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Project Report 3

Under the guidance of

Prof. Preeti Aghalayam

&

Dr. K.R.Krishnamurthy National Centre for Catalysis Research

Indian Institute of Technology, Madras

Contents

Summary of earlier work

Further characterization of catalysts

Calibration of GC

Testing of Catalysts

Initial conversion and selectivity trends.

Optimization of different parameters of reaction.

Future work

Summary of earlier work

Reaction scheme

Literature survey

Problem for research

Catalyst prepared

Characterization (XRD, UV)

Reaction scheme

Contents • Summary of earlier work • Further characterization of catalysts • Calibration of GC •

Fig.1 Reaction scheme of hydrogenation of Cinnamaldehyde to its products.

CAL=cinnamaldehyde, HCAL=hydrocinnamaldehyde, COL=cinnamyl alcohol, HCOL=hydrocinnamyl alcohol.

The aim of the project is to selectively produce cinnamyl alcohol from cinnamyl aldehyde but this reaction is thermodynamically not favorable which can be seen from Gibbs free energy values depicted in the reaction scheme, so the challenge is to design a catalyst system which would overcome thermodynamic barrier and facilitate the desired reaction.

Literature survey

According to literature the best catalyst known which give very good selectivity and conversion is a platinum based bimetallic system whose details are given in Table 1.

----------------

The aim of the project is to selectively produce cinnamyl alcohol from cinnamyl aldehyde but this

Table.1 best catalyst known for selective hydrogenation of cinnamaldehyde to cinnamyl alcohol

The platinum based catalyst is a bimetallic system with Co, the nanoparticles are protected by capping agent PVP.

Problem for research

As we see from Table 1 that Pt-Co/PVP is a very good catalyst for selective hydrogenation of cinnamaldehyde but the TON is considerably low when compared to other noble metals like Ru, Rh and Pd, so here lies a challenge to design a catalyst which can give good selectivity with high TON. A comparison of selectivity conversion and TON is shown in Table 2, which reveals that amongst Ir, Pt,, Ru, Rh, Pd, Palladium is having the highest TON of 6.7s -1 which is 600 times greater than Pt, so we have chosen Pd noble metal to design a catalyst as the problem for our research.

Table.2 comparison of selectivity conversion and TON of noble metals. Catalyst prepared Below listed catalysts were

Table.2 comparison of selectivity conversion and TON of noble metals.

Catalyst prepared

Below listed catalysts were prepared and characterized by UV and XRD by the end of the project evaluation 2

Shape controlled catalysts

Tetrahedral Pd/Hydrotalcite

Octahedral Pd/Hydrotalcite

Spherical Pd/Hydrotalcite

TiO 2 supported catalysts

PVP-1.5% Pd/Ti0 2 P25

PVP-1 % Pd/Ti0 2 P25

Further characterization of catalysts

The above listed catalysts were Characterized by TEM/HR-TEM, TG-DTA, XPS.

TEM/HR-TEM

Tetrahedral -Pd/Hydrotalcite

TEM/HR-TEM Tetrahedral -Pd/Hydrotalcite Figure.2 TEM of Tetrahedral -Pd/Hydrotalcite Fig.2 shows the TEM images of Tetrahedral Pd/Hydrotalcite,

Figure.2 TEM of Tetrahedral -Pd/Hydrotalcite

Fig.2 shows the TEM images of Tetrahedral Pd/Hydrotalcite, the goal of preparing this catalyst was to prepare tetrahedral shaped Pd crystallites, Fig.2 shows some Tetrahedral shaped Pd but other shapes of Pd crystallites are also present, the reason to prepare tetrahedral Pd crystallite was tetrahedral shaped crystallites exposes only (111) plane, exposure of a single plane gives selectivity towards adsorption of a specific functional group which will give selectivity towards a specific product.

TEM/HR-TEM Tetrahedral -Pd/Hydrotalcite Figure.2 TEM of Tetrahedral -Pd/Hydrotalcite Fig.2 shows the TEM images of Tetrahedral Pd/Hydrotalcite,

Figure.3 EDAX of Tetrahedral Pd/Hydrotalcite.

Fig.3 shows the EDAX(energy dispersive X-ray spectroscopy) of Tetrahedral Pd/Hydrotalcite which confirms the presence of Pd tetrahedral crystallites.

Fig.4 give the crystallite size distribution of Tetrahedral Pd/Hydrotalcite, the crystallite size is centered around 25nm.

Fig.4 give the crystallite size distribution of Tetrahedral Pd/Hydrotalcite, the crystallite size is centered around 25nm.

Fig.4 Crystallite size distribution of Tetrahedral Pd/Hydrotalcite

Octahedral Pd/Hydrotalcite

Fig.4 give the crystallite size distribution of Tetrahedral Pd/Hydrotalcite, the crystallite size is centered around 25nm.

Fig.5 HR-TEM images of octahedral Pd/Hydrotalcite

Fig.5 depicts the HR-TEM images of octahedral Pd/Hydrotalcite, we can see octahedral crystallites with other shaped crystallites of Pd nanoparticles. The goal of preparing octahedral shaped particle was to expose specific planes, octahedral specifically exposes (111) and (110)

planes in comparison with tetrahedral which exposes only (111), it would be very interested to see what might be the effect on the selectivity of products.

Fig.6 depicts the crystallite size distribution, the crystallites are centered around 22-28nm.

planes in comparison with tetrahedral which exposes only (111), it would be very interested to see

Fig.6 Crystallite size distribution of octahedral Pd/Hydrotalcite

Spherical Pd/Hydrotalcite

Figure 7 depicts the HR-TEM images of spherical Pd/Hydrotalcite, the images show mostly spherical shaped Pd crystallites.

planes in comparison with tetrahedral which exposes only (111), it would be very interested to see

Figure.7 HR-TEM images of spherical Pd/Hydrtotalcite

In comparison with tetrahedral and octahedral, spherical shaped crystallites expose multi- planes, and it would be interesting to see the variation in selectivity towards product formation.

In comparison with tetrahedral and octahedral, spherical shaped crystallites expose multi- planes, and it would be

Figure.8 Crystallite size distribution of spherical Pd/Hydrotalcite.

PVP 1.5% Pd/TiO 2 P25

Figure.9 shows the TEM images of PVP1.5%Pd/TiO 2 -P25, which shows that the Pd nanoparticles are impregnated on the Titania nanoparticles.

In comparison with tetrahedral and octahedral, spherical shaped crystallites expose multi- planes, and it would be

Fig.9 TEM images of 1.5%PVP Pd/TiO 2 P25

Fig.10 depicts the EXDX of 1.5%PVP Pd/TiO 2 P25 catalyst and we can clearly see the presence of Pd, Ti, O.

Fig.10 EDAX of 1.5%PVP Pd/TiO P25 Fig.11 give the crystallite size distribution of 1.5%PVP Pd/TiO P25

Fig.10 EDAX of 1.5%PVP Pd/TiO 2 P25

Fig.11 give the crystallite size distribution of 1.5%PVP Pd/TiO 2 P25 which shows that crystallites are centered around 3nm.

Fig.10 EDAX of 1.5%PVP Pd/TiO P25 Fig.11 give the crystallite size distribution of 1.5%PVP Pd/TiO P25

Fig.11 Crystallite size distribution of 1.5%PVP Pd/TiO 2 P25

PVP 1.5% Pd/TiO 2 P25

TG-DTA

PVP 1.5% Pd/TiO P25 TG-DTA Figure.12 TG-DTA of PVP1.5% Pd/TiO P25 The purpose of doing TG-DTA

Figure.12 TG-DTA of PVP1.5% Pd/TiO 2 P25

The purpose of doing TG-DTA was to know till what temperature the catalyst is stable or do not undergo any weight change, this information is essential to decide the reaction condition. In this case we see significant weight loss at 270 o C may be due to decomposition of organic matter like ethylene glycol or PVP which means that we can conduct reaction below 250 o C only, reaction carried away above 270 o C will lead to weight loss in catalyst which will lead to change in basic design of catalyst. The endothermic peak at 270 o C is due to PVP decomposition.

Octahedral Pd/Hydrtotalcite

Figure.12 depicts the TG-DTA of octahedral Pd/Hydrtotalcite, here we see three consecutive weight losses between 200-400 o c, the first loss is attributed to loss of interlayer water, second weight loss is attributed to decomposition of interlayer carbonate anion and the third one is attributed to dehydroxilation of OH groups. All these peaks are exothermic in nature. Fig.12

also helps us to fix the reaction temperature, the reaction temperature can be only below

  • 200 o C.

also helps us to fix the reaction temperature, the reaction temperature can be only below 200

Figure.12 TG-DTA of octahedral Pd/Hydrtotalcite

XPS

Fig.13 is the full scan XPS of PVP1.5% Pd/TiO 2 P25, which shows the presence of Pd, O,Ti,C.

XPS Fig.13 is the full scan XPS of PVP1.5% Pd/TiO P25, which shows the presence of

Fig.13 XPS Full scan of PVP1.5% Pd/TiO 2 P25

XPS Fig.13 is the full scan XPS of PVP1.5% Pd/TiO P25, which shows the presence of

Figure.14 XPS of Pd 3d peak

Fig.13 gives the full scan of PVP1.5% Pd/TiO 2 P25 showing the presence of Pd, Ti, O, c. Fig.14 is the xps of Pd 3d which shows two peaks corresponding to 3d 5/2 and 3d 3/2 which are generated

because of spin-orbit coupling. The standard binding energies of the Pd 3d peaks and observed values are given in table 3.

 

Standard BE(eV)

Observed BE(eV)

Pd 5/2

335 ± 0.2

335.22

Pd +2

340± 0.2

340.50

     

Table 1. Binding energies of Pd in PVP1.5% Pd/TiO 2 P25

Figure.15 is the deconvoluted plot of figure.14, this plot gives information about the %surface ratios of Pd in its oxidized and reduced form, this information is given in table 4.

because of spin-orbit coupling. The standard binding energies of the Pd 3d peaks and observed values

Figure.15 Deconvolution of Pd 3d peak.

%Pd 0

%Pd+2

54

46

   

Table 4. % surface ratios of Pd and Pd +2

Testing of Catalyst

Hydrogenation of cinnamaldehyde is carried in a parr reactor to test them performance of catalyst and the obtained products are analyzed by GC with RTX-5 MS column. Before analyzing products the GC has to be calibrated for the reactant and products of the reaction, Fig.16 depicts the chromatogram of the GC calibration.

Testing of Catalyst Hydrogenation of cinnamaldehyde is carried in a parr reactor to test them performance

Figure.16 chromatogram showing the calibrated peaks of reactant and products.

Initial reaction condition

Reaction set 1

Temperature = 120 o c

Catalyst wt. = 150mg

Solvent = Methanol

Reactant = 1.2g(9mmol)

H 2 Pressure

= 10bar

Catalyst

Conversion

Selectivity%

 
 

HCAL

HCOL

COL

Tetra Pd/HT

100

 
  • 78.9 0.3

20.8

 

Octa Pd/HT

 

100

 
  • 78.3 0.2

21.5

 

1.5%Pd/TiO

         

2

100

7.3

19.5

73.2

1% Pd/ TO

2

100

1.2

13.2

85.6

Table.5 selectivity and conversion at 150mg,120 o C. ( Tetra=tetrahedral, HT=hydrotalcite, Octa=Octahedral)

Table.5

depicts the selectivity and conversion of hydrotalcite supported catalysts and

titania supported catalyst under initial conditions chosen for reaction. Form table.5 it is clearly evident that
titania supported catalyst under initial conditions chosen for reaction. Form table.5 it is
clearly evident that all catalyst systems are showing 100% conversion but only Titania
based catalyst are showing very good selectivity towards cinnamyl alcohol, whereas poor
selectivity is seen for hydrotalcite supported catalysts. Since all catalyst are showing 100%
80
conversion it means all the reactant has converted to reactant, but for the comparison of
60
catalyst systems it is important that we get some unreacted reactant. In order get
unreacted reactant we have to optimize the reaction conditions.
Figure .17 gives a graphical presentation of the activities of hydrotalcite and titania based
catalysts.
40
20
0
THT
OHT
1.5%Pd/Ti
1.0%Pd/Ti
%Selectivity

Catalyst type

Figure.17 plot comparing selectivity of THT(Tetrahedral Pd/Hydrotalcite, OHT(octahedral Pd/Hydrotalcite, 1.5% Pd/TiO 2 , 1% Pd/TiO 2

Reaction set 2 Effect of Temperature

Temperature = 100 o c and 80 0 c

Catalyst wt. = 150mg

solvent = methanol

Reactant = 1.2g

H 2 Pressure

= 10bar

In this reaction set we have decreased the reaction temperature form 120 0 C to 100 and 80 o C, we want to see if by decreasing the temperature their might be decrease in conversion and we might get some unreacted reactant, but we could not get any unreacted reactant, but the selectivity at 100 o C is much better than selectivity at 120 o C, the results of reaction set 2 are presented in table6, form this data we can conclude that selectivity at 100 0 C is much better than selectivity at 120 0 C. Figure.18 gives a graphical representation of the comparison of

selectivity of 1.5%Pd/TiO 2 at 100 and 80 o C.

Catalyst

Conversion

 

Selectivity%

 

HCAL

HCOL

COL

 

0

       

1.5%Pd/Tio

100

C

  • 100 0.7

9.3

90

2

 

0

       

1.5%Pd/Tio

80

C

  • 100 1.2

15.8

82.6

2

Table.6 selectivity and conversion of 1.5%Pd/TiO 2 at 100 and 80 o C.

80 60 40 20 0 110 105 100 95 90 85 80 75 70 %Selectivity
80
60
40
20
0
110
105
100
95
90
85
80
75
70
%Selectivity

Temperature

Figure.18 comparison of selectivity of 1.5% Pd/TiO 2 at 100 and 80 o C.

Temperature = 120 0 c

Catalyst wt. = 75mg

solvent = methanol

Reactant = 1.2g

H 2 Pressure = 10bar

Reaction set 3 Effect of Catalyst wt.

Results of Reaction set 1 and 2 reveal that changing the temperature had not much effect on the conversion and we could not get any reactant peak, so in this reaction we kept the temperature at 120 o C and decreased the catalyst wt to half of amount used in reaction set 1 which comes to 75mg. the result of this reaction is presented in table.7, even under these conditions we were unable to get any reactant peak but the selectivity is retained.

Catalyst

Conversion

 

Selectivity%

 

HCAL

HCOL

COL

1.5% Pd/ TiO

2

100

3.9

7.1

89

Table7 selectivity and conversion of 1.5% Pd/TiO 2 at 75mg, 120 o C.

Reaction set 4 Change in catalyst wt. and temperature Temperature = 100 0 c

Catalyst wt. = 40, 30, 20mg

solvent = methanol

Reactant = 1.2g

H 2 Pressure

= 10bar

Reaction sets 1,2 didn’t fetch us the desired unreacted reactant, so in reaction set 4 we have decreased the catalyst wt. further down to 40,30,20 at a Temperature of 100 o C. In this reaction set we got unreacted reactant at 30mg catalyst wt with a conversion of 99.7 and selectivity of 79.7, the trend has continued at 20mg wherein we got more unreacted reactant, this signifies that at 30mg and 20mg the active Pd sites are not enough to bring

about complete conversion. The selectivity is comparatively less at 30mg compared to selectivity at 40mg. the results are presented in table 8 and figure.19.

.

Catalyst

 

Conversion

 

Selectivity%

 
 

HCAL

HCOL

COL

UK

1.5%Pd/TiO

(40mg)

         
 

2

100

2.8

8

89.2

0

1.5%Pd/TiO

(30mg)

         
 

2

99.7

9.7

10.3

79.7

0.3

1.5%Pd/TiO

(20mg)

         
 

2

91

13.4

5.4

71.2

10

Table.8 selectivity and conversion of 1.5% Pd/TiO 2 at 40,30,20 at 100 o C.

80 60 40 20 0 40 30 20 Selectivity%
80
60
40
20
0
40
30
20
Selectivity%

Catalyst wt(mg)

Figure.19 comparison of selectivity of 1.5% Pd/TiO 2 at 40, 30, 20mg at 100 o C

Reaction set 5

Effect of catalyst wt. at

constant Temperature

In reaction set

4

we got

some unreacted reactant

as

we

were desiring, in

this set

of

reactions we wanted to see what will happen if we further reduce the temperature at catalyst wt. used in reaction set 4. The results of reaction set is presented in table.9 and

figure.20, from these data it is evident that with decrease in temperature there is decrease in conversion and selectivity, if we compare the results of reaction set 4 with 40mg, 100 o C and same conditions in reaction set 5 we observe that the selectivity is better at 40mg and 100 0 C, from this observation we can say that the optimum catalyst wt and optimum temperature for 1.5% Pd/TiO 2 catalyst are at 40mg and 100 o C.

Catalyst

 

Conversion

 

Selectivity%

 
 

HCAL

HCOL

COL

UK

1.5%Pd/TiO

(50mg)

         
 

2

100

12.6

8.6

78.8

0

1.5%Pd/TiO

(40mg)

         
 

2

98.7

7.6

6.4

84.7

1.3

1.5%Pd/TiO

(30mg)

89.7

21

5.7

66

7.3

 

2

Table.9 selectivity and conversion of 1.5% Pd/TiO 2 at 50,40,30 at 75 o C.

80 60 40 20 0 20 30 40 50 Selectivity%
80
60
40
20
0
20
30
40
50
Selectivity%

Catalyst wt(mg)

Figure.20 comparison of selectivity of 1.5% Pd/TiO 2 at 50, 40, 30mg at 75 o C

An interesting thing we can observe in sets 4 and 5 that whenever we are getting some reactant peak we are getting an unknown peak around retention time 5.3. this unknown

peak is also visible in reaction mix prepared 15min before. Fig.21,22 shows the appearance of this unknown peak.

Unknown peak
Unknown peak

Figure.21 chromatogram of reaction products of of1.5%Pd/TiO 2 (40mg,75 o C)

Unknown peak
Unknown peak

Figure.22 chromatogram recorded after 15min of preparation of reaction mix.

The unknown product appearing in the reaction product may be cinnamic acid which is formed by the oxidation of cinnamaldehyde in presence of air or cinnamaldyde may also form acetal with the solvent methanol, but the acetal of cinnamaldehyde is a vicinal alcohol which is generally unstable but in the reaction mix the unknown product is persistent so the unknown product may be cinnamic acid, even thermodynamically change in gibbs free energy for cinnamaldehyde to cinnamic acid is -224kJ/mol whereas cinnamaldehyde to cinnamaldehyde acetal is -92Kj/mol, since change in gibbs free energy for the formation of cinnmic acid is more negative its formation is favored and cinnamic acid is stable, so most probably unknown product is cinnamic acid.

Reaction set 6 Effect of calcination on catalyst performance

Temperature = 120 0 c

Catalyst wt. = 150mg

solvent = methanol

Reactant = 1.2g

H 2 Pressure = 10bar

Till now all the reaction conducted were using as-synthesized catalysts, now in this reaction we have used an calcined 1.5% Pd/TiO 2 catalyst which was calcined at 300 o C for 3h in N 2 atmosphere, the results of this reaction are shown in Table.10 were very surprising, the same catalyst which was not calcined was giving very good selectivity but calcined catalyst is giving poor selectivity, rather selectivity for Hydrocinnamyl aldehyde has increased, the formation of Hydrocinnamaldehdye takes place when cinnamaldehyde adsorbs through olefinic bond, when a catalyst is calcined there is a chance that there may be change in increase in size of crystallite, TEM results for Tetrahedral, octahedral and spherical shaped Pd/Hydrotalcite shown in fig.4,6,8 shows that the crystallites are in the range 20-30nm in case of tetrahedral and octahedral Pd/Hydrotacite and 5-7nm in Spherical Pd/Hydrotalcite, these catalyst show poor selectivity for cinnamyl alcohol, whereas Pd/TiO 2 shows good selectivity in this catalyst crystallites are centered around 3nm, , that means for good selectivity towards cinnamyl alcohol small particles are favorable.

Catalyst

Conversion

Selectivity%

   

HCAL

HCOL

COL

Calcined 1.5% Pd/ TiO

2

100

53.2

33.9

12.9

Table.10 effect of calcination on selectivity in 1.5% Pd/TiO 2

Reaction set 7 Effect of solvent

Temperature = 100 0 c

Catalyst wt. = 20mg Reactant = 1.2g

Solvent- isopropanol, AMW- (Ammonium accetate, methanol, water), methanol.

H 2 pressure =10bar

Till now we have used methanol as solvent for carrying out reaction, now we have attempted to see the effect of solvent on selectivity and conversion, the other reason for using other solvent is whether we can avoid formation of the unknown product, we have tested the catalyst with isopropanol and a mixture of ammonium acetate, methanol and water. The results are very surprising which are tabulated in table.11 and plotted in fig.23

Catalyst

Conversion

 

Selectivity%

 
 

HCAL

HCOL

COL

UK

1.5% Pd/TiO

(isop)

         

2

  • 42.6 5.6

58.5

17.4

18.5

1.5% PdTiO

AMW

         

2

  • 14.8 2.4

81.1

7.2

3.5

1.5%Pd/TiO

meth

         

2

91

13.4

5.4

71.2

10

Table.11 effect of different solvents on selectivity and conversion in 1.5% Pd/TiO 2

70 60 50 40 30 20 10 0 Isopropanol AMW Methanol %Selectivity
70
60
50
40
30
20
10
0
Isopropanol
AMW
Methanol
%Selectivity

Solvant type

figure.23 graphical representation of effect of solvent on selectivity towards cinnamyl alcohol

The results are very surprising as the selectivity and conversion has decreased significantly when we used isopropanol, AMW has shown much more drastic results with lowest convection of 14.8, whereas methanol gives very good selectivity and conversion, the probable reason for low conversion is due to low solubility of H 2 in isopropanol and AMW, water is known be have the lowest solubility for H 2 hence AMW gives least conversion, Solubility of H 2 is necessary for H 2 to reach catalyst surface and get adsorbed and participate in reaction, when there is not enough H 2 reaction conversion will come down which is evident form the results.

Reaction set 8 Effect of catalyst wt.

Temperature = 100 0 C

Catalyst wt. = 40,20mg.

H 2 Pressure

= 10bar

solvent = methanol

Reactant=1.2g

We have optimized the parameters for the reaction as 40mg, 100 o C , now we are trying to compare catalyst 1.5% and 1% Pd/TiO 2 to see which amongst is best. The results are shown in table.12 and graphically represented in fig.24.

Catalyst

Conversion

 

Selectivity%

 
 

HCAL

HCOL

COL

ACETAL

1% PdTiO

(40mg)

         
 

2

96.1

3.9

11.6

81.1

3.4

1% PdTiO

(20mg)

77.2

       
 

2

22.8

5.2

53.7

18.4

Table.12 selectivity and conversion of 1% Pd/TiO 2 at 40mg, 100 o C.

When we compare the results in table.8 and table.12 we can come to the conclusion that

1.5%Pd/TiO 2 is better than

1% Pd/TiO 2

,

the

possible

reason for such

a result

could the

optimum

loading

of

Pd

in

1.5%Pd/TiO 2

which

avoids

over

hydrogenation

or

under

hydrogenation.

 

Conclusions

The optimum parameters for 1.5% and 1% Pd/TiO 2 were determined as 40mg catalyst, temperature = 100 o C, P = 10bar.

Among Hydrotalcite supported catalyst and Titania supported catalyst, Titania supported catalyst systems are better for selective hydrogenation of cinnamaldehyde to cinnamyl alcohol.

Small Pd crystallite sized catalyst give good selectivity compared to larger crystallites.

Out of 1% and 1.5% Pd/TiO 2 , 1.5% is better in terms of selectivity and conversion.

Methanol is most suitable solvent for better conversion and selectivity.

Future work

Preparation of following catalysts, their characterization and testing of catalysts

Determination of effect of support on selectivity and conversion

Pd/TiO 2 (pure anatase phase)

Pd/TiO 2 (pure rutile phase)

Pd/TiO 2 (mesoporus)

Bimetallic systems

Pd-AU/TiO 2 and Pd-Ag/TiO 2

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