Preparation of a Novel Active Fischer–Tropsch Co–Ni Catalyst Derived from Metal-Organic Framework

Article abstract of DOI:10.1134/S0965544120090121

Abstract: In the present study, a typical metal-organic framework has been employed for preparation of a novel active Fischer–Tropsch Co–Ni catalyst. Co–Ni catalyst was prepared by glycine–MOF combustion method and was heated in a tube furnace (2°C min^–1) under air at 750°C for 6 h. Scanning electron micrograph of metal-organic framework shows regularly cubic shaped crystals and they were being deformed into a low density, loose and porous material after it was calcined in the tube furnace. BET surface area and pore volume are 276 m²/g and 0.31 cm³/g respectively. This active catalyst showed selectivity for long-chain hydrocarbons (Formula presented.) of ~52% and for short-chain hydrocarbons (C₂–C₄) 30%. The relatively high activity (TOF of 2.08 s^–1 at 340°C) was ascribed to its high porous structure and large pore size of the catalyst which facilitated the diffusion of hydrocarbons. The unique features of this catalyst, including structural tailor ability such as high surface area, porosity, homogeneity and stability enable it to be an active Fischer–Tropsch catalyst.

Full text of DOI:10.1134/S0965544120090121

ISSN 0965-5441, Petroleum Chemistry, 2020, Vol. 60, No. 9, pp. 1059–1065. © Pleiades Publishing, Ltd., 2020.
Published in Russian in Neftekhimiya, 2020, Vol. 60, No. 5, pp. 671–678.
Preparation of a Novel Active Fischer–Tropsch Co–Ni Catalyst
Derived from Metal-Organic Framework
a,
a,
a,
H. Janani *, A. Rezvani **, and A. A. Mirzaei ***
a
Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, Zahedan, 98135-674 Iran
*
e-mail: halimehjanani@yahoo.com
*e-mail: rezvani2001ir@yahoo.ca
**e-mail: mirzaei@hamoon.usb.ac.ir
Received April 10, 2019; revised April 24, 2020; accepted May 12, 2020
*
*
Abstract—In the present study, a typical metal-organic framework has been employed for preparation of a
novel active Fischer–Tropsch Co–Ni catalyst. Co–Ni catalyst was prepared by glycine–MOF combustion
–1
method and was heated in a tube furnace (2°C min ) under air at 750°C for 6 h. Scanning electron micro-
graph of metal-organic framework shows regularly cubic shaped crystals and they were being deformed into
a low density, loose and porous material after it was calcined in the tube furnace. BET surface area and pore
2
3
volume are 276 m /g and 0.31 cm /g respectively. This active catalyst showed selectivity for long-chain hy-
+
drocarbons С of ~52% and for short-chain hydrocarbons (C –C ) 30%. The relatively high activity (TOF
(
5
)
2
4
of 2.08 s–1 at 340°C) was ascribed to its high porous structure and large pore size of the catalyst which facili-
tated the diffusion of hydrocarbons. The unique features of this catalyst, including structural tailor ability
such as high surface area, porosity, homogeneity and stability enable it to be an active Fischer–Tropsch cat-
alyst.
Keywords: metal-organic framework, glycine–MOF combustion method, Fischer–Tropsch synthesis, Co–
Ni catalyst
DOI: 10.1134/S0965544120090121
INTRODUCTION
on Fe, Ni, Co, Ru or Rh as the active metal, with Fe
and Co being practical choices. Among them, Co-
based catalysts have the features of affordable price,
Metal-organic frameworks (MOFs) are an import-
ant class of materials composed of metal ions and
organic ligands. They can be converted to porous net-
works via different methods such as hydrolysis, pyrol-
ysis, hydrothermal or solvothermal crystallization,
etc. Design and manufacturing of MOFs has attracted
great attention in recent years because of their unique
structures and functional properties [1–3]. These
organic-inorganic hybrid materials are widely used in
gas storage, enantioselective separation, sensor tech-
nology, optical application, drug delivery, catalysis,
etc. [1–4]. In particular, catalysis is one of the most
recently promising applications for MOFs. These
materials are able to catalyze a large number of chem-
ical reactions with high efficiency. MOFs-derived
materials exhibit high porosity, great surface area, high
pore volume and well dispersed metal particle, which
are suitable for the catalytic process performance.
high activity, lower CO emission, and lower water gas
2
shift activity which are the most widely used catalysts
for commercial FTS process. The synthesis of bime-
tallic catalysts containing two or more metallic or
oxide phases from metal-organic framework is a novel
approach that represent several advantages, such as the
superior metal interactions, the homogeneous disper-
sion of the metal phases, and maximum loading
amount, which all conclude to development of ideal
catalysts for FT synthesis [7, 8]. Recently, Fe and Co-
based catalysts derived from MOFs show high CO
conversion, superior selectivity and stable operation.
The obtained MOFs derived catalysts exhibited highly
dispersed metal phase confined within a porous
matrix and high FT activity. These MOFs derived cat-
alysts have been prepared by pyrolysis, hydrolysis, and
solvothermal methods [9, 10].
Fischer–Tropsch synthesis (FTS) is a well-recog-
nized catalytic process for the conversion of synthesis
gas into high quality diesel fuel; the reaction yields a binuclear metal-organic complex for preparation of an
mixture of hydrocarbons of different molecular active FT catalyst. Such a metal-organic framework is
weights [5, 6]. The common FTS catalysts are based favorable for manufacture of FT catalyst. Herein, we
In the present work, we report the utilization of a
1059

1060
JANANI et al.
–
1
demonstrate an approach for preparation of active and H flow (60 mL min ) at 400°C for 10 h before being
2
stable FTS catalyst using combustion synthetic
method of glycine–MOF process. This preparation
procedure is derived from the glycine-nitrate combus-
tion method [11] and demonstrates an alternative
method for the design of new active FT catalysts. No
type of promoter or support has been used in the
preparation of this catalyst. Usually supported catalyst
are more mechanically stable and have better catalytic
activity. However, the strong interaction between
metal and support can have a negative effect on cata-
lytic efficiency. Based on the nature of the interaction
between metal and support, supported catalysts
exhibit significant different catalytic and adsorptive
tested on the reaction line for FT synthesis.
Catalytic reaction. The Co−Ni catalyst was tested
in the FTS in a tubular stainless steel micro-fixed bed
reactor at 1 MPa pressure. 1 g of catalyst was reduced
–1
in H gas (total flow of 60 mL min ) at atmospheric
2
pressure and 400°C for 10 h. Hydrogen flow was then
stopped and temperature was decreased down to
2
00°C. At this temperature, the pressure was increased
to 1.0 MPa. The catalytic tests were carried out
between 260–340°C, 10 h for each temperature at the
steady state, syngas with a volume ratio of H /CO=2
2
(
gas mixture containing 32% CO, 63% H , 5% N )
2 2
–1
properties. Metal-support interactions affect the cata- and gas hourly space velocity (GHSV) of 3600 h . The
lyst activity and product distribution [12].
reaction was started by raising the temperature to the
desired reaction temperature. The reaction products
were analyzed on-line by gas chromatograph equipped
with a 10-port sampling valve (Supelco company,
USA, Visi Model), a sample loop, a thermal conduc-
tivity detector, a packed column (Hayesep DB, Alltech
Company, USA) and an FID. The selectivity of final
products was computed on a carbon basis (Fig. S1).
Therefore, in order to eliminate the effects of
metal-support interactions on catalytic performance,
we prepared and utilized un-supported catalyst for
FTS. By using this strategy, highly loaded and dis-
persed cobalt catalyst was synthesized and tested for
Fischer–Tropsch synthesis. This catalyst displayed
notable CO conversion (75%) and good selectivity
towards long-chained hydrocarbons. This MOF-
derived catalyst is one of the few cases that, although
no additional promoter or support was used for its
preparation, it has a good catalytic efficiency in FTS
compared to other MOF-derived cobalt catalysts [1–
Instrumentation. Thermogravimetric behavior
of the MOF was recorded under air using the BAHR-
STA 503 (Germany) thermal analyzer from room tem-
–1
perature to 800°C (heating rate of 3° min ). Elec-
tronic spectra, using a JASCO 7850 spectrophotome-
ter. FT-IR spectrum was recorded using a Perkin
Elmer FT-IR spectrometer with KBr pellets (Fig. S2).
Powder X-ray diffraction (PXRD) measurement were
performed on an Inel Equinox 3000 X-Ray Diffrac-
4
, 10]. This work would open up a new way to design
new Fischer–Tropsch catalysts with a good activity
and preferable selectivity by using the appropriate
preparation strategy and befitting MOF precursors.
tometer using CuK radiation. The BET surface areas
α
were measured on a micro metrics adsorption equip-
ment (Quantachrome Instrument, model Nova 2000,
USA) determining nitrogen (99.99% purity) as the
EXPERIMENTAL
Preparation procedure. Metal-organic complex was analysis gas and the samples were slowly heated to
prepared according to the literature [13]. Addition of 300°C for 6 h under nitrogen atmospheric at –196°C.
2-methyl-2,4-bis(6-iminopyridin-2-yl)-1H-1,5-benzo-
(
The scanning electron microscope (SEM) image,
diazepine) to equimolar of cobalt (II) dichloride in the electron microprobe analysis (EPMA) and energy dis-
mixture of dichloromethane/ethanol generated mononu- persive X-ray spectrometer (EDS) were obtained
clear Co complex. Obtained complex reacted with nickel on Philips XL30 scanning electron microscopy
(
II) dichloride in ethanol to get the Co−Ni heteronuclear (Netherland). The elemental analysis in the catalyst
complex. Yellow microcrystals were obtained in good was measured by atomic adsorption spectroscopy
yields (75%). Elemental analysis, FT-IR and UV-vis spec- (AAnalyst 200, Perkin Elmer, USA) and ICP-MS
tra of the MOF were in agreement with what was reported (PerkinElmer’s NexION 2000 ICP Mass Spectrome-
in the reference. The purity of the sample was confirmed ter).
–1
by single crystal X-ray diffraction. FT-IR (KBr, cm ):
361, 1620 cm (νC=N), 1590, 1470, 1369, 1200, 808.1, and
–1
3
7
RESULTS AND DISCUSSION
–
1
69.1 cm .
MOF characterization. The crystal structure of this
Then, this MOF precursor was used for the synthe- MOF consists of one nickel(II) cation, one cobalt(II)
sis of FT catalyst. In this strategy, 0.01 mol of metal cation, one ligand molecule (2-methyl-2,4-bis(6-imi-
organic complex and 0.04 mol glycine were added into nopyridin-2-yl)-1H-1,5-benzodiazepine), one etha-
distilled water. This mixture was stirred by magnetic nol molecule and four chlorides. The bis-chelate
mixer at 60–70°C until the homogenous sol-like solu- ligand bridges between cobalt and nickel. The cobalt
tion was obtained. Then this solution was calcined in a center adopts distorted trigonal pyramid. The equato-
tube furnace at 750°C for 6 h with a heating rate of rial position is occupied by the nitrogen (N5) of pyri-
–1
2
° min . Afterwards, the sample was reduced under dine and the two chlorides. Other two nitrogen atoms
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PREPARATION OF A NOVEL ACTIVE FISCHER–TROPSCH Co–Ni CATALYST
1061
Co–Ni
Co
Ni
NiCo O4
2
0
10
20
30
40
θ, deg
50
60
70
2
Fig. 1. PXRD pattern of the catalyst.
(
N4, N6) are in the axial plane. The coordination from 12 to about 30 nm, indicating that these particles
geometry at nickel center is distorted octahedron. The have high specific surface area and good anti-sintering
FT-IR and elemental analysis were consistent with the ability. After reaction, the particle size of Co–Ni
literature [13]. The purity of the sample was confirmed alloy and single metal phases increased to 22 and
by the powder X-ray diffraction. The TGA curve of ~40–46 nm respectively. It has been reported in the
metal organic framework shows that the first weight literature that the particle sizes of Co–Ni alloy are
lost occurred before 150°C was attributed to the evap- smaller than that of single metal particles of Ni and
oration of ethanol and the second weight loss around Co, which indicates that the particles of Co–Ni alloy
6
50°C was corresponded to the full destruction of have better anti-sintering ability than that of corre-
MOF. So to ensure the complete metal reduction, a sponding single metal particles [15]. These results are
high temperature of 700°C was chosen for calcination consistent with the surface area data, SEM and EMPA
(
Fig. S3).
results, which showed more porous structure led to
high surface area. The high specific surface area allows
a high degree of metal dispersion.
Catalyst characterization. The obtained catalyst
was characterized by powder X-ray diffraction
PXRD), Barnauer-Emmett-Teller (BET) nitrogen
(
From the N adsorption test, the Brunauer-
2
adsorption, scanning electron microscopy (SEM), Emmett-Teller (BET) surface area and total pore vol-
2
–1
electron microprobe analysis (EPMA), energy disper-
sive X-ray spectrometer (EDS) and Atomic adsorption
spectroscopy (AAS).
ume of the catalyst were calculated as 276 m g and
3
–1
0
.31 cm g respectively. The N adsorption/desorp-
2
tion isotherm of catalyst presented a sharp inflection
XRD pattern of fresh catalyst is shown in Fig. 1. at a relative pressure in the range of 0.5 (Fig. 2) and
The fresh catalyst exhibits diffraction peaks of spinel exhibit type IV isotherm with hysteresis (type H3)
mixed metal oxides NiCo O , Co−Ni alloy and metal- between adsorption and desorption branches, indicat-
2
4
ing the existence of mesoporous cavities with a very
wide size distribution. In such a high pore volume of
the catalyst, there is the possibility of more active met-
als for the desired reaction. Larger pore size of the cat-
alyst (20 nm) can facilitate the diffusion of long-chain
hydrocarbon products. These data are consistent with
lic (Co and Ni) phases. X-ray diffractograms showed
that the mixed metal oxides crystallized in the spinel
phase with space group Fd3m. As shown in Fig. 1 the
diffraction peaks of Co−Ni are located at 2θ = 16°,
2
1.5°, 24.4°, 30.6°, 41.3°, and 61°. This demonstrates
that metal nickel and cobalt reduced in the state of
alloy. The characteristic diffraction peaks are weak
and broad. The broad and low-intensity identity of
these characteristic peaks represents the fine particle
size and the high distribution of metal species. Parti-
cles size of Co–Ni alloy, single metal and spinel-type
oxide are listed in Table 1 according to the Debbye-
Scherrer equation [14]. The particle size of Co–Ni,
Table 1. The sizes of particles (nm) derived from PXRD
results
Samples
Co–Ni
Ni
Co
NiCo O
2
4
Fresh catalyst
12
22
25
40
30
46
15
23
single metal phases of Ni, Co and NiCo O ranges Used catalyst
2
4
PETROLEUM CHEMISTRY Vol. 60 No. 9 2020

1062
JANANI et al.
600
400
200
0
0.2
0.4
0.6
0.8
1.0
Relative pressure, P/P
0
Fig. 2. N adsorption-desorption of the catalyst.
2
10 μm
(а)
(b)
Fig. 3. SEM images of MOF (a) and derived catalyst (b).
the average size acquired from the peak broadening in catalytic applications. Figure 4 shows the EPMA
PXRD studies. Smaller size of the particles leads to results for the catalyst. The distribution of Co and Ni
higher specific surface area. Furthermore, higher sur- is entirely homogeneous and it was uniform on an
face area will cause to better distribution of particles. atomic level.
Moreover, wider pore mesoporous is also appropriate
Additional analysis by combining EDS was con-
to the diffusion of gas, resulting in a higher catalytic
ducted to analyze the surface elemental composition.
activity [10]. These results confirmed by SEM and
The EDS spectrum of the catalyst (Fig. 5) reveals
EPMA studies.
the presence of both Co, Ni, C and N, which is con-
Scanning electron microscopy analysis in combi- firmed by powder X-ray diffraction data. The Co and
nation with elemental mapping (EPMA and EDS) Ni contents in the catalyst were measured by atomic
give further information on the morphology of MOF adsorption spectroscopy (AAnalyst 200, Perkin-
precursor and its corresponding MOF-derived cata- Elmer, USA). These data are consistent with ICP-MS
lyst. It is apparent that MOF precursor has well- (PerkinElmer’s NexION 2000 ICP Mass Spectrome-
defined cubic shape (Fig. 3a). During the calcination ter) results (22.38% Co and 21.97% Ni). Results
in the tube furnace, the morphological characteristics showed the high metal loading and superb dispersion
of the MOF-derived catalyst are completely different of Co and Ni (44.35%) at the surface of the catalyst.
and it was deforming into a highly porous, loose and The elemental composition characterization of the
low density sample (Fig. 3b) that is appropriate for catalyst showed presence of nitrogen, oxygen and car-
PETROLEUM CHEMISTRY
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2020

PREPARATION OF A NOVEL ACTIVE FISCHER–TROPSCH Co–Ni CATALYST
SEM
1063
Co
10 μm
Ni
Co–Ni
Fig. 4. Elemental mapping (EPMA) of the catalyst.
Co
O
Ni
C
Sum spectrum
C
Ni
C
Co
Ni
N
N
5
Co
1
2
3
4
6
7
8
9
10
11
keV
Fig. 5. EDX spectrum of the catalyst.
bon in the derived catalyst (C 45.18%, O 5.41% and N showed that desired catalyst exhibited high FT activity
.06%).
compared with most reports in the literature [2, 9, 10,
6]. The notable CO conversion of the catalyst should
5
1
Catalytic performance results. The MOF-derived
be attributed to high surface area (according to BET
measurements), high metal loading percentage (based
on elemental analysis and EPMA results) and porous
texture of the catalyst (confirmed by SEM results).
Furthermore, larger pore size of the catalyst can facil-
itate the diffusion of gas in the carbon matrix there-
catalyst was tested in FTS reaction under 1 MPa pres-
sure and H /CO = 2. The product distribution and
2
catalytic activity are presented in Table 2. The activity
of the catalyst was tested between 260–340°C. It
should be noted that CO conversion was low at tem-
peratures below 260°C (~40%). The CO conversion
was increased almost linearly with increasing tem-
perature reaction. Obviously, the reaction rate
increases at high temperatures. Due to the increase in
the number of effective collisions, the reaction condi-
tions are more suitable and the faster the reaction rate.
fore, enhanced the catalytic activity (based on N
2
sorption test). The product selectivity of the catalyst is
also perceptible against other MOF-derived cobalt
catalysts. Since in Fischer-Tropsch reaction, CO con-
verts to CO and hydrocarbon products (C −C ) and
2
1
n
+
5
At 320°C the CO conversion increased to 75%, which because С products are volatile liquid, they often
PETROLEUM CHEMISTRY Vol. 60 No. 9 2020

1064
JANANI et al.
Table 2. Catalytic performance of the MOF-derived catalyst in FT synthesis
Hydrocarbon selectivity, %
TOF, s–1
Temperature, °C CO conv., %
+
C −C4
CH4
CO selectivity, %
2
С
2
5
2
2
3
3
3
60
80
00
20
40
48
51
63
75
75
26.0
27.5
28.1
30.3
30.8
39.6
46.0
48.4
51.8
51.9
14.0
14.8
15.2
15.7
16.6
9.8
6.4
4.1
1.2
0.4
1.33
1.41
1.75
2.08
2.08
+
5
Total sum of the selectivity values is less than 100%. It can be attributed precisely to the loss of the volatile part of С hypothetically and
its value systematically increases with decreasing temperature.
remain in the path of the reactor and are not detected results shown, the catalytic performance is related to
+
5
physicochemical characteristics of the catalyst. The
catalytic properties are often affected by two factors:
the preparation procedure and the nature of the pre-
cursor. Above mentioned results highlighted the
importance of the preparation route onto catalytic
properties and FTS efficiency. We compared this cat-
alyst with a variety of mono and heterobimetallic
cobalt-based catalysts prepared via different prepara-
tion procedures. Many of the characteristics and per-
formances of this catalyst are comparable to pervious
reports and according to the catalyst novelty, it has
notable performance. For example, catalyst stability
was higher (200 h of work without significant changes
of the catalyst performance) than 102 h [2] and 50 h
by GC. The selectivity of С products reached
5
2% and the selectivity towards short-chain olefins
C –C ) were 30.3% (at 320°C). It is obvious that
2 4
(
Co–Ni based FTS catalysts commonly have higher
selectivity towards long-chain hydrocarbons. These
catalytic performance results are much higher than the
most FTS catalysts reported in the literature [2, 9, 10,
1
6–18]. It was reported in the literature that nitrogen
species are prominent components in the catalyst
framework. In fact, N species are considered as
impressive electron donor for increasing the CO
adsorption-dissociation process and selectivity of final
products in Fischer–Tropsch synthesis. The presence
of nitrogen species as effective electron donor,
enhanced the CO adsorption-dissociation, varied
cobalt valance state and thus, enhanced the synthesis
of the short-chain hydrocarbon products. This strong
electrostatic interaction has significant impact on the
physicochemical properties of cobalt particles espe-
[
23]. In comparison with the other cobalt-based cata-
lyst reported in literature [2, 8, 17, 18], this catalyst
showed good selectivity towards short-chain hydro-
carbons (selectivity to C –C products of 30% com-
2
4
pared with 6 [2], 14 [8], 22 [17], and 11% [18]. The cat-
+
5
cially in the reduction behavior. The electrostatic alyst also had a relatively high selectivity to С prod-
interaction of cobalt oxide and nitrogen can cause that ucts of ~52% compared to the other Co-based
the reduction of oxides proceeds by releasing the oxy- catalysts, which are reported in literature: 10 [8], 54
gen atoms from the lattice and the free particles would [17], and 49.83% [18]. Turnover frequency (TOF) for
be easily reduced. Similar results were obtained by the the presented catalyst were calculated (Table 2) and
other reports [9, 10, 19–22].
comparable to (or greater) those measured on typical
MOF-derived catalysts (TOF of 0.0.019, 0.031,
The stability of the catalyst was investigated by run-
ning the reaction for 200 h at 320°C, 1 MPa, H /CO = 2
–
1
–1
–1
0
.028 s [2], 0.027, 0.091 s [9], and 0.07, 0.11 s
2
–1
[16]). The CO conversion in this catalyst (75%) is also
high compared to the reported values: 15.8 [2], 30 [10],
and GHSV of 3600 h . There was no evidence of cat-
alyst deactivation at 200 h. The activity of the catalyst
and selectivity towards hydrocarbons did not undergo
considerable changes during the test. Supreme stabil-
ity of the catalyst is also affected by its texture struc-
4
4.5 [8], 16 [17], and 37.34% [18]. Above mentioned
results demonstrate that this new catalyst is very prom-
ising in FTS against other MOF-derived cobalt cata-
lysts.
ture. Based on N sorption test, the pore size of the
2
catalyst is large. Wide pore mesoporous in addition to
increasing catalytic activity, because of the facilitated
diffusion of gas into the carbon matrix, causes deacti-
vation of the catalyst to be postponed. Conversely, in
CONCLUSIONS
In the present study, a heteronuclear Co–Ni com-
tight pore catalysts by forming hydrocarbons, the plex was used as a metal-organic framework for prepa-
active sites covered by products and thus the catalyst ration of an active Co–Ni FTS catalyst. MOF-derived
was deactivated. Along with the formation of active FT catalyst prepared via glycine–MOF combustion
phases, the notable performance of this MOF-derived method. It was utilized as an unsupported catalyst
catalyst should be related to its high loading percent- without any promoter, which resulted a high
age, abundant porosity and high pore volume of the metal content (44.35 wt %) in the catalyst. By using
catalyst. Catalysts with these properties can be served this method, highly loaded metal nanoparticles
as ideal catalysts for Fischer–Tropsch process. As the (22.38 wt % Co, 21.97 wt % Ni) with well dispersion
PETROLEUM CHEMISTRY
Vol. 60
No. 9
2020

PREPARATION OF A NOVEL ACTIVE FISCHER–TROPSCH Co–Ni CATALYST
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