Cu, Al and Ga based metal organic framework catalysts for the decarboxylation of oleic acid

Article abstract of DOI:10.1039/c4cy01609b

Herein we demonstrate the catalytic decarboxylation and conversion of oleic acid to paraffins and hydrocarbons over bare and Pt supported Cu, Al and Ga based metal organic frameworks. Moderate degrees of decarboxylation were observed for all metal organic framework catalysts. The incorporation of Pt with the porous frameworks resulted in high degrees of decarboxylation. All MOF catalysts showed high thermal stability, resulting in recyclable catalysts displaying low catalytic activity loss. Of all studied catalysts, Ga-MOF catalysts were the most effective catalysts, displaying moderate to high degrees of decarboxylation. In addition, the Pt-Ga-MOF catalyst displayed selectivity to heptadecane, an important industrial chemical. Octadecane, heptadecane, dodecane, undecane, decane, nonane, octane, and heptane were observed as the main side products. To our best knowledge, the catalytic ability of a metal organic framework both as catalyst and support for the decarboxylation of a model fatty acid molecule is reported for the first time.

Full text of DOI:10.1039/c4cy01609b

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Cu, Al and Ga based metal organic framework
catalysts for the decarboxylation of oleic acid
Cite this: DOI: 10.1039/c4cy01609b
L. Yang, G. L. Ruess and M. A. Carreon*
Herein we demonstrate the catalytic decarboxylation and conversion of oleic acid to paraffins and
hydrocarbons over bare and Pt supported Cu, Al and Ga based metal organic frameworks. Moderate
degrees of decarboxylation were observed for all metal organic framework catalysts. The incorporation of
Pt with the porous frameworks resulted in high degrees of decarboxylation. All MOF catalysts showed high
thermal stability, resulting in recyclable catalysts displaying low catalytic activity loss. Of all studied catalysts,
Ga-MOF catalysts were the most effective catalysts, displaying moderate to high degrees of decarboxyl-
ation. In addition, the Pt–Ga-MOF catalyst displayed selectivity to heptadecane, an important industrial
chemical. Octadecane, heptadecane, dodecane, undecane, decane, nonane, octane, and heptane were
observed as the main side products. To our best knowledge, the catalytic ability of a metal organic frame-
work both as catalyst and support for the decarboxylation of a model fatty acid molecule is reported for
the first time.
Received 4th December 2014,
Accepted 27th February 2015
DOI: 10.1039/c4cy01609b
www.rsc.org/catalysis
these reports, the support is a catalytically inert material like
carbon or relatively, non-acidic components, like silica or
1
. Introduction
The removal of oxygen from fatty acids (deoxygenation) leads
to the formation of paraffinic hydrocarbons that can poten-
tially serve as or be converted to direct replacements for tradi-
non-acidic alumina. Recently, our group has reported the cat-
alytic decarboxylation and conversion of oleic acid to
branched and aromatic hydrocarbons in a single process
tional petroleum-derived liquid transportation fuels and par-
step, over acidic and basic supports including Pt–SAPO-11
1
32
affinic
petrochemical
feedstocks.
Typically,
the
and Pt/chloride Al O
and Pt/hydrotalcite.
Metal organic frameworks (MOFs)
and Pt/SAPO-34, Pt/DNL-6, Pt/RHO
2
3
3
3
deoxygenation of unsaturated fatty acids is accomplished via
hydrogenation of double bonds and further removal of the
carboxyl group by releasing carbon dioxide and producing a
paraffinic hydrocarbon, a process known as decarboxylation,
or by releasing carbon monoxide and producing an olefinic
3
4,35
have emerged as an
appealing type of crystalline microporous materials which
combine highly desirable properties, such as uniform micro-
pores, high surface areas, and exceptional thermal and chem-
ical stability, making them ideal candidates for catalytic
applications. MOFs consist of metal cations or metal-based
clusters linked by organic molecules forming a crystalline
network, which after removal of guest species may result in
2–5
hydrocarbon, a process known as decarbonylation.
Considerable studies on liquid phase deoxygenation of
4
–16
free fatty acids and fatty acid esters have been carried out.
Different metals including Ni, Ni/Mo, Ru, Pd, Pd/Pt, Pt, Ir, Os
and Rh impregnated on different supports have been evalu-
ated for their deoxygenation performance under elevated
temperatures and pressures.
3
4,36,37
three dimensional structures with permanent porosity.
Although the catalytic ability of several MOF compositions
has been demonstrated for diverse relevant chemical reac-
3
8,39
Several studies of the decarboxylation of the unsaturated
tions
to our best knowledge the catalytic performance of
5
,17–31
oleic acid have been documented.
ples include Pt–Re/C, Pt/C,
Representative exam-
MOFs for the decarboxylation of fatty acid molecules has not
been reported.
2
1
21,25
22,23,25
Pd/C,
molybdenum
nitrate, tungsten nitride and vanadium nitride supported on
Herein, we report the catalytic decarboxylation of oleic acid
to paraffins and hydrocarbons over isostructural MOFs com-
posed of Cu, Al and Ga catalysts of different acidity. Interest-
ingly, all MOFs displayed moderate catalytic activity even in
the absence of Pt. Of all studied catalysts, Ga-MOF catalysts
were the most effective catalysts, displaying moderate to high
degrees of decarboxylation. Furthermore, the Pt–Ga-MOF
2
4
25
26
27
γ-Al
2
O
3
,
Pt/SiO
2
,
hydrotalcite,
2 3
Ni/MgO–Al O ,
2
8
29
H PO /Al O , Ru/CeO ,16 Pt/CeO , natural aluminosilicate
3
4
2
3
2
2
3
0
and nano-sized titanium and magnesium oxide. In most of
Chemical and Biological Engineering Department, Colorado School of Mines,
Golden CO 80401, USA. E-mail: mcarreon@mines.edu
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catalyst displayed selectivity to the linear paraffin
heptadecane, a highly valuable industrial product.
reactor was heated to the reaction temperature (320 °C)
under a constant stirring rate and the temperature was kept
constant during the 2 hour reaction period. After the reac-
tion, the catalyst was separated by centrifugation from the
product and washed with acetone and hexane for further use.
2
. Experimental
2
.1 Catalyst synthesis and characterization
Reaction conditions were chosen based on our previous expe-
MOFs were prepared via conventional solvothermal
a
32,33
rience in the decarboxylation of fatty acids
the yield of hydrocarbons.
to optimize
4
0
approach. The employed inorganic sources were copper
nitrate hemi-pentahydrate (Alfa Aesar, 98%), aluminum iso-
propoxide (Sigma-Aldrich, ≥99.99%) and gallium nitrate
hydrate (Alfa Aesar, 99.9%). The employed organic linker was
2.3 Product analysis
The liquid product was collected after reaction and analyzed
with a gas chromatograph (GC, 6980N) equipped with a HP-5
MS column (with dimensions of 30 m × 250 μm × 0.25 μm)
and a 5973N MSD detector. Before the GC analysis, samples
were silylated with N,O-bisIJtrimethyl)-trifluoroacetamide
1
,3,5-benzenetricarboxylic acid (Alfa Aesar, 98%). The molar
ratio of inorganic source to linker was kept constant at 1.36 :
. In a typical synthesis, 0.6 g of the inorganic metal source
1
was dissolved in 15 mL of deionized water, and 0.4 g of linker
was dissolved in 7.5 mL of deionized water and 7.5 mL of
ethanol. The mixture was stirred thoroughly for 2 h. The
resultant solution was transferred into a 45 mL teflon-lined
stainless steel autoclave and heated at different temperatures
and times (depending on the inorganic source). For Cu-MOF,
the solvothermal temperature was 120 °C and the synthesis
time 18 h. For Al-MOF and Ga-MOF, the solvothermal tempera-
ture was 180 °C and the synthesis time 24 h. After this time, the
autoclave was cooled down to room temperature, and the resul-
tant crystals on the bottom of the autoclave were washed with
methanol 3 times. The crystals were dried overnight in an oven
at 80 °C. These three isostructural MOF compositions were cho-
sen based on the different degree of acidities of the metal spe-
cies (gallium as hard acid metal and the most acidic and Cu a
borderline acid metal and the less acidic).
(
BSTFA, Sigma-Aldrich, ≥99.0%) and kept at 60 °C for 1 h. After
that, a sample of 0.2 μL was injected into the GC column (250
C, 10.52 psi) with a split ratio of 100 : 1. The carrier gas was
°
−
1
helium and the flow rate was 1.0 mL min . The following GC
temperature program was used for analysis: 100 °C for 5 min,
−
1
3
00 °C (1 °C min for 2 min). Product identification was con-
firmed with a gas chromatograph-mass spectrometer (GC-MS).
The decarboxylation conversion of oleic acid was esti-
mated from the reduction in the number of oleic acid's car-
boxylic acid groups during the reaction. The amount of car-
boxylic acid groups remaining in the products after the
reaction was evaluated by quantifying the acid number
(
ASTMD974). Acid number is the mass of potassium hydrox-
ide (KOH) in milligrams that is required to neutralize one
gram of chemical substance.
The three MOFs were impregnated with tetraamine Pt
nitrate at 5 wt% Pt loading. In a typical impregnation step a
stoichiometric amount of the Pt source was dissolved in
deionized water and then impregnated on 1.8 g of the MOF
meanwhile the suspension was stirred. The mixture was dried
overnight at 100 °C. After that the mixture was calcined at
To quantify the acid number, a known amount of sample
(
0.1 g) was dissolved in a solvent (ethanol + petroleum ether),
then titrated with a solution of sodium hydroxide (NaOH, 0.1
N) using phenolphthalein as a color indicator.
The acid number is calculated from this equation:
4
00 °C for 5 h to remove the ligands of the precursor.
The catalysts were characterized by X-ray diffraction
NV
Acid number  56.1
W
N = 0.1 (N)
(XRD), field emission scanning electron microscopy (FESEM)
and thermal gravimetric analysis (TGA). XRD patterns were
collected on a Kristalloflex 800 from Siemens at 25 mA and
V = volume of NaOH consumed (ml)
W = mass of the sample (g)
3
0 kV with Cu Kα radiation. FESEM images were taken on a
JEOL ISM-7000F using a field emission gun and an accelerat-
ing voltage of 200 kV. TGA profiles were obtained on a TGA
Q50 under a constant flow of nitrogen.
The % decarboxylation was calculated using the acid num-
ber of oleic acid and the acid number of the product using
the following relation:
2
.2 Reaction procedure
%
Decarboxylation = (acid number of oleic acid − acid num-
ber of the product)/acid number of oleic
acid × 100 %
Oleic acid (99%, Alfa Aesar) was employed as the model
unsaturated fatty acid molecule. Prior to the catalytic tests,
all the catalysts were pre-activated in the oven for 3 h at 150
°C. The reactions were conducted in a 100 mL stainless steel,
high pressure batch reactor (Parr model 4560). Oleic acid and
the catalyst were loaded into the reactor in a mass ratio of
3
. Results and discussion
1
8 : 1. Before the reaction started, the air in the reactor was
The SEM images of Cu, Al, and Ga MOFs are shown in Fig. 1.
Fig. 1a shows a representative SEM of Cu-MOF displaying
well faceted hexagonal crystals with relatively narrow size
removed by flushing hydrogen. After that, the pressure was
increased to the desired value (usually 20 bar). Then the
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4
1,42
the typical known structure of Cu IJBTC) .
The metal
3
2
organic framework Cu IJBTC)
(BTC
=
benzene-1,3,5-
3
2
tricarboxylate) is an appealing material to employ as catalyst
for the decarboxylation of fatty acid molecules due to the
presence of Lewis acid coordination sites (Cu) in its frame-
3 2
work. Cu IJBTC) is a porous metal organic framework which
forms a face-centered cubic crystalline structure which is
composed of dimeric cupric tetracarboxylate units, which
give an intersecting 3D-channel system with a micropore
4
1
diameter of 0.7–0.8 nm. Fig. 2b and c show the XRD pat-
terns of Al-MOF and Ga-MOF, respectively. A shift to lower 2
theta angles in the XRD reflections (as compared to Cu-MOF)
for these two samples is evident. This shift suggests a higher
degree of local structural disorder which is expected to be
due to the incorporation of larger atoms in the porous
framework (Cu atomic radius = 0.127 nm; Ga atomic radius =
43
0
.136 nm; Al atomic radius = 0.143 nm). The XRD patterns
of the Pt-supported MOF samples were identical to those of
the bare MOFs (not shown here).
Fig. 3 shows the decarboxylation of oleic acid over Cu-
MOF, Al-MOF and Ga-MOF at 320 °C. The degree of decarbox-
ylation increased in the following order: Ga-MOF > Al-MOF >
Cu-MOF. More specifically, ~66%, ~45% and ~42% degrees
of decarboxylation were observed for Ga-MOF, Al-MOF and
Cu-MOF, respectively. Interestingly the catalytic performance
of these isostructural MOFs correlates with the degree of
metal acidity. Gallium as hard acid metal is the most acidic,
and Cu a borderline acid metal is the less acidic. The
observed catalytic activity of these particular MOF composi-
tions (even in the absence of a noble metal) is not surprising
since these MOFs have the particular property of exposing
their open metal centers making them chemically reactive. In
addition, we have recently demonstrated that acid supports
can help in promoting the decarboxylation of fatty acid mole-
cules such as oleic acid. The presence of H promoted the
2
hydrogenation of oleic acid to stearic acid which then
undergoes facile decarboxylation.
Fig. 4 shows the decarboxylation of oleic acid over Cu-MOF,
Al-MOF and Ga-MOF impregnated with 5 wt% Pt at a reaction
temperature of 320 °C. As expected, the degree of decarboxyl-
ation considerably increased with the addition of Pt. Similar
Fig. 1 Representative SEM images of (a) Cu-MOF, (b) Al-MOF, and (c)
Ga-MOF.
distribution and average particle size in the ~0.8–1 μm range.
Fig. 1b shows a representative Al-MOF showing hexagonal
crystals with a broad size distribution and average particle
size in the 0.2–0.8 μm range. Fig. 1c shows a representative
SEM of Ga-MOF showing larger (~10 μm) dodecahedral crys-
talline morphology.
3
3
Fig. 2 shows the XRD patterns of the Cu, Al, and Ga MOFs.
Fig. 2a shows the XRD pattern of Cu-MOF corresponding to
Fig. 3 Decarboxylation of oleic acid over Cu-MOF, Al-MOF, Ga-MOF
catalysts and blank run (reaction conditions: 10 ml oleic acid, 0.5 g
catalyst, 2 h, and pressure 20 bar at 320 °C).
Fig. 2 XRD patterns of (a) Cu-MOF, (b) Al-MOF, and (c) Ga-MOF.
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all samples were thermally stable at least up to ~330 °C. More
specifically, Cu-MOF displayed ~10% weight loss at ~330 °C,
Al-MOF displayed ~15% weight loss at ~520 °C and Ga-MOF
displayed ~15% weight loss at ~500 °C.
We performed EDX analysis, and no significant changes
in metal content were observed for Ga-MOF based samples,
suggesting that there is no metal leaching. For example for
Pt–Ga-MOF before reaction (% wt Pt 4.3 ± 0.8) after reaction
(
% wt Pt 4.1 ± 0.6). For Ga-MOF before reaction (% wt Ga
5
6.5 ± 0.5) after reaction (% wt Ga 55.8 ± 0.9).
The detailed product distribution for the most active cata-
Fig. 4 Decarboxylation of oleic acid over fresh and recycled Pt/Cu-
MOF, Pt/Al-MOF and Pt/Ga-MOF catalysts (reaction conditions: 10 ml
oleic acid, 0.5 g catalyst, 2 h, and pressure 20 bar at 320 °C).
lysts (Ga-MOFs with and without Pt) is given in Table 1. The
components in the liquid product included branched paraf-
fins formed by isomerization of the initially formed
heptadecane, and lower molecular weight hydrocarbons
to the catalytic trend observed for the bare MOFs, the follow-
ing order was observed for the Pt impregnated MOF catalysts:
Pt/Ga-MOF > Pt/Al-MOF > Pt/Cu-MOF. In particular, ~92%,
(
mostly C7–C18 paraffins) formed by cracking of the
heptadecane. No oleic acid was observed in the products
under all reaction conditions, suggesting total conversion of
oleic acid. Octadecane, heptadecane, dodecane, undecane,
decane, nonane, octane, and heptane were observed as the
main side products.
~90% and ~46% degrees of decarboxylation were observed for
Pt/Ga-MOF, Pt/Al-MOF and Pt/Cu-MOF, respectively.
The higher catalytic activity of Pt-based catalysts prepared
3
,33,44,45
from PtIJNH ) ij(NO )] has been reported earlier.
3
4
3 2
2
+
3 4
Cationic complexes (like Ptij(NH ) ] ) likely lead to better
As shown in Fig. 6, under similar reaction conditions
dispersion and anchoring to the MOF surface and, conse-
quently, an improved catalytic activity.
Recyclability is an important and essential feature of any
catalyst to be considered for use in industrial applications.
Therefore, we investigated the influence of catalyst recycle on
the catalytic performance. Upon recycling the catalysts
(
temperature, pressure, reaction time), the selectivity to
heptadecane over Pt/Ga-MOF was comparable to other Pt
supported porous crystalline supports, such as zeolite RHO
and hydrotalcite, but lower than supports such as zeolites
(Fig. 4), slightly lower % decarboxylation was observed. This
relatively low loss in catalytic activity for the recycled catalysts
can be explained in part by the remarkable thermal stability
of Cu-MOF, Al-MOF and Ga-MOF crystals. As shown in Fig. 5,
Fig. 6 Heptadecane selectivity for several Pt supported catalysts.
(Reaction conditions: 10 ml oleic acid, 0.5 g catalyst, 2 h, and pressure
Fig. 5 TGA profiles of (a) Cu-MOF, (b) Al-MOF, and (c) Ga-MOF.
20 bar at 325 °C. Only for Ga-MOF temperature was 320 °C).
Table 1 Liquid product distribution for the decarboxylation of oleic acid over Pt/Ga-MOF and Ga-MOF catalysts
Reaction conditions
Catalyst Pressure
Hydrocarbon products (%)
a
Temperature Time Octadecane Heptadecane Dodecane Undecane Decane Nonane Octane Heptane Gas
(
20
bar)
(°C)
320
(h)
2
5
wt%
55.13
21.52
5.70
—
0.92
9.19
1.46
9.32
1.71
1.81
1.53
15.92
27.65
Pt–Ga-MOF
Ga-MOF
20
320
2
—
6.72
12.76
15.84 12.82
a
Mass balance (CO
2
, CH
4
, others).
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Fig. 7 Scheme showing the general pathway of the reaction.
3
3
DNL-6 and SAPO-34. The lower selectivity may be related to
Currently, we are exploring the use of MOFs with pore
sizes that in principle may lead to the molecular sieving
effect observed in DNL-6 and SAPO-34. These MOF composi-
tions include ZIF-8 and ZIF-67 which have limiting pore aper-
tures of 0.34 nm.
The general decarboxylation reaction scheme of the con-
version of oleic acid to hydrocarbons over MOF catalysts is
shown in Fig. 7.
4
6
a restricted transition state selectivity observed in small pore
zeolites like SAPO-34 and DNL-6. More specifically, on
supported metal, bifunctional catalysts, like those used in
3
3
the present and in our previous report, the selectivity for
the initially formed linear paraffin heptadecane (amongst the
reaction products) is inversely proportional to the ability of
the catalyst to isomerize it further to branched paraffins over
the acidic sites of the support. In addition to the acidity, the
pore diameter of the support also plays a crucial role: sup-
ports with smaller pore diameters (like SAPO-34 and DNL-6)
prevent the further isomerization reaction of heptadecane
since the large size of the transition state needed for the
isomerization cannot be accommodated in the constrained
confines of the small pores (restricted transition state selec-
4. Conclusions
The decarboxylation and further conversion of oleic acid to
gasoline/diesel-range hydrocarbons has been demonstrated
over bare and Pt supported Cu, Al and Ga based metal
organic frameworks. Moderate degrees of decarboxylation
4
6
tivity). In restricted transition state-type selectivity, certain
reactions (like the isomerization of linear to branched ole-
fins/paraffins) are prevented because the transition state is
too large for the cavities of the catalyst. SAPO-34 belongs,
structurally, to the chabazite group of zeolites. It contains
(
42–66%) were observed for all metal organic framework cata-
lysts. The incorporation of Pt with the porous frameworks
resulted in high degrees of decarboxylation (above 90% for
Al-MOF and Ga-MOF). All MOF catalysts displayed high ther-
mal stability, resulting in recyclable catalysts displaying low
catalytic activity loss. In particular, Ga-MOF catalysts were the
most effective catalysts, displaying moderate to high degrees
of decarboxylation. The improved catalytic performance of
Ga-MOF may be related to the higher acidity of Ga. In addi-
tion, the Pt–Ga-MOF catalyst displayed selectivity to
heptadecane, an important industrial chemical. Octadecane,
heptadecane, dodecane, undecane, decane, nonane, octane,
and heptane were observed as the main side products. To
our best knowledge, the catalytic ability of a metal organic
framework both as catalyst and support for the decarboxyl-
ation of a model fatty acid molecule is demonstrated for the
first time.
8
-membered ring pores with openings of 0.38 nm. DNL-6 is
structurally related to zeolite RHO with a pore size of 0.36
nm (close to SAPO-34). Interestingly, both supports with very
close pore size show the highest selectivity to heptadecane,
suggesting the “molecular sieving” effect. On the other hand,
the other supports showing lower heptadecane selectivity
have larger or smaller pore sizes. For instance, Ga-MOF (iso-
structural form of Cu-MOF) has a pore size of ~0.8 nm.
Hydrotalcite also has larger pore size. Zeolite RHO has a pore
system comprising 8-membered rings with pore openings
that can be as small as 0.29 nm. In the case of RHO, the
smaller pore size may impose diffusion limitations, resulting
in low heptadecane selectivities.
Therefore, the isomerization of heptadecane to bulkier
branched isomers will, hence, be sterically more difficult, rel-
atively, in the narrow pores of SAPO- 34 or DNL-6 than in the
other supports having larger or smaller pore sizes (like Ga-
MOF, hydrotalcite, and zeolite RHO), accounting for its
higher selectivity for the linear heptadecane.
Acknowledgements
M. A. Carreon thanks the Coors Foundation for financial sup-
port of this work.
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