CHEMISTRY INVESTIGATORY

PROJECT

TO INCREASE IN THE ACTIVITY AND

SELECTIVITY IN THE CATALYSIS VIA
SURFACE MODIFICATION WITH SELF
ASSEMBLED MONOLAYERS

SESSION : 2021-22
SUBMITTED BY: SUBMITTED TO:
nEMCHAND MISS. DIVYA
PANDEY
CALSS : 12TH PGT CHEMISTRY
At the outset, I Express a great sense
of gratitude towards my guide Miss
Divya Pandey for his writing effort
and guidance which he has
culminated in this project. I am also
grateful to him for giving me an
insight into the various aspects with
regards to my project work. I would
also like to thank my esteemed
principal madam for giving me the
opportunity to completed my work.
Finally, I am thankful to my
acquaintance.
This is to certify that Nemchand of Class
XII(Science) of Jawahar Navodaya
Vidyalaya,Lakhimpur Kheri has completed his project
work under the guidance and supervision of Miss
Divya Pandey.

I Certify that this project is upto the expectation of CBSE

guidelines.

………………………………………………..
(Principal’s Signature)
 Teacher’s Certificate
This is to certify that Nemchand of Class XII(Science)
of Jawahar Navodaya Vidyalaya,Lakhimpur Kheri has
completed his project under my guidance and
supervision.

I Certify that this project is upto the expectation of CBSE

guidelines.

……………………
(Teacher’s Signature)

INDEX
 TOPIC PAGE NO.

INTRODUCTION 6

MATRIALS & METHOD 7-9

RESULTS & DISCUSSION 10-19

CONCLUSION 20-21

BIBLIOGRAPHY 21
 As the use of catalysis is extended to more complex chemical systems,
the issue of chemical selectivity often prevails over that of overall
chemical activity.1,2 Avoiding the formation of undesirable side
products prevents the waste of chemicals, minimizes the need of
purification steps, and makes the processes more environmentally
friendly. Therefore, it is often worth sacrificing speed for the sake of
selectivity in chemical industrial processes. In order to improve selectivity,
undesirable sites on the surfaces of heterogeneous catalysts are often
blocked via pretreatments with specific chemicals; this is what is done, for
instance, with hydrocarbon reforming catalysts, which are exposed to small
amounts of H2S before introducing the crude oil feeds. In that case, it has
been established that sulfur selectively blocks the surface sites for
hydrocarbon hydro- genolysis, affecting those for skeletal isomerization
to a much lesser extent.3 It has also been shown recently that selectivity
can be improved for other reactions by using self-assembled
(SAMs) capping monolayers.4−8 Unfortunately, as stated above,
selectivity in those cases comes at the expense of
reactivity.
Here we report on a unique case where both activity and selectivity can
be enhanced by surface modification, for the enantioselective
hydrogenation of α-keto esters promoted by platinum catalysts.9,10 This is
accomplished by combining the selective site-blocking power of alkyl
thiol SAMs with the enantioselectivity provided by cinchona alkaloids as
surface comodifiers.9,11 In colloidal solutions, SAM modification of Pt
nanoparticles leads to significant improvements in both activity and
enantioselectivity. With supported catalysts a trade-off is required
between activity and selectivity depending on the concentrations used
for the surface modifiers, but even there conditions were identified
leading to total activities and enantiomeric excesses quite close to those
obtained with the best cinchonidine-modified Pt/Al2O3 platinum
catalysts. In fact, the performance of our cinchonidine-derivatized thiol-
SAMs- modified catalysts ranks among the best ever reported for all-
heterogeneous catalysts in terms of enantioselectivity.

Materials. Cinchonidine (>98% purity), 1-propanethiol (99%), 1-

hexanethiol (95%), 1-nonanethiol (95%), 1-hexade- canethiol (92%),
 1,3-propanedithiol (99%), 1,6-hexanedithiol (96%), 1,9-nonanedithiol
(95%), ethyl pyruvate (98%), and all solvents were purchased from
Sigma-Aldrich and used as supplied. 1 wt% Pt/SiO2 and 1 wt% Pt/Al2O3
powder catalysts were also purchased from Sigma-Aldrich and used as
supplied. Hydrogen gas (>99.995%) was purchased from Liquid
Carbonic and used as received.
Catalyst Preparation. 2.2.1. “Naked” Pt Nano- particles (NPs).12 A 0.5
M NaOH solution in ethylene glycol/H2O (12.5/2.5 mL) was added
to a second ethylene glycol solution (12.5 mL) containing
H2PtCl6·6H2O (24.6 mg,
50 μmol) while stirring under an inert atmosphere until obtaining a
transparent yellow solution; the solution was heated to 433 K for 3 h
under a N2 flow to remove all water and organic byproducts, after
which a transparent dark brown homogeneous colloidal solution of the
Pt NPs was obtained. These “unprotected” Pt NPs were dispersed in
ethanol,without using any stabilizer, and the solvent removed prior to
their use for the hydrogenation reactions.
Derivatized Alkyl Thiols. 0.1764 g of cinchonidine (0.6 mmol) was
dissolved in 15 mL of CHCl3 and refluXed under N2 for 0.5 h; a
solution of AlBN (60 μmol, 9.9 mg) and 1,x-alkanedithiol (1,3-
propanedithiol, 1,6-hexanedithiol, or 1,9- nonanedithiol, 6 mmol) in 6
mL of CHCl3 was added over 1 h via a dropping funnel while refluXing,
which was continued for 24 h; the solvent was then removed under
reduced pressure, and pentane (15 mL) was added to the residual
yellow sticky solid to precipitate the crude product. The solid was
collected and washed with pentane, dried under vacuum overnight, and
purified by silica chromatography. Product identification was
corroborated by 1H NMR, 13C NMR, FT-IR, and liquid injection field
desorption ionization-mass spectrometry (LIFDI-MS).
Thiol-Covered Pt Nanoparticles. An ethylene glycol solution of
“naked” Pt nanoparticles (50 μmol) was miXed with a 20 mL of toluene
solution of the thiol (1-propanethiol, 1- hexaethiol, 1-nonanethiol, or 1-
hexadecanethiol, amount determined by the desired S:Pt ratio) and
stirred overnight; 50 mL of water was added, after which a black
precipitate (thiol-coated Pt NPs) appeared in the two-phase liquid; the
black solid was collected via centrifugation, washed with toluene and
ethanol to remove the excess thiol and residual glycol, and dried
under vacuum overnight at ambient temperature.
 Homemade Supported Catalysts. Catalysts were made by using both
silica and alumina supports. Pt-NPs/SiO 2 was prepared by dispersing
the “naked” Pt nanoparticles (1 wt%) in ethanol and adding the Aerosil
200 support, filtering the miX, and drying under reduced pressure. A
similar procedure was followed to disperse the thiol-covered Pt
nanoparticles.
Thiol-Covered Supported Catalysts. A fiXed amount of the Pt/SiO2 or
Pt/Al2O3 supported catalysts was dispersed in CH2Cl2 or toluene while
stirring under N2; the thiol (alkanethiol or cinchonidine-derivatized
thiol, amount deter- mined by the desired S:Pt ratio) was added and let
to react for 2 h; the miXture was filtered, washed with CH2Cl2 several
times, and dried under vacuum overnight.
Infrared Absorption, TEM, and XPS Character- ization. Infrared
absorption spectra of the catalysts were taken in transmission mode by
using a Bruker Tensor 27 Fourier transform IR (FT-IR) instrument.
Some samples were diluted with KBr powder to facilitate the making
of the solid sample disks. Transmission electron microscopy (TEM)
images were taken using a Tecnail T12 instrument. X-ray
photoelectron spectroscopy (XPS) data were acquired by using a
Kratos analytical AXIS instrument equipped with a 165 mm mean
radius semihemispherical electron energy analyzer and a 120- element
delay line detector. A monochromatized Al-anode X- ray gun was used
as the excitation source, and an electron flood source was employed as
needed to compensate for sample charging.
Catalytic Tests. The hydrogenation of ethyl pyruvate was tested by using
a 300 mL high-pressure liquid-phase Parr reactor. The Pt catalyst (5
μmol) was suspended in 10 mL of toluene, to which the rest of the
compounds, namely, the ethyl pyruvate (1.25 mmol) and cinchonidine
(Cid; amount determined by desired Cid:Pt ratio), were added. The
reactor was closed and pressurized with 20 bar of H2; the reaction
miXture was continuously stirred, and an external buret was used to
keep the internal pressure constant during reaction. The reactions were
carried out at room temperature. Liquid aliquots were taken periodically
for analysis by gas chromatog- raphy (Agilent 6890N equipped with a CP
Chirasil-Dex CB, 25 m × 0.25 mm × 0.25 μm, chiral column) to follow the
progress of the reaction. The conversion and enantioselectivity excess
values reported here were reproducible within 10% and 5%,
respectively. The ethyl pyruvate (Sigma-Aldrich, 98% purity) was
 distilled under vacuum prior to its use to minimize any possible
interferences from impurities.

Figure 1. Activity (in %conversion after 24 h of reaction) and

enantioselectivity (%enantiomeric excess, %ee) of Pt-nanoparticle-
based catalysts for the hydrogenation of ethyl pyruvate in the
presence of cinchonidine (Cid), which in these experiments was added
in the reaction miXture for chiral modification. (a) Contrast in
performance among “naked”, sodium sulfide-treated, and alkyl thiol-
treated nanoparticles. Three alkyl thiols were usedC3H7SH, C9H19SH,
and C16H33SHand constant 1:3:9 S:Cid:Pt ratios were used in all
cases. (b) Activity and enantioselectivity of C9H19SH-treated Pt
nanoparticles as a function of the ratio of cinchonidine to platinum
used. A constant 1:27 thiol:Pt ratio was used in all samples.
(c) Activity and enantioselectivity of C9H19SH-treated Pt
nanoparticles as a function of the ratio of the thiol (C 9H19SH) to
platinum used. A constant 1:3 Cid:Pt ratio was used in all samples.
Reaction conditions: 1.25 mmol of ethyl pyruvate, 20 bar of H 2, 5 μmol
of Pt, 10 mL of toluene (solvent), 300 K.

Pt Nanoparticles in Solution. The initial experiments were carried out by

using platinum nanoparticles suspended in solution, to which
cinchonidine was added for chiral modification. It was found that
the original “naked” (or “unprotected”) Pt nanoparticles, prepared by
 reduction of chloroplatinic acid with ethylene glycol (TEM, XPS, and
IR characterization provided in the Supporting Information in Figures
S1, S2, and S3, respectively),12 display quite poor performance for the
promotion of the hydrogenation of ethyl pyruvate to ethyl lactate
(Figure 1a). The activities are much lower that those reported for other
similar systems, although this may be due, at least in part, to the fact
that we have here used lower H2 pressures,13,14 or perhaps because we
have used the total number of Pt atoms, not only the surface Pt atoms,
in our turnover frequency (TOF) calculations. In any case, both activity
and enantioselectivity could be significantly enhanced by pretreating
those nanoparticles with alkyl thiols (Figure 1a). Under similar reaction
conditions, the reaction initial TOF (molecules converted per total
number of platinum atoms per second, calculated at conversions
below 20%) could be increased from about 0.004 s−1 with the naked Pt
nanoparticles
to approXimately 0.03 s−1 with the nanoparticles treated with
C16H33SH. A 100 %conversion is shown in Figure 1, but total
conversion is reached in this case at a much earlier time; to better be
able to compare activities for the more active samples, TOFs for all the
samples in Figure 1a are provided in Table S1 of the Supporting
Information. Enantioselectivity was improved as well, from less than 5
%enantiomeric excess (%ee) to more than 65 %ee with C9H19SH. The
concentrations of both the cinchonidine (Figure 1b) and the thiol
(Figure 1c) required for the catalytic hydrogenation reaction were then
optimized by using the C9 thiol. Intermediate S:Cid:Pt molar ratios of
1:3:9 were found to be the best, leading to complete ethyl pyruvate
conversion by 24 h of reaction at room temperature and an
enantiomeric excess of 66.3 %ee.
One possible explanation for the low activity of the naked Pt
nanoparticles is that they may become poisoned early on in the reaction
because of the deposition of EtPy, cinchonidine, or any products resulting
from reactions of those on the surface of the metal. With Na2S, it may be
that sulfur is the agent that poisons that surface. It could then be argued
that the thiols may protect the surface from such poisons and therefore
afford the retention of catalytic activity. However, thiols also bind
through their sulfur atoms, and therefore sulfur poisoning similar to that
seen with Na2S would be expected (but not seen) in those cases.
Moreover, the changes in enantioselectivity observed in the series of
catalyst reported in Figure 1 are not easy to explain purely on the basis
of surface poisoning. An additional effect must be in play in these samples
one that we believe relates to a synergistic interaction between the thiol
SAMs and the cinchonidine modifier.
It is already well established that the addition of cinchonidine to the
reaction miXture in these α-keto ester hydrogenation reactions not only
adds enantioselectivity but also accelerates the reaction. Much discussion
has been published on the reasons for this effect, and the subject is still
a matter of some debate. Nevertheless, most explanations rely on
kinetic arguments, and advocate for an effect that depends on the
equilibrium of cinchonidine on the surface of the platinum catalyst. In
this context, we propose that the enhancement in reaction rate seen
here upon the addition of thiol SAMs to the surface of the Pt
nanoparticles may be due to an increase in the adsorption equilibrium
constant of cinchonidine, which may be held in the vicinity of the surface
for longer times by the alkyl chains of the thiol adsorbates.
Unfortunately, this is a hypothesis difficult to test because it is not easy to
measure the cinchonidine coverages on the surface in situ in catalysts
covered with SAMs layers and immersed in the liquid reaction solution.
Moreover, our explanation is an oversimplification because it has also
been established that the performance of cinchonidine as a chiral
modifier also depends on the adsorption configuration it adopts on
the surface and on the freedom it has to rearrange around the
quinoline−
quinuclidine linking moiety.11 Regardless, the important
empirical observation here is that the thiol SAMs improve both the
activity and the enantioselectivity of this reaction, by about an order of
magnitude each, with solution-suspended Pt nanoparticles. Incidentally, it
could be thought that the role of the thiols in these systems may be to
stabilize the platinum nanoparticles in solution, since the initial catalysts
are based on unprotected particles. However, no aggregation of those
particles was ever seen in our experiments, not even in the absence of
the thiol SAMs (Supporting Information, Figure S1); the “naked”
nanoparticles seem to be stable by themselves under the conditions of
the reactions probed here.
The behavior of the thiols responsible for the improvement
of catalytic activity and enantioselectivity reported above was investigated
in more detail. It was determined that the observed catalytic performance
enhancement cannot be due exclusively (or even primarily) to the
addition of sulfur on the surface, since treatment of the platinum
nanoparticles with sodium sulfide does not lead to any appreciable
changes in catalytic performance (Figure 1a). In fact, short-chain thiols,
C3H7SH in particular, are also not effective modifiers. It is clear that the
alkyl chains play an important role in the changes in catalytic
performance. This is in contrast with the recent case of the use of thiol-
modified Pd catalysts for the selective hydrogenation of unsaturated
epoXides, where the sulfur atoms were shown to be the main responsible
elements for the selectivity changes. It is suggested that a different
mechanism is operative here, perhaps the reason why the increase in
selectivity is not obtained at the expense of activity (which is enhanced
as well).
Some information on the collective ordering of the alkyl
chains in the SAMs may be deduced from infrared (IR) absorption
spectroscopy data. Figure 2 displays IR data in the C−H stretching
region, together with Gaussian fits using well- established frequency
assignments, for a number of thiol- treated Pt nanoparticles, and Table
S2 summarizes the main parameters extracted from analysis of the data.
In Figure 2a, a study is presented of the evolution of the IR spectra for
the C9H19S−Pt case as a function of dilution of the SAMs (expressed
as a molar ratio between the thiol and the Pt precursor used in the
sample preparation). The main observation is that an increase in thiol
dilution leads to a decrease in the ordering of the alkyl chains. This is
particularly evident by the almost stepwise change in frequency seen for
the peaks associated with the methyl symmetric and Fermi resonance
modes (νs(CH3) and νFR(CH3), respectively) between the 1:1 and 1:3
S:Pt cases: the positions of the peaks switch from approXimately 2871
and 2895 cm−1−to 2875
and 2897 cm 1, respectively. These shifts are small but
consistent, and outside the experimental error of our IR
instrument. Similar frequency increases have been seen with alkyl thiols
when transitioning from crystalline to liquid phase, and have also been
ascribed to an increase in alkyl chain disorder.
 Figure 2. Infrared (IR) absorption spectra in the C−H stretching region for
thiol-treated Pt nanoparticles. Shown are the raw traces together with fits to five
Gaussian peaks centered at the frequencies expected for thiol-based self-
assembled monolayers (the assignment is
provided in the right panel).22 (a) Spectra for C9H19S−Pt as a function of the ratio of
C9H19SH to Pt. (b) Spectra for CxH2x+1S−Pt samples as a function of alkyl chain
length (x = 3, 9, and 16). Data are also provided for the free C9H19SH and
C16H33SH thiols for reference

In addition, most of the peaks in Figure 2a become broader, by up to

∼50% in some cases, around the same dilution values. These
observations correlate well with the sharp increases in activity and
enantioselectivity reported in Figure 1c. It appears that a degree of alkyl
chain disorder is required to provide access to the metal surface for
catalysis.
A similar increase in alkyl chain disorder is seen as a function of
decreasing alkyl chain length in Figure 2b. This becomes particularly
clear in the evolution of the peak for the methylene symmetric mode
(νs(CH2)), the width of which transitions from 17 cm−1 with C16H33SH
to 27 cm−1 with C3H7SH. However, the story may be more complex here,
because there may also be changes in the orientation of those chains.
To note in particular is the relative increase in the peak intensity ratio
between the symmetric and asymmetric CH2 stretching modes with
decreasing chain length. Those features, centered at 2853 and 2924 cm−1,
respectively, have dynamic dipole vectors perpendicular to each other
but both in the plane of the CH2 moieties. The symmetric CH2 stretching
peak is usually weak in SAMs because the dynamic dipoles from the
individual methylene moieties cancel out as the alkyl chains adopt an
 all-trans configuration. In our case, however, it appears that such all-
trans arrangement is less stable with the shorter chains. Based on the
catalytic performance trends reported in figure 1a, it is concluded that
a compromise may be needed in terms of the nature of the SAMs in
order to induce sufficient alkyl chain disorder to allow for the
penetration of the reactants while at the same time retaining enough
interchain interactions to help shape particular adsorption sites on the
surface of the metal.
Supported Pt Catalysts. The catalysts discussed above consist of
platinum nanoparticles suspended in solution. In order to facilitate their
handling and separation from reactants and products, it is usually
desirable to use solid catalysts instead. With that in mind, a number of
experiments were designed to prepare heterogeneous catalysts based on
the same type of platinum nanoparticles covered with thiol SAMs.
Several parameters were considered to optimize performance. In
general, it was found that the use of silica as a support yields worst
results than when using alumina. Regular Pt/SiO2 catalysts displayed
low activities and only moderate enantiose- lectivities (when modified
with cinchonidine added in solution), and that performance was
found to deteriorate significantly upon the addition of small amounts
of thiols (Figure S4). Better results were obtained when dispersing the
platinum nanoparticles pretreated with the thiols on a fresh silica
support, but even then the reaction conversion rates were low.
Interesting, an optimum intermediate ratio of thiol to platinum of
about 1:27 was identified for maximum perform- ance, in qualitative
agreement with the behavior seen with the colloidal Pt nanoparticles
(even if the best ratio is lower in this case, Figure S5).
Much better behavior was observed with Pt/Al2O3 catalysts. Regular
supported Pt catalysts are in fact much more active than the free Pt
nanoparticles for the α-keto ester hydro- genation reaction,
displaying conversions close to 100% after
∼1 h of reaction under the conditions used in our experiments
(approXimately one day is required for comparable conversions with the
Pt nanoparticles). Typical kinetic curves for these
samples are provided in Figure S6. Moreover, the addition of
cinchonidine to the reaction miXture also increases both activity and
enantioselectivity, as discussed above for the case of the platinum
nanoparticles (Figure 3, green bars). Other studies with colloidal Pt
nanoparticles dispersed on alumina supports have yielded similar
results as well.13,14,23 On the other hand, it was found that, although
both activity and enantioselectivity can be modified on these Pt/Al2O3
catalysts upon the formation of thiol SAMs, it is not possible to
increase both at the same time as with the free Pt nanoparticles (Figure
3, center rows). The main effect of adding SAMs to the platinum
surface (and cinchonidine to the reaction solution) is to decrease the
catalytic activity, an effect that is more significant with longer alkyl chains.
Enantioselectivity follows the same trend, although the effect is less
pronounced.
In the preceding examples, the catalysts are not truly heterogeneous,
because a chiral modifier (cinchonidine) still needs to be added to the
solution. As a final step, the original thiols were derivatized in order to
add the cinchonidine to the end of their alkyl chains. For this,
cinchonidine was appended via its vinyl moiety to one end of the
appropriate dithiol according to a published protocol, shown in Scheme
1 (details are provided in the Materials and Methods section).24,25
Pt nanoparticles covered with SAMs made out of these Cid- derivatized
thiols proved to be poor catalysts for the ethyl pyruvate reaction
(Figure S6). Catalysts made out by adsorbing Cid-thiol SAMs on
Pt/Al2O3, on the other hand, displayed reasonable performance.
Typical values for their activity and enantioselectivity are contrasted
with those from the other types of catalysts in Figure 3 (the new data
are provided in the right row), and results from a more detailed study of
the effects of chain length and (Cid)CxH2xSH:Pt molar ratio are
summarized in Figure 4. The main effect in these systems is seen in the
conversion rate, which decreases rapidly when deviating from the ideal
conditions, in particular when longer alkyl chains are used. Also, for a
given Cid-derivatized thiol, optimum catalytic activity was seen for
Cid:Pt ratios around 1:24. In terms of enantioselectivity, the effects
were not as pronounced, but again, increasing chain lengths were seen
to lead to decreases in %ee. Interestingly, optimum enantiose- lectivity
requires higher Cid:Pt ratios than those needed for high activity, around
1:6; the intermediate case of Cid:Pt = 1:12 with (Cid)C3H6S−Pt/Al2O3
may represent a compromise
where activity is reduced by ∼50% while the loss in
enantioselectivity amounts to only ∼20%. On the other hand,
preserving enantioselectivity may be more important in many
applications, in which case the 1:6 Cid:Pt ratio would be
preferred. No (Cid)thiol-covered supported Pt sample in this family of
catalysts can improve on the performance of the regular Pt/Al2O3
catalyst modified with cinchonidine added in solution, but some come
close to that performance and offer the advantage of having the chiral
modification already added to the solid.
The molecular details of the catalysts prepared by adding cinchonidine-
derivatized thiols were also characterized by infrared absorption
spectroscopy. One concern in this case is that the organic ligands may
bind to the metal via either of their two ends. It was determined that
binding through the thiol moiety, as needed for the formation of the
SAMs, still occurs in these cases. This is evidenced by the IR spectra in
the S−H stretching region reported in Figure 5. The broad peak for that
S−H stretching mode, seen around 2570 cm−1 with all free thiols,
disappears almost completely upon adsorption on the metal surfaces.
(Some peaks are seen in that region of the IR spectrum for the RS-Pt
samples, but those are not reproducible and quite weak.) The data in the
left panel show that this is true for the colloidal platinum nanoparticles
as well as for platinum particles dispersed on a silica support. Even on
pure silica thiol adsorption leads to the loss of some of the S−H
bonds, although the interaction in that case is weaker, and a small
amount of intact S−H bonds can be detected still in spite of the large
surface area of the oXide. The spectra reported in the right panel of Figure
5 indicate that thiol attachment via the scission of the S−H bond occurs
with all thiols regardless of their alkyl chain length, although it may be
that the reactivity with the shorter chains may be lower. (A small
remnant of the IR signal for the S−H stretching mode is observed
with (Cid)C3H6SH upon adsorption on the Pt/SiO2 catalyst.) The data in
Figure 5 were obtained with the silica-based catalysts, but similar
behavior was observed with those made with alumina supports. In order
for the catalyst to display enantioselectivity, the cinchonidine moiety
also needs to interact with the surface of the metal, and our IR
spectroscopic studies show that this is indeed the case. It should be said
that the interpretation of the data in these studies is not
straightforward and that the observations obtained from ex-situ
characterization experiments may not fully reflect the performance of
these catalysts. Nevertheless, a number of lessons can be extracted
from the appropriate IR spectra, some of which are reported in Figure
6. The most characteristic vibrational modes from cinchonidine in these
spectra are those associated with the in-plane deformation of the
quinoline aromatic ring, specifically the peaks seen at 1591, 1569, and
1508 cm−1 with solid cinchonidine (Figure 6, third trace from
bottom).26 Additional peaks are also seen at 1463 and 1453 cm−1,
associated out-of-plane CH2 scissoring modes within the quinuclidine
moiety, but those sometimes interfere with similar modes from the
alkyl chains of the thiols (Figure 6, bottom two traces). All the
cinchonidine vibrational modes tend to blue-shift upon adsorption on
surfaces, and that is what is seen here with the (Cid)CxH2xSH thiols.
However, the interaction between cinchonidine and the solid seems to be
more moderate than that seen on pure platinum foils, 21,26 and affected
by the presence of the silica. For instance, the reference data in Figure 6
show that the quinoline deformation modes shift to 1599, 1581, and
1516 cm−1 on the Pt foil (Figure 6, siXth trace from bottom), but only
to 1594, 1577, and 1513 cm−1 on Pt/SiO2 (Figure 6, fourth trace from
bottom). Moreover, cinchonidine adsorbed on pure silica also displays
peaks at 1593, 1577, and 1513 cm−1 (Figure 6, fifth trace from bottom).
In a similar fashion, the values for those modes with the thiol-modified
platinum catalysts used in this study (using C9 alkyl chains) are 1590,
1572, and 1509 cm−1 with the Pt
nanoparticles (Figure 6, second trace from top) and 1513 cm−1
with the silica-supported catalyst (Figure 6, top trace; only the latter
mode is visible in this case).
It could be concluded from the discussion above that cinchonidine
adsorption in our systems occurs primarily on the silica surface. However,
clear evidence can be extracted from Figure 6 to conclude that the metal
plays an important role in this interaction as well. The observation to
highlight for this is the change in the relative intensities of the key quinoline
IR peaks observed in the samples containing platinum. A surface dipole
selection rule that applies to adsorption on metal surfaces indicates that
only the component of the dynamic dipoles of molecular vibrations oriented
perpendicular to the surface can be detected by IR absorption
spectroscopy.27 Application of that rule to adsorbates on metal surfaces
affords an estimation of their adsorption geometry.28,29 In our case, the
orientation of the quinoline ring may be described qualitatively by
comparing the relative intensities of the 1569 cm−1 (Ag) and 1508 (B3u)
cm−1 modes, which have dynamic dipoles aligned with the short and long
axis of the aromatic ring, respectively. The fact that the former peak is not
visible in the samples involving the supported Pt particles (Figure 6, fourth
trace from bottom and first trace from top) indicates that the ring in
those cases interacts with the metal and that it is oriented with the long
axis perpendicular to the Pt surface. This is not the case with the pure
 silica (Figure 6, fifth trace from bottom), and also not seen with the
catalysts based on the colloidal Pt nanoparticles (Figure 6, second
trace from top). Ultimately, the IR data show that the supported Pt
nanoparticles may still become covered with SAMs when using the
cinchonidine- derivatized thiols but that the cinchonidine in those cases
also interacts with the surface, most likely at the interface between the
platinum metal and the silica support. Similar results were obtained with
other chain lengths and with platinum catalysts dispersed on alumina
(Figure S7).

Scheme 1

Figure 3. The %conversion (top) and %ee (bottom) for the

hydrogenation of ethyl pyruvate with thiol-treated 1 wt%
Pt/Al2O3 catalysts after 5 min of reaction. Shown are data
for the original catalyst as is (green) and after being
treated with regular (CxH2x+1SH, two left rows) and
cinchonidine-derivatized ((Cid)CxH2xSH, right row) thiols
of two alkyl chain lengths (x = 3, blue, and x = 9, red).
EXperiments with the regular thiols were carried out both
with (center row) and without (left row) adding
Figure 4. The %conversion (top) and %ee (bottom) for the
hydrogenation of ethyl pyruvate with thiol-treated 1 wt%
Pt/Al2O3 catalysts after 5 min of reaction. Shown are data for
the original catalyst as is, promoted by the addition of
cinchonidine in solution (blue), and after being treated with
cinchonidine-derivatized thiols ((Cid)CxH2xS−Pt) of three
different alkyl chain lengths (x = 3, red, x
= 6, green, and x = 9, purple). Data are also provided for
Figure 5. IR absorption spectra in the S−H stretching mode
region for catalysts prepared by using cinchonidine-
derivatized alkyl thiols. Reference spectra are also
provided for comparison. (a) IR traces for (Cid)C9H18SH by
itself (bottom, blue) and adsorbed on colloidal Pt
nanoparticles (second from bottom, magenta), on silica-
supported
Pt (third from bottom, purple), and on pure silica (fourth
from bottom, red). Additional traces are shown for
cinchonidine-free C9H19SH alone (second from top, green)
and adsorbed on Pt nanoparticles (top, brown). (b) IR
traces for Cid-derivatized thiols of three different lengths,
(Cid)CxH2xSH (x = 3, bottom green and purple traces; x = 6,
middle blue-green and dark red traces; x = 9, top blue and
red traces), by themselves (bottom set) and adsorbed on Pt/
SiO2 (top set). In all cases, the disappearance of the S−H
stretching
mode peak at 2570 cm−1 corroborates the formation of
thiol self-
assembled layers on the Pt surfaces.
Figure 6. IR absorption spectra in the hydrocarbon
deformation mode region for catalysts prepared by
using cinchonidine-derivatized (Cid)C9H18SH thiols.
Reference spectra are also provided for
comparison. The traces correspond, from bottom to
top, to free C9H19SH (dark green), C9H19SH adsorbed
on colloidal platinum nanoparticles (green), solid
cinchonidine (blue-green), cinchonidine adsorbed on
Pt/SiO2 (blue), cinchonidine adsorbed on silica (darker
blue), cinchonidine adsorbed on a Pt foil (darkest
blue), free (Cid)C9H18SH (dark red), (Cid)C9H18SH
adsorbed on Pt nano- particles (red), and
(Cid)C9H18SH adsorbed on Pt/SiO2 (brick color). The
cinchonidine interacts with both silica and Pt
surfaces, as indicated by the shifts and relative intensity
changes seen in the main peaks associated with the
quinoline ring (see details in text).
In summary, the data reported here show that it is possible to improve
on the performance of platinum catalysts in terms of both activity and
selectivity upon the deposition of alkyl thiol self-assembled monolayers.
In the particular case of the use of platinum nanoparticles in liquid
suspension for the hydro- genation of ethyl pyruvate, the optimum
initial turnover frequencies obtained with the naked nanoparticles are
∼0.004 s−1, and the enantioselectivities (under the reaction conditions
used in our experiments and when adding cinchonidine to the
solution) are approXimately 5 %ee. Addition of alkyl thiol SAMs to those
nanoparticles was found to lead to significant increases in both values, to
0.02 s−1 and 66 %ee, respectively (with C9H19SH). Of course, the free Pt
nanoparticles display quite a poor performance for this reaction, but our
results still show how improvements in selectivity may be accompanied by
concomitant improvements in activity in some cases where thiol SAMs are
used to modify catalysts.
This is not the case with supported Pt catalysts, where the initial
performance is much better: the TOFs and enantiose- lectivities of regular
Pt/Al2O3 catalysts (plus cinchonidine in solution) exhibit values around 60
s−1 and 74 %ee in our studies. Nevertheless, reasonable compromises can
still be reached with supported Pt catalysts treated with cinchonidine-
derivatized thiols. For instance, most of the enantioselectivity can be
preserved upon addition of (Cid)C3H6SH at a 1:6 Cid:Pt ratio (73 %ee),
although the TOF does decrease in that case by a factor of about 4, to a
value of 13 s−1. If activity is an important consideration, using a 1:24 Cid:Pt
ratio can increase the TOF to approXimately 55 s−1 with only a moderate
decrease in enantioselectivity, to 58 %ee. In no case studied here the thiol-
treated catalysts could outperform the regular Pt/ Al2O3 sample (plus
cinchonidine in the liquid phase) in terms of both activity and
enantioselectivity, but the modest losses associated with the examples cited
above may be a reasonable price to pay for having an all-heterogeneous
catalyst, where cinchonidine does not need to be added to the reaction
miXture (and separated from the products). Certainly, these are among the
most enantioselective all-heterogeneous catalysts ever reported.31,32 In
more general terms, it has been shown here that the addition of two
functionalities to solid catalysts via the deposition of specifically derivatized
self-assembled monolayers can lead to improvements in both activity and
selectivity.
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