Glycerol Oxidation Catalyzed

by Bimetallic Metal Organic

Frameworks
PREPARED BY
05130000120 Elif TAŞDÖVEN
05140000099 Ezgi HEPİLERİ

SUBMITTED TO
PROF.DR. FERHAN SAMİ ATALAY
ASSIST.PROF.DR. EMİNE SERT
What is Glycerol?
• Glycerol is an important by product of biodiesel production. Due to the
highly functionalized nature of glycerol, it is an important biochemical that
can be utilized as a platform chemical for the production of high-added-
value products.
• Over the last 10 years, there has been huge development of potential
catalytic processes using glycerol as the platform chemical
• Glycerol is a highly functionalised molecule that is readily available from
biosustainable sources, for example it can be obtained as a byproduct of
the utilisation of grape seed and sunflower.
• A large number of products can be obtained from glycerol oxidation.
What is Glycerol?
• Glycerol represents a suitable eco-friendly solvent for synthesis and
catalysis
• The recyclability of catalytic phases in glycerol enables sustainable
processes
Oxidation of Glycerol
What is MOF ?
• Metal-organic frameworks (MOFs), a new emerging class ofcrystalline
materials that consist of coordination bonds betweennodes of metal ions
and multidentate organic linkers, haveattracted much recent attention as
functional materials foradsorption, gas separation and storage techniques,
as well as het-erogeneous catalysis. MOFs possess a unique
combinationof properties that includes extremely high surface areas and
porevolumes, tunable pore size and functionalities, and large fraction
ofuniform and accessible metal sites. However, relatively low thermaland
hydrothermal stability may constrain their practical applica-tions, in
particular, in gas-phase heterogeneous catalysis.
What is MOF ?
Bimetallic MOFs
• Bimetallic MOFs have gained particular attention as a subclass of MOFs
because of their designable framework structures that are modularly built
from two transition-metal clusters as nodes and organic ligands as struts.
• Actually, bimetallic systems have already been proven to be effective, for
instance, bimetallic nanoparticles often exhibit higher catalytic activities
than their monometallic counterparts.
• In principle, the incorporation of bimetallic nodes in the same framework
will allow the the excellent synergistic effects between different metals.
‘‘Oxidation of glycerol using supported Pt,
Pd and Au catalysts’’
• The oxidation of aqueous solutions of glycerol is described and discussed
for Pd, Pt and Au nanoparticles supported on graphite and activated
carbon. The oxidation in a batch reactor at 60°C and 1 bar pressure
using air as oxidant was initially investigated.
• Oxidation reactions are important for the synthesis of fine chemicals.
• In this investigation, it is shown that supported gold nanoparticles can be
very effective catalysts for the oxidation of alcohols, including diols.
‘‘Oxidation of glycerol using supported Pt,
Pd and Au catalysts’’
• In particular, the oxidation of alcohols and
polyols to chemical intermediates represents a
demanding target. Supported platinum and
palladium nanoparticles are generally
acknowledged as effective catalysts for the
oxidation of polyols.
‘‘Oxidation of glycerol using supported Pt,
Pd and Au catalysts’’
• Under these conditions, supported Pd and Pt catalysts give some
selectivity to glyceric acid, but the main reaction products are considered
to be non-desired 𝐶1 by-products, e.g. CO2 , HCHO and HCOOH. In
addition, under these conditions, supported Au catalysts were totally
inactive. And, for Pt and Au catalysts, the formation of C1 by-products was
eliminated when NaOH was added. In particular, it was noted that, in the
absence of NaOH, the Au/C catalyst was inactive. For 1 wt.% Au/graphite
or activated carbon, 100% selectivity to glyceric acid at high conversion
was readily achieved.
‘‘An efficient one pot conversion of glycerol to lactic
acid using bimetallic gold-platinum catalysts on a
nanocrystalline CeO2 support’’
According to The one pot conversion of glycerol to lactic acid using
monometallic Au and Pt as well as bimetallic (Au–Pt) catalysts supported on
nanocrystalline CeO2 (n-CeO2) in aqueous solution in the presence of a
base and oxygen was investigated.
• Gold, previously being considered as an inert metal, shows very good
catalytic activity when present as nano particles and catalytic
transformations using gold are now well established.
• For instance, glycerol can be oxidised selectively to glyceric acid at
aqueous alkaline con-ditions in a temperature range of 303–333 K
• Catalyst performance can be improved significantly by the incorporation of
a second metal such as palladium or platinum
‘‘Glycerol Oxidation catalyzed by bimetallic metal
organic frameworks’’
‘‘Glycerol Oxidation catalyzed by bimetallic metal
organic frameworks’’
 ‘‘Glycerol Oxidation catalyzed by bimetallic metal
organic frameworks’’
As a conclusion;
• Monometallic Au and Pt based catalyst on a commerciallyavailable
nanocrystalline CeO2support are efficient catalystsfor the one pot
oxidative conversion of glycerol to lactic acid.
• Lactic acid yields of up to 80% were obtained for a 20 min batchtime;
mainbyproducts are glyceric acid and subsequent oxidation products(such
as tartronic acid, glycolic acid, formic acid and acetic acid)
 ‘‘Propylene glycol oxidation with tert-butyl
hydroperoxide overCr-containing metal-organic
frameworks MIL-101 and MIL-100’’
• The aim of this work was to explore
the potential of thechromium-based
MOFs, MIL-101 and MIL-100, for
the selectiveoxidation of PG.
• The effects of the oxidant nature
and reaction conditions
(temperature, concentrations of
reagents, solvent nature,and
atmosphere) on the product
selectivity and yield have been
investigated.Catalyst reusability is
evaluated.
• In recent years, there has been
immense interest in the use of gold
catalysts for oxidation reactions
 ‘‘Propylene glycol oxidation with tert-butyl
hydroperoxide overCr-containing metal-organic
frameworks MIL-101 and MIL-100’’
Three organic solvents, acetonitrile, ethyl
acetate and methanol, aswell as water were
used to evaluate the effect of solvent natureon
PG oxidation over Cr-MIL-101. The results are
presented inTable 2. The highest conversion of
PG (14%) was attained in ethylacetate.
• Effect of Temperature
The title reaction is very slow at room
temperature (only 2%PG conversion after 7 h).
The increase in the reaction temperature from
40 to 70◦C accelerated the reaction and
increased the attain-able PG conversion;
however, it had very little effect on the product
selectivity.
As a conclusion;

• Propylene glycol oxidation is supplied with tert-butyl hydroperoxide over

Cr-containing metal-organic frameworks MIL-101 and MIL-100.
• Temperature is investigated as a parameter. The nature of catalysis
depends on the reaction temperature. At 50◦C, the nature of the catalysis
over MIL-101 is truly heterogeneous and no metal leach-ing into solution
occurs.
• The MIL-101 catalyst can be recycled with maintenance of the catalytic
performance and the MOF structure during, at least, three operation
cycles.
 Selective Oxidation of Glycerol by Highly Active
Bimetallic Catalysts at Ambient Temperature under
Base-Free Conditions
• The previous studies have focused on the catalytic oxidation of glycerol at
elevated temperatures. Here we show that high glycerol conversion and
selectivity to specific C3 products (glyceric and tartronic acids) can be
achieved at ambient temperatures without employing a base.
• Bimetallic catalysts were synthesized by immobilizing colloidal metal
particles on an MgO support.
• X-ray diffraction (XRD) analysis revealed that the support material is
converted to Mg(OH)2 due to hydrolysis during the immobilization process,
which iscarried out in aqueous solution.
 Selective Oxidation of Glycerol by Highly
Active Bimetallic Catalysts at Ambient
Temperature under Base-Free Conditions
• Initial catalyst testing was performed at 60°C (0.3 molL1 glycerol solution,
glycerol/metal mole fraction 1000, pO2 ¼300 kPa, 4 h) with supported Au–
Pt (1:3 mole fraction, 1% by mass total metal loading). A substantially
higher activity was observed than has previously been reported for Au–Pt
catalysts, suggesting that the selection of the metal molar ratios and
support material for this bimetallic catalyst has a strong influence on
activity. The Au– Pt catalyst with 1:3 mol fraction retained significant
activity when the temperature was decreased to 40°C. By extending the
reaction time to 24 h and further decreasing the reaction temperature to
ambient (238°C), high conversion was retained with a simultaneous
increase in the C3 product selectivity (> 88% by mol).
 Selective Oxidation of Glycerol by Highly
Active Bimetallic Catalysts at Ambient
Temperature under Base-Free Conditions
• In contrast, Au–Pd catalyst prepared with a 1:3 mol fraction and
similar metal loading demonstrated significantly lower activity
under these conditions, and the selectivity to glyceric acid was
lower than that displayed for the Au–Pt catalyst, despite the
lower conversion observed. These results suggest that at
similar conversion levels, the Au– Pd bimetallic catalysts are
significantly less selective to the desired C3 products and data
at iso-conversion shows this is the case .
Selective Oxidation of Glycerol by Highly
Active Bimetallic Catalysts at Ambient
Temperature under Base-Free Conditions
 Selective Oxidation of Glycerol by Highly
Active Bimetallic Catalysts at Ambient
Temperature under Base-Free Conditions
• Finally, we explored the reusability of the 1:3 molar ratio AuPt/Mg(OH)2
catalyst both for reactions at ambient temperature and at 60°C.After
recovering the used catalyst by filtration, the activity for glycerol oxidation
was found to be unchanged within experimental error and reusable under
these conditions.
• In summary, Au–Pt and Au–Pd nanoparticles supported on Mg(OH)2 are
highly active for the selective oxidation of glycerol under base-free
conditions at ambient temperature.
Thank you for your attention 