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Original Article

Production of cobalt-copper from partial reduction of La(Co,Cu)O

3

perovskites for CO hydrogenation

Nguyen Tien Thao

, Le Thanh Son

Faculty of Chemistry, Vietnam National University Hanoi, 19 Le Thanh Tong ST, Hanoi, 10999, Viet Nam

a r t i c l e i n f o

Article history:

Received 15 June 2016
Accepted 28 July 2016
Available online 18 August 2016
Keywords:

CO hydrogenation
Metal dispersion
CueCo
Perovskite

a b s t r a c t

La(CoCuO3) nanoperovskites have been prepared by the mechano-synthesis method and treated with

hydrogen to yield a high dispersion of bimetallic CoeCu sites. The reduced LaCo1-xCuxO3samples were

characterized by XRD, H2-TPR, CO and H2chemisorption and tested for CO dissociation and for alcohol

synthesis from syngas. The experimental results indicated that the activities in CO dissociation and
hydrogenation on copper-cobalt metals extracted from perovskite lattice crystals are signiﬁcantly
different from those in the extra-perovskite lattice. The overall catalytic activity in syngas conversion is
correlated with the CoeCu metal surface, but the alcohol productivity e productivity of alcohols
de-creases in the order of LaCo0.7Cu0.3O3> LaCo0.4Cu0.6O3> Cu2O/LaCoO3> LaCo0.9Cu0.1O3> LaCoO3. The

highest catalytic activity and alcohol productivity was obtained over sample of the reduced LaCo0.7
-Cu0.3O3perovskite catalyst.

© 2016 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.
This is an open access article under the CC BY license ( />

1. Introduction

Perovskites, mixed oxides of the general formula ABO3, have

extensively been applied in many ﬁelds due to their particular

compositional structure [1]. In principle, the ideal perovskite

structure is cubic with the space-group Pm3m-Oh in which the A
cation occupies at the body center, the cation (B) is at the cube

corner, and the oxygen stays at the midpoint of the cube edges[1,2].

By this way, the perovskite derivatives may be synthesized by the

replacement of another element in A and/or B position[1,3,4]. In

the present work, we have partially substituted Co3ỵin

lanthanum-cobaltate by Cu2ỵ to obtain La(Co,Cu)O3 perovskite catalyst

pre-cursors. The partial reduction of La(Co,Cu)O3 perovskites may

further produce metallic copper-cobalt metals those originate

intentionally from the perovskite lattice. As a result, a ﬁnely

dispersed metal catalyst from perovskite precursors would be

ex-pected to use for several applications[2,4]. In experimental, Crespin

and Hall[5]had produced Co0/La2O3from the reduction of LaCoO3

under hydrogen atmosphere. Fierro et al.[6]received the Ni/La2O3

after the complete reduction of LaNiO3at 705 K. Bedel et al.[4]only

carried out the partial reduction of La(Co,Fe)O3 orthorhombic

perovskites at 723 K, producing a small amount of metallic cobalt
while the perovskite lattice still preserved. Thus, the perovskite
product has exhibited a high catalytic activity in many applications

such as CO oxidation[7]hydrogenation of ethylene[8], reforming

of CO2 [9], and conversion of syngas (H2/CO) into many useful

chemicals and liquid fuels[10,11]. The latter conversion is a very

important process since a mixture of alcohols is a crucial gasoline

additive or green vehicle fuel today[12e14].

In our previous work, we have reported some novel

character-istics of lanthanum-cobaltate nanoperovskites prepared by

mechano-synthesis method[10,11,14]. The reduction of such

ma-terials leads to the formation of a well-homogenized supported
bimetallic alloy. Furthermore, the co-existence of two transition
metal ions in the solid lattice results in the formation of dual sites
which are active for many oxidation-reduction applications
[4,15e19]. This article is to present a way for the preparation of
metals supported catalysts for the conversion of carbon monoxide
into oxygenated compounds.

2. Experimental
2.1. Catalyst preparation

A series of CoeCu bases perovskites were synthesized by

mechano-synthesis method. The stoichiometric proportions of
commercial lanthanum, copper, and cobalt oxides (99%, Aldrich)
* Corresponding author. Fax: ỵ84 (04) 3824 1140.

E-mail address:(N. Tien Thao).

Peer review under responsibility of Vietnam National University, Hanoi.

Contents lists available atScienceDirect

Journal of Science: Advanced Materials and Devices

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were mixed together with three hardened steel balls

(diameter¼ 11 mm) in a hardened steel crucible (50 mL). A SPEX

high energy ball mill working at 1000 rpm was used for
mechano-synthesis. Milling was carried out for 8 h prior to a second milling
step with an alkali additive. Then, the resulting powder was mixed
to 50% sodium chloride (99.9%) and further milled under the same
conditions for 12 h before washing the additives with distilled
water. A sample was added into a beaker containing 1200 mL water
and stirred by magnetic stirring for 90 min prior to being

sedi-mented for 3e5 h. After the clean water is removed, the slurry was

dried in oven at 60e80C before calcination at 250C for 150 min.

2.2. Characterization

The elemental chemical analysis of copper and cobalt in the
perovskites was performed by atomic absorption spectroscopy

using a PerkineElmer 1100B spectrometer. Phase analysis and

crystal domain size determination were performed by powder
X-ray diffraction (XRD) using a SIEMENS D5000 diffractometer with

CuKaradiation (l¼ 1.54059 Å). Bragg's angles between 15 and 75

were collected at a rate of 1/min.

To measure the real surface area of the reduced perovskites, two

other BET experiments were performed using aﬂow system

(RXM-100, Advanced Scientiﬁc Designs, Inc., ASDI). First, 70e100 mg of

catalyst was calcined at 773 K (ramp of 5 K/min) under 20 mL/min

of O2/He (20 vol. %) for 90 min and then evacuated at 723 K for

90 min (P 8.5 108mmHg). Nitrogen adsorption was carried

out at 77 K. Each point of the adsorption isotherm was established
by introducing a given amount of nitrogen from the reaction
manifold into the reactor. Temperature Programmed Reduction

(TPR) experiments were carried out after evacuating N2adsorption

(BET measurement). TPR of the catalysts was then carried out by

ramping under 4.65 vol.% of H2/Ar (20 mL/min) from room

tem-perature to 773 K (5 K/min) for 90 min. The second BET
measure-ment of the sample after reduction was also done in situ.

Chemisorption performance with H2at 373 K and CO at room

temperature was carried out after the second BET measurement.

The H2-chemisorption performance was similar to steps for BET

measurement of nitrogen. After the ﬁrst isotherm that contains

both physical adsorption and chemisorption was collected, the

sample was evacuated at adsorption temperature for 5e10 min in

order to remove all physically adsorbed species prior to do the

second adsorption. The difference between theﬁrst and the second

isotherm gives the chemisorption isotherm. H2-and CO-uptake

were determined by extrapolating the straight-line portion of the

adsorption isotherms to zero pressure as represented inFig. 1.

CO dissociation tests on the reduced samples were carried out

using a RXM-100 system. Prior to pretreatment, 40e50 mg of

catalyst was ramped at 10 K/min up to the calcination temperature

(773 K) under 20 vol.% O2/He (20 mL/min) for 90 min and then

cooled down to room temperature under aﬂow of 20 mL/min He

for 60 min in order to remove the physically adsorbed gas. The
pretreatment of the catalysts was then carried out from room
temperature up to 798 K (5 K/min) for 90 min under 4.65 vol. % of

H2/Ar (20 mL/min) and then cooled down to reaction temperature

under aﬂowing 20 mL/min of He. A number of CO/He (0.586 vol. %)

pulses (0.25 mL) were then injected and passed through the reactor
prior to on line analysis using mass spectrometer (UTI-100). The m/
z signals 2, 18, 28, 44 were collected.

2.3. Catalytic activity

The catalytic tests were carried out in a stainless-steel

contin-uous ﬁxed-bed ﬂow micro-reactor (BTRSeJr PC, Autoclave

Engi-neers). The reaction pressure was controlled using a back-pressure

regulator. The syngas mixture (H2/CO¼ 2/1) was diluted in helium

(20 vol. %). A mixture of reactants and inert gas was supplied from a

pressurized manifold via individual mass ﬂow controllers. The

catalyst pellet size was 40 mesh. Catalysts were pretreated in situ

underﬂowing 5 vol.% of H2/Ar (20 mL/min) prior to each reaction

test. The temperature was kept at 523 K (3 h), and 773 K (2h30)
with a ramp of 2 K/min. Then, the reactor was cooled down to the
reaction temperature while pressure was increased to 69 bars by
feeding a reaction mixture of gases. The products were analyzed
using a gas chromatograph equipped with two capillary columns
and an automated online gas sampling valve maintained at 443 K.
The temperature of transfer line between the reactor and the valves
was kept at 493 K in order to avoid any product condensation.
Carbon monoxide and carbon dioxide were separated using a

capillary column (Carboxen™ 1006 PLOT, 30 m 0.53 mm)

con-nected to the TCD. Quantitative analysis of all organic products was
carried out using the second capillary column (Wcot fused silica,

60 m 0.53 mm, Coating Cp-Sil 5CB, DF ¼ 5.00

m

m) connected to a

FID detector (Varian CPe 3800) and mass spectrometer (Varian

Saturn 2200 GC/MS/MS).
3. Results and discussion
3.1. Catalyst characteristics

The physical properties of all fresh catalyst samples are

measured and shown inTable 1. X-ray diffraction spectra of all

samples were collected (but not shown) and the crystal phase is

presented inTable 1 [10]. Although Table 1 shows each sample

contains at least two components, but it is noted that the main
phase is perovskite a long with a very small amount of starting

metal oxide material(s) as impurities [10]. Both LaCoO3 and

La(Co,CuO)O3 perovskites are presented as the well-structured

0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40

0 10 20 30 40 50

Pressure (torr)

H2

)g/

l

m(

e

ka

t

p

u

de

bo

ro

si

me

h

C

-Total adsorption

Chemisorption
Physisorption

Fig. 1. H2e Chemisorption at 373 K over LaCo0.4Cu0.6O3reduced at 773 K.

Table 1

Properties of the synthesized perovskites.

Nominal Sample XRD analysisa BET surface

area (m2/g)b

Chemical
composition

Co Cu

LaCoO3 P, Co3O4 60 21.1 e

LaCo0.9Cu0.1O3 P, Co3O4 20 19.3 1.9
LaCo0.7Cu0.3O3 P, Co3O4,CuO 22 18.6 5.8
LaCo0.4Cu0.6O3 P, Co3O4,CuO 21 9.8 11.6
Cu2O/LaCoO3 P, Cu2O, CuO 16.8 20.0 3.3
aXRD spectra were compared to JCPDSﬁles: P: Perovskite (JCPDS No. 48e0123);
Co3O4(JCPDS No. 42e1467); CuO(JCPDS No. 45e0937).

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rhombohedral perovskite as shown inFig. 1 [3e5,10]. The crystal

domain, determined from the FWHM of the (102) diffraction peak
using Scherrer's equation after Warren's correction of instrumental
broadening, is in the range from 7.9 to 10.5 nm. The third column in
Table 1indicates that all ground perovskites samples have medium

surface area, ranging from 20 to 60 m2/g.Fig. 2.

The reducibility of the ground perovskites is interpreted

through the H2-TPR analysis as represented inFig. 3. It is clearly

observed that the copper efree perovskite sample shows two

distinct visible peaks at 670 and 960 K. The low temperature peak is

ﬁrmly ascribed to the reduction of Co3ỵto Co2ỵand the other broad

peak is attributed to the complete reaction of cobalt divalent to
metallic phase, in good harmony with the results reported by

several groups [1,4e6,9,10]. A similar H2-TPR feature is also

observed for LaCo0.9Cu0.1O3, the proﬁle slightly shifts to the lower

temperature (Fig. 3). Thus, the ﬁrst shaped-peak is observed at

650 K while the second is at 840 K. It is worthily noted that the H2

-TPR baseline was completely recovered at 950 K showing that the
reduction is essentially terminated at much lower temperature as

compared with the case of LaCoO3 [10,12]. The calculation of H2

consumed amount balance indicates that the reduction of Co3ỵand

Cu2ỵto Co2ỵand Cu0below 671 K, whereas that of Co2ỵto Co0at

840 K [4,11,15]. An increased amount of intra-perovskite lattice

copper leads to a signiﬁcant affect on the perovskite reducibility

[15]. For LaCo0.7Cu0.3O3sample, the lower peak is visible, but the

other is very broadening from 643 to 943 K. When a larger amount
of intra-lattice cobalt is replaced by copper ions, the two distinct

peaks in H2-TRP trace of the perovskite sample seems to coalesce

into a single peak at 687 K while that of the physical mixture of

Cu2O/LaCoO3still preserves two visible peaks at 670 and 1018 K.

This is interpreted by the assumption of mutual interaction
be-tween cobalt and copper ions in the reduced form; the reduced
copper metal is to promote the reducibility of cobalt ions in the
framework when copper was essentially extracted from the
perovskite lattice at lower reduction temperature as demonstrated

by H2-TPR results[1,10,15,19]. Moreover, hydrogen is well known to

be easily dissociated to hydrogen atoms on metallic copper sites.

Consequently, the reduction of cobalt ions (Co3ỵ and Co2ỵ) by

atomic hydrogen is presumably taken place at lower temperatures
[1,10,15]. Thus, the reduction of La(Co,Cu)O3is to provide aﬁnely

dispersed CoeCu atoms on the catalyst surface and the formation of

bimetallic alloy is not ruled out[19].

To determine the dispersion of metals formed, we have

measured both H2and CO chemisorptions for the reduced

perov-skite forms. Unfortunately, the determination of each individual

component dispersion level is a very difﬁcult task due to a synergic

interaction between two metals after the partial reduction of

perovskites[10,11,15,19]. In this case, we have recorded total H2and

CO chemisorbed volume (mL/g) of each sample (Fig. 1). The volume

of H2and CO uptake of all reduced samples is in turn presented in

Table 2.

The reduced samples were investigated the ability of CO

dissoci-ation to C* intermediate which further hydrogenates to carbon
skel-eton through performing the dissociation of CO versus temperature
programmed from room temperature to 798 K. The relationship
be-tween CO dissociation conversion and temperature is displayed in
Fig. 4. It seems that the CO decomposition level is related with the

chemical composition and dissociation temperatures[15,17,20]. The

presence of copper component gives rise to slight decreased CO

dissociation conversion in the temperature range of 500e798 K. The

CO dissociation conversion decreases with the order of LaCoO3> CuO/

LaCoO3> LaCo0.7Cu0.3O3> LaCo0.4Cu0.6O3 LaCo0.9Cu0.1O3(Fig. 4). It

is well known that cobalt metal has shown a very good activity in the
dissociation of CO while copper is inactive for the CO splitting
[17,21,22]. In this case, copper plays an important role in the synthesis
of alcohols through the protection of the OH functional groups during

the hydrogenation conditions[11,20,22]. Thus the higher CO

con-versions over the cobalt-rich samples are certainly comprehensive
[4,21]. Based on the ability of the reduced samples to dissociate CO

molecule, we are ﬁrmly expected that the reduced copper-free

perovskite is active for the synthesis of hydrocarbons while the
perovskite containing copper may act as promising catalysts for the

hydrogenation of CO to linear primary alcohols.

3.2. Catalytic activity in hydrogenation of carbon monoxide

All the prepared samples are pretreated under hydrogen

ﬂow-rate at 798 K prior to test for the hydrogenation of carbon monoxide

at 548 K, 68.9 bars and space velocity VVH¼ 5000 h1(H2/CO/

He¼ 8/4/3). The products contain a mixture of linear primary

al-cohols and n-alkane in addition to small amounts of secondary

alcohols and isoparaﬁns and the formation of products is believed

to be associated with the catalyst metal surface[22].

Thus, we presented the correlation between CO conversion and
product selectivity versus the CO-chemisorbed volume uptake.

With the exception of mixture Cu2O/LaCoO3sample,Fig. 5shows

an increased CO conversion with the CO chemisorbed-volume in

order of LaCo0.7Cu0.3O3 > Cu2O/

LaCoO3> LaCoO3> LaCo0.4Cu0.6O3> LaCo0.9Cu0.1O3. The selectivity

to alcohols obtained over these catalyst samples are presented in

Fig. 6. Although product selectivity seems to be well correlated with
the CO-chemisorbed volume, it should be less meaningful as
compared the product selectivities at different conversion values
(Fig. 6). Thus, a comparison between the productivities may give

more insight into the catalytic behavior[10,22]. Undoubtedly,Fig. 6

0
300
600
900
1200
1500
1800

20 30 40 50 60

Li

n

(C

ps

)

LaCo Cu O
LaCo Cu O
LaCo Cu O

Cu O/LaCoO

LaCoO
2θ (degree)

Fig. 2. XRD patterns of all catalyst precursor samples.

0
5
10
15
20
25

300 450 600 750 900 1050

Temperature (K)

T

C

D

S

ign

al

(a.u

)

LaCoO3

LaCo0.7Cu0.3O3

LaCo0.4Cu0.6O3

Cu2O/LaCoO3

LaCo0.9Cu0.1O3

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shows the productivity of alcohols decreases monotonically with

CO uptake in the order of LaCo0.7Cu0.3O3> LaCo0.4Cu0.6O3> Cu2O/

LaCoO3 > LaCo0.9Cu0.1O3 > LaCoO3. This observation is not with

respect to the order of CO chemisorbed volume, but in good

agreement with the ratio of H2volume uptake/BET surface area of

the sample after reduction (Fig. 7). This phenomenon is explained
by the composition of the catalyst surface and the available
abun-dance of bimetallic cobalt-copper sites on the catalyst surface after

reduction[11,16,22e24].

Certainly, the presence of intra-lattice copper (LaCo0.7Cu0.3O3)

has a promotional effect on the formation of alcohols as compared

with the extra-lattice copper (Cu2O/LaCoO3) or the copper-free

perovskite sample [11,23]. The formation of La(Co,Cu)O3

perov-skite precursors would provide intimidate dual copper-cobalt sites

which are prerequisite for the formation of alcohols from CO and H2

[17,19,25]. This issue is further supported by the examination of the

catalytic activity at different pretreatment conditions.Table 2

dis-plays the alcohol selectivity/productivity versus the reduction

temperatures obtained on LaCo0.7Cu0.3O3. It is noted that the

alcohol productivity gradually increases and reaches a maximal
value at 773 K and then sharply decreased at higher reduction
temperatures. This observable trend is explained by the fact that
the surface composition is strongly associated with pretreatment

temperature because of the reduction of CoeCu based perovskites

happening in a multiple-step process at different temperatures
[1,2,4,8,10]. The surface concentration of cobalt and copper metals

is very sensitive to the reduction temperatures[4,5,9,11,15,21,25].

As an increased in H2-reduction temperature, the (Cu0eCo0)surface/

(CueCo)totalmolar surface ratio is varied and probably approached

a highest value around 773 K as elucidated by hydrogen

chemi-sorption data (Table 2)[23].

A higher reduction temperature gives rise to a sintering of
atomic copper metals and as consequence the active sites for the
formation of OH alcohol functional group gradually decreases.
Indeed, it was widely reported that the reduction of perovskites can
be described either by the contrasting-sphere model or by the
Table 2

Effect of hydrogen pretreatment temperature on alcohol productivity over sample LaCo0.7Cu0.3O3in CO hydrogenation at 548 K (VVH¼ 5000 h1, 69 bar, H2/CO/He¼ 8/4/3).
Reduction temperature (K) H2evolume (mL/gcat) CO conversion (%) Alcohol selectivity (%) Alcohol productivity (mg/gcat/h)

623 0.78 17.5 27.2 43.0

723 0.93 16.1 41.9 49.4

773 0.84 25.1 42.9 70.1

823 0.56 8.7 43.5 33.4

20
30

40
50
60
70
80
90
100

450 500 550 600 650 700 750 800

Temperature (K)

)

%(

noi

tai

co

si

d

O

C

LaCoO3
CuO/LaCoO3
LaCo0.7Cu0.3O3
LaCo0.9Cu0.1O3

LaCoO3

CuO2/LaCoO3

LaCo0.7Cu0.3O3

LaCo0.9Cu0.1O3

LaCo0.4Cu0.6O3

Fig. 4. CO dissociation ability at different temperatures on the reduced samples after
pre-treatment at 798 K in H2/Ar (0.586 vol. % CO/He pulses (0.25 mL) were then
injected through the catalyst).

5 15 25 35 45 55 65 75

CO Conversion (%) and Alcohol productivity (mg/gcat/h)

0.012
0.014
0.016
0.018
0.028

g/

L

m(

ek

at

pu

de

br

osi

me

h

C-O

C

ca

t

h)

Conversion
Alcohols
Cu2O/LaCoO3

LaCo0.4Cu0.6O3

LaCo0.7Cu0.3O3

LaCo0.9Cu0.1

LaCoO3

Fig. 5. Correlation between the volume of CO chemisorbed uptake and CO
hydroge-nation activity at 548 K (VVH¼ 5000 h1, 69 bar, H

2/CO/He¼ 8/4/3).

0 10 20 30 40 50 60 70 80 90 100

Alcohol and hydrocarbon selectivity (wt.%)
0.012

0.014
0.016
0.018
0.028

)t

ac

g/

L

m(

e

ka

t

p

u

de

br

osi

me

h

C-O

C

Hydrocarbons

Alcohols

Cu2O/LaCoO3

LaCo0.4Cu0.6O3

LaCo0.7Cu0.3O3

LaCo0.9Cu0.1O3

LaCoO3

Fig. 6. Correlation between the volume of CO chemisorbed uptake and CO
hydroge-nation activity at 548 K (VVH¼ 5000 h1, 69 bar, H

2/CO/He¼ 8/4/3).

0.01
0.02
0.03
0.04
0.05

0.06
0.07

LaCoO3 Cu2O/LaCoO3

Perovskite catalysts

Vo

lum

e o

f H

2

-upt

ak

e / S

BET

(m

L

.g

/m

2)

LaCoO3LaCo0.9Cu0.1O3LaCo0.7Cu0.3O3LaCo0.4Cu0.6O3Cu2O/LaCoO3

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nucleation mechanism[1,2,5,8,9]. Thus, the total metal surface area

is strongly dependant on the pretreatment conditions[8,10,18,20].

In the present study, the LaCo0.7Cu0.3O3is reduced at 773 K gives

the most effective catalyst for the formation of higher alcohols from
CO hydrogenation reaction.

The alcohol product distribution is presented inFig. 8which

contains a mixture of linear primary alcohols from methanol to

heptanol [10,22]. The product distribution is recalculated as

Anderson-Schulz-Flory (ASF) rule and the plot between ln(wt.%/n)

versus carbon number (n) is drawn in Fig. 9 [20,22]. Since the

carbon chain growth factor of alcohols (designated as

a

1) is not on

par with that of hydrocarbons (

a

3), we have recalculated the second

one (a2) excluding methanol because methanol may be

indepen-dently produced by different pathways[11,19,26e30]. In the case,

the alcohol chain growth factor (

a

2) of C2OHe C7OH stays at middle

value between

a

1 and

a

3. This indicates that the formation of

skeletal carbons of primary alcohols occurs parallel to that of

hy-drocarbons on cobalt catalyst surface[20,22,24e27]. A close

dis-tance between cobalt and copper sites on catalyst surface has
steered the formation of hydrocarbons into primary alcohols by
insertion of undissociated CO molecule absorbed on copper sites
[11,19,20,22,28e30].

4. Conclusions

A set of La(Co,Cu)O3perovskite samples prepared by grounding

method was pretreated in H2prior to test for the CO hydrogenation

reaction. The presence of copper ions in the perovskite lattice

results in a signiﬁcant effect on the perovskite reducibility. Under

the same pretreatment conditions the LaeCoeCu based perovskites

is easily reduced, yielding metallic cobalt and copper sites

dispersed over a La2O3matrix. The CO dissociation ability of cobalt

is remarkably affected by the presence of neighboring copper
atoms. The overall activity of the catalysts in syngas conversion
strongly depends on pretreatment temperature and the metal
surface area. The intra-framework copper increases the formation
of higher alcohols. Alcohol and hydrocarbon productivity are
strongly dependant on reducing conditions. The highest alcohol

productivity was about 0.07 galcohol/gcat/h on the LaCo0.7Cu0.3O3

perovskite precursor.

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M
et
ha
nol
M
et
ha
nol
M
et
ha
nol
M
et
ha

nol
Eth
an
ol
Eth
an
ol
Eth
an
ol
Eth
an
ol
Propa
nol
Propa
nol
Propa
nol
Propa
nol
Bu
tan
ol
Bu
tan
ol
Bu
tan
ol

Bu
tan
ol
Pe
nt
anol
+
Pe
nt
anol
+
Pe
nt
anol
+
Pe
nt
anol
+
0
5
10
15
20
25
30
35
40
45
50

623 723 773 823

Temperature (K)
)
%(
noi
tu
bi
rts
i
Dl
oh
ocl
A

Fig. 8. Effect of hydrogen pretreatment temperature on alcohol distribution over
sample LaCo0.7Cu0.3O3in CO hydrogenation at 548 K (VVH¼ 5000 h1, 69 bar, H2/CO/
He¼ 8/4/3).

-4
-3
-2
-1
0
1
2
3
4
5

6

0 1 2 3 4 5 6 7 8 9 10 11

Carbon number

Ln

[(w

t.%)/

n]

α3 = 0.43
α2 = 0.42

α1 = 0.38

</div>
(6)<div class='page_container' data-page=6>

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</div>


<a href=' /><a href=' />

journal of science advanced materials and devices

Original Article

Production of cobalt-copper from partial reduction of La(Co,Cu)O

<sub>3</sub>

perovskites for CO hydrogenation

Nguyen Tien Thao

, Le Thanh Son

a r t i c l e i n f o

a b s t r a c t

Journal of Science: Advanced Materials and Devices

m

a

a

a

a

a

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