Journal of Energy Chemistry 24 (2015) 637–641

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Journal of Energy Chemistry

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journal-of-energy-chemistry/
journal homepage: www.elsevier.com/locate/jechem

Sputtered nano-cobalt on H-USY zeolite for selectively converting syngas

to gasoline
Peng Lu a,b, Jian Sun b,c,∗, Pengfei Zhu b, Takayuki Abe d, Ruiqin Yang a, Akira Taguchi d,
Tharapong Vitidsant e,∗, Noritatsu Tsubaki b,∗
a
Zhejiang Provincial Key Lab for Chem. & Bio. Processing Technology of Farm Product, School of Biological and Chemical Engineering, Zhejiang University of
Science and Technology, Hangzhou 310023, Zhejiang, China
b
Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku, Toyama 930-8555, Japan
c
Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
d
Hydrogen Isotope Research Center, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan
e
Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: Selectively converting CO and H2 to gasoline product (isoparaffin and olefin) in one step still remains a great
Received 8 May 2015 challenge. We demonstrate effective H-USY zeolite supported nano-cobalt bifunctional catalysts for this cat-
Revised 31 May 2015
alytic reaction, which are prepared by the novel physical sputtering process. Particles of the sputtered cobalt
Accepted 9 June 2015
exist in nano-level and are well-dispersed on acid USY zeolite. Easy activation of the loaded nano-cobalt is
Available online 31 August 2015
also achieved in a low-temperature hydrogen reduction atmosphere. In the tandem catalytic reaction, the
Keywords: sputtered bifunctional Co/USY catalyst exhibits a much higher CO conversion and higher isoparaffin selectiv-
Cobalt ity than the conventional impregnated one. Compared with H-Mor, H-Beta and other zeolites supported cata-
USY lysts, H-USY zeolite supported cobalt catalyst shows the clearest promotional effect on the activity of Fischer-
Zeolite Tropsch synthesis. The described synthesis herein provides a new pathway to solve the problem caused by
Fischer-Tropsch synthesis the strong metal-support interaction (MSI) in heterogeneous catalysis.
Hydrocarbon
© 2015 Science Press and Dalian Institute of Chemical Physics. All rights reserved.

1. Introduction
Owing to the rapid depletion of oil resources and upgrading of
environmental protection in latest years, Fischer-Tropsch synthesis
(FTS) as the core of the gas-to-liquids (GTL) processes, has recently re-
ceived a renewed interest as a versatile catalytic route for producing
environmentally benign and ultraclean fuels from syngas [1,2]. Gen-
erally, hydrocarbon products from FTS follow the Anderson-Schulz-
Flory (ASF) distribution law. Although it is difficult to disobey the
ASF law, quantitative works have been performed in order to obtain
more selective products expected, especially gasoline-ranged middle
isoparaffins from FTS [3]. Owing to its well catalysis of hydrocrack-
ing and isomerization of heavy hydrocarbons, acid zeolite is regarded
as an excellent support candidate for selectively producing branched
paraffins [4,5].
Some attempts have been performed to directly derive isoparaf-
fins from syngas by one step on a bifunctional catalyst [4,6,7]. For
instance, isoparaffins can be produced by physical mixed catalysts,
∗
Corresponding authors. Tel: +81 76 445 6846; Fax: +81 76 445 6846.
E-mail addresses: sunj@dicp.ac.cn (J. Sun), tharapong.v@chula.ac.th (T. Vitidsant),
tsubaki@eng.u-toyama.ac.jp (N. Tsubaki).
composed of FTS metal and acid zeolite [8]. Generally, the hybrid cat-
alyst is a simple physical mixture with random distribution of active
sites, exhibiting a lower reactivity and lower selectivity of C5+ hydro-
carbons. In addition, the impregnation method is widely employed
to synthesize zeolite supported FTS catalysts. However, the strong
metal-support interactions (MSI) between FTS catalysts and support
severely hindered the reduction of FTS catalysts, leading to suppres-
sion of H2 and CO chemisorptions after reduction at high tempera-
tures [9,10]. Moreover, sintering of active FTS sites is reinforced, ac-
companied with the treatment of high temperature. In line with the
above, a novel route is needed to synthesize an efficient bifunctional
catalyst of high activity and isoparaffin selectivity with high metal
dispersion and without high temperature reduction treatment.
As illustrated before [3,11], the physical sputtering is an efficient
process to deposit noble metals on powder supports. Assisted by
the rotation or swing motion during sputtering, well-dispersed metal
nanoparticles are physically deposited on powder substrate homoge-
neously. Compared with conventional chemical wet methods of cat-
alyst preparation, this dry route can synthesize bifunctional catalysts
with a weak MSI property.
Herein, we design an ultra-stable Y (USY) zeolite supported cobalt
catalyst prepared by the self-made polygonal physical sputtering
method for directly synthesize gasoline-ranged isoparaffins from

http://dx.doi.org/10.1016/j.jechem.2015.08.004
2095-4956/© 2015 Science Press and Dalian Institute of Chemical Physics. All rights reserved.
638 P. Lu et al. / Journal of Energy Chemistry 24 (2015) 637–641
Scheme 1. Schematic representation of the sputtering apparatus.
syngas via modified FTS reaction. Physical and chemical properties
of the Co/USY catalysts prepared by the sputtered or impregnated
method (Co/USY-I) were compared in detail. Isoparaffin synthesis
performances on both catalysts as well as on different zeolite sup-
ported catalysts were also discussed.
2. Experimental
2.1. Catalyst preparation
Commercial H-USY powders (Tosoh Co., SiO2 /Al2 O3 = 6.3 molar
ratio, 466 m2 /g) were pre-calcined at 550 °C for 3 h in air followed
by cooling down to room temperature. The physical sputtering ap-
paratus was demonstrated in Scheme 1. Metallic cobalt plate (purity
99.9%) was used as the sputtering target. 5.0 g of the pretreated zeo-
lite powders was loaded into the cavity barrel. After that, the vacuum
chamber was evacuated to 8.0×10−4 Pa, followed by introducing pure
Ar (purity: 99.995%) with a flow rate of 29 mL/min into the chamber
until the pressure reached 2.0 Pa. The input power was controlled to
350 W. After 200 min sputtering, about 7 wt% of Co loaded onto the
zeolite powder was obtained. Thereafter, a 1.0% O2 /N2 flow was grad-
ually introduced into the cavity barrel to reach common pressure, and
kept for 1 h to stabilize the metallic Co supported catalyst, denoted as
Co/USY-S. The obtained catalyst was reduced in H2 at 260 °C for 1 h,
denoted as Co/USY-S-260.
For comparison, another catalyst denoted as Co/USY-I with the
same Co loading was prepared through a conventional impregnation
method. Co(NO3 )2 ·6H2 O (Kanto Chemical Co. Inc.) was dissolved in
distilled water, followed by incipient wetness impregnation of the
aqueous solution onto 5.0 g of USY powder. The precursor was then
dried at 80 °C under vacuum, and calcined at 400 °C for 2 h. Then, the
obtained Co/USY-I catalyst was reduced at 260 °C for 1 h or at 400 °C
for 10 h, denoted as Co/USY-I-260 and Co/USY-I-400, respectively.
In addition, other zeolite (H-Mor and H-Beta) supported cobalt
catalysts were prepared with the same method as above. Com-
merical H-Mor and H-Beta powders were also from Tosoh Co.,
Japan (H-Mor:SiO2 /Al2 O3 = 18.3 molar ratio, 349 m2 /g; H-
Beta:SiO2 /Al2 O3 = 5.6 molar ratio, 394 m2 /g). The corresponding bi-
functional catalysts are denoted as Co/Mor-I, Co/Mor-S, Co/Beta-I and
Co/Beta-S.
2.2. Catalyst characterization
A FEI Tecnai G220 S-Twin high-resolution transmission electron
microscope (HRTEM) with an accelerating voltage of 200 kV was
employed to characterize the particle morphology and distribution.
Surface analysis with X-ray photoelectron spectroscopy (XPS) was
obtained from the Thermo Scientific ESCALAB 250Xi equipment, and
XPS peak fit was performed with Avantage Data System software.
The catalyst analyzer BELCAT-B-TT (Bel Japan Inc.) was employed
to perform NH3 temperature-programmed desorption (TPD). Sam-
ples were pretreated at 150 °C in a He flow followed by cooling down
to 80 °C. A flow of 5% NH3 (He balance) was introduced at a rate of
30 mL/min for 0.5 h. Then, sweeping by He until a constant TCD sig-
nal was conducted. Desorption curves of NH3 were recorded with a
heating rate of 10 °C/min.
To determine the reduction degree of the pre-reduced impreg-
nated catalyst and directly sputtered catalyst, the O2 titration exper-
iment was carried out at 400 °C (for Co/USY-I) and 260 °C (for Co/
USY-S) using the catalyst analyzer BELCAT-B-TT with the assumption
that the metallic Co atoms oxidized totally to Co3 O4 .
H2 chemisorption experiments were performed with Autosorb-1
vacuum apparatus. About 50 mg of samples was placed in a quartz
cell. Prior to the measurement, the samples were degassed at 300 °C
and 3.0 Pa for 1 h. The impregnated and sputtered catalyst were re-
duced in flowing H2 at 400 °C for 10 h and 260 °C for 1 h, respectively.
And they were evacuated for 1 h to desorb any H2 , followed by cooling
to 100 °C. The chemisorption temperature was conducted at 100 °C,
and the equilibration time was 30 min. Co dispersion was calculated
assuming an H/Co adsorption stoichiometry equal to 1.
2.3. Evaluation of one-step gasoline synthesis via syngas
FTS tests for one-step gasoline synthesis were performed with a
continuous flowing fixed-bed reactor from syngas (CO: 33.7 vol%; Ar:
3.04 vol%; balance with H2 ). Details of the FTS steps were described
elsewhere [5]. Briefly, an ice trap with 2.0 g of n-octane as solvent was
equipped to capture the heavy hydrocarbons in the effluent. Reaction
conditions were 260 °C, 1.0 MPa, and Wcatalyst /F = 10 (g·h)/mol. Gas
products (C1 –C6 ) were analyzed by two on-line gas chromatographs.
One of that was an active charcoal column equipped with a thermal
conductivity detector (Shimadzu, GC-8A). Another used a capillary
column (J&W Scientific GS-Alumina) and an FID detector (Shimadzu,
GC-14B) to analyze light hydrocarbons. Liquid products from the ice
trap were analyzed by an off-line gas chromatograph with an FID de-
tector (Shimadzu, GC-2014).
3. Results and discussion
The particle size comparison of Co/USY-I and Co/USY-S is demon-
strated in HRTEM images of Fig. 1. The impregnated Co particles ex-
hibited large aggregation on USY zeolite with an average particle size
of about 20 nm. But in the case of sputtered catalyst, cobalt nanopar-
ticles were well-dispersed on zeolite with an average diameter of
about 5 nm. Smaller and narrower particle distribution on the sput-
tered catalyst was attributed to the stir assistance of mechanical ap-
paratus during the atomic-scale sputtering process [12,13]. In detail,
cobalt atoms derived from the attack by Ar plasma stream are ho-
mogenously deposited onto the USY zeolite surface with continuous
hexagonal rotation and spin, as well as mechanical vibration provided
by the rolling barrel. From H2 chemisorption, a high Co dispersion
of 17.2% was also observed for the sputtered Co/USY-S, much higher
than that of 5.3% for the impregnated one. Herein, the higher cobalt
dispersion on sputtered Co/USY-S catalyst contributed to better spa-
tial arrangement of two kinds of active sites, making a more suitable
distance between FTS sites and acidic sites nearby, if compared to the
conventional impregnated one.
To demonstrate the chemical state of cobalt in different catalysts,
surface analysis of the cobalt species was performed by XPS mea-
surement. For the Co 2p spectra (Fig. 2), the binding energy peaks lo-
cated at around 781 and 778 eV were generally attributed to Co2+ and
metallic Co(0) species, respectively [14]. The satellite peak at 786 eV
further confirmed the existence of Co2+ species in all catalysts. The
presence of the cobalt oxides for these catalysts was due to the sta-
bilization treatment in 1% O2 after H2 reduction. We compared the
metallic cobalt content in different catalysts by the XPS element anal-
ysis (Table 1).
 P. Lu et al. / Journal of Energy Chemistry 24 (2015) 637–641 639

Fig. 1. HRTEM images of the Co/USY-I (a) and Co/USY-S (b).

ent. From XPS surface element analysis, the sputtered Co particles

showed a Co content of 15 wt%, much higher than the theoretical
value (7.0 wt%) and that of impregnated one (6.8 wt%). The surface en-
richment of Co demonstrated that sputtered Co particles were mainly
located on the external surface of H-USY support, different from con-
ventional bulk-dispersed impregnated catalyst.
Acidic sites on USY Zeolite can catalyze hydrocracking and isomer-
ization reactions of long-chain hydrocarbons in FTS reactions. To in-
vestigate the acid amount on both catalysts, the NH3 -TPD experiment
was carried out and compared in Fig. 3. The commercial H-USY zeo-
lite showed an NH3 uptake of 3.0 mmol/g, including weak acid sites at
130 °C and strong acid site at 400 °C. After being deposited with 7 wt%
cobalt, the acid amount was clearly decreased. In detail, the sputtered
Co/USY-S catalyst exhibited total acid amount of 2.7 mmol/g, a slight
loss compared with that of H-USY zeolite. But for the impregnated
one, acid amount of only 1.7 mmol/g remained on USY zeolite, ac-
companied by a great loss of strong acid sites. The obvious decrease of
Fig. 2. Co 2p XPS spectra of the reduced Co/USY-I and Co/USY-S catalyst.
acid amount was due to the coverage of aluminum sites in the frame-
work of USY by impregnated cobalt species. However, the physical
Table 1. Co0 and Co2+ content from XPS analysis.
sputtered cobalt was only wedged on USY zeolite with a weak in-
Catalyst Reduction condition Co content (%) teraction. The physical structure of zeolite, especially pore structure
Co0 Co2+ and acid amount, was not broken in this physical depositing process.
In general, branched product selectivity increases with an increase
Co/USY-S 260 o C/1 h 36 64
in Brønsted acid site strength of the zeolite catalysts [16]. Therefore,
Co/USY-I 400 o C/10 h 8 92
Co/USY-I 260 o C/1 h 5 95
more reservation of acid amount was highly beneficial to promote
isoparaffin selectivity in FTS reactions, as behaved on Co/USY-S.
FTS performance of different prepared catalysts was compared in
Table 2. To compare the FTS activity, we firstly reduced both catalysts
After reduction at 260 °C for 1 h, the impregnated Co/USY-I-260
catalyst consisted of only 5% metallic cobalt in all Co species. Even af-
ter reduction at 400 °C for 10 h (Co/USY-I-400), the increase content
of metallic cobalt is rather limited. In contrast, the sputtered Co/USY-
S-260 exhibited a higher metallic Co0 amount of 36%, indicating the
easier reduction process on the sputtered catalyst. We also employed
the O2 titration method to determine the reduction degree for two
catalysts. For the sputtered one, the reduction degree reached 70% at
260 °C, clearly exceeding the value of 45% for the impregnated one
at 400 °C. As mentioned before [15], sputtered metallic nanoparti-
cles were generally wedged on zeolite, forming a weak physical in-
teraction between metal and support. This weak interaction deter-
mined facile metal reduction process, as compared to the strong in-
teraction between the impregnated metal and zeolite. In addition, we
found a similar Co° content comparison on the sputtered and impreg-
nated Co/ZSM-5 catalyst (48% vs. 29%), supported on H-ZSM5 zeolite.
Further, the position of Co particles on the two catalysts is differ- Fig. 3. NH3 uptake curves of different catalysts.
640 P. Lu et al. / Journal of Energy Chemistry 24 (2015) 637–641

Fig. 4. Hydrocarbon distribution on the Co/USY-I and Co/USY-S catalysts under iso-conversion FTS conditions.

Table 2. FTS performance of different prepared catalysts.

Catalyst CO conversion Selectivity (%) Ciso /Cn a

(%) CH4 C5+

b
Co/USY-S-260 71 23 33 0.45
Co/USY-I-260 42 35 33 0.60
Co/USY-I-400 52 32 26 0.74
Co/MOR-S-260 71 16 51 0.59
Co/MOR-I-400 70 18 43 0.34
Co/Beta-S-260 75 21 51 1.77
Co/Beta-I-400 74 17 60 0.90
Iso-conversion (%)
Co/USY-S-260 50 28 42 1.02
Co/USY-I-400 50 32 26 0.74

FTS condition: 260 °C, 1.0 MPa, and Wcatalyst /F = 10 (g·h)/mol.

a
Ciso /Cn is the molar ratio of all isoparaffins to all normal paraffins with n > 3.
b Scheme 2. Schematic of the tandem reaction including F-T synthesis and acid catalysis
The last number stands for the reduction temperature.
achieved on the sputtered Co/USY bifuctional catalyst.

in situ in the fixed-bed FTS reactor under the same hydrogen reduc-
tion condition (260 °C, 1 h). As a result, the sputtered Co/USY-S cata-
lyst exhibited a CO conversion of 71%, much higher than that of 42%
over the impregnated one. After promoting the reduction condition
to 400 °C by as long as 10 h, the impregnated Co/USY-I showed an en-
hanced FTS activity of 52%, still much lower than the sputtered cata-
lyst. Owing to the well-dispersed and easily-reduced cobalt nanopar-
ticles, higher CO conversion was achieved on the sputtered Co/USY-S
catalyst. Under the same FTS conditions, FTS activity on Co/zeolite
catalysts of various zeolite type, such as H-Mor, and H-Beta, was
also compared. Interestingly, FTS activity of sputtered catalysts sup-
ported on the three different zeolites was very close to the same level
(71%–75%), indicating that CO conversion is independent of zeolite
type of these sputtered catalysts. For the cases of other zeolite sup-
ported sputtered catalysts, the promotion of FTS activity was not
so obvious if compared to the corresponding impregnated catalysts.
These findings demonstrated that catalytic activity for the chemical
impregnated catalysts strongly depended on physical structure of ze-
olite. On the contrary, the physical sputtered catalysts showed almost
no obvious relationship with zeolite structure, resulting from their
surface enriched active sites.
To compare the product selectivity, we adjusted the condition
of FTS reactions to obtain the CO conversion of same level for the
Co/USY-I-400 and Co/USY-S-260. Under iso-conversion of about 50%,
the sputtered Co/USY-S-260 showed very high Ciso /Cn value of 1.02,
clearly exceeding that of 0.74 on the Co/USY-I-400 one. More reserved
acid amount should be responsible for the enhanced isoparaffin se-
lectivity. Moreover, light and heavy hydrocarbon products were dis-
tributed differently on the two catalysts (Fig. 4). For the Co/USY-I-
260, the main products were light hydrocarbons, including CH4 and
C2 –C5 . But for the case of sputtered one, hydrocarbons from C1 to C4
were decreased, and more C5 –C11 gasoline-ranged isoparaffins were
derived. Herein, higher CH4 selectivity on Co/USY-I was attributed to
more unreduced cobalt oxides on zeolite.
In addition, the stability tests on Co/USY-I-400 and Co/USY-S-
260 catalyst were conducted during a time-on-stream FTS reaction
of more than 20 h. After a long-time reaction, the sputtered cata-
lyst showed an activity loss of about 20%, slightly lower than that of
the impregnated one as 21%. This result demonstrated that the bi-
functional sputtered catalyst was efficient in one-step production of
gasoline-ranged isoparaffins, as indicated in Scheme 2.
4. Conclusions
The bifuntional Co/USY catalyst for directly conversion of syngas
to isoparaffins was successfully prepared by physical-sputtering
route. The synthesized catalyst after the sputtered process was
mainly composed of nano-Co0 atoms and little Co oxides under a
mild reduction temperature of 260 °C. Different from conventional
impregnation method, the physical wedging bound between Co
atoms and zeolite support results in the weak interaction, due
to which the prepared catalyst was of high metal dispersion and
reducibility. The sputtered Co/USY-S catalyst exhibited much higher
CO conversion and isoparaffins selectivity than that prepared by
conventional impregnation. FTS activity was independent of zeolite
type on sputtered catalysts. The described synthesis herein provides
a new pathway to solve the problem caused by the strong MSI in
heterogeneous catalysis.
 P. Lu et al. / Journal of Energy Chemistry 24 (2015) 637–641 641

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