Luzmary Sabino

Chris Keturakis

BET Analysis/ Pore Volume Write Up

This is a general overview on how to perform a pore analysis on your respective catalysts in
order to find the BET surface area, pore volume, and pore distribution of your catalyst.

Things to know before beginning analysis:

1) Approximate surface area from literature or company specs of your catalyst
Second, for a pore analysis, you typically want approximately 1000 m
2
/g as your
sample size. So if your sample is 500 m
2
/g, than you want to use between .25 to .5
g of your catalyst as a sample size.
2) General porosity of your sample
This is needed in order to choose the best analysis method depending on whether
you have a very mesoporous or microporous sample.

Sample Preparation:

In the lab, we currently have 4 sample tubes, 4 sample tube stoppers, and a custom made pipette
arrangement in order to load the sample in the tube. One sample tube and stopper is needed for
every experiment performed.

The steps for the sample prep described will be detailed with a 10 % Al-Si mezoporous sample
with an approximate surface area of 300 m
2
/g. All the steps will be the same for any sample used
except for the initial sample size.

1. Use an empty bottle and place on balance. TARE. The bottle will be needed in order to
weight the sample tube.
2. Place empty sample tube with stopper inside bottle and record mass. Repeat 4 times.
Record the average for the empty sample tube.
3. Weigh .15 g of sample. Remove stopper and using pipette arrangement, place inside
sample tube.
4. Place sample tube with stopper and sample inside bottle and record mass. Repeat 4 times.
Record the average. This step is to know the initial mass of your sample before
degassing.

Degassing your examples:

All the experiments are completed up in Prof Snyders lab, RM 343 (???). The Micrometrics
ASAP 2010 Surface Area and Porosity Analyzer is the instrument used for the experiments.


Figure 1: Micrometrics ASAP 2010 Surface Area and Porosity Analyzer

As seen in Figure 1, the ASAP has 3 chambers. The first is the degassing chamber. The chamber
contains 2 degassing ports, so you can degas two sample at the same time.

During the degassing process, your flowing air through your sample. The purpose is to eliminate
any impurities stuck in the pore of the samples in order to get a more accurate reading. Because
youre starting at a high partial pressure (around 100 mmHg), as the sample is degassing, youre
partial pressure will decrease as well as the weight of the sample once all the impurities are
removed. The second mass measurement of your sample tube is to ensure that your third
measurement is lower than your second, indicating that some impurities have been removed from
the pores of your sample.

Placing sample in degas port:

1. Go to shortcut to data on the desktop and create a folder for your experiments.
2. Remove gray screen from port and place it on top the instrument.
3. Unscrew the nut from the port and remove glass tube with O ring. Set the small glass tube
aside and remove O ring. You will need to put this back after you degas your sample in
order to keep the port from being exposed to the atmosphere.
4. Place nut on sample tube and then place O ring. Make sure O ring is aligned with the
middle turn of the sample within tube (sometimes it wont align perfectly in the middle,
but get it as close as you can)
5. Place thermo jacket over sample bulb and clamp it. Cover port with the gray screen. Your
sample should like similar to Figure 1.
6. On the computer, open ASAP 2020 program (it is usually always opened).
7. Press F2 button on computer. A panel, Open Sample Information, will open. On the right
side of the panel where it says Directories: find your folder.
8. On the top of the screen, where it says File name, put the name of your sample and click
enter. A panel will pop up asking if you want to create a file with this sample name. Click
yes. An SMP file with your sample name will open. Click on the Sample Tube and
unclick option use filler rod)
9. Go to Degas Conditions and make sure that the conditions wont harm your sample.
Close panel.
10. Go to Unit 1 up top and click Start Degas. Make sure your sample is shown on the port
that you put it in. Start degas. A blue panel will appear showing that your sample is now
degassing.

The degas process make take up to a day depending on your sample.

Sample analysis (mesopores):

For the samples analysis, were basically doing N2 adsorption. N2 flows through the sample tube.
The sample tube is cooled by liquid N2 which causes the N2 molecules to stick.

1. On the blue panel, click Check on the degas option that shows your sample. Wait for a
minute as your partial pressure changes. If your partial pressure is around 5mmHg, tap
continue button then tap Skip. It will give the option on whether you want to end this
step, hit yes.
2. Now the temperature of thermo jacket will start to cool down. Wait a few minutes, and
hit continue then skip, ending the temperature cool down. It will state the sample s
backfilling and then tell you that the degas for port () is complete. Remove the thermo
jacket, wait a few minutes for the sample to cool down, and then remove sample.
3. Reweight your sample 5 times and take the average. Confirm that this measurement is
lower than the 2
nd
one.
4. Subtract the 3
rd
and 1
st
measurement. This is your sample weight.
5. Press F2. Input your sample weight.
6. Insert sample into analysis port. The setup is the same as degassing except that you add a
white tube over sample before you add the nut.
7. Make sure that the thermocouple is aligned to the sample and parallel to the white tube.
8. Remove tanks shown in figure 1 and refill with liquid N2. Be careful removing the tank
in chamber 2 so that you dont damage the thermometers. Use a bit holder to make sure
that tanks are filled up to the hole. Fill the tank that goes in chamber 2 a little higher than
the other one. This is because once you replace tank 2, since the thermometers may have
cooled down, some of the liquid N2 may spill out. Replace tanks in appropriate slots.
9. Press Analysis Conditions. This is where it gets tricky to explain since you have a lot of
options available. For pore volume, mark X by clicking on empty space on the highest
relative pressure before it starts decreasing. For pore distribution curve, go to BJH tab
and mark X on all the point up to and including the highest relative partial pressure. For
BET surface area, if you have a microporous sample, mark X on points between .01 (the
lowest relative pressure the equipment can do) and .1. For a mezopore sample, mark X on
points between .1 and .4. You can add points within these sections by clicking insert and
then clicking on the point to change it into any number you choose. It is probably best to
talk to Dan Gregory or Prof Snyder before you start since they can guide you on what
data you want for your sample. Click save and then close.
10. Click Unit 1 and click Sample Analysis. Change ambient temperature using thermometer
in computer area. Start analysis.

Sample Analysis (micropore):

If you want to do a micropore analysis (since micropore wont show up on the in the analysis
since there pores usually get filled up at below a relative pressure of .01), the setup is a little
different. After your first degas, measure the free space in the analysis port.

The free space is the dead volume of your sample. In case of nitrogen adsorption measurement,
the sample is cooled down by liquid nitrogen. Upon the cooling, there will be two different
temperature zones in the sample cell. The gas density of cooled zone is higher and it is
influenced by the coolant temperature and by the change in the coolant level. The volumetric
method counts the number of un-adsorbed gas molecules (density), and in the process, the free
space plays an important role. The conventional volumetric measurement procedure is to cool
down the sample by liquid nitrogen, measure the free space by non-adsorbing He gas at the
liquid nitrogen temperature, and then, measure the nitrogen or other adsorptive gas isotherm.
During the adsorption measurement, the coolant level needs to be maintained. (Taken directly
from http://www.nippon-bel.co.jp/tech/seminar04_e.html)

After measuring the free space, the sample is degased, weighed again, and then degassed in the
analysis port. After the last degas, the sample is set up in the Analysis conditions tab to do spurts
of N2 until .01 relative pressure, and the do then standard analysis. Because Ar adsorption tends
to be more accurate due to the spherical shape of Ar, Ar is used for micropore analysis. The gas
can be changed in the analysis conditions tab. Before doing a micropore analysis, Prof Synder or
Dan should be consulted since there may be additional steps not addressed in this write up.

Result Analysis:

You will know that the analysis is done when you see a complete isotherm of ADS and DES
points. Press F8, and then click on your sample to report options. Check to make sure you have a
C value positive and as close to 1 in your BET Tabular report tab. A negative C value indicates
an inaccurate BET. You will need to change the points around in the Report Options tab of your
sample file and the reopen the report. Repeat until you get a positive C value.

Save your report as an excel file. The report gives you several sections of plots and data for your
sample.

The BET surface area and the pore volume should be located in the first section.

For the isotherm, plot the isotherm tabular plot points.

For the pore distribution, plot the dV/dlog(w) desorption points. If you want points in the
micropore region, mark X in the same values as you did for BJH, but do it in the DFT tab
instead. DFT is more accurate for micropores. The DFT results will show up in dV/dw points