing to the low cost, good stability, and excellent performance.Basically, these materials can be divided into two major types according to the chemical com-position: hybrid silica-based monolith (HSM) and hybrid polymer-based monolith (HPM).Compared to the HPM, HSM monolith has been attracting most wide attentions, and itis commonly synthesized by the sol–gel process. The conventional preparation proceduresof two type’s hybrid organic–inorganic monoliths are addressed. Applications of hybridorganic–inorganic monoliths in optical devices, capillary microextraction (CME), capillaryelectrochromatography (CEC), high performance liquid chromatography (HPLC), and chiralseparation are also reviewed.

Keywords: Applications / Hybrid organic—inorganic / Monoliths / Preparations

DOI 10.1002/jssc.201200084

1 Introduction

Over the last few decades, monolithic materials have rapidlybecome highly popular media in many research areas, suchas high performance liquid chromatography (HPLC), elec-trophoresis, on-chip chromatography, etc. [1–5]. Monolithicmaterials with excellent performance have been attractingwidely attentions, due to their fast dynamic transport andtime-saving process. Monoliths can have interconnectedchannel networks and pore structures with high surfacearea and satisfactory loading capacity [6]. Various types ofmonolith materials can be obtained by different preparationmethods with desirable functional groups, such as weak ion-exchange monolith [7], ionic liquids (ILs)-based monolith [8,9]and molecular imprinting monolith [10].

Hybrid organic–inorganic materials are referred to asmaterials consisting of two or more integrating components

Correspondence: Professor Kyung Ho Row, Department of Chem-ical Engineering, Inha University, Incheon 402-751, KoreaE-mail: [email protected]: +82-32-872-4046

Abbreviations: APTES, aminopropyltriethoxysilane; ATRP,transfer radical polymerization; CEC, capillary electrochro-matography; CME, capillary microextraction; CP-silica,chloropropyl-functionalized silica; FT-IR, Fourier transforminfrared; HSM, hybrid silica-based monolith; HPM, hybridpolymer-based monolith; IL, ionic liquid; NP, nanoparti-cle; PIPS, polymerization-induced phase separation; PMMA,poly(methyl methacrylate); PVAL, polyvinyl alcohol; SBF,simulated body fluid; TEOS, tetraethoxysilane

combined at the molecular or nanometer level. They have sev-eral advantages, such as flexibility, long life, excellent biocom-patibility, and mechanical properties [11–14]. Organic func-tional groups can be distributed evenly in the structure ofthe inorganic matrix, which facilitates excellent performance[15–17]. Hybrid materials can be used in many chemical areasbecause they are easy to process and are amenable to designon the molecular scale. Owing to the individual advantagesof monolith and organic–inorganic hybrids [18–20], hybridorganic–inorganic monolith has attracted considerable con-cerns as a potential ideal material with high surface area,high selectivity, excellent mechanical strength, and thermalstability [21].

According to the chemical composition, hybrid organic–inorganic monolith can be divided into two main types: hy-brid silica-based monolith (HSM) and hybrid polymer-basedmonolith (HPM). HSM is a monolith made of a silica precur-sor containing organic moieties, and it is commonly preparedby sol–gel process [22–24]. The sol–gel technique is used pri-marily to fabricate materials starting from a colloidal solutionthat acts as a precursor for an integrated network polymer[25]. The mild reaction conditions and high adaptability ofthe sol–gel process are quite promising in the design of hy-brid inorganic–organic matrices. Typical precursors includemetal alkoxides and metal salts, which undergo a range ofhydrolysis and polycondensation reactions. In general, silica-based monolithic materials can have better organic solventresistance and mechanical stability but they also have cer-tain application restrictions, such as difficult to control theentire preparation process and a narrow pH working range(pH: 2–8). The preparation of silica-based monolithic

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J. Sep. Sci. 2012, 35, 1294–1302 Other Techniques 1295

columns is time consuming with poor reproducibility, andit is subject to insufficient hydrolysis of the Si–O–C linkage,particularly under moderately acidic or slightly alkaline con-ditions [14].

As an alternative, HPM materials are created by chemical-bonding methods with desirable functional groups [14].These chemical modifications can retain a specific structureand make the materials more suitable for applications incatalysis, sensors, and separation materials [26]. However, thedisadvantages of HPM materials are also obvious. The majordrawback of HPM is their tendency to swell in organic sol-vents, leading to undesirable changes in their pore structureand mechanical instability [27]. This instability can cause thepore structure to crash and produce unreliable results afterrepeated use [28]. Nevertheless, these two types of monolithsare significant chemical materials that have attracted consid-erable attention in many research areas.

Compared to other types of monolithic materials, hy-brid organic–inorganic monoliths are highly advantageousas they exhibit flexibility, low density, and long shelf-life withexcellent biocompatibility and mechanical properties [9, 10].Many combinations of inorganic and organic componentsof hybrid monoliths are scaled at molecular level, and thesehybrid monoliths can be tailored specifically to impart de-sirable properties or to suppress undesirable ones in a widerange of application researches, such as chemical sensors[29], enzyme microreactors [30], HPLC [14], and capillary elec-trochromatography (CEC) [31–34]. Moreover, it is thoughtthat synthesis of hybrid monolithic materials can be as a newapproach to find more ideal chemical materials.

This review introduces the properties of hybrid organic–inorganic monolithic materials, which provides an overviewof recent developments in the preparation and applicationsof hybrid organic–inorganic monolithic materials.

2 HSM materials

In recent years, HSM materials with enhanced mechanicalstrength, permeability, and thermal stability have attractedconsiderable attentions [35, 36]. The extensive combinationsof the formation of inorganic and organic components ofthese systems have been studied most extensively, particu-larly sol–gel synthesis including the combination of networksof inorganic and organic polymers at a molecular level [37,38].The sol–gel method is a wet-chemical technique that is usedwidely in materials science and ceramic engineering. Thistechnique is a waste-free method for producing hybrid poly-mers that makes it ecologically optimal. The key role in suchnonequilibrium self-organized systems belongs to interfacialinteractions between components [39, 40]. HSM prepared bythe sol–gel process have a range of applications in optics [41],electronics [42], and biology [43, 44].

The conventional sol–gel procedure applied in the prepa-ration of HSM is based on two harmonious steps, hydrolysisand polycondensation. Tetraethoxysilane (TEOS) is a typical

Figure 1. A type chemical structure of siloxanes. Reproducedfrom [45] with the permission of Springer.

chemical precursor for sol–gel synthesis because they reactreadily with water. TEOS is firstly hydrolyzed to yield reactivesilanol groups as follows:

Si−(OR)4 + H2O → HO−Si−(OR)3 + R−OH

Depending on the amount of water and catalyst present,hydrolysis may proceed to completion. After the initial hydrol-ysis step, two partially hydrolyzed molecules can link togetherin a polycondensation reaction to form a three-dimensional,cross-linked solid network of siloxane [Si–O–Si] bond:

(OR)3 − Si−OR + HO−Si−(OR)3

→ [(OR)3−Si−O−Si−(OR)3] + R−OH (1)

During the sol–gel process, the two steps of hydrolysisand polycondensation proceed in parallel rather than in se-quence, and their relative rates determine the final structureof the sol–gel process. The type of solvent, reactant ratios,temperature, and type of catalyst are major factors affectingthe relative rates of hydrolysis and condensation reactions,and thus determine the ultimate morphology and pore struc-tures of the formed materials. Therefore, these parameterscan be carefully investigated in order to obtain the satisfac-tory monolithic materials [17, 18, 35, 48].

Noble et al. [45] prepared siloxane–silica nanocompositeswith well-defined porosity from a polyfunctional siloxane net-work precursor. Porous HSM materials were fabricated by thesol–gel processing of TEOS and 1,3,5,7-tetramethyl-tetrakis(ethyltriethoxysilane)-cyclotetrasiloxane in the presence of acationic surfactant, cetyltrimethylammonium bromide. Thechemical and physical properties of these materials havebeen analyzed by Fourier transform infrared (FT-IR) spec-troscopy, solid state 29Si nuclear magnetic resonance spec-troscopy, powder X-ray diffraction, and nitrogen adsorption–desorption studies. These HSM materials have an organiccore with multiple flexible arms, terminating at the functionaltrialkoxysilane groups. The core can be a single silicon atom,a disiloxane chain or a ring system. Siloxanes (Fig. 1) havepreviously been reported to possess at least 12 reactive sitesper molecule, and are known as “star-gel” precursors [46].The multifunctional nature of these precursors leads to veryfast rates of hydrolysis and condensation. Transparent mono-lithic gels can be prepared from star precursors with physical


1296 T. Zhu and K. H. Row J. Sep. Sci. 2012, 35, 1294–1302

properties intermediate between those of conventionalglasses and rubbery elastomers [47].

A poly(methyl methacrylate) (PMMA)/SiO2 system hasattracted particular interest as a matrix for rare earth ionsand organic dyes in optical devices. In the study of Sunet al. [48], PMMA/SiO2 hybrid monoliths were synthesizedusing a sol–gel approach based on the polymerization ofTEOS in the presence of PMMA. Three different organic–inorganic ratios (P80, P50, and P20) were examined. Theeffects of the PMMA/TEOS ratio on the thermal stability, mi-crostructure, morphology, and optical properties were stud-ied systematically. Finally, the hybrid monoliths prepared bythis sol–gel process with more than 50 wt% PMMA havepotential applications in optical devices. Compared to thesol–gel approach using alkoxysilyl-containing organic pre-cursors or coupling agents, PMMA/SiO2 hybrids containinghydrogen bonding are easier to prepare, and form homoge-nous hybrids with good mechanical properties and opticaltransparency

Liu et al. [49] reported a novel route for synthesizingmesoporous silica by calcination-induced phase separationin a nonaqueous system. Initially, organic–inorganic hy-brids are synthesized by the solvothermal polymerization ofpolyvinyl alcohol (PVAL) with TEOS in dimethyl sulfoxide.After calcining the hybrids in air or nitrogen, mesoporoussilica, and carbon materials with worm-like mesopores werefinally obtained. The synthesized samples exhibited worm-like mesostructures with large surface areas and uniformpore size distributions. Figure 2 shows the formation pro-cess of mesoporous silica and carbon materials. Initially, anorganic–inorganic hybrid was synthesized by the polymer-ization of PVAL and TEOS under solvothermal conditions.Subsequently, the organic–inorganic hybrid was calcined inair or nitrogen, respectively.

Martin et al. [50] prepared CaO–P2O5–SiO2–PVALorganic–inorganic hybrid monolith and characterized thembefore and after soaking them in a solution mimicking hu-man plasma. This hybrid monolith was obtained by addingPVAL (0.9, 1.8, and 3.6 wt%) to three CaO–(P2O5)–SiO2 gelglasses containing 25 mol% CaO and P2O5 (0, 2.5, and 5mol%). Figure 3 shows the schematic diagram of preparationprocess of this type hybrid monolith by sol–gel technology.The influence of PVAL and P2O5 on the monoliths, their tex-tural properties and in vitro behavior was analyzed. The ad-dition of PVAL favored the synthesis of crack-free monolithsthat could be coated with bone-like apatite after being soakedin Kokubo’s simulated body fluid (SBF). Increasing P2O5 con-tents made the synthesis of hybrids difficult and decreasedtheir in vitro bioactivity. In addition, the in vitro degradationof the hybrids increased with increasing of PVAL and P2O5

content. Therefore, hybrids with the highest amounts of bothcomponents showed significant degradation in SBF that im-peded apatite layer formation. Organic–inorganic hybrids inthese systems could be used clinically as bone defect fillersin nonload-bearing applications or as matrices in controlledrelease systems.

Figure 2. Formation process of mesoporous silica and carbonmaterials. Reproduced from [49] with the permission of Elsevier.

Chen et al. [51] introduced an organic–inorganic HSMcolumn with octyl and sulfonic acid groups that wereprepared by a sol–gel technique for capillary electrochro-matography. The structure of this HSM was optimized bymodifying the composition of TEOS, octyl-TEOS, and 3-mercaptopropyltrimethoxysilane in a mixture of precursors.Subsequently, the obtained HSM was oxidized with hydrogenperoxide (30%, w/w) to yield sulfonic acid groups. This HSMwas characterized by scanning electron microscope (SEM)(Fig. 4), and it was applied to the analysis of theophylline andcaffeine in beverages. Figure 4A shows a cross section of anintact and homogeneous column bed. The formed organic-silica monolith was well attached to the inner walls of thecapillary (Fig. 4B). The micro-globules were interconnectedto form large clusters that yielded a continuous skeleton, re-sulting in a uniform organic-silica hybrid monolithic matrixwith approximately 2 �m through pores (Fig. 4C).

Over the last decade, there has been increasing fo-cus on synthesizing silica-based monolithic capillaries usingminiaturized separation techniques, such as CEC, capillarymicroextraction (CME), nano-LC, and chip electrochromatog-raphy owing to their unique chromatographic properties andpossible in situ synthesis [52]. Roux et al. [53] prepared HSM



Figure 3. Schematic diagram of preparation process of CaO–SiO2–(P2O5)–PVAL hybrid monolith by sol–gel technology. Reproduced from[50] with the permission of Elsevier.

functionalized with octyl groups within capillaries that werededicated to chromatographic separation in reversed-phasemode. Several modifications to the synthesis protocol weremade to improve the resulting morphology of the monolith,making it suitable for nano-LC separation. Good efficiencyin nano-LC mode combined with the excellent performancealready present in CEC mode led to rapid and highly effi-cient separation in pressurized CEC mode. A simple andsensitive CME method based on aminopropyltriethoxysilane(APTES)-HSM capillary combined with inductively coupledplasma mass spectrometry was developed by Zhang et al.[23] for the determination of trace elements in biologicalsamples. The microstructure of APTES-HSM capillary wasinvestigated by SEM photographs at magnifications of 160×(Fig. 5A) and 7000× (Fig. 5B), respectively. As it could be seen,this APTES-HSM was homogeneous and also tightly attachedto the inner surface of the capillary. No large voids along the

wall of the fused silica capillary formed by gel shrinkage orcracking were observed. The cross-sectional image of APTES-HSM at magnification of 7000× (Fig. 5B) obviously revealsporous structure consisting of interconnecting spheres withthe diameter of about 1 mm. The uniform particles in smallsize could offer high surface area for the retention of targetanalytes, whereas the macroporous structure would result inlow backpressure and high permeability. This APTES-HSMhas also been applied for the analysis of trace elements inhuman hair and urine samples with the recoveries for thespiked samples in the range of 89–106%.

ILs are salts composed of cations and anions and are liq-uids at ambient temperatures [54–56]. In recent years, therehas been increasing interest in ILs as novel solvents forsynthesis, separation, electrochemistry, and process chem-istry because of their unique properties that make them use-ful in a range of areas in modern chemistry [57–60]. Wang

Figure 4. SEM images of the cross-section of HSM modified with octyl and sulfonic acid groups (A, wide view; B and C, closeup view).Reproduced from [51] with the permission of Elsevier.



Figure 5. SEM images of the cross-section of APTES-HSM capillary (A, wide-view; B closeup view). Reproduced from [23] with thepermission of Wiley.

et al. [61,62] explored a room temperature, ILs-mediated non-hydrolytic sol–gel protocol for fabrication of new molecularlyimprinted HSMs. ILs was incorporated to reduce gel shrink-age and also to act as the pore template for increasing porosity,and these hybrid monoliths were used for chiral separationof zolmitriptan by CEC. Han et al. [63] introduced ILs toan organic-silica hybrid monolithic column as the station-ary phase for CEC. This ILs-HSM column starting from thechloropropyl-functionalized silica (CP-silica) hybrid mono-lith, which was synthesized via the cocondensation of (3-chloropropyl)-trimethoxysilane and tetramethoxysilane by a

sol–gel process, and then N-methylimidazole was bonded tothe CP-silica column via the chloropropyl group. The electro-osmotic flow of the ILs-HSM column was reversed at acidicpH, and the morphology of this column was characterized bySEM. Figure 6 shows methanol and four aromatic hydrocar-bons were separated on ILs-HSM (A) and CP-silica monolith(B) in CEC. The results showed five targets were separatedwell on this ILs-HSM column using 20 mM NaH2PO4 buffercontaining 40% v/v ACN at pH 3.0 as the mobile phase,and the performance of CP-silica column was poorer thanthe ILs-HSM column. To further validate the performance of

Figure 6. Electrochromatograms of methanol andfour aromatic hydrocarbons (1, methanol; 2, ben-zene; 3, naphthalene; 4, anthracene; 5, chrysene) onILs-HSM (A) and CP-silica monolith (B) at 254 nm.Reproduced from [63] with permission of Wiley.



Figure 7. FT-IR spectrum of vinyl ester resin(A) and ATRP-HPM (B). Reproduced from [14]with the permission of Elsevier.

ILs-HSM, the separation of seven inorganic ions was executedefficiently with the phosphate buffer in CEC.

3 HPM materials

The preparation process of HPM material is normally pre-pared by polymerizing monomers in a sealed column, andmany monomers can be used to prepare monoliths with inte-grated structures that can have much higher external poros-ity and greater flexibility than the particulate-based column[64,65]. Bai et al. [14] reported a novel preparation method tomake a new HPM for HPLC. This monolith was first devel-oped by atom transfer radical polymerization (ATRP) usinga simple and rapid method, in which vinyl ester resin wasused as the monomer, and NaHSO3 was used both as theorganic adjunct and coadunate initiator to alter the activity ofthe free radical in the process of polymerization and then con-trol the molecular mass. The typical preparation of this typeATRP-HPM was as follows: 1.0 mL vinyl ester resin, 0.05 mLCCl4, 1.0mL dodecyl alcohol, 0.1 mL methanol, and 0.05 g

FeCl2 were added to a dry ampule. Then, 0.05 g NaHSO3

was added to the ampule after being dissolved in 0.1 mL wa-ter. The solution was dissolved to transparent and degassedwith an ultrasonator. And then the solution was poured intoa stainless-steel chromatographic column (30 mm × 4.6 mmid), which was sealed at both ends with close column heads.The polymerization was allowed to proceed at 70�C for 24h, and then the monolith was washed by methanol for 12h at the flow rate of 0.1 mL min−1 to remove dodecyl al-cohol and other soluble compounds present in the polymerrod. In this process, vinyl ester resin and CCl4 were usedas monomer and initiator, respectively, and NaHSO3 wasemployed as both the coadunate initiator and adjunct. In ad-dition, FeCl2, dodecyl alcohol, and methanol were used asthe catalytic agent, porogen agent, and solvent, respectively.FT-IR spectrum of the vinyl ester resin and the preparedATRP-HPM were performed and shown in Fig. 7. Compareto Fig. 7A and Fig. 7B shows that the absorption spectrumof this ATRP-HPM displays readily identifiable peaks at 2852cm−1 and 2930 cm−1, which are characteristic of the C–Hsymmetric and anti-symmetric stretching vibrations, respec-



Figure 8. Chromatograms of lysozyme from eggwhite on ATRP-HPM (A) and ordinary organicmonolith (B). Reproduced from [14] with the per-mission of Elsevier.

tively. The strong absorption observed at 1510 cm−1 wascaused by C–O–C. The absorptions observed at 1200 cm−1 and1050 cm−1 were assigned to –SO3. The stretching band at3500 cm−1 indicated the presence of the O–H multimer.

Under optimized conditions, this ATRP-HPM was usedto separate lysozyme from chicken egg white with good res-olution and reproducibility, which were obtained in a shorttime (10 min) by HPLC. Figure 8 shows that chromatogramsof lysozyme from egg white on ATRP-HPM (A) and ordinaryorganic monolith (B). Figure 8A shows three distinct peaksin the chromatogram, and lysozyme was separated from eggwhite in a short time with high resolution, but Fig. 8B showsthe ordinary organic monolith cannot separate the target. Inaddition, the effects of the buffer concentration and pH onelution were investigated, and this ATRP-HPM was success-fully used to separate benzene and its homologs from themixture.

Lee et al. [66] reported a new strategy for the synthesisand fabrication of a HPM material coated with gold nanopar-ticles (NPs). This material was produced by polymerization-induced phase separation (PIPS). The dual functionality ofHPM material was attributed to the presence of gold NPsembedded in the polymer surface and the presence of func-tional groups on the polymer surface that were furthermodified for bio-specific recognition. The sensing and de-tection of low molecular weight and biological analytes onthe surface of HPM were demonstrated using surface en-hanced Raman scattering spectroscopy and fluorescence mi-croscopy. Under optimized conditions, the majority of NPssegregate to the surface of pores and hence, they are not“hidden” in the bulk of the polymer material. The NPs arestrongly attached to the polymer surface, due to their partial

embedding in the polymer matrix. This PIPS method can beused for producing porous hybrid monoliths and micrometer-sized particles. Moreover, the simultaneous detection of �-L-glutamyl-L-cysteinylglycine and streptavidin functionalizedwith fluorescein isothiocyanate was governed by the strongand differently “directed” affinities of these analytes for thebiotinylated polymer and gold NPs, respectively. The abil-ity to detect other multiple analytes can be extended inmany ways using various combinations of polymers, NPs andanalytes.

4 Concluding remarks

This review presented an overview of the properties of hy-brid organic–inorganic monolithic materials, and it criti-cally summarizes the recent developments in the prepara-tion and applications of hybrid organic–inorganic monolithicmaterials. Two main types of hybrid monolithic materials,HSM and HPM, have been attracting widely attentions inrecent years. Compared to other types of monolithic materi-als, hybrid monoliths are highly advantageous as they exhibitflexibility, low density, and long shelf-life with excellent bio-compatibility and mechanical properties. Moreover, manycombinations of inorganic and organic components of hy-brid monoliths are scaled at molecular level, and it is thoughtthat synthesis of hybrid monolithic materials can be as anew approach to find more ideal chemical materials. Overall,hybrid monolithic materials will undoubtedly have more ap-plications, and it is likely that this area will continue growingin the near future.



This research was supported by the Basic Science ResearchProgram through the National Research Foundation of Korea(NRF) funded by the Ministry of Education, Science and Tech-nology (2012-0005250).

The authors have declared no conflict of interest.

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preparation and applications of hybrid organic–inorganic monoliths: a review

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