The influence of nickel loading on the structure and performance of a Ni-Al2O3 catalyst for the hydrogenation of 1,4-butynediol to produce 1,4-butenediol

Article abstract of DOI:10.1039/d0nj00350f

In combination with a planetary ball-milling machine, a Ni-Al₂O₃ catalyst was prepared by a mechanochemical method. The effect of Ni loading on the crystal structure, reduction characteristics, and hydrogenation performance of the Ni-Al₂O₃ catalyst was investigated. The prepared catalysts were characterized using EDX, XRD, H₂-TPR, BET, TEM and NH₃-TPD methods. The results of the XRD characterization showed that the peak intensity of the active Ni component increased with an increase in the Ni content. The ratio of the measured Ni content to the theoretical Ni content of the MC25percent and MC30percent samples exceeded 1.1. As the Ni addition was increased up to 10percent, the sample consisted of uniform spherical particles, which could provide more contact surfaces. The medium acid peak temperature shifts towards the high temperature direction as the Ni loading increased from 5percent to 20percent, and then (>20percent) decreased to a lower temperature. The corresponding peak area firstly increased and then decreased, presenting a visual representation of changes in the number of acid centers on the catalyst. Evaluation of the results showed that the MC20percent catalyst presented a large specific surface area of 279 m² g^-1, and it showed good hydrogenation performance, with a BYD conversion of 25.0percent, BED selectivity of 89.3percent, and BED yield of 22.3percent.

Full text of DOI:10.1039/d0nj00350f

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Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
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Influence of Nickel loading on the Structure and
Performance of Ni-Al2O3 Catalyst for
Hydrogenation of 1,4-Butynediol to produce 1,4-
butenediol
Received 00th January 20xx,
Accepted 00th January 20xx
Xianlong Gao, a Wenlong Mo a* , Fengyun Ma a and Xing Fan a
DOI: 10.1039/x0xx00000x
Combination with planetary ball-milling machine, Ni-Al2O3 catalyst
was prepared by mechanochemical method. Effect of Ni loading on
the crystal structure, reduction characteristics and hydrogenation
performance of Ni-Al2O3 catalyst was investigated. And the EDX,
XRD, H2-TPR, BET, TEM and NH3-TPD methods were introduced to
characterize the prepared catalysts. Results showed that the peak
intensity of the active component Ni from XRD characterization
increased with the increase of Ni content; the ratio of the measured
Ni content to the theoretical Ni content of MC25% and MC30%
samples exceeded 1.1; as the Ni addition up to 10%, the sample
performed uniform spherical particles, which could provide more
contact surfaces; the medium acid peak temperature shifts toward
the high temperature direction as the Ni loading increased from 5%
to 20%, and then (>20%) moves to the low temperature, and the
corresponding peak area firstly increased and then decreased,
presenting the same change of the number of acid centers on the
catalyst. Evaluation results showed that the MC20% catalyst
presented large specific surface area of 279 m2·g -1, showed well
hydrogenation performance, with BYD conversion of 25.0%, BED
selectivity of 89.3%, and BED yield of 22.3%.
Introduction
1,4-butenediol is an important intermediate material for chemical
industry, widely used as pesticides, pharmaceutical intermediate [1]
There are five methods to produce 1,4-butenediol, including 1,4-
butynediol (BYD) hydrogenation, 1,4-dichloro-2-butene hydrolysis,
1,3-butadiene method, 1,2-epoxy-3-butene method, 1,4-
.
diacetoxybutane method. And 1,4-butynediol (BYD) hydrogenation
is extremely extensive [2-3]. Ni-based catalyst was frequently applied
in many important catalytic reaction processes and exhibited
excellent cost effect. Industrial hydrogenation of 1,4-butynediol to
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produce 1,4-butenediol was researched for many years and the
used catalyst was usually nickel-based catalyst [4-6]
Material synthesis
.
Ni-Al2O3 catalyst was prepared by mechanochemical method.
Ni(NO3)2•6H2O (A.R., Shanghai Shanpu Chemical Co., Ltd.) and
Al(NO3)3•9H2O (A.R., Tianjin Zhiyuan Chemical Reagent Co.,
Ltd.) were weighted with stoichiometric ratio, and a certain
It was reported that the loading of the active component had a
great influence on the performance of the catalyst. Shamskar F R et
al. [7] prepared Ni-CeO2-Al2O3 catalyst by co-precipitation method,
and the physical properties of CeO2 modified samples were
investigated. Results showed that as the Ce loading increased from
1 wt.% to 5 wt.%, the crystal size of Nickle decreased from 7.1 nm
to 5.8 nm, and the specific surface area increased from 154 m2·g -1
to 178 m2·g -1, with high NiO dispersion. Badawy W A et al. [8]
signified the effect of Ni loading on the electrochemical behavior of
Cu-Ni alloys in chloride solutions. Results presented that the
corrosion rate of Cu-Ni alloy reduced in chloride solution with the
increasing of Ni content, and the alloy sample with Ni content of 65
wt.% exhibited low corrosion rate. Garbarino G et al. [9] have
explored the methanation performance of carbon dioxide on Ni-
Al2O3 catalyst under normal pressure. It was found that Ni metal
particles could be formed in situ with the increasing of Ni loading.
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amount of precipitant NH3•H2O (A.R., Tianjin Zhiyuan Chemical
Reagent Co., Ltd.) was added to the tank of the planetary ball-
milling machine (XQM-2, Changsha Tianchuang Powder
Technology Co. LTD, China). During precipitation process, the pH
value was adjusted at about 8.0 with NH3•H2O to get the sediment
Ni(OH)2. The catalyst was taken out and dried at 110
℃ for 12 h,
calcinated at 500 °C for 3 h. The reduction of the catalyst was
performed out of the autoclave. Before the activity tests, the
catalysts were reduced in a tubular furnace under pure H2
with the heating rate of 5 °C•min-1 up to 500 °C, and kept at
this temperature for 3 h, and then cooled under H2 flow. The
prepared catalysts were labeled as MCX according to the mass
fraction of the active component Ni of 5, 10, 15, 20, 25, 30 %
(X represents the mass fraction of the active component Ni, e.g.
ball milling of 5 %, named MC5%).
It was reported that mechanochemistry is a new method combining
mechanical motion with chemical reaction [10-12]. Studies have
shown that mechanochemical method was widely applied in the
preparation of materials because of its simple operation, easy
control and massive production. The method is a solvent-free or
low-solvent reaction and is thought of a green chemistry synthesis
method. However, its use, especially in the preparation of industrial
catalysts, was scarce. The method has nearly not been exploited in
the preparation of a catalyst for hydrogenating 1,4-butynediol to
1,4-butenediol. Compared with traditional preparation methods
(including precipitation method, impregnation method, spray
evaporation method and hot melting method), the
mechanochemical method avoided the cumbersome preparation
process of the impregnation method and the conditions of high-
efficiency filtration and washing equipment required for the
precipitation method [13]. Mo et al.[14] has employed planetary ball-
milling machine to prepare Ni-Al2O3 catalyst. Results showed that
the small particle size of 141 nm could be observed for RT60
catalyst prepared at a ball-milling time of 60 min, and the catalyst
exhibited well performance, with CO conversion and CH4 yield as
high as 87.9% and 74.3%, respectively.
Material Characterization
X-ray diffraction (XRD) analysis was carried out on a X-ray
diffraction (Rigaku D/Max-2500, Japan) using nickel filtered Cu
Ka (λ= 0.15406 nm) radiation. The scan rate, diffraction range,
o
o
o
tube voltage and tube current were 8 /min, from 5 to 85 ,
40 kV and 100 mA, respectively. Nitrogen adsorption-
desorption profiles at -196 °C were obtained by
a
Quantachrome Automated Gas Sorption apparatus
(Micromeritics ASAP 2020). X-ray energy dispersive (EDX)
analysis was carried out on LEO 1530VP spectrometer from
Germany with accelerating voltage of 20 kV, working distance
of 15 mm and acquisition time of 120 s. Scanning electron
microscopy (SEM) image was obtained on a Hitachi H-600
microscope with an accelerated voltage of 100 kV.
Transmission electron microscopy (TEM) micrograph was
obtained using a JEOL JEM-2100 election microscope operating
at 200 kV. Acidic properties of the catalysts were measured via
a temperature-programmed desorption of ammonia (NH3-TPD)
using a Quantachrome Chemisorb instrument. Temperature-
programmed reduction with H2 (H2-TPR) was carried out on an
automated chemisorption analyzer (chem-BET pulsar TPR/TPD,
Quantachrome).
In this work, the mechanochemical method is adopted to prepare
catalyst with different Ni loading, and the prepared catalyst was
used for the hydrogenation performance of 1,4-butynediol to
produce 1,4-butanediol. The catalysts were characterized by EDX,
XRD, H2-TPR, BET, TEM and NH3-TPD methods. And the effect of
different Ni contents on the structure and performance of Ni-Al2O3
catalyst was investigated.
Catalytic performances
BYD hydrogenation was conducted in a 50 mL high-pressure reactor
(Dalian Tongda reactor factory, CJF-605, China), and liquid phase
products were analyzed using a gas chromatography (GC-2014C,
Shimadzu instrument Co. Ltd, Japan). Fig.1 shows the schematic
setup of hydrogenation and product analysis system. The reduced
catalyst and BYD were mixed in the autoclave. The BYD was
hydrogenated at 110 °C under 4.0 MPa for 3 h, with stirring rate of
Experimental
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500 r/min and catalyst addition of 0.3 g. The feedstock was 30 mL
aqueous solution containing 35 wt.% 1,4-butynediol.
Table 1 The measured value of the Ni content on the catalyst surface
Measured/
Theoretical Ni
content/wt.%
Measured Ni
content/wt.%
Sample
Theoretical Ni
loading
0.994
1,4-butanediol, 1,4-butene glycol, 1,4-butynediol and
4-hydroxybutyral are the main substances in the catalytic
hydrogenation product of 1,4-butynediol, which were detected by
SH-Rtx-Wax capillary column. The performance of hydrogenation
catalyst is evaluated by BYD conversion, BED selectivity and yield,
which can be calculated by equation (1), (2) and (3), respectively.
Main reactions:
MC5%
MC10%
MC15%
MC20%
MC25%
MC30%
5.00
4.97
9.14
12.36
17.42
31.42
35.44
10.00
15.00
20.00
25.00
30.00
0.914
0.824
0.871
1.257
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1.181
catalyst. However, the ratio of the MC25% and MC30% samples
exceeded 1.1. It was presumed that the phenomenon of migration
of bulk NiO to the surface occurred during the calcination process
due to the addition of more Ni precursor, resulting in that the
surface Ni of the catalyst was enriched with more Ni species.
1,4-butynediol (3)
1,4-butene glycol (2)
1,4-butanediol (1)
1,4-butene glycol
Side reaction:
Figure 2 shows the SEM images of the catalysts after calcination at a
magnification of 50 000. It could be learned from the figure that the
MC5% sample was distributed in the form of massive particles, and
the size of each particle was different; as the loading of Ni over 10%,
the sample performed uniform spherical particles, which could
provide more contact surface; as the loading exceeded 25%, the
spherical particles presented small diameter, more densely
distributed, and even agglomerate. In addition, the size of the used
catalyst in the evaluation experiment was 40-60 mesh after
tabletting and screening.
HO-CH2-CH2-CH = CH-OH → HO-CH2-CH2-CH2-COH
1,4-butene glycol
4-hydroxybutyral (4)
Performance of the catalyst:
BYD conversion X (%) = 1-(C3/(C1+C2+C3+C4)) ×100
BED selectivity S (%) = C2/(C1+C2+C4) ×100
BED yield Y (%) = X×S×100
(1)
(2)
(3)
Ci represent molar percentage of the corresponding substance. i=1,
2, 3 and 4 represent components 1,4-butanediol, 1,4-butene glycol,
1,4-butynediol and 4-hydroxybutyral, respectively.
Fig. 2 SEM image of the catalyst after calcination
(a) MC5%; (b) MC10%; (c) MC15%; (d) MC20%; (e) MC25%;
(f) MC30%
Fig. 1 Scheme of the evaluation device for 1,4-butynediol
hydrogenation
Results and discussion
Textural characteristics
Figure 3 gives the XRD pattern of the catalysts after calcination. All
the catalysts present the same characteristic diffraction peaks of
Al2O3 at 2θ=37.3 °, 45.6 ° and 66.2 °, indicating that Al2O3 as a
support was not destroyed after loading with different Ni content.
It could also be discovered from the figure 3 that the characteristic
diffraction peak of NiO was not found in the catalyst as the Ni
content less than 15%, demonstrating that there might be
EDX element quantitative analysis was carried out for the prepared
catalysts, and the results are given in Table 1. It could be seen from
Table 1 that the ratio of the measured Ni content to the theoretical
Ni content of the surface active component of the MC10%, MC15%
and MC20% samples did not exceed 0.95. The reason might be that
the process of mechanical ball milling, drying and roasting might
cause the loss of active metal Ni during the preparation of the
amorphous NiO or very small NiO grain size which not be detected
by XRD. As Ni content over 20%, the gradual enhancement of the
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characteristic diffraction peak of NiO was found at 2θ=42.9 °, 63.5 °
and 75.2 °, meaning that the high Ni loading would lead to the
agglomerate of the active component precursor NiO.
reduction peak with high temperature (more than 500 °C). The first
type with reduction peak temperature at about 400 °C was ascribed
to the weak interaction between the active component and the
support. The area of α-NiO peak increased with the increasing of Ni
addition [15-16]. The second reduction peak would be assigned to β-
type with reduction temperature of about 650 °C, presenting the
strong interaction between the active component and the carrier
[17-18]. In general, the narrower the peak, the better the
homogeneity of the species. The better the dispersibility of the
active component after reduction, the more uniform of the particle
size of the active metal could be obtained. The wider the peak, the
worse the homogeneity of the species, and it might be the overlap
of the reduction peaks of several NiO species. In addition, the areas
of high-temperature reduction peaks gradually increases with the
increase of Ni content. The reduction peak area ratio of MC10%,
MC20% and MC30% samples is about 1:2:3, which is basically
consistent with the loading of active metal Ni. The β-type reduction
peak area is not as large as possible, and excessive active
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Fig.3 XRD pattern of the catalysts after calcination
Fig. 4 shows the XRD patterns of the prepared catalysts after
reduction. The characteristic peaks of NiO disappeared,
demonstrating that the catalyst has been successfully reduced and
could be used for hydrogenation of 1,4-butynediol. The
characteristic peak of Ni was not found in the samples MC5% and
MC10%, implying that the catalyst prepared by mechanochemical
method could achieve high dispersion at low Ni content. The
overlapping peaks of Ni and Al2O3 were detected in the samples
MC15% and MC20% at 2θ=45 °, while the characteristic peaks of Ni
were not found in other positions for the two catalysts,
demonstrating that 15% and 20% Ni addition might also achieve
better active components dispersion. The characteristic diffraction
peaks of the active component Ni were observed in the samples
MC25% and MC30% at 2θ=44.7 °, 52.0 °, 63.5 °, 75.2 °, signifying
that the active component was heavily crystallized and its
dispersion on the surface of the carrier was reduced as the Ni
loading higher than 25%.
component loading might be deactivated by Ni sintering or
agglomeration during high temperature or long reaction time.
Fig. 5 H2-TPR results of the calcinated samples
Figure 6 depicts the N2 adsorption-desorption isotherms (a) and
pore size distributions (b) of the prepared catalysts. All samples
presented similar trend of the N2 adsorption-desorption curves of
the catalysts at different milling time. According to the IUPAC
classification, the N2 adsorption-desorption isotherms of all the
samples were attributed to type IV. It could be seen from Fig. 6(a)
that the Ni content has little effect on the linear form of the N2
adsorption-desorption curve, while the adsorption-desorption
hysteresis loops increases again after a slight decrease. Figure 6(b)
is a BJH pore size distribution curve for the catalysts. As could be
seen from the Figure that the most probable pores of each sample
are concentrated around 58 nm.
Fig.4 XRD patterns of the reduced catalysts
Figure 5 shows the H2-TPR results of the catalysts. There are two
types of reduction peaks in the catalysts. The α type reduction peak
with low reduction temperature (less than 500 °C) and the β type
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the high temperature desorption zone (300-600 °C), corresponding
to the medium strong acid center [21-22]
.
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Comparing the MC5% and MC10% samples, the Ni loading has an
important effect on the catalyst surface acidity. The medium acid
peak area of MC10% is larger than MC5%, accounting for 62% of the
desorption peak area, which is of more strong acid centers. The
peak temperature of medium-strong acid moves from low
temperature to high temperature with the increasing of Ni loading,
and the peak temperature of NH3 desorption of MC20% is larger
than others, which is 463 °C. The medium acid peak temperature
reverts to the low temperature direction as increasing the Ni
loading, and the corresponding peak area also showed a trend of
increasing first and then decreasing, indicating that the number of
acid centers and acid amount of adsorbed ammonia firstly increase
and then decrease.
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Fig. 6 N2 adsorption-desorption isotherms of the catalysts
According to N2 adsorption-desorption isotherms, the specific
surface areas of the samples were calculated by BET equation, and
the pore volumes and average pore diameters were calculated by
BJH equation, as shown in Table 2. It could be seen from the table
that the specific surface area of all samples was 150-280 m2·g -1, and
decreases with the increasing of Ni content, indicating that the
active component enters the abundant internal pores of the
catalyst, and the surface area was reduced. The average pore
diameter was between 4.40 and 4.90 nm, which is inconsistent with
the result of the most probable pore size of about 60 nm in the N2
adsorption-desorption curve of Fig. 6(b). Because the pore structure
parameters were calculated from the microporous portion of the
material, and the results of the N2 physical adsorption showed only
the mesopores and macropores, the pore size distribution picture
cannot be anything but the pores above 10 nm, and no micropores
were included. MC25% and MC30% present similar specific surface
area, meaning that the excessive Ni addition (≥25 wt.%) easily leads
to the accumulation of active metal oxide (NiO) on the outer
surface of the catalyst, and the effect on its specific surface area has
not been obvious.
Fig. 7 NH3-TPD results of the calcinated samples
Figure 8 gives TEM results of the prepared Ni-Al2O3 catalysts after
reduction. According to Fig.8, the network structure emerged with
the increase of Ni loading. In addition, the active component Ni for
the ample MC5% catalyst was relatively dispersed in the form of
particles on the Al2O3 carrier; the sample MC10% displayed
obviously the mesh structure; the MC20%, MC25% and MC30%
samples presented a multi-layer superimposed morphology. The
surface of the MC20% sample was more dense, which is related to
its large specific surface area and moderate addition of active
component.
Table 2 Specific surface area, pore volume, average pore diameter of the
catalysts
Specific surface
Pore volumeb
(cm3·g -1)
0.38
Average pore
diameterc (nm)
4.85
Samples
areaa (m2·g -1)
278
MC5%
MC10%
MC15%
MC20%
MC25%
MC30%
210
186
178
154
0.32
0.29
0.40
0.38
4.40
4.53
4.45
4.72
150
0.37
4.76
aCalculated by BET (Brunauer-Emmett-Teller) equation; bBJH (Barret-Joyner-
Hallender) desorption average pore diameter; cBJH (Barret-Joyner-Hallender)
desorption pore volume
NH3-TPD patterns for different catalysts are shown in Figure 7.
Figure 7 presented that each sample has two distinct NH3
desorption peaks at around 180 °C and 450 °C. The former is
located in the low temperature desorption zone (100-300 °C),
corresponding to the weak acid center[19-20]; the latter is located in
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tetrahydrofuran (BULTHF) might also be formed by condensation
reaction. While it's more favorable for the side reactions with the
increase of Ni loading. The conversion of BYD of 25.0% and the
selectivity of BED of 89.3% have a huge impact on the subsequent
hydrogenation to produce BDO or separation and purification, and
the catalyst preparation or reaction conditions should be further
adjusted to increase the conversion of the reactants and the
selectivity of the desired product.
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Fig. 8 TEM images of the catalysts after reduction
(a) MC5%; (b) MC10%; (c) MC15%; (d) MC20%; (e) MC25%;
(f) MC30%
The activity results of the catalysts for BYD hydrogenation are
showed in Figure 9. It could be observed from the figure that the
BYD conversion of all the samples was between 12% and 27%,
indicating that the catalyst with different Ni content has great
influence on the hydrogenation activity of 1,4-butynediol in the
reaction system. The BYD conversion increased from 12.6% for MC5%
to 25.0% for MC20%. The above results indicated that the increase
of Ni content was beneficial to the improvement of the
hydrogenation performance of 1,4-butynediol, while it was not
conducive to the increase of BED selectivity. The conversion of BYD
for MC20%, MC25% and MC30% were not much different, all about
25.0%, indicating that the activity of the catalyst does not change
much as the Ni loading higher than 20 wt.%. The reason might be
that the addition amount of 20 wt.% is basically the complete
loading of the carrier Al2O3, and the active component would be
loaded in multiple layers as the Ni loading higher than 20%, and the
influence on the performance of the catalyst would not be obvious,
which is consistent with the XRD and SEM characterization results.
The excellent performance of MC20% might be related to its multi-
layer superimposed morphology, moderate addition of active
component and large specific surface area. Combined with XRD
characterization, the overlapping peak of Ni and Al2O3 was detected
in the catalyst at 2θ=45 °, which might lead to better Ni dispersion
and improve the hydrogenation activity of the catalyst.
Furthermore, the conversion of BYD reached to a maximum value
of 25.0% as the Ni content up to 20 wt.%, with BED selectivity of
89.3% and BED yield of 22.3%. The selectivity drop of BED might be
related to that the products from BYD hydrogenation are cis-2-
butene-1,4-diol (cis-BED) and trans-2-butene-1,4-diol (trans-BED).
There might be two pathways for the generation of by-products.
one of which is hydrogenation of cis-BED and trans-BED to obtain
1,4-butanediol (BAD). Another route acquires 4-hydroxybutanal
(HALD) via the hydrogenolysis of trans-BED. And HALD generates
hemiacetal 2-hydroxytetrahydrofuran (HTHF) via cyclization, while
2-(4-hydroxybutoxy)-tetrahydrofuran (HBOTHF) and 2-butyl
Fig.9 The conversion of BYD and selectivity and yield of BED of the
catalysts
Basing on previous reports [23-30] and current experimental results, a
possible reaction pathway is proposed in Figure 10. Initially, the
products from BYD hydrogenation are cis-2-butene-1,4-diol (cis-BED)
and trans-2-butene-1,4-diol (trans-BED). Thereinto, there are two
pathways for the generation of further products, one of which is
hydrogenation of cis-BED and trans-BED to obtain 1,4-butanediol
(BAD). Another route acquires 4-hydroxybutanal (HALD) via the
hydrogenolysis of trans-BED. HALD further generates hemiacetal 2-
hydroxytetrahydrofuran (HTHF) via cyclization, as like 2-(4-
hydroxybutoxy)-tetrahydrofuran
(HBOTHF)
and
2-butyl
tetrahydrofuran (BULTHF) formed by condensation reaction.
Figure 10 Proposed mechanism for hydrogenation of 1,4-butynediol
The enduranced catalysts were subjected to XRD characterization,
and the results are shown in Fig.11. The characteristic diffraction
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peak of the active component Ni still appears at 2θ=44.7 °, 52.0 °,
63.5 ° and 75.2 °, and the peak intensity and the semi-peak width
have not changed significantly, indicating that the active
component Ni is stable after the hydrogenation process. And no
sintering or agglomeration occurred compared with the fresh
catalysts.
BED 1,4-butene glycol
BET Brunner−Emmet−Teller
IUPAC International Union of Pure and Applied Chemistry
BJH Barret-Joyner-Halenda
L length, m
t time, s
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m quality, g
SBET specific surface area, m2·g -1
D diameter, nm
In addition, the Al2O3 diffraction peak positions was not changed
compared to Fig.4(b), indicating that the crystal structure of the
carrier was relatively stable in the 1,4-butynediol hydrogenation
process.
V volume per unit mass, mL·g-1
P pressure, Mpa
ν rotate speed, r/min
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Conclusions
Ni-Al2O3 catalyst was prepared by mechanochemical method. Effect
of Ni content on the structure of Ni-Al2O3 catalyst and 1,4-
butynediol hydrogenation performance was investigated. The
surface morphology, acidity and crystal structure of Ni-Al2O3
catalysts presented a significant difference with different Ni loading.
The MC20% sample exhibited a strong metal-support interaction
force due to the proper amount of active component loading, and
presented a large specific surface area and high dispersion, and
showed well catalytic performance with BYD conversion rate of
25.03%, BED selectivity of 89.34% and yield of 22.36%.
Conflicts of interest
There is no conflicts to declare.
Acknowledgements
This work was supported by the Xinjiang Uygur Autonomous Region
Key R&D Program (2017B02012) and Xinjiang University Natural
Science Foundation Project (BS160221).
References
XRD X-ray diffraction
SEM Scanning electron microscopy
TEM Transmission electron microscope
NH3-TPD NH3 temperature programmed desorption
EDX Energy dispersive X-ray
BYD 1,4-butynediol
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