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Jarmolińska, S.; Nowak, I.; Feliczak-Guzik, A. HMM and SBA Porous Materials. Encyclopedia. Available online: https://encyclopedia.pub/entry/7946 (accessed on 06 September 2024).
Jarmolińska S, Nowak I, Feliczak-Guzik A. HMM and SBA Porous Materials. Encyclopedia. Available at: https://encyclopedia.pub/entry/7946. Accessed September 06, 2024.
Jarmolińska, Sylwia, Izabela Nowak, Agnieszka Feliczak-Guzik. "HMM and SBA Porous Materials" Encyclopedia, https://encyclopedia.pub/entry/7946 (accessed September 06, 2024).
Jarmolińska, S., Nowak, I., & Feliczak-Guzik, A. (2021, March 11). HMM and SBA Porous Materials. In Encyclopedia. https://encyclopedia.pub/entry/7946
Jarmolińska, Sylwia, et al. "HMM and SBA Porous Materials." Encyclopedia. Web. 11 March, 2021.
HMM and SBA Porous Materials
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This entry is adapted from the peer-reviewed paper 10.3390/ma13194385

Mesoporous silicas have enjoyed great interest among scientists practically from the moment of their discovery thanks to their unique attractive properties. Many types of mesoporous silicas have been described in literature, the most thoroughly MCM-41 and SBA-15 ones. The methods of syntheses, characterization and use of mesoporous silicas from SBA (Santa Barbara Amorphous) and HMM (Hybrid Mesoporous Materials) groups are presented. The first group is represented by (i) SBA-1 of three-dimensional cubic structure and (ii) SBA-2 of three-dimensional combined hexagonal and cubic structures. The HMM group is represented by (i) HMM-1 of two-dimensional hexagonal structure and (ii) HMM-2 of three-dimensional structure. The paper provides comprehensive information on the above-mentioned silica materials available so far, also including the data for the silicas modified with metal ions or/and organic functional groups and examples of the materials applications.

porous materials SBA-1 SBA-2 HMM-1 HMM-2

1. General Information about Porous Materials

For almost 30 years, much attention has been paid to designing and obtaining new nanomaterials. The interest in such materials stems from the fact that they have at least one component of their structure on the nanoscale (of size from 1 nm to 100 nm) and thus show a number of unique properties and have a wide range of applications [1][2]. A considerable number of such materials belong to nanoporous ones characterized by the presence of channels or pores, classified by IUPAC (International Union of Pure and Applied Chemistry) as micropores (diameter below 2 nm), mesopores (diameter in the range 2–50 nm) and macropores (diameter above 50 nm) [3][4]. The group of porous materials includes for example, zeolites [5], porous carbons [6] and mesoporous silicas [7]. The latter ones are of particular interest as they show highly ordered and stable mesoporous structure, well-developed surface area, ordered system of uniform pores of narrow size distribution and large volume, high thermal, chemical and hydrothermal stability, are nontoxic and their surface can be easily modified [1][8][9].

The history of porous materials started with discovery of natural zeolites, that are microporous aluminosilicates of crystal structure, having a developed system of micropores [10]. Their use in the chemical and petrochemical industry has brought significant benefits both to economy and the natural environment. The success of zeolites has resulted in the syntheses of a number of materials of zeolite structure, however, the size of pores was found to be a substantial limitation as they could not have been used in transformations of larger molecules [11]. The need aroused to obtain mesoporous materials, whose larger pores and large surface area could make them applicable for adsorption, separation, catalysis, as drug delivery carriers, sensors, in photonics for energy storage and conversion and as nanodevices working with large molecules [12].

The first report on the synthesis of mesoporous materials was published in the beginning of the 1990s and it has been a milestone in materials chemistry. In 1992, the first ordered mesoporous silicas were synthesized by the Mobile Research and Development Corporation [13][14]. The materials obtained were called the M41S family and included MCM type materials (Mobile Composition of Matter): MCM-41, MCM-48 and MCM-50, differing in the type of pore ordering. These silicas showed well-developed surface area and a uniform size pore system [15]. The synthesis of M41S materials has opened the way to obtaining new ordered mesoporous silicas [16]: SBA (Santa Barbara Amorphous), MSU (Michigan State University), FSM (Folded Sheet Materials), FDU (Fudan University) and KIT (Korean Advanced Institute of Science and Technology). They were synthesized by modifications of the earlier proposed method by addition of different compounds directing structural development [8][17].

Syntheses of ordered mesoporous silicas of well-defined structure need first of all precise planning of the process, the choice of a suitable compound directing structural development and a suitable precursor of silica. At a proper molar ratio of substrates and proper conditions of synthesis, such as: the time and temperature, pH of solution, time of hydrothermal treatment (ageing), the way and conditions of removal of the structure directing compound from silica pores, it is possible to obtain silicas of desired pore size and structure [18][19].

The best known and most thoroughly studied so far are the SBA-1 type silicas. In general SBA type silicas (SBA-11, SBA-12, SBA-15, SBA-16) are obtained using non-ionic surfactants as structural directing agents [20], however, SBA-1 has been for the first time synthesized using a cationic surfactant with a large head component of its molecule [21]. SBA-2 was synthesized using a gemini surfactant. Perhaps because of the necessity of independent synthesis of these two surfactants needed for obtaining SBA-1 and SBA-2, these two silicas have not been so thoroughly described in literature as the other SBA type materials synthesized with the use of commonly available non-ionic surfactants. It should be emphasized that the 3D system of pores present in SBA-1 ensures easier accessibility of these pores to the reagent molecules than the 1D cylindrical pores, so SBA-1 has high application potential, for example, in adsorption and catalysis [22].

HMM materials are organic-inorganic hybrids that have been obtained as a result of condensation of bis-silylated organic compound (R’O)3Si–R–Si(OR’)3 used as a precursor of silica. The type of material obtained, HMM-1 or HMM-2 of different structures, depends on the proportions of the reagents in the reaction mixture [19]. The materials belong to the group of mesoporous materials referred to as PMOs (Periodic Mesoporous Organosilicas).

2. SBA-1

Mesoporous SBA-1 silicas have three-dimensional cubic structure of Pmn symmetry with open 3D cage type pores joined through open windows (Figure 1) [23][24]. The materials of SBA-1 type show unique textural properties, including the specific surface area in the range 1200–1450 m2/g and pore diameters varying from 2.1 nm to 2.6 nm. The 3D pore network is resistant to blocking and provides a large number of adsorption sites thanks to the large specific surface area. Moreover, the pores are easily accessible to the reagents molecules [25][26]. Thanks to the textural parameters and high thermal stability, SBA-1 is considered as a good catalyst support [23]. Its cubic structure is more stable than that of the silicas of hexagonal structure (MCM-41 or SBA-15). Stability of the silicas is of particular importance because the catalysts supported on them are often subjected to processes endowing them with a required type of form (e.g., tablets) [26].

Figure 1. Structure of SBA-1. Reprinted with permission from The Royal Society of Chemistry.

3. SBA-2

SBA-2 type silicas have not been so thoroughly described as SBA-1. The former have a 3D pore network made of spherical cavities ordered in hexagonal close-packed (hcp) system and cubic close-packed system (ccp), joined through cylindrical channels [27][28][29]. It should be emphasized that the structure of SBA-2 silicas is similar to that of SBA-12 showing 3D hexagonal structure and P63/mmc symmetry. The latter have been obtained using triblock copolymer as a mesoporous structure directing compound [30][31]. After the first synthesis of SBA-2 silica, only the hexagonal pore system was identified in its structure, while the presence of the cubic system of pores was found later as a result of detailed investigation [32]. The hitherto literature has provided only a few applications of these silica materials in catalysis and adsorption, as described below.

Figure 2. The network of pores in SBA-2. Reprinted with permission with minor modification.
Copyright (2003) Elsevier B.V.

4. HMM-1 and HMM-2

Materials of HMM-1 and HMM-2 types belong to Periodic Mesoporous Organosilicas (PMOs) as they contain in their structure organic and inorganic groups making a hybrid organic-inorganic lattice linked by covalent bonds [33]. The HMM group is divided into HMM-1 and HMM-2 subgroups. Their structure is built of uniform ethyl fragments (–CH2–CH2–) and silica groups (Si2O3), making a network joined through covalent bonds [34][35][36]. The porous structure of these materials is completely different than that in mesoporous materials built of an inorganic lattice with organic modifiers grafted on the surface. HMM-1 and HMM-2 show highly-ordered mesoporous structure and well-defined morphology of hexagonal rods and spherical particles, respectively [34]. These two materials were synthesized using the same reagents: 1,2-Bis(trimethoxysilyl)ethane (BTME) and octadecyltrimethylammonium chloride (ODTMACl), in basic conditions. Their structure was controlled by the temperature of synthesis and molar ratio of the components of the synthetic mixture. The removal of surfactant by extraction with a solvent opened the uniform pores in the materials and it did not deteriorate the ordered structure. The materials were characterized by hydrothermal stability [33][37]. HMM-1 showed a 2D hexagonal structure of p6mm symmetry with 1D pores of diameters smaller than 10 nm and well-developed surface area reaching even 1000 m2/g. Thanks to these properties HMM-1 was applied as a template for the synthesis of nanoparticles and nanowires of metals [38][39]. HMM-2 of a 3D structure of P63/mmc symmetry found similar applications [40].

5. Application of Mesoporous Silica Materials - Summary

Nanoporous silica materials, due to their physicochemical properties, show a number of applications [41][42][43]. Table 1 summarizes potential applications of SBA-1, SBA-2, HMM-1 and HMM-2 materials.

Table 1. Potential use of the SBA and HMM-type materials.

Type of material Metal/Organic Groups Application Ref.
Synthesis in Acidic Conditions
SBA-1 Ti Oxidation of styrene with hydrogen peroxide [44]
SBA-1 Fe
SBA-1 Mo Partial oxidation of methane with oxygen [45]
SBA-1 Al Isomerization of n-decane [46]
SBA-1 Al Synthesis of 7-methoxy-4-methylcoumarin [47]
SBA-1 Al
Al and Mg		 Acetalization of heptanal [48]
SBA-1 Ti Epoxidation of styrene to styrene oxide [49]
SBA-1 Cr Dehydrogenation of ethane with the use of CO2 [50]
Dehydrogenation of propane with the use of CO2 [51]
SBA-1 Ga tert-butylation of phenol [25]
Alkylation of naphthalene with propylene [52]
SBA-1 Mn Oxidation of ethylbenzene with the use of TBHP [53]
SBA-1 alkali metals
Li, Na, K, Rb, Cs		 Knoevenagel condensation between benzaldehyde or benzylacetone and ethyl cyanoacetate [54]
SBA-1 amino groups Adsorption of oxyanions (chromates and arsenates) [55]
SBA-1 Hoveyd-Grubbs catalyst Olefin metathesis catalyst [56]
SBA-1 unmodified For obtaining highly-ordered carbon materials [57]
Synthesis in Basic Conditions
SBA-1 Al Alkylation of 2, 4-Di-tert-butylphenol with cinnamyl alcohol [58][59]
Alkylation of toluene with benzyl alcohol [60]
SBA-1 Ti Oxidation of 2, 3, 6-trimethylphenol [61]
SBA-1 unmodified Immobilization of lysozyme [62]
SBA-1 carboxyl groups Immobilization of papain [63]
SBA-1 carboxyl and amino groups Adsorption of toxic anionic or cationic dyes [27]
SBA-2 thiol groups Esterification of glycerol with oleic acid (very low activity) [64]
SBA-2 sulfonic groups Esterification of glycerol with oleic or lauric acid (very low activity) [65]
SBA-2 Ti Oxidizing desulfurization of Diesel oil [28]
SBA-2 unmodified Adsorbent of volatile organic compounds (adsorbent for separation of a mixture of benzene/cyclohexene) [66]
HMM-1 Rh or Pt and Rh Hydrogenation of n-butane [36]
HMM-1 sulfonic groups Hydrolysis of saccharose of starch [67]
HMM-1 unmodified Matrices for syntheses of nanowires and metal nanoparticles (bimetallic Pt-Rh, Pt-Pd as well as monometallic Pt or Rh) [68]
HMM-1 Pd nanowires or nanoparticles CO oxidation [38]
HMM-2 unmodified Matrices for syntheses of nanowires and metal nanoparticles (Au, Pt) [69]
HMM-2 Au nanoparticles CO oxidation [70][71]

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Sylwia Jarmolińska
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Izabela Nowak
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Agnieszka Feliczak-Guzik
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Update Date: 18 Mar 2021
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