Polymer-Supported Palladium and Rhodium Species

as Hydrogenation Catalysts

P. C. SELVARAJ* and V. MAHADEVAN

Department of Chemistry, Indian Institute of Technology, Madras-600 036. India

SYNOPSIS

The synthesis of new copolymers containing amino and heterocyclic ligands and their
use for anchoring Pd and Rh species is described. The supported catalysts are effective
for the hydrogenation of alkenes, dienes, alkynes, and nitrobenzene under very mild
conditions. The catalysts have been characterized by chemical analysis, particle size
measurement, IR, and x-ray photoelectron spectroscopy. Relative reactivities and the
effects of substrate structure, solvents, catalyst loading, anchoring ligands, metal spe-
cies, and particle size on the rates of hydrogenation have been determined using a wide
variety of substrates. The kinetics of hydrogenation have been analyzed using concepts
suitable under slurry reaction conditions. Comparisons between different oxidation
states of the same metal and between different metal species have also been made.
The recycling efficiencies of the catalysts have been determined and found to be very
good. q 1997 John Wiley & Sons, Inc.
Keywords: polymer-supported catalysts j hydrogeneration j Pd and Rh species

INTRODUCTION
A great deal of interest has been shown recently in
the design and use of polymer-supported transition
metal species as catalysts for a variety of reac-
tions.13 Several such catalysts have been devel-
oped using phosphinated polystyrene as support
matrix.46 Polymer supports with nitrogen con-
taining ligands have also been studied as supports
because of their stability to oxidation.79 In earlier
reports we have described the synthesis of such
catalysts based on hydrogel copolymers useful in
both aqueous and nonaqueous media.10,11 In this
article we report the synthesis and use of some new
copolymers which have been used to anchor Pd and
Rh species yielding highly active catalysts for the
hydrogenation of alkenes, dienes, alkynes, and ni-
trobenzene under very mild conditions.
* To whom all correspondence should be addressed. Pres-
ent address: SIP Resins Ltd, Plot No. 46, SIPCOT Industrial
Complex, Ranipet, North Arcot District-632 403, Tamil Nadu,
India.
Retired.
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 35, 105122 (1997)
q 1997 John Wiley & Sons, Inc. CCC 0887-624X/97/010105-18
EXPERIMENTAL
All reagents and chemicals used were AR grade. They
were further purified by distillation or recrystalliza-
tion as required. The monomers used were distilled
under vacuum in an atmosphere of nitrogen. They
were (i) 2-hydroxy ethylmethacrylate (HEMA), (ii)
2,3-epoxypropyl methacrylate (GMA), (iii) 4-vinylpyr-
idine (4-VP), (iv) N-vinylpyrrolidinone (N-VP), (v)
methyl methacrylate (MMA), (vi) N,N*-dimethylami-
noethyl methacrylate (DMAEM), and (vii) p-divinyl-
benzene (DVB). N,N*-methylenebisacrylamide was
recrystallized from methanol (mp 3007C). Cyclopenta-
diene was obtained by cracking dicyclopentadiene.
Pd(OAc)2 and RhCl3XH2O were JohnsonMatthey
products and used as received.
Infrared spectra were recorded on a Shimadzu
IR470 spectrometer using KBr pellets. 1H-NMR
Spectra were recorded on a Hitachi R600 NMR
spectrometer with tetramethylsilane as the inter-
nal standard. X-ray photoelectron spectra were ob-
tained on a VG Scientific ESCALAB Mark II spec-
trometer using MgKa radiation. A Carl-Zeiss PMQ
II spectrometer with cells of 1 cm path length was
used for UV-visible absorption measurements. Gas
chromatographic analysis were carried out on a
105

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106 SELVARAJ AND MAHADEVAN

Table I. Data on Elemental Analysis of the was then subjected to Soxhlet extraction with acetone
Copolymersa for 6 h followed by vacuum drying. The yield of the
copolymer was 85% [P(1)]. The epoxy group of the
Polymer C H N copolymer [P(1)] was opened by sodium imidazole or
Support Ligands Used (%) (%) (%)

P1 50.25 7.70
P2 Imidazole 51.57 7.21 5.12
P3 Pyridine 52.05 6.20 5.64
P4 2-Aminopyridine 50.60 7.45 2.80
P5 Pyridine 49.29 6.63 10.20
P6 55.01 6.91 5.88
P7 Diethylenetriamine 47.93 7.30 8.75
P8 Triethylenetetramine 48.62 7.78 8.07
P9 52.20 7.00
P10 2-Aminopyridine 42.46 8.21 8.93
P11 63.71 7.98
P12 2-Aminopyridine 60.68 7.76 3.22
P13 Pyridine 58.35 6.69 12.93
a
Structures of polymers are given in Scheme 1.

CIC gas chromatograph with flame ionization de-

tector. Average particle sizes of the catalysts were
measured using a Malvern particle size analyzer
3600E. The copolymers were analyzed for their ni-
trogen content using a C, H, N analyzer. The swell-
ing of the catalysts in different solvents was deter-
mined as described in an earlier article.10 The metal
content of the catalyst was determined by using
the procedures described earlier.10,11 The details of
hydrogenetion procedure have been described else-
where.12 The rates of hydrogenation were deter-
mined by measuring the uptake of hydrogen as a
function of time in a constant pressure apparatus.

Synthesis of Copolymers
Copolymer 1 (P1)
This copolymer was prepared as follows: 48 mol %
each of 2 hydroxyethyl methacrylate, 2,3-epoxypro-
pyl methacrylate, and 4 mol % p- divinylbenzene
were suspended in 500 mL of 30% aqueous NaCl in
a 1 L three-necked flask fitted with mercury seal,
stirrer, condenser, and nitrogen inlet. This suspen-
sion was stabilized by vigorous stirring under nitro-
gen atmosphere for 1 h. Then 250 mg of benzoyl
peroxide in 15 mL toluene was added and the mix-
ture deaerated for a further 30 min. Heating on the
steam bath with vigorous stirring and passage of N2
for approximately 4 h completed the polymerization.
The polymer was filtered, washed thoroughly by
stirring with hot distilled water, followed by similar
treatments with methanol and acetone. The polymer

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 HYDROGENATION CATALYSTS 107

Table III. Data on the Polymer Supports Employed, Metal Salts Loaded, Metal Content, and Average Particle
Diametera

Metal Content Average Particle Diameter

Polymer Support Metal Salt Catalyst (%) (m) N/Metal

P2 Pd(OAc)2 Cat 1 2.57 145 15.2

P3 Pd(OAc)2 Cat 2 3.88 105 11.19
P4 Pd(OAc)2 Cat 3 4.92 105 4.34
P5 Pd(OAc)2 Cat 4 5.42 105 14.56
P7 Pd(OAc)2 Cat 5 5.10 77.86 13.29
P8 Pd(OAc)2 Cat 6 15.0 44.53 3.89
P10 Pd(OAc)2 Cat 7 2.82 43.0 24.22
P12 Pd(OAc)2 Cat 8 4.0 153.0 6.21
P13 Pd(OAc)2 Cat 9 2.80 14.51 35.0
P7 RhCl3rXH2O Cat 10 7.50 83.0 8.58
P13 RhCl3rXH2O Cat 11 2.42 14.51 39.27
a
Structures of polymers and catalysts are given in Scheme 1.

2-aminopyridine and the hydroxyl group was con-
densed with nicotinic acid chloride. These reactions
were carried out by heating about 5 g of the copolymer
with 2.5 g of appropriate reagents in DMF at 1007C
for about 10 h followed by thorough washing and
drying. The copolymers with imidazole, pyridine or
2-aminopyridine functions have been designated P2,
P3, and P4 respectively (Table I).
Copolymer 5 (P5)
Since the monomers 4-vinylpyridine, N-vinylpyrroli-
dinone, and N,N*-methylenebisacrylamide are water
soluble, a water-in-oil suspension technique was em-
ployed for the synthesis. A mixture of 48 mol % each
of 4-vinylpyridine and N-vinylpyrrolidinone and 4
mol % of methylenebisacrylamide was used. The po-
lymerization procedure is described elsewhere.11 The
yield of the copolymer [P(5)] was 85%.
Copolymer 6 (P6)
enetetramine functions have been designated P7
and P8 respectively (Table I).
Copolymer 10 (P10)
Linear soluble polymethacrylic acid [P(9)] of molec-
ular weight 75,000 g/mol was crosslinked and
functionalized as follows:
About 6 g of polymethacrylic acid was dissolved in
60 mL dry benzene and refluxed with excess SOCl2
with vigorous stirring under nitrogen atmosphere for
10 h. The gaseous HCl and SO2 were entrained using
a slow stream of dry N2. The excess SOCl2 and ben-
zene were removed by distillation. The polymer acid
chloride was redissolved in 50 mL dry distilled DMF
and heated with 7 mL of diethylenetriamine and 2.5
g of 2-aminopyridine at 1007C for 10 h. The polymer
was filtered, washed thoroughly by stirring with hot
distilled water followed by similar treatment with
methanol, acetone, and vacuum-dried. The yield of
the final copolymer [P10] was 85%.

This copolymer was prepared by the suspension co- Copolymer 11 (P11)

polymerization of 48 mol % each of N-vinylpyrroli-
dinone and 2,3-epoxypropyl methacrylate and 4 mol
% of methylenebisacrylamide in 500 mL of 30%
aqueous NaCl. The procedure employed was simi-
lar to that used for the preparation of copolymer 1.
The yield of the copolymer [P(6)] was 80%. The
epoxy group of [P(6)] was opened by diethylenetria-
mine or triethylenetetramine. The reaction was car-
ried out by heating about 5 g of the copolymer with
10 mL of diethylenetriamine or triethylenetet-
ramine in 100 mL dry DMF at 1007C for 10 h. The
copolymers with diethylenetriamine or triethyl-
This was prepared by suspension copolymerization
of 48 mol % each of methyl methacrylate, 2,3-
epoxypropyl methacrylate, and 4 mol % of p-divinyl-
benzene suspended in 500 mL of 30% aqueous
NaCl. The procedure employed was similar to that
used for the preparation of copolymer 1. The yield
was 80% [P(11)]. The epoxy group of the copoly-
mer [P(11)] was opened by heating about 5 g of the
copolymer with 2.5 g of 2-aminopyridine in DMF at
1007C for about 10 h. The polymer with aminopyri-
dine function has been designated P12 (Table I).

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108 SELVARAJ AND MAHADEVAN
Scheme 1. Preparation of polymer supports and catalysts.
Copolymer 13 (P13)
Monomers capable of coordinating to transition metal
ions were polymerized by the template method.13
About 4 g of MnCl2.2H2O (0.02 mol) was dissolved in
10 mL of hot ethanol to which was added 8.7 mL
(0.08 mol) of freshly distilled 4-vinylpyridine and the
mixture was cooled in an ice bath. The complex which
precipitated out was filtered, washed thoroughly with
ethanol, acetone, and vacuum-dried. The composition
of Mn (4-VP)4Cl2 was confirmed by the elemental
analysis and the estimation of Mn content.
ANAL. Calcd: C, 61.48%; H, 5.12%; N, 10.25%. Found: C,
61.2%; H, 5.18%; N, 10.28%. Mn content: Calcd: 23.04%.
Found: 22.84%.
The complex was copolymerized with methylene-
bisacrylamide as follows: About 6 g Mn(4-VP)4Cl2
(0.012 mol) was dissolved in 50 mL distilled DMF
with constant stirring. The mixture was deoxyge-
nated with nitrogen. To this solution, 3 g of
methylenebisacrylamide (0.019 mol) was added fol-
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lowed by 250 mg of AIBN in toluene (20 mL) and
the mixture was heated to 807C under nitrogen with
vigorous stirring. The polymerization was carried out
for approximately 5 h. The initially homogeneous so-
lution yielded the copolymer as discrete fine particles
upon polymerization. The polymer was filtered,
washed thoroughly with hot distilled water followed
by similar treatments with methanol and acetone,
and vacuum-dried. The yield of the copolymer was
90%.
The Mn2/ coordinated to the polymer was re-
moved by stirring 8 g of copolymer with 400 mL of
aqueous EDTA (4%) for 24 h at room temperature.
Polymer was filtered, washed free of EDTA, and
the process repeated to obtain Mn2/-free copolymer.
The complete removal of Mn2/ from the copolymer
was confirmed by carrying out the test for Mn2/.
The dried copolymer [P(13)] was used to load the
catalytically active metal species or its precursor.
All the dried copolymers were powdered and
sieved through standard mesh sieves. The elemen-
tal analysis of copolymers appear in Table I.
The characteristic frequencies observed in IR
polca W: Poly Chem

spectrum of copolymers are given with assignments
in Table II.
Loading of Metal Ions on Polymer Supports
Loading of Pd(OAc)2
About 4 g of the appropriate copolymers (P2, P3,
P4, P5, P7, P8, P10, P12, or P13) was stirred with
a solution of Pd(OAc)2 (500700 mg) in 50 mL of
3 : 2 DMF/water mixture containing 1 mL acetic
acid for 24 h at room temperature. During this time
all the metal was absorbed by these polymers and
the supernatent become clear. The polymer thus
loaded was filtered, washed thoroughly with DMF,
water, methanol, acetone, and vacuum-dried.
Loading of RhCl3XH2O
Rhodium chloride (RhCl3.XH2O) (500 mg) was dis-
solved in methanol (30 mL) and 4 g of the copolymer
(P7 or P13) was stirred with this solution for 24
h at room temperature. The polymer was filtered,
washed thoroughly with water, methanol, acetone,
and vacuum-dried.
Since the loading process involved stirring for 24
h, further subdivision of particles is likely. Thus, the
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HYDROGENATION CATALYSTS 109
particle size distribution analysis was carried out on
the final loaded copolymers. The average particle
diameter dp was calculated using the equation
1
dp n
( (Xi/dpi)
i1
where Xi is the weight percentage of the particles
of average diameter dpi. Care was taken to use only
samples with reasonably narrow distribution. The
polymer supports used, the metal salt loaded, the
average particle diameter, and the metal content
of the catalysts are given in Table III.
Cat 13 were used as such whereas Cat 411
were activated as follows: About 2 g of the catalyst
was stirred with methanol (50 mL) in a 100 mL
flask. The mixture was cooled to 07C and sodium
borohydride (500 mg) was added in small portions
over a period of 2 h. The solution was allowed to
attain room temperature and stirred for a further
30 min. The lustrous black catalyst obtained was
filtered, washed thoroughly with hot distilled wa-
ter, followed by methanol and acetone, and vac-
uum-dried. The metal content remained un-
changed even after the treatment with NaBH4.
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110 SELVARAJ AND MAHADEVAN

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The possible structures of the copolymers and the
catalysts are given in Scheme 1.
The oxidation state of the metal ions in the
loaded catalysts was ascertained by carrying out
XPS studies on all the catalysts. The data on
the binding energy values based on C 1s binding
energy (285 eV) are given in Table IV. For com-
parison literature data on the XPS on Pd and
Rh species in various oxidation states are also
/ 8G32$$0008 03-03-97 15:58:04
HYDROGENATION CATALYSTS 111
included. It can be seen that there is no signifi-
cant change in the oxidation state of the Pd spe-
cies in the recovered catalysts which had Pd still
in the /2 oxidation state. Cat 4 9 showed bind-
ing energy values 337.3 337.7 eV for the 3d5/2
level and 343.2 343.5 eV for 3d3/2 level of Pd
which are characteristic of Pd(II) species as ob-
served for Cat 1 3. Moreover when Cat 1 9
were treated with aq. KCN in ethanolic medium
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112 SELVARAJ AND MAHADEVAN

Table IV. XPS Data on Metal Salts and Supported binding energy values 335.2 335.75 eV for the
Catalystsa 3d5/2 level and 340.70 341.25 eV for the 3d3/2
level. These are in good agreement with the re-
Binding Energy ported binding energy values of Pd(0).
(eV)b
With polymer supported rhodium chloride (Cat
10 and 11) the binding energy values are 310 eV
Species 3d5/2 3d3/2 Reference
(3d5/2) and 314 eV (3d3/2) which are characteristic of
Pd(0) (metal) 335.70 341.0 17 Rh(III).21 On reduction with sodium borohydride,
PdI2 336.60 341.9 17 the catalysts (Cat 18 and 19) showed the binding
PdCl2 337.90 343.2 17 energy values 307.6308 eV (3d5/2) and 312.2
P-CH2P (C6H5)2 312.5 eV (3d3/2) which are in good agreement with
PdCl2 338.6 344.0 18 the data reported for Rh(I) species.10,20 This indi-
P-CH2bipy Pd cates that Rh(II) species which has been shown to
(0) 335.6 341.0 19 be active in certain other catalysts19,22 is not formed
Cat 1 337.50 342.25 this work in the present case.
Cat 2 337.25 342.20 this work
Cat 3 337.25 342.75 this work
Cat 3
(recovered) 337.15 342.70 this work RESULTS AND DISCUSSION
Cat 4 337.50 342.20 this work
Cat 12 335.70 341.0 this work The effect of various solvents upon hydrogenation
Cat 5 337.10 343.0 this work was studied by the reduction of acrylamide in a few
Cat 13 335.50 341.25 this work polar and nonpolar solvents. The data on hydrogen
Cat 6 337.25 342.20 this work solubility in these solvents, their effectiveness in
Cat 14 335.75 340.87 this work swelling the polymer supports and the rate of reduc-
Cat 7 337.75 343.0 this work tion of acrylamide in terms of turn-over number (TON
Cat 15 335.60 341.0 this work mol/g atom Cat/h) using Cat 3, 15, and 19 are given
Cat 8 337.0 342.50 this work
in Table V. The conversion with respect to substrates
Cat 16 335.50 341.0 this work
Cat 9 337.60 342.75 this work
was checked to be identical with those calculated from
Cat 17 335.20 340.70 this work H2 consumption by means of gas chromatography.
Rh(0) (metal) 307.10 311.80 20 Similar results were obtained for other catalysts as
Rh(CO)PPh3(H) 308.10 312.90 21 well. The rates were larger in solvents with high hy-
RhCl3(PPh3)2 308.20 312.70 22 drogen solubility. It is clear that the solubility of hy-
RhCl3r3H2O 309.70 314.40 27 drogen in a particular solvent is the deciding factor
Rh2(OAc)4 rather than the ability of the solvent to swell the
2(DMSO) 308.5 313.4 20 polymer matrix. Similar trends have been observed
Rh2(OAc)4 in earlier reports from our laboratory.10,11 Since the
2(Py) 308.5 313.3 20 percent swelling of the polymer matrices is of the
(P)-Rh(III) 310.10 315.0 22
order of 1015% in most solvents, it is likely that
(P)-Rh(I) 308.10 313.0 22
(P)-Rh(I) 308.10 312.10 10
most of the loaded metalions would be on the surface,
Cat 10 310.0 314.10 this work with only a small percentage being entrapped. Fur-
Cat 18 308.0 312.2 this work thermore, there was no difference in swelling between
Cat 11 310.23 314.0 this work metalion loaded polymers compared to the active cat-
Cat 19 307.6 312.5 this work alysts obtained by reduction. This is in contrast to
the observation of Hines et al.23 Thus, maximum
a
Structures of catalysts are given in Scheme 1. rates were obtained in methanol, and all further work
b
All binding energy values referenced to C1s at 285 eV.
FWHM values ranged from 1.5 to 2 eV. was confined to this medium.

Relative Reactivities of Different Substrates

Pd(II) was stripped off from the support,21 pro-
viding further evidence for the /2 oxidation
state of Pd in these systems. However upon the
reduction of the Cat 4 9 with sodium borohy-
dride, the species obtained (Cat 12 17) had the
In Table VI are compared the relative reactivities
of different substrates using Cat 13. Simple olefins
like terminal alkenes were slightly more reactive
than the cyclic olefin like cyclohexene. The cis-ge-
ometry in an olefin such as diethyl maleate en-

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 HYDROGENATION CATALYSTS 113

Table V. Data on Hydrogen Solubility, Swelling Efficiency, and Rate of Reduction of Acrylamide in Various
Solventsa

Cat 3 Cat 15 Cat 19

Pd (II) Pd (0) Rh(I)

H2 Solubilityb Swelling Swelling Swelling

Solvent (mL of H2/mL of solvent) (%) TON (%) TON (%) TON

Methanol 0.068 12 974 16 3016 25 1928

Ethanol 0.065 13 772 13 2221 18 1217
2-Propanol 0.045 17 532 20 1801 16 1015
1-Butanol 10 478 15 1681 12 846
Acetone 0.0525c 7 558 18 2400 24 1420
DMF 0.037 19 532 15 1260 18 676
THF 3 551 14 1741 12 973
Water 0.015 14 109 13 540 16 372
Benzene 0.052c 2 55 6 240 2 135
Dioxan 7 74 13 300 11 338
a
Structures of catalysts are given in Scheme 1.
b
Reference 23.
c
Reference 24.
[Acrylamide] 0.025 mol L01; temperature 303 K; pH2 (760-vapour pressure of solvent) mm; [Cat 3] 1.5 1 1003 g/cc;
[Cat 15] 0.75 1 1003 g/cc; [Cat 19] 1.5 1 1003 g/cc.
Percent swelling (Ws 0 Wd)/Wd 1 100, Ws weight of swollen catalyst, Wd weight of dry catalyst.
TON moles of sub reduced (g atom metal)01 h01.

hances the rate of reduction compared to the trans

Table VI. Comparison of Relative Reactivities of v u
Different Substratesa isomer diethyl fumarate. The C|C with only
u v
TON one substituent (butyl acrylate) is found to be more
Substrate [mol (g atom Pd)01h01] v u
reactive than the C|C in which both carbons
1-Hexene 165 u v
Cyclohexene 122 bear substituents (diethyl maleate and diethyl fu-
Acrylamide 1538 marate) or one carbon bears two substituents
Butyl acrylate 820
v
Methyl methacrylate 145 (methyl methacrylate). Alkenes in which C|
Methyl vinyl ketone 952 u
Crotonic acid 200
Diethyl maleate 158
Diethyl fumarate 51
1,3-Cyclooctadiene 884 Table VII. Comparison of Reactivities of Supported
1,5-Cyclooctadiene 120 Pd(II) Catalystsa
Cyclopentadiene 700
Sorbic acid 759 TON
Norbornadiene 1443 [mol (g atom Pd)01 h01]
Norbornene 800
Dicyclopentadiene 516 [Sub] Cat 1 Cat 2 Cat 3
Propargyl alcohol 665 Substrate (mol L01) (145 m) (105 m) (105 m)
Allyl alcohol 565
2-Butyne-1,4-diol 439 Acrylamide 0.025 310 785 974
Cis-2-butene-1,4-diol 239 Diethyl maleate 0.075 103 229 253
Phenylacetylene 399 1,5-Cyclooctadiene 0.065 67 91 94
Styrene 811 Styrene 0.017 138 243 344
a a
Structure of catalyst is given in Scheme 1. [Cat 13] 1 Structures of catalysts are given in Scheme 1. [Cat] 2
1 1003 g/cc; pH2 578 mm of Hg; temperature 303 K; 1 1003 g/cc; temperature 303 K; pH2 578 mm of Hg;
Solvent, methanol; [sub] 0.017 mol L01. solvent, methanol.

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114 SELVARAJ AND MAHADEVAN

O Table IX. Comparison of Reactivities of Pd(II) and

u v x Pd(0) Catalysts Loaded on the Same Support
C is conjugated with C|O{, {C{NH2, (P8, 44.53 m)a
v u
O TON [mol (g
x atom Pd)01 h01
{C{OEt, or CGN group were found to be more
reactive than the unconjugated substrate. Simi- [Sub] Cat 6 Cat 14
larly conjugated dienes were more reactive than Substrate (mol L01) Pd(II) Pd(0)
nonconjugated ones. Thus, 1,3-cyclooctadiene is
much more easily reduced than 1,5-cycloocta- Butyl acrylate 0.029 51 235
diene. Cyclopentadiene was also rapidly reduced. Methyl methacrylate 0.041 24 93
Strained olefins especially in bicyclic systems were Styrene 0.017 78 175
very rapidly reduced. In such systems, a 2,5-diene Phenylacetylene 0.017 58 93
Acrylamide 0.025 71 378
such as norbornadiene is more reactive than di-
Methyl vinyl ketone 0.029 120 438
cyclopentadiene. With aliphatic alkynes such as
propyne-1-ol and 2-butyne-1,4-diol as substrates a
Structures of catalysts are given in Scheme 1. [Cat] 1
the rate of reduction of alkyne was found to be more 1 1003 g/cc; temperature 303 K; pH2 578 mm of Hg;
than that of product alkene. With the pair phenyl- solvent, methanol.
acetylene and styrene, it was found that styrene
was more reactive than phenylacetylene.
former it is 2-aminopyridine while in the latter it
is pyridine. Cat 3 also has a much lower N/Pd ratio.
Relative Reactivities of Different Catalysts The lower reactivity of Cat 1 is due to imidazole
(P)Pd(II) Species being the ligand in addition to its larger average
particle diameter.
Using the same catalytic species the effect of chang-
ing the support matrix and the particle size was (P)-Pd(0) Species
studied using a few substrates. In Table VII are
given TON data for three catalysts (namely Cat 1 In Table VIII are given data on TON for common
3) for the reduction of few substrates. It is clear substrates for catalysts which contain Pd(0) as the
that Cat 3 2 1 in their activity. Of these, Cat active species. These catalysts differ in both in aver-
3 and 2 have the same particle size (105 m) but age particle diameter as well as polymer matrix.
differ in the ligands binding the metal ion. In the Taking Cat 13 and 14 as a pair the former has

Table VIII. Comparison of Reactivities of Supported Pd(0) Catalystsa

TON [mol (g atom Pd)01 h01]

[Sub] Cat 12 Cat 13 Cat 14 Cat 15 Cat 16 Cat 17

Substrate (mol L01) (105 m) (77.88 m) (44.53 m) (43 m) (153 m) (14.51 m)

Acrylamide 0.025 668 2262 378 3016 721 3325

Allyl alchol 0.017 282 565 977 318 1453
Propargyl alcohol 0.017 336 665 1622 477 1816
Styrene 0.017 411 811 175 1225 445 2270
Butyl acrylate 0.029 1399 235 2568 674 2607
Methyl mathacrylate 0.041 349 93 601 339 1334
Diethyl maleate 0.05 315 474 174 856 387 1212
Diethyl fumarate 0.05 103 150 87 211 127 591
1,3-Cyclooctadiene 0.032 549 1663 516 2704 724 3048
1,5-Cyclooctadine 0.065 96 458 168 722 278 981
Norbornadiene 0.029 598 2462 514 4403 764 4608
Norbornene 0.029 411 1364 177 2798 679 3274
a
Structures of catalysts are given in Scheme 1. [Cat] 1 1 1003 g/cc; temperature 303 K; pH2 578 mm of Hg; solvent,
methanol.

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 HYDROGENATION CATALYSTS 115

Table X. Comparison of the Reactivities of Table XII. Data on the Reduction of Nitrobenzene,
Supported Rh(I) Catalystsa Nitrosobenzene, and Phenyl Hydroxylaminea

TON [mol (g atom TON [mol (g atom

Rh)01 h01] Pd)01 h01]
[Sub]
[Sub] Cat 18 Cat 19 Substrate (mol L01) Cat 2 Cat 13 Cat 15
Substrate (mol L01) (77.86 m) (14.51 m)
Nitrobenzene 0.06 429 538 2237
Acrylamide 0.025 513 1928 Nitrosobenzene 0.04 872 898 3356
Butyl acrylate 0.029 545 2440 Phenyl
Methyl methacrylate 0.041 235 609 hydroxylamine 0.04 192 382 1239
Diethyl maleate 0.050 352 957
a
Diethyl fumarate 0.050 143 406 Structures of catalysts are given in Scheme 1. [Cat 2]
1,3-Cyclooctadiene 0.032 756 2541 2 1 1003 g/cc; temperature 303 K; pH2 578 mm of Hg;
[Cat 13] and [Cat 15] 1 1 1003 g/cc; solvent, methanol.
1,5-Cyclooctadiene 0.065 393 665
Styrene 0.017 279 1184
a
Structures of catalysts are given in Scheme 1. [Cat] 1 Pd content of Cat 14 (used to estimate TON) not
1 1003 g/cc; temperature 303 K; pH2 578 mm of Hg; all the catalytic sites are accessible. Cat 15 and
solvent, methanol.
Cat 16 have 2-aminopyridine as the ligand binding
Pd(0). However, they differ in particle diameter as
a larger average particle diameter. Although the well as the type of polymer matrix. It can be seen
polymer matrices are the same, the ligands differ. that Cat 15 has a high N/Pd ratio compared to Cat
In Cat 13 it is diethylenetriamine whereas in Cat
14 it is triethylenetetramine. Cat 13 also has larger
N/Pd ratio. Nevertheless Cat 13 is more active than
Cat 14. It may be noted that in both these catalysts
Pd(0) species is anchored through the flexible
spacer group. It is possible that despite the higher

Table XI. Comparison of the Reactivities of Pd(0)

and Rh(I) Loaded on P13 (14.51 m)a

TON [mol (g
atom metal)01
h01]

[Sub] Cat 17 Cat 19

Substrate (mol L01) Pd(0) Rh(I)

Acrylamide 0.025 3325 1928

Methyl vinyl ketone 0.029 2971 2199
Diethyl maleate 0.05 1212 957
Diethyl fumarate 0.05 591 406
Butyl acrylate 0.029 2607 2440
Methyl methacrylate 0.041 1334 609
1,3-Cyclooctadiene 0.032 3048 2541
1,5-cyclooctadiene 0.065 981 665
Cyclopentadiene 0.034 2607 1720
Styrene 0.017 2270 1184
Figure 1. (a) UV spectra of the reduction products
Norbornadiene 0.029 4608 3050
of nitrobenzene at various time intervals: (1) after 0.5
Norbornene 0.029 3274 1922
equiv. H2 absorption, (2) after 1 equiv. H2 absorption,
Dicylopentadiene 0.034 1726 1316
(3) after 2 equiv. H2 absorption, (4) after 3 equiv. H2
a
Structures of catalysts are given in Scheme 1. [Cat] 1 absorption. (b) UV spectra of authentic samples: (1)
1 1003 g/cc; temperature 303 K; pH2 578 mm of Hg; nitrobenzene, (2) nitrosobenzene, (3) phenyl hydroxyl-
solvent, methanol. amine, (4) aniline.

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116 SELVARAJ AND MAHADEVAN

Figure 2. Dependence of rates of hydrogenation on Figure 3. Dependence of rates of hydrogenation on

[substrate]: (1) butyl acrylate, [Cat 18] 2 1 1003 g
cc01; (2) acrylamide, [Cat 3] 1.5 1 1003 g cc01; (3)
propargyl alcohol [Cat 15] 1.5 1 1003 g cc01; (4) di-
ethyl furmarate, [Cat 16] 7.5 1 1003 g cc01.
16. The high activity of Cat 15 is primarily due to
the much lower average particle diameter.
As regards of the pair Cat 12 and 17 both use
pyridine ligands to bind the metal. Cat 17 has a
very small average particle diameter and is the
most effective catalyst in the set.
hydrogen concentration [Ce]: (1) [acrylamide] 0.025
mol L01, [Cat 17] 0.75 1 1003 g cc01; (2) [sorbic acid]
0.038 mol L01, [Cat 16] 1.25 1 1003 g cc01; (3)
[phenylacetylene] 0.017 mol L01, [Cat 13] 2.5
1 1003 g cc01; (4) [dicyclopentadiene] 0.034 mol L01,
[Cat 19] 1 1 1003 g cc01; (5) [1,5-cyclooctadiene]
0.065 mol L01, [Cat 3] 4.5 1 1003 g cc01.
ing metal ion coordinated to ligands spaced from
the backbone (Table X). The average particle size
being very much lower for Cat 19 accounts for its
higher activity.

(P)Pd(II) and (P)Pd(0) Species

In Table IX are collected some data on the relative
reactivities of Pd(II) and Pd(0) loaded on the same
support matrix and possessing identical average
particle diameter as well as metal content. It is
clear that Pd(0) species are very much more effec-
tive than Pd(II) species for hydrogenation.

(P)Rh(I) Species
Cat 18 and 19 both have Rh(I) as the active species.
Cat 18 has a particle diameter nearly six times that
of Cat 19. Cat 19 is much more effective than Cat
18 despite the higher metal content (7.5%) of the
latter compared to the former (2.42%) besides hav- Scheme 2. Mechanism of hydrogenation.

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 HYDROGENATION CATALYSTS 117

Reduction of Nitrobenzene
Polymer supported Pd(II) and Pd(0) species were
able to catalyze the reduction of nitrobenzene, ni-
trosobenzene, and phenyl hydroxylamine, the final
product in all cases being aniline. A comparison of
the reactivities of all these substrates is given in
Table XII. Nitrosobenzene is more reactive than
nitrobenzene which in turn is more reactive than
phenyl hydroxylamine. Reaction mixtures were an-
alysed spectrophotometrically after the consump-
tion of 0.5, 1, 2 and 3 equiv. of hydrogen (Fig. 1). The
spectrum obtained after 0.5 equiv. of H2 absorption
corresponds to nitrobenzene alone and that ob-
tained after 1 equiv. of H2 consumption shows the
presence of nitrobenzene and phenyl hydroxyl-
amine. Nitrosobenzene could not be observed due
to its higher activity. After 2 equiv. of H2 absorp-
tion, the peak due to nitrobenzene completely van-
ished and phenyl hydroxylamine is the only product
detected. After 3 equiv. of H2 absorption, the spec-
trum obtained corresponds to that of aniline.

Figure 4. Dependence of rates of hydrogenation on

catalyst loadings (M): (1) [norbornadiene] 0.029 mol
L01, Cat 13; (2) [1,3-cyclooctadiene] 0.032 mol L01,
Cat 15; (3) [styrene] 0.035 mol L01, Cat 18; (4) [methyl
methacrylate] 0.037 mol L01, Cat 3.

(P)Rh(I) and (P)Pd(0) Species

In Table XI are data which allows a comparison

between supported Rh(I) and Pd(0) species. Here,
the polymer matrices as well as the binding ligands
are the same. Also, the particle sizes are identical.
It is clear that Pd(0) is much more effective than
Rh(I) species.
For most of the polymer-supported palladium
and rhodium species reported in the literature, data
on the particle size of the catalytic species employed
are not available. Furthermore the reaction condi-
tions employed differ from system to system. These
make the comparison rather difficult. Under condi-
tions of 1 atm H2 pressure and ambient tempera-
tures, Cat 3 is less effective than the homogeneous
system16 and more effective than other Pd(II) sys-
tems.9,12,25 Polymer supported Pd(0) species used in Figure 5. Plots of Ce/Nv vs. M01 for few substrates at
this study are very much more effective than other high M: (1) [1,3-cyclooctadiene] 0.032 mol L01, Cat 3;
supported Pd(0) systems reported earlier.9,17,26,27 (2) [acrylamide] 0.025 mol L01, Cat 19; (3) [styrene]
Cat 19 is much more effective than all the other 0.017 mol L01, Cat 17; (4) [norbornadiene] 0.029 mol
reported Rh(I) systems.2830 L01, Cat 15; (5) [norbornene] 0.029 mol L01, Cat 13.

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118 SELVARAJ AND MAHADEVAN
Figure 6. Plots of Ce/Nv vs. M01 at low M: (1) [diethyl
maleate] 0.05 mol L01, Cat 13; (2) [methyl vinyl ke-
tone] 0.029 mol L01 Cat 3; (3) [diethyl maleate]
0.05 mol L01, Cat 15; (4) [acrylamide] 0.029 mol
L01, Cat 16; (5) [norbornene] 0.029 mol L01, Cat 19.
Product Analysis
GC analysis confirmed that groups such as car-
boxyl, nitrile, and phenyl etc are not reduced under
the experimental conditions. Even though norbor-
nadiene is much more reactive than norbornene, no
selective reduction could be observed in the reduc-
tion of norbornadiene. GC analysis of 1,3-cycloocta-
diene after 1 equiv. of H2 absorption using (P)
Pd(II) or (P)Pd(0) species showed the presence of
cyclooctene alone. However, for the reduction of 1,5-
cyclooctadiene the GC analysis after 0.5 equiv. of
H2 absorption showed the peaks corresponding to
1,3-cyclooctadiene in addition to cyclooctene, indi-
cating considerable isomerization. With the column
employed, it was not possible to detect any 1,4-
cyclooctadiene. However the peaks corresponding
to 1,3-cyclooctadiene or 1,4-cyclooctadiene were not
observed in the gas chromatogram of the reduction
of 1,5-cyclooctadiene using (P)Rh(I) species. The
absence of signal due to 1,3-cyclooctadiene would
point to the absence of isomerization. This is in
contrast to the course of reduction of 1,5-cycloocta-
/ 8G32$$0008 03-03-97 15:58:04
diene using (P)Pd(II) or (P)Pd(0) species. After
1 equiv. of H2 absorption cyclooctene was the only
compound found indicating that the dienes are get-
ting selectively reduced to monoenes.
With phenylacetylene as the substrate there was
no detectable amount of ethylbenzene up to 20%
conversion using Pd(II) catalysts. However, 2% eth-
ylbenzene was detected in addition to styrene even
for 10% conversion using Pd(0) catalysts. This can
be due to the greater reactivity of styrene compared
to phenylacetylene.
The 1H-NMR spectrum of the partially reduced
product of 2-butyne-1,4-diol showed the signals cor-
responding to cis-2-butene-1,4-diol [d5.5(t, 2H,
{CH|CH{), d4.4 (S, 2H, HO), d4.05 (d, 4H,
{CH2{)]. The product was identified as cis-2-bu-
tene-1, 4-diol using GC by comparison with an au-
thentic sample. The absence of butynediol or bu-
tanediol was evidenced from the spectrum. This im-
plies a selectivity of almost 100%. Similar
selectivity was obtained for the reduction of pro-
pyne-1-ol also.
The 1H-NMR spectrum of partially reduced sorbic
acid showed the presence of three hexenoic acids.
Thus, there is evidence for 1,2- as well as 1,4-addition.
Card and Neckers have shown that when methyl sor-
bate was reduced using polystyrene Pd(0), the prod-
uct obtained was the mixture of hexenoates.27
With dicyclopentadiene as the substrate the re-
duction of the strained double bond was confirmed
by product analysis after 1 equiv. of H2 had been
absorbed. The melting point of the reaction product
was found to be 577C. Based on this the product of
reduction is assigned to be bicyclo [5, 2, 1, 0, 2, 6]
dec-4-ene.31 1H-NMR spectrum of the product has
a signal at d5.2 due to the olefinic protons in the
cyclopentene ring and an unresolved multiplet at
d12 due to aliphatic protons. Thus, the product
obtained has the cyclopentene ring intact. Disap-
pearance of the signal at d5.6 (the olefinic protons
in the norbornene ring) provides further support
for the structure.
Kinetic Analysis
With almost all substrates the rates increased with
increase in substrate concentration reaching satura-
tion values at high concentration of substrate. The
critical concentration above which saturation rates
could be obtained varied from substrate to substrate.
Figure 2 depicts the variation of initial rates of reduc-
tion with [substrate]. With propyne-1-ol and 2-bu-
tyne-1,4-diol as substrates high [substrate] led to
rates which were less than expected due probably to
polca W: Poly Chem
 HYDROGENATION CATALYSTS 119

Table XIII. Data on the Estimated Values of kc and ks for Few Substrates Using
Pd(II), Pd(0), and Rh(I) Speciesa

Cat 3 Cat 15 Cat 19

(105 m) (43 m) (14.51 m)

Substrate kc ks kc ks kc ks

1-Hexene 0.02 0.21 0.04 0.54

Acrylamide 0.08 2.10 0.01 0.60
Methyl vinyl ketone 0.05 0.79 0.05 1.23 0.01 0.49
Butyl acrylate 0.04 0.80 0.06 1.62 0.02 0.61
Methyl methacrylate 0.02 0.22 0.01 0.36 0.003 0.16
Diethyl maleate 0.07 0.67 0.02 0.52 0.006 0.35
Diethyl fumarate 0.01 0.3 0.008 0.2 0.002 0.13
Sorbic acid 0.03 1.13 0.05 1.30
1,3-Cyclooctadiene 0.02 1.25 0.12 1.70 0.02 0.77
1,5-Cyclooctadiene 0.02 0.32 0.03 0.39 0.004 0.22
Cyclopentadiene 0.03 0.75 0.04 1.20 0.01 0.36
Norbornadiene 0.06 1.26 0.10 2.50 0.02 0.79
Norbornene 0.03 0.68 0.07 1.90 0.01 0.4
Dicyclopentadiene 0.02 0.42 0.04 0.95 0.01 0.25
Allyl alcohol 0.03 0.76 0.06 1.10
Propargyl alcohol 0.03 0.98 0.06 1.81
Styrene 0.05 1.80 0.01 0.53
Phenylacetylene 0.03 0.80
Butenediol 0.04 0.81 0.46 0.70
Butynediol 0.04 0.98 0.05 1.0
Nitrobenzene 0.05 0.66
Nitrosobenzene 0.08 1.50
Phenylhydroxylamine 0.08 0.56

Structures of catalysts are given in Scheme 1. kc and ks, cm01.

a type of substrate inhibition. It was also found that
polymer-supported Pd(II) as well as Pd(0) species cat-
alyzed the reduction of alkynes to alkenes while Rh(I)
species was not effective in such reduction.
Partial pressure of H2 was varied by using mix-
tures of argon and hydrogen with total pressure
being 1 bar. The direct dependence of rates on par-
tial pressure of hydrogen is shown in Figure 3. No
attempt was made to study the reduction at higher
H2 pressures. The data support the mechanism in-
volving reaction of an initially formed substrate-
catalyst complex with H2 in the rate-determining
step (Scheme 2).
The effect of catalyst loadings (M) on the reaction
rates is shown in Figure 4. At low levels of catalyst
loading the rates were directly proportional to the
amount of catalyst. However, at high values the
rates level off reaching a limiting value. This is
typical of slurry system32 where the rate determin-
ing step changes from the reaction on the surface
of the catalyst to the rate of dissolution of the gas
from gas phase in the solvent. Since the reactions
are heterogeneous the above mechanism does not
lend itself to kinetic analysis using the approach of
MichaelisMenten.33
Using the treatment outlined by Satterfield32
which has been employed earlier by us10,11 and
other groups34 the rates under conditions of excess
substrate is given by the following equation:
Ce/Nv 1/kLAb / dprp/6M(1/kc / 1/ks) (1)
where Ce is the equilibrium concentration of hydro-
gen in the solvent, Nv is the rate of hydrogenation
(mol L01 s01), kL is the mass transfer coefficient for
the transport of hydrogen from gas phase to the
liquid phase (cm s01), kc is the mass transfer coeffi-
cient for the transport of dissolved H2 from liquid
phase to the surface of the catalyst particles (cm
s01), ks is the pseudo first-order reaction rate con-
stant (cm s01), Ab is the interfacial area of the gas
bubble per unit volume of the slurry, dp is the aver-
age particle diameter (cm), rp is the density of the

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120 SELVARAJ AND MAHADEVAN

Table XIV. Data on the Recycling Efficiencies of the Catalystsa

No. of Cycles

0 2 4 6

Cat 1:
Pd content (mg/g) 25.7 24.10 22.60 20.90
Rate 1 104 (mol/L/s) 0.99 0.96 0.92 0.86
Cat 2:
Pd content (mg/g) 38.8 36.8 34.60 32.40
Rate 1 104 (mol/L/s) 1.19 1.16 1.13 1.08
Cat 3:
Pd content (mg/g) 49.25 46.10 43.05 40.0
Rate 1 104 (mol/L/s) 1.76 1.72 1.69 1.62
Cat 12:
Pd content (mg/g) 54.25 53.85 53.45 53.0
Rate 1 104 (mol/L/s) 1.73 1.71 1.69 1.66
Cat 13:
Pd content (mg/g) 51.0 50.80 50.70 50.60
Rate 1 104 (mol/L/s) 2.256 2.24 2.22 2.19
Cat 14:
Pd content (mg/g) 148.0 146.0
Rate 1 104 (mol/L/s) 1.46 1.36
Cat 15:
Pd content (mg/g) 28.25 28.20 28.10 28.0
Rate 1 104 (mol/L/s) 1.67 1.64 1.62
Cat 16:
Pd content (mg/g) 40.0 39.5 39.40
Rate 1 104 (mol/L/s) 1.13 1.11 1.06
Cat 17:
Pd content (mg/g) 28.0 27.8 27.6
Rate 1 104 (mol/L/s) 1.83 1.81 1.79
Cat 18:
Rh content (mg/g) 75.0 74.25 73.50
Rate 1 104 (mol/L/s) 2.19 2.12 2.09
Cat 19:
Rh content (mg/g) 24.21 24.20 24.10
Rate 1 104 (mol/L/s) 1.19 1.18 1.16
a
Structures of catalysts given in Scheme 1. [Acrylamide] 0.025 mol L01; temperature 303 K; pH2 578 mm of Hg; solvent,
methanol.
[Cat 1] 5 1 1003 g/cc; [Cat 2] 4 1 1003 g/cc; [Cat 3, 16, and 19] 1.5 1 1003 g/cc; [Cat 14] 2.0 1 1003 g/cc; [Cat 12 and
18] 1 1 1003 g/cc; [Cat 13, 15, and 17] 0.75 1 1003 g/cc.

catalyst particle (g cc01), and M is the weight of the
catalyst per unit volume of the slurry (g cc01).
Thus, plots of Ce/Nv vs. 1/M at high catalyst loading
are linear with intercept on the Y axis (Fig. 5). Ac-
cording to the equation the intercept corresponds to
the value of 1/kLAb. In the present study a total of 1
atm. H2 pressure was maintained over a well stirred
liquid. At a stirring speed of 300 rpm vortex formation
became unavoidable and the interfacial area was em-
ployed for the calculation of kL. Since it was not possi-
ble to maintain the geometry of the vortex constant,
the interfacial area is subject to change. Thus an
approximate value for kL was estimated and was
equal to 0.142 { 0.02 cm s01. The value of kL can vary
with substrate due to the solubility of H2. However
since the concentration of substrate employed does
not exceed 100 mmol, kc is not expected to vary with
the type of substrate being reduced.
At low catalyst loading kL is faster than the reac-
tion at the catalytic site, the later being a slow
process controls the overall reaction. Under these
conditions eq. (1) reduces to the form:
Ce/Nv dprp/6M(1/kc / 1/ks) (2)
Thus, the plots of Ce/Nv vs. 1/M give straight

/ 8G32$$0008 03-03-97 15:58:04 polca W: Poly Chem


lines passing through the origin with the slopes
equal to 1/kc / 1/ks (Fig. 6).
Equation (2) would reduce to
Ce/Nv dprp/6M 1 1/kc (3)
under the conditions that ks @ kc. The plots of Ce
vs. Nv (at low catalyst loadings) for few substrates
are shown in Figure 3. Thus, kc can be calculated
from these plots and from the knowledge of kc, ks
can be calculated. The estimated values of kc and
ks for few substrates using Cat 3, 15, and 19 are
given in Table XIII. Similar data were obtained for
other catalysts also.
However, these values are arrived at the assump-
tion that all particles are of uniform size and that
they are spherical neither of which is correct. Also,
the measurements of rates are subject to {5% error
and the data on the mass transfer coefficients as well
as the surface reaction rate constants are good only to
{10% accuracy. Nevertheless, they indicate general
trends in activity which are reasonably reliable. It
was found that the diffusion coefficient kc showed a
variation between 0.01 to 0.1 cm s01 which has been
attributed to the nonuniform particle size of the cata-
lysts. The data on ks are subject to the same con-
straint. However, the more reactive substrate has the
higher value for ks the catalyst being common. In
addition, ks was larger for catalyst with larger particle
size compared to the smaller one when the same
metal species was involved, due to the smaller area
per unit weight of the former.
Recycling Efficiencies
One of the important consideration of supporting a
metal catalyst or metal ion on a polymer is the
recovery and reuse of the catalyst. For each of the
catalysts used in this work, analysis of the metal
content was carried out after various cycles of use.
The recycled catalyst was used for the hydrogena-
tion of a test substrate acrylamide to propionamide.
The data appear in Table XIV.
Cat 13 lost up to 3% of the metal per cycle
whereas the remaining catalysts showed the loss of
metal ranged from 0.5 to 1%. However, even after
various cycles of use all the catalysts retain almost
90% of their original activity. Thus, it may be
concluded that the catalyst systems are very robust
and can be used several times with excellent effi-
ciency.
Assistance with ESCA measurements by RSIC, IIT Ma-
dras is gratefully acknowledged.
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HYDROGENATION CATALYSTS 121
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