Experiment 7: Preparation and Analysis of Mesoporous and Microporous Materials

Abstract

In attempting to construct microporous and mesoporous materials, synthesis of

SBA-15 (Santa Barbara Amorphous) and MOF-5 (Metal Organic Framework)

was attempted. IR analysis for MOF-5 revealed two sharp peaks, seen at 1576 and

1364 cm-1. For SBA-15, two broader peaks were observed at 1058 and 444 cm-1,

indicating higher energy levels in microporous MOF-5. Surface area and pore size

for SBA-15 and MOF-5 were found to be relatively consistent with IUPAC

definitions of mesoporous and microporous materials.

Introduction

Microporous, mesoporous, and macroporous materials vary in order of increasing pore

sizes. Whereas microporous materials have pore diameters less than 2 nm, mesoporous materials

contain pore diameters between 2 nm and 50 nm, and macroporous materials contain pore

diameters greater than 50 nm. Synthesis of the former two types of materials, microporous MOF-

5 and mesoporous SBA-15, were attempted in this experiment.

Metal organic frameworks (MOFs) are composed of metal ions coordinated to organic

ligands. MOFs have applications in catalysis, drug delivery, and as it relates to this experiment,

gas separation techniques involving adsorption, which assists in measuring the specific surface
area and pore size distribution of MOF-5. MOF-5, one of several MOFs, consists of Zn4O units

connected by 1,4-benzenedicarboxylate struts (organic ligand), forming a cubic network.

SBA-15 is an example of mesoporous silica (SiO2) that can be synthesized using

surfactants, or detergents, such as P123 in solution. Surfactants in solution aggregate and form

bundles of micelles, which act as scaffolds for formation of porous materials. The chemical

conversion of Si to SiO2 under conditions of high heat allows for the surfactant to be burned out,

and create porous SBA-15.

Experimental

Synthesis of SBA-15. 2.4 g of P123 was weighed in a 200 mL beaker, which was dissolved by

adding 84 mL of 1.07 M HCl and set to stir with a magnetic stirrer. After ensuring all surfactant

had dissolved, 13.9 g of decane was added via pipette and set to stir for one hour. 0.027 g NH4F,

a catalyst, was added. Lastly, 5.1 g of tetraethyl orthosilicate (TEOS) was added to solution. The

solution was covered with a watch glass and set to stir at 40 C. Two days later, the mixture was

transferred to a plastic bottle, sealed with PTFE tape, and placed in an oven set to 100 C. The

following week, SBA-15 was isolated through vacuum filtration onto a Buchner funnel, washed

with distilled water, allowed to air dry. The product was transferred to a labeled porcelain boat

and calcined at 540 C in a furnace oven. Finally, SBA-15 yield was recorded and found to be

2.8 g. IR was recorded for both pre-calcined and calcined SBA-15, with peaks at 1058 and 444

cm-1 for pre-calcined SBA-15, and peaks at 1076 and 457 cm-1 for calcined SBA-15.

Synthesis of MOF-5. 0.50 g of 1,4-benzene dicarboxylic acid was weighed and dissolved in 40

mL DMF in 200 mL beaker with a magnetic stir bar. 0.85 mL triethylamine was added to this

solution. 1.70 g Zn(OAc)2 2H2O was dissolved into 50 mL DMF in a separate 100 mL beaker.
Once fully dissolved, the solution was added drop-wise via pipette into stirred solution over 15

minutes. Approximately one drop was added every 30 seconds, for a total of 30 drops. This

mixture was stirred for 2 hours. The solids were isolated through vacuum filtration and air dried.

A small sample of solid was obtained and IR spectroscopy was performed, resulting in peaks at

1576 and 1364 cm-1 for MOF-5, and peaks at 1578 and 1366 cm-1 for calcined MOF-5.

Surface area determination was performed using BET theory, which attempts to measure gas

adsorption at a given pressure to measure surface area. Pore size analysis was conducted with

BJH method.

Data and Observations

Figure 1. IR spectrum of MOF 5

Figure 2. IR spectrum of dried MOF 5

Figure 3. IR spectrum of SBA-15

Figure 4. IR spectrum of calcined SBA-15

Table 1. Surface Area, Pore Diameter, and Yield of MOF-5 and SBA-15

MOF-5 SBA-15

Surface Area (m2/g) 109.5 m2/g 731 m2/g

Pore Diameter () 54.99 100.1

Yield (g) 0g 2.8 g

Results and Discussion

Mesoporous silica SBA-15 was synthesized using a mixture of surfactant P123, 1.07 M HCl,

decane, NH4F catalyst, and tetraethyloxysilane TEOS. Yield of SBA-15 was found to be 2.8 g.

Surface area of SBA-15 was found to be 731 m2/g, and pore diameter was found to be 100.1 ,
which converts to 10.1 nm, and confirmed to be within the accepted range in pore diameter of

mesoporous materials (2 nm < 50 nm).

Microporous MOF-5 synthesis was attempted using 1,4-benzene dicarboxylic acid,

triethylamine, N,N-dimethylformamide (DMF), chloroform (CHCl3), and zinc acetate hydrate

Zn(OAc)2 2H2O. Unfortunately, MOF-5 yield was not achieved. This is likely due to a lack of

precipitate after adding the Zn(OAc)2 2H2O/DMF solution, which indicates possibility that the

Zn(OAc)2 2H2O did not fully dissolve into DMF. This is most plausible explanation, since

isolation of solids through vacuum filtration did not result in any tangible MOF-5 yield. For

future experiments, it would be advised to ensure full dissolution of zinc acetate hydrate into

DMF before proceeding in the experiment.

Surface area of MOF-5 was found to be 109.5 m2/g and pore diameter was found to be 54.99 ,

which converts to 5.499 nm, which is admittedly above the IUPAC definition of accepted pore

diameters in microporous material (< 2 nm). Ideally, MOF-5 should be under 2 nm in pore size,

since a larger pore diameter can inhibit MOF-5 ability to store gases, such as H2, in large

quantities.

Analysis of IR spectroscopy notably reveals sharp peaks in MOF-5 at 1576 and 1364 cm-1, and

broader peaks in SBA-15 at 1058 and 444 cm-1. This is consistent with what would be expected,

with MOF-5 bonds demonstrating higher frequency and energy level due to higher peaks in

wavenumber. Higher peaks were observed in calcined SBA-15, with peaks at 1076 and 457 cm-1

as opposed to pre-calcined SBA-15. Marginally higher peaks were observed in dried MOF-5,

with peaks at 1578 and 1366 cm-1, relative to MOF-5. The smaller peaks in dried MOF-5 were

similar to the smaller peaks in MOF-5. Ideally, calcinated SBA-15 should have indicated higher
gas adsorption capacity. Perhaps keeping SBA-15 in the oven for longer periods of time or at

higher temperatures, thus more accurately emulating the natural formation of mesoporous zeolite

material and burn out any remaining surfactant, will result in higher gas adsorption capacity.

Conclusion

Synthesis of mesoporous silica SBA-15 was achieved, while MOF-5 yield was subpar, possibly

due to incomplete dissolution of Zn(OAc)2 2H2O in DMF resulting in lack of precipitate.

Surface area and pore diameter measurements were found to be consistent with those commonly

found in microporous and mesoporous materials. IR spectroscopy indicated sharper, higher

peaks for MOF-5 and broader, smaller peaks for SBA-15, indicating higher frequency and

energy in MOF-5 bonds. Chemically synthesized mesoporous and microporous materials will

become more relevant as ongoing research will explore different techniques that can be used to

promote gas adsorption capacity.

Discussion Question:

1.) Materials that occur naturally have similarities with and differences from those that are

chemically synthesized. Some rocks are formed under specific conditions of high temperature

and pressure, such as in the Earths crust, whereas structurally similar materials that are

chemically synthesized do not require these conditions, and instead can be synthesized at room

temperature with the aid of surfactants such as P123 and spontaneous formation of micelles.

2.) The chemical bonds present in Metal-Organic Framework materials are stronger than those

found in zeolite-type materials. This is evident from IR analysis, which demonstrate higher peaks

in MOF-5 than in SBA-15, which indicate higher frequency and energy levels, resulting from

stronger bonds.