Hydrazinylbenzenesulfonic Acid-Modified Nieuwland Catalyst for Acetylene Dimerization Reaction

Article abstract of DOI:10.1007/s10562-019-03088-9

Abstract: A novel Nieuwland catalytic system, containing 5?mol% of 4-hydrazinylbenzenesulfonic acid (S₈), was developed and exhibited an excellent catalytic performance and good stability in the acetylene dimerization reaction. The acetylene conversion reached 57.1%, while the selectivity of monovinylacetylene (MVA) was 75.1%. The yield of MVA was maintained at 42.9% under an acetylene gas hourly space velocity (GHSV) of 80?h^?1 at 80?°C, which was increased by 18.8% over the control Nieuwland catalytic system. The addition of S₈ increased the dissolution of CuCl in water, inhibited the polymer formation, and hindered the Cu⁺ loss during the reaction process, thus improving the activity and the long-term stability of the modified Nieuwland catalyst. Graphic Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-019-03088-9

Catalysis Letters
https://doi.org/10.1007/s10562-019-03088-9
Hydrazinylbenzenesulfonic Acid‑Modiꢀed Nieuwland Catalyst
for Acetylene Dimerization Reaction
1
1
1
1
2
1
Qixia Zhang · Congcong Li · Juan Luo · Jianwei Xie · Jinli Zhang · Bin Dai
Received: 15 October 2019 / Accepted: 21 December 2019
©
Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
A novel Nieuwland catalytic system, containing 5 mol% of 4-hydrazinylbenzenesulfonic acid (S ), was developed and
8
exhibited an excellent catalytic performance and good stability in the acetylene dimerization reaction. The acetylene con-
version reached 57.1%, while the selectivity of monovinylacetylene (MVA) was 75.1%. The yield of MVA was maintained
−
1
at 42.9% under an acetylene gas hourly space velocity (GHSV) of 80 h at 80 °C, which was increased by 18.8% over the
control Nieuwland catalytic system. The addition of S increased the dissolution of CuCl in water, inhibited the polymer
8
+
formation, and hindered the Cu loss during the reaction process, thus improving the activity and the long-term stability of
the modiꢀed Nieuwland catalyst.
Graphic Abstract
Keywords Acetylene dimerization · Monovinylacetylene · Modiꢀed Nieuwland catalyst · Cu-based catalyst
1
Introduction
Chloroprene rubber (CR) is a synthetic polymer rubber
material with broad application prospects in various ꢀelds
of production and life. Catalytic dimerization of acetylene
over the Nieuwland catalysts (NC), which is performed with
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-019-03088-9) contains
supplementary material, which is available to authorized users.
the dissolution of CuCl, NH Cl (or KCl) and HCl in water
4
*
Jianwei Xie
to produce monovinylacetylene (MVA) [1, 2], is an impor-
tant industrial process of the acetylene-based CR produc-
tion [3–5]. Despite years of eꢁorts in the development and
improvement of the NC, obstacles still exist, such as the low
acetylene conversion and the poor MVA yield.
cesxjw@foxmail.com
1
School of Chemistry and Chemical Engineering/Key
Laboratory for Green Processing of Chemical Engineering
of Xinjiang Bingtuan, Shihezi University, North 4th Road,
Shihezi 832003, China
Recently, second-metal-added [6–9] or catalyst-ligand
modiꢀcation methods [10–13] that enhance the catalytic
2
School of Chemical Engineering and Technology, Tianjin
University, Tianjin 300072, China
Vol.:(0
1
123456789)
3

Q. Zhang et al.
eꢂciency and selectivity of the acetylene dimerization have
been suggested. For example, Liu et al. have reported the
sulfonic acid derivatives were applied, and their eꢂcacy
was evaluated based on the resulting acetylene conversion
and the MVA selectivity. Moreover, the eꢁects of the sul-
fonic acids on the catalyst structure and its active compo-
nents were examined through various techniques, including
transmission electron microscopy (TEM), X-ray diꢁrac-
tion (XRD), Fourier-transform infrared spectroscopy (FT-
IR), thermogravimetry/derivative thermogravimetry (TG/
DTG), temperature programed desorption-mass spectrom-
etry (TPD-MS), inductively coupled plasma spectroscopy
(ICP), and X-ray photoelectron spectroscopy (XPS).
addition of LaCl in NC can inhibit the formation of divi-
3
nylacetylene (DVA) and polymer, and improve selectivity
of MVA. The ratio of MVA/DVA in the gas phase product
increased from 6 to 19, and the selectivity of MVA increased
from 80 to 95% at 80 °C [7]. Chen et al. have reported the
eꢁect of substituted acetic acid as a catalyst promoter of
the acetylene dimerization reaction in NC. The addition of
thioglycolic acid ligands in NC changed the mechanism of
acetylene dimerization and the selectivity of acetaldehyde
reached 99.7% [10]. In 2016, Liu found that the addition of
2
+
+
Cu in anhydrous NC inhibited the oxidation of Cu into
2
+
Cu and enhanced the catalytic performance and lifetime.
It can achieve 40% conversion of acetylene with a molar
2
Experimental
+
2+
ratio of Cu to Cu of 2:1 [6]. Recently, it was proven that
the addition of nitrogen-containing carboxylic acids [11,
2.1 Materials
1
2] increases the conversion of acetylene, the selectivity of
4
-Aminobenzenesulfonic acid (S ), 2-(bis(2-hydroxyethyl)
1
MVA and the catalyst lifetime because of their ability to
amino)ethane-1-sulfonic acid (S ), 2-((1,3-dihydroxy-
+
2
strongly coordinate and stabilize the Cu ions. The yield of
2
-(hydroxymethyl)propan-2-yl)amino)ethane-1-sulfonic acid
MVA in NC containing N-(2-acetamido) iminodiacetic acid
was 17.1% higher than that of NC [12].
(
(
(
S ), 2,2′-(piperazine-1,4-diyl) bis(ethane-1-sulfonic acid)
3
S ), sulfamic acid (S ), 5-aminonaphthalene-1-sulfonic acid
4
5
Sulfonic acids, a class of organic compounds containing
S ), benzenesulfonic acid (S ), 4-hydrazinylbenzenesulfonic
6
7
the –SO OH group, are employed as catalysts in various
2
acid (S ), CuCl (99%), and NH Cl (purity ≥ 99.5%), were
8
4
reactions, while they are used as additives for the modiꢀca-
tion of known catalytic systems [14–17]. Lately, Amoozadeh
et al. have reported several sulfonic acid modiꢀed catalysts.
purchased from Adamas-beta and directly used without
puriꢀcation.
The catalyst used as control was labeled as NC and the
catalysts containing S additive were denoted as S -NC,
Particularly, in 2015, they revealed nano-WO -supported
3
x
x
sulfonic acid as an eꢂcient and highly recyclable heteroge-
neous nano-catalyst for organic reactions [14]. Meanwhile,
nano-γ-Fe O –SO H, a nanomagnetic-supported sulfonic
where x is the ligand number. The amount of each S was
x
calculated in mole, based on the CuCl. The structures of the
eight sulfuric acid ligands are shown in Table 1.
2
3
3
acid, was developed for the Hantzsch condensation [15]. In
2
016, nano-ZrO –SO H was disclosed with several advan-
2 3
tages such as low cost, low toxicity, ease of preparation,
good stability, high reusability, and operational simplicity
2.2 Catalyst Preparation
[
17]. They suggested that nano-MO –SO H (M=W, Fe or
The NC was prepared by dissolving 5.35 g (0.1 mol) of
X
3
Zr) acts as a Lewis and a Brønsted acid simultaneously (sul-
NH Cl and 9.9 g (0.1 mol) of CuCl in 10 ml of deionized
4
fonic acids acts as the Brønsted acid and nano-MO acts
water at 80 °C, a reddish-brown homogeneous mixture was
X
as Lewis acid). Hydrogen bonds provided by Brønsted acid
obtained. Then, a certain mole amount of S was added to
x
initiates the catalytic process. Compared with nano-MO ,
the NC, which varied among the eight applied ligands, based
on the CuCl quantity.
X
nano-MO –SO H has better catalytic activity, good stability
X
3
and high reusability. In the study of acetylene dimerization,
Deng et al. found that the catalyst activity was improved
by adding hydrochloric acid to control the pH [18]. We
previously found that the addition of nitrogen-containing
carboxylic acids increases the MVA yield and the catalyst
lifetime because of strong coordination between ligands
Before the reaction, the reactor was purged with nitrogen
to eliminate the air. Then, 5.35 g of NH Cl and 10 mL of
4
deionized water were added at 80 °C. After 10 min of stir-
ring, 9.9 g of CuCl and a certain amount of each ligand,
which varied among the distinct sulfonic acids, were added
in the above solution under nitrogen atmosphere. Stirring
continued for at least 15 min, until the solids had completely
dissolved, and the modiꢀed catalyst was obtained.
+
and Cu [12]. These interesting results inspired us to study
whether the sulfonic acids can improve NC during acetylene
dimerization.
The fresh NC and S -NC, and the used NC and S -NC
x
8
This study describes the development of a novel modiꢀed
Nieuwland catalyst using sulfonic acids and its application
on the acetylene dimerization reaction. A series of distinct
were left in the refrigerator at 3 °C for 6 h (NC and S -NC
8
after 7 h of reaction was deꢀned as used NC and S -NC).
8
Then they were ꢀltered from the catalytic solution, washed
1
3

Hydrazinylbenzenesulfonic Acid‑Modiꢀed Nieuwland Catalyst for Acetylene Dimerization…
Table 1 Additive and catalytic performance of S -NC–S -NC in acetylene dimerization
1
8
Additive
Acetylene conversion (MVA selectivity)a
0.6 h 1.6 h 3 h
25.0% (69.6%) 31.3% (68.9) 33.7% (68.2%) 32.2% (67.5%) 31.8% (68.7%)
Name (number)
Structure
None
4.6 h
6 h
None
4
-Aminobenzenesulfonic acid (S1)
31.0% (72.2%) 34.0% (72.3%) 38.8% (72.8%) 40.8% (72.2%) 41.2% (71.5%)
2
-(bis(2-hydroxyethyl)amino)ethane-
34.9% (68.1%) 39.2% (71.4%) 44.0% (72.1%) 43.6% (72.5%) 42.3% (72.1%)
1
-sulfonic acid (S )
2
2
2
-((1,3-dihydroxy-2-(hydroxymethyl)
propan-2-yl)amino)ethane-1-sulfonic
39.3% (75.4%) 39.5% (73.7%) 44.2% (74.0%) 45.9% (72.0%) 44.6% (71.8%)
acid (S )
3
,2′-(piperazine-1,4-diyl) bis(ethane-
47.2% (72.2%) 46.1% (73.3%) 47.7% (74.6%) 45.0% (75.3%) 42.3% (75.0%)
34.7% (69.0%) 34.4% (68.7%) 37.1% (70.1%) 39.0% (71.2%) 38.2% (71.4%)
33.9% (78.8%) 34.0% (77.6%) 36.7% (76.6%) 37.1% (76.2%) 37.2% (76.4%)
1
-sulfonic acid) (S )
4
sulfamic acid (S5)
5
-Aminonaphthalene-1-sulfonic acid
S )
(
6
Benzenesulfonic acid (S7)
-Hydrazinylbenzenesulfonic acid (S8)
22.3% (70.1%) 24.7% (67.3%) 25.4% (64.1%) 25.1% (62.0%) 25.5% (61.4%)
52.7% (71.5%) 50.4% (72.2%) 53.0% (73.6%) 54.9% (73.9%) 53.7% (73.4%)
4
−1
Reaction conditions: Temperature (T)=80 °C, GHSV(C H )=105 h , S :CuCl=0.045:1
2
2
x
a
Whole data was shown in Fig. S2
2.4 Determination of the Catalytic Performance
The criteria of the catalytic performance, namely the conver-
sion of acetylene (X) and the selectivity of MVA (S) were
deꢀned by the following equations, respectively.
ꢀ2
+ ꢀ + 2ꢀ + 2ꢀ + 3ꢀ
5
+ 2ꢀ + 2ꢀ + 3ꢀ
3 4 5
X =
× 100%
ꢀ1
2
3
4
Scheme 1 Gas phase products of the acetylene dimerization
2
ꢀ3
+ 2ꢀ + 2ꢀ + 3ꢀ
5
S =
× 100%
with water and dried in a vacuum oven at 55 °C to obtain a
solid catalyst, ready for characterization.
ꢀ2
3
4
where λ , λ , λ , λ , and λ are the volume fractions of
1
2
3
4
5
the gas products C H , CH CHO, MVA, CP, and DVA,
2
2
3
respectively.
2.3 Acetylene Dimerization Reaction
The modiꢀed catalysts were tested in a self-designed bubble
column reactor (length: 400 mm, outer diameter: 40 mm,
inner diameter: 10 mm), which was used for the acetylene
dimerization reaction (Fig. S1). Pure acetylene was then
poured into the reactor. Immediately afterwards, the gas
phase products (Scheme 1) were analyzed on-line by GC-
2
.5 Methods for Catalyst Characterization
The pH of the catalyst was measured using a pen-like pH
meter (Sanxin PHB-3). The FT-IR spectra of the samples
were obtained using the Bruker Vertex70 FT-IR spectrome-
−1
ter (wavenumber range of 500–4000 cm ). TG/DTG experi-
ments were performed using the NETZSCH STA 449 F3
2
014C gas chromatograph (Shimadzu, GDX-301 and a ꢃame
ionization detector).
1
3

Q. Zhang et al.
Jupiter, under nitrogen atmosphere. The temperature ranged
0 °C–900 °C at an increasing rate of 10 °C/min. XRD pat-
conversion and selectivity of MVA. Therefore, we next are
5
focus on the eꢁect of S -NC in the present transformation.
8
terns were collected using a Bruker D8 advanced X-ray dif-
fractometer (10°–90° in 2θ). XPS data were recorded using
a Kratos AXIS Ultra DLD spectrometer with a monochro-
matized Al-Kα X-ray source, the deconvolution of the XPS
peaks are obtained by the XPSPEAK41 software to pro-
cess XPS data. TEM images were recorded on a JEM2100F
TEM instrument. The Micromeritic ASAP 2720 was used to
obtain the TPD-MS experiments. The absolute content of Cu
in all catalysts was determined using the ICP-AES technique
The loading of S was then investigated, and the results
8
were shown in Fig. 1 (whole data in Fig. S3 and Table S1).
Figure 1 shows relationship of C H conversion after 0.6 h
2
2
and 4 h to the amount of S additive. It suggests that increas-
8
ing the additive increases the initial reaction rate, but the
additive with higher content than 5% causes decrease of the
C H conversion. Too much additive may cause damage of
2
2
the catalyst. Studies on reaction temperatures have shown
that the most suitable temperature is 80 °C (Fig. S4 and
Table S2). Investigation of the acetylene GHSV indicated
(
710ES, Varian, USA).
−
1
the value of 80 h as the most suitable rate (Fig. S5 and
Table S3). Furthermore, the results of long-term stability
3
Results and Discussion
experiments demonstrated that S -NC exhibited an excellent
8
acetylene conversion, MVA selectivity, and stability over a
24-hour period (Fig. 2).
3
.1 Catalytic Activity of NC and S ‑NC
x
Previously, we have reported that the addition of nitro-
gen-containing carboxylic acids [11, 12] can signiꢀcantly
enhance the catalytic performance of NC in acetylene
dimerization. Inspired by these results, we initially tested
the eꢁect of four nitrogen-containing sulfonic acid additives,
3.2 Catalyst Analysis
3.2.1 Eꢁect of the S Additive on the pH and Appearance
8
of the Catalysts
i.e., the 4-aminobenzene sulfonic acid (S ), aliphatic chain
Considering that the addition of the ligand S has a great
1
8
+
nitrogen-containing sulfonic acids (S and S ), and a nitro-
inꢃuence on the reaction activity and that Cu is the main
2
3
gen-containing heterocyclic sulfonic acid (S ). The results
catalytic component of the acetylene dimerization reaction,
4
of these experiments are presented in Table 1. All four addi-
tives exhibited higher acetylene conversion (>40.0%) and
MVA selectivity (>70.0%) than the control NC, while the
catalytic activity order was S -NC > S -NC > S -NC > S -
we characterized the fresh NC, S -NC and used NC S -
8
8
NC catalysts investigating their structure and coordination
ability.
Deng et al. stated that the pH value of the catalyst solu-
tion was adjusted to preserve a higher catalytic activity [18].
4
3
2
1
NC>NC under the same reaction conditions.
We then screened the performance of alternative, includ-
As shown in Table 2, S -NC possessed a lower initial pH
8
ing aryl substituted sulfonic acids (S –S ) as additives for
5
8
the investigated transformation (Table 1). Compared to
other nitrogen-containing sulfonic acids, sulfamic acid (S )
5
displayed relatively lower catalytic activity, revealing that
the phenyl group is beneꢀcial for the additive’s eꢂciency.
This was further conꢀrmed by the replacement of the phe-
nyl group with naphthalene (S ), which led to a similar
6
decreased catalytic activity. It is noteworthy that the addi-
tive without amino group (S ) provided the worst activity
7
among the present additives, suggesting that both the acidity
of the sulfonic group and the coordination capacity of the
amino group are essential for the catalytic activity. Replace-
ment of the NH group with the NHNH moiety resulted
2
2
in the S -modiꢀed NC (S -NC), which exhibited the high-
8
8
est average catalytic activity, with 53.0% of acetylene con-
version, 72.9% of MVA selectivity, 38.63% of MVA yield,
and satisfying stability. In addition, the reaction without an
additive requires more than 2 h before reaching the highest
acetylene conversion, but most of the additives forms the
Fig. 1 Eꢁect of the S quantity on the acetylene dimerization. The
8
production highest performance within 1 h. In summary, S
8
whole data was shown in Fig. S3 and Table S1. Reaction conditions:
−1
is the best additive among the examined, and resulted in high
T=80 °C, GHSV(C H )=105 h
2 2
1
3

Hydrazinylbenzenesulfonic Acid‑Modiꢀed Nieuwland Catalyst for Acetylene Dimerization…
Fig. 2 Lifetime testing of NC and S -NC. a Acetylene conversion and b MVA selectivity in acetylene dimerization over S -NC. Reaction condi-
8
8
−1
tions: T=80 °C, GHSV(C H )=80 h , S : CuCl=0.05:1
2
2
8
Table 2 The pH of the NC and
Sample
pH
0 h
S -NC at diꢁerent times during
8
the acetylene dimerization
reaction
1 h
2 h
3 h
4 h
5 h
6 h
7 h
NC
S8-NC
1.1
0.8
1.1
0.8
1.2
1.0
1.1
1.0
1.2
1.2
1.3
1.2
1.3
1.3
1.3
1.2
value, and over time the pH values of both catalytic systems
indicated that the pH value is not a major activity index for
the currently investigated catalyst.
remained almost similar. This because the S is an acidic
8
amphoteric compound, which can reduce the initial pH
Figure 3 depicts the reactor at diꢁerent reaction times. It
value of S -NC solution. However, in the reaction solution,
is clearly that the amount of precipitate was greater when
8
+
the acidic environment will inhibit the ionization of -SO H
NC was applied and consisted of the active Cu , C H ,
3
2
2
group and lead to both catalytic systems remained almost
and NH species [19]. In contrast, no obvious precipitate
3
similar after the reaction time is longer than 2 h. The results
was observed using S -NC, explaining the higher catalytic
8
Fig. 3 Pictures of the bubble column reactor at diꢁerent times during the reaction
1
3

Q. Zhang et al.
Fig. 4 TG/DTG thermograms a Fresh NC, b Fresh S -NC
8
Table 3 The crystals’ weight loss rates of the fresh NC and S -NC
8
catalysts
Catalysts
First stage (%)
Second stage Third stage (%)
%)
(
Fresh NC
2.2
1.0
34.1
37.5
63.6
61.5
Fresh S -NC
8
performance and stability of S -NC compared to the control
8
NC.
3.2.2 Catalysts Composition
Figure 4 shows the TG/DTG thermograms of the fresh NC
Fig. 5 XRD patterns of fresh and used catalysts
and fresh S -NC catalysts. It is noticed that the weight loss
8
of the catalytic system took place in the temperature ranges
9
0 °C–180 °C, 200 °C–430 °C and 460 °C–710 °C, and
diꢁraction peaks of CuCl were sharp and strong and no
impurity peaks were found. Obviously, the diꢁraction peaks
of the Cu (111) in used NC were less intense than in fresh
NC. The diꢁraction peak of Cu (111) was weakened, prob-
Table 3 shows the weight loss rates. The ꢀrst stage of weight
loss began at 90 °C for both catalysts, which was mainly due
to the quality loss of crystal water [11, 12]. In the case of
+
fresh NC, the second stage included the loss of NH (relative
ably due to the reduction or oxidation of Cu [20, 21]. The
3
molecular mass=17), which was also conꢀrmed by TPD-
addition of S did not change the diꢁraction peak of the Cu
8
MS (Fig. S6). But for fresh S -NC, the second stage had
(111) after the reaction, indicating that S inhibited the loss
8
8
a diꢁerence of 3.4%, due to the weight loss of the ligand,
of Cu. These results were also supported by the ICP analysis.
corresponding to the mass ratio of the S . The ꢀnal stage of
TEM and HRTEM images of fresh and used NC and fresh
8
weight loss included the loss of CuCl.
and used S -NC are shown in Fig. S7. Some irregular forma-
8
tions that can be observed in Fig. S7a are attributed to Cu
3
.2.3 Eꢁect of the S Additive on the Micromorphology
crystals, while in the case of the fresh S -NC, several black
8
8
of the Catalyst
spheres are detected in the TEM photo (Fig. S7c). Inter-
estingly, it can be concluded that the active Cu component
In order to elucidate the crystal structure of Cu in the cata-
lyst, we calcined fresh and used catalysts in a tube furnace
might exist in a spherical form in the fresh S -NC. As is
8
shown in Fig. S7 e, f, g, and h, it can be found that the high
crystallinity and the CuCl single-crystal. Typical d-spacing
of 0.31 nm and 0.26 nm corresponded to the (111) and (200)
under N atmosphere at 450 °C for 0.5 h. Figure 5 shows
2
the obtained XRD patterns of fresh and used catalysts. The
1
3

Hydrazinylbenzenesulfonic Acid‑Modiꢀed Nieuwland Catalyst for Acetylene Dimerization…
planes of the CuCl crystal, respectively. Many CuCl (200)
catalyst. Fig. S8b shows the FT-IR spectra of the fresh NC,
crystal faces (d=0.26 nm) appear in fresh and used S -NC.
S -NC, S -NC and S -NC, indicate that eꢁect of N-phenyl-
1 7 8
8
sulfonic (N=amino, none and hydrazine, respectively) for
the catalysts. No obvious peaks of N–H vibrational bond
3.2.4 Eꢁect of the Additives on the Catalysts’ Functional
Groups
appear in the fresh S -NC. Meanwhile, the larger peaks of
7
N–H vibrational bond in the fresh S -NC than other cata-
8
Figure 6 shows the FT-IR spectra recorded to determine
lysts, which could be attributed to the existence of hydrazino
group. Combined with the results of the catalytic activity,
we can see that phenyl and hydrazino group play a vital role
the functional groups of the fresh NC, S -NC catalysts and
8
−
1
the pure S ligand. The strong bands at 3442.94 cm and
8
−
1
1
596.50 cm of fresh NC corresponded to the vibration
in highest catalytic activity of the S -NC among the modi-
8
region of N–H bonds [11, 12, 22], which belong to NH . The
ꢀed catalysts.
3
−
1
strong bands at 3164.52 cm corresponded to O–H groups,
which correspond to chemisorbed water [23]. In case of the
3.2.5 Valence Changes of the Active Species
XPS analysis was carried out to investigate the chemical
fresh S -NC, the vibration region of N–H bonds blue-shifted
8
−1
by approximately 0.59 cm and increased in size compared
−
1
+
to fresh NC, because the NH–NH group (at 3431.63 cm )
state and distribution of Cu species in the catalysts. Cu
2
of the ligand and Cu exists weak bonding action. Moreover,
is the main catalytic component in the acetylene dimeriza-
tion and loss of this active component occurs in the reaction
process with the formation of precipitate [25]. As shown in
Fig. 7 and Table 4, peaks at 932.13 eV and 933.66 eV repre-
the strong band of the O–H groups blue-shifted by approxi-
−
1
mately 5.3 cm , indicating that the O–H groups of S coor-
8
dinate with Cu ions [24]. Therefore, it is concluded that the
+
2+
S is present in fresh S -NC and coordinates with Cu ions.
sented Cu and Cu , respectively [11, 12]. In the fresh S -
8
8
8
+
A portion of the modiꢀed catalysts were also character-
NC, the peak position of Cu was shifted (−0.35 eV) due to
+
ized by FT-IR to further explore the eꢁect of functional
groups of ligands on the catalysts. Fig. S8a shows the FT-IR
spectra of the fresh NC, S -NC, S -NC and S -NC, which
the interaction between the ligand S and Cu , which leads
8
+
to electron transfer from the ligand to the Cu and increases
+
the electron cloud density of Cu . This also demonstrated
1
5
6
illustrate the eꢁect of amino-R-sulfonic (R=phenyl, none
and naphthalene, respectively) for the catalysts. The obvi-
ous diꢁerence is that the peak of the N–H vibrational bond
the coordination ability between the ligand and the active
2
+
component (Cu). The content of Cu in fresh S -NC was
8
2
+
lower than that in fresh NC, while the Cu content of the
only appears in the FT-IR spectra of the fresh S -NC. It is
used NC and S -NC was 37.24% and 25.97%, respectively.
1
8
inferred that the existence of benzene is beneꢀcial to the
Additionally, the metal ion content of Cu in the used NC
and S -NC was 34.97% and 38.79%, respectively, while it
8
is observed that the Cu loss in NC was twice than that of
S -NC. These results, along with the pictures of the bubble
8
column reactor (Fig. 3), prove that the addition of S inhib-
8
ited the polymer formation, which in turn inhibited the loss
+
of the active component (Cu ).
4
Conclusions
The activity of the Nieuwland catalysts is generally hindered
by deactivation that occurs during the reaction due to the
high polymerization or oxidation of the active component,
+
Cu . In this study, 4-hydrazinylbenzenesulfonic acid (S )
8
was introduced as a stabilizer in the NC, and the S -NC
8
catalytic system was studied in the context of the acetylene
dimerization reaction. The catalytic system containing 5%
S exhibited excellent catalytic performance and good sta-
8
bility. The yield of MVA was maintained at 42.9% at 80 °C,
−
1
with an acetylene GHSV of 80 h , which was increased by
1
8.8% over the control catalytic system. Moreover, the cata-
lyst characterization proved that the addition of S increased
Fig. 6 FT-IR spectra of the fresh NC, fresh S -NC and the pure S
8
8
8
ligand
the dissolution of CuCl in water, while it inhibited the
1
3

Q. Zhang et al.
Fig. 7 a XPS spectra of the
heating product of the catalysts
for Cu 2p; b XPS spectra of
Cu 2p 3/2 of the fresh and used
catalysts
Table 4 The relative content and binding energy of Cu+ and Cu2+ of
3. White WC (2007) Chem Biol Interact 166:10–14
4. Ismail H, Leong H (2001) Polym Test 20:509–516
the fresh and used catalysts, determined by XPS and ICP
5. Carothers WH, Williams I, Collins AM et al (1931) J Am Chem Soc
Sample
Area% (Cu)a
Cu% (Metal ion Cu loss (%)
5
3:4203–4225
b
content)
Cu+
Cu2+
6.
Liu H, Xie J, Liu P et al (2016) Catalysts 6:120–131
7
8
9
.
.
.
Liu Z, Yu Y, Du J et al (2014) CIESC J 65:1260–1266 (in Chinese)
Lu J, Xie J, Liu H et al (2014) Asian J Chem 26:8211–8214
Lu J, Liu H, Xie J et al (2014) J Shihezi Univ (Nat Sci Ed) 32:213–
Fresh NC
Used NC
72.48
62.76
76.89
74.03
27.52
37.24
23.11
25.97
42.08
34.97
41.98
38.79
16.90
7.60
2
17 (in Chinese)
Fresh S -NC
8
10. Lu J, Liu H, Xie J et al (2015) Chem Eng 43:60–64 (in Chinese)
Used S -NC
11. You Y, Luo J, Xie J et al (2017) Catalysts 7:394–404
8
1
2. You Y, Luo J, Xie J et al (2018) Catalysts 8:337–347
a
Determined by XPS
Determined by ICP
13. Chen R, Deng G, Mu R et al (1995) Chin J Inorg Chem 11:89–92
b
(in Chinese)
1
4. Amoozadeh A, Rahmani S (2015) J Mol Catal A: Chem 396:96–107
5. Otokesh S, Koukabi N, Kolvari E et al (2015) S Afr J Chem
1
68:15–20
polymer formation and the Cu loss that usually take place
during the acetylene dimerization. Thereby, the addition of
1
6. Amoozadeh A, Golian S, Rahmani S (2015) RSC Adv
5:45974–45982
S improves the activity and the long-term stability of NC
17. Amoozadeh A, Rahmani S, Bitaraf M et al (2016) New J Chem
40:770–780
8
catalysts, providing a powerful platform for further research
of high-eꢂcient catalysts.
1
8. Deng G, Mu R, Liu Z (1986) China Syn Rubber Ind 9:90–93 (in
Chinese)
1
9. Liu J, Zuo Y, Han M et al (2012) J Nat Gas Chem 21:495–500
0. Zheng H, Ren J, Zhou Y et al (2011) J Fuel Chem Technol
Acknowledgements We acknowledge the National Natural Science
Foundation of China (Nos. 21776179 and 21463021) for their ꢀnan-
cial support.
2
39:282–286
2
1. Xiao Z, Wang X, Xiu J et al (2014) Catal Today 234:200–207
2. Poignant F, Saussey J, Lavalley J et al (1996) Catal Today 29:93–97
2
Compliance with Ethical Standards
23. Biniak S, Pakuła M, Szymański G et al (1999) Langmuir
1
5:6117–6122
4. Ramli R, Khan MMR, Yunus RM et al (2014) Adv Nanoparticles
3:65–71
5. Tachiyama T, Yoshida M, Aoyagi T et al (2008) Chem Lett 37:38–39
2
2
Conflict of interest There are no conꢃict to declare.
0
References
Publisher’s Note Springer Nature remains neutral with regard to
1
.
.
Nieuwland JA, Calcott WS, Downing FB et al (1931) J Am Chem
Soc 53:4197–4202
jurisdictional claims in published maps and institutional aꢂliations.
2
Nishiwaki K, Kobayashi M, Takeuchi T et al (2001) J Mol Catal A:
Chem 175:73–81
1
3