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Ethylene Oligomerization into Linear α‑Olefins Catalyzed by VSB‑5

without Alkyl-Aluminum Cocatalysts
Cong Wang, Gang Li,* Zheng Huang, and Anfeng Peng
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ABSTRACT: The cumbersome air isolation process is one of the

main constraints in the development of linear α-olefins prepared by
ethylene oligomerization. An effective way to solve this problem is
to eliminate the use of an alkyl-aluminum cocatalyst. Herein, two
forms of Versailles/Santa Barbara-5 (VSB-5) (VSB-5-H3PO4 and
VSB-5-NaH2PO2) are prepared and used as heterogeneous
catalysts in ethylene oligomerization in the presence of LiAlH4 as
a cocatalyst. Compared to other Ni-MOFs and Ni silica−aluminate
catalysts, VSB-5s maintain a wider distribution of Linear α-olefin
(LAO) products at relatively high activity. In the reuse test of the
catalyst, the Al species from LiAlH4 cover the surface of the catalyst
and decrease its activity, which could be removed by acid
treatment. In situ IR studies show that active centers for ethylene
oligomerization may form in VSB-5 assisted by LiAlH4. In addition, a Cossee−Arlman-type mechanism is proposed.

1. INTRODUCTION oligomerization activity and LAO product selectivity can be

Linear α-olefins (LAOs) are seen as the key “building block” achieved at room temperature, but the catalyst must be
intermediates for the synthesis of valuable products, i.e., linear activated under extremely anhydrous and oxygen-free con-
low-density polyethylene (LLDPE, 1-C4, 1-C6, and 1-C8), ditions (e.g., in a glovebox filled with high-purity N2) by
high-density polyethylene (HDPE, 1-C4, 1-C6, and 1-C8), addition of an alkyl-aluminum cocatalyst to create Ni−H or
synthetic lubricants (1-C8 and 1-C10), plasticizer alcohol (1-C6, Ni-alkyl centers.4 These active centers are key to driving the
1-C8, and 1-C10), and lubricant additives (1-C10 and 1-C12).1−4 reaction, but a vast majority of the Ni-MOF catalysts are
Currently, oligomerization of ethylene is the prevalent method unable to generate them autonomously.15,16 Moreover, the
for the synthesis of LAOs, due to the dramatic increase in entire catalytic process is very complicated and these catalysts
ethylene production.5,6 Benefiting from the advantages of the are more inclined to catalyze dimerization.18,22,28 The second
homogeneous system, such as high activity and selectivity, group of catalysts is the materials based on silica aluminates,
well-defined reactive centers, and established reaction mech- which produce Ni active centers through postsynthesis
anisms, ethylene oligomerization is still catalyzed by homoge- modification,29,30 in situ incorporation,31,32 and ion ex-
neous transition metal catalysts in existing industrial change.25,33,34 The carriers of these catalysts are themselves
processes.7 However, such catalysts still commonly suffer catalytically active.35,36 At a certain temperature, olefinic
from the complexity of the catalytic process and the inability to substances are adsorbed on their Brønsted acid sites through
reuse the catalysts. In light of this, different heterogeneous protonation and deprotonation, and then, the reaction occurs.
catalytic systems, such as the Cr-based catalyst,8−10 CoO The addition of nickel species, however, will generate linear
catalyst,11 Fe-MOF catalyst,12 and other transition metal butenes mainly in the prereaction period when the conversion
catalysts,13,14 were explored in this reaction. Among them, of ethylene is low; thus, more LAO products are obtained. As
nickel-based catalysts have emerged as the primary focus of the ethylene conversion rate increases, there is more
research interest, due to its broad range of metal sources, adsorption of ethylene onto the catalyst surface so that the
gentle reaction conditions, and high reaction activity.15−17
Combined with previous reports, there are two major types
of heterogeneous catalysts based on nickel that are used in Received: April 15, 2024
ethylene oligomerization. One category is metal−organic Revised: July 3, 2024
frameworks (MOFs), which are prepared in a variety of Accepted: July 5, 2024
ways, such as heat treatment,18,19 ion exchange,20,21 postsyn- Published: July 13, 2024
thesis modification,22−25 and one-pot synthesis,26,27 to provide
Ni active centers for ethylene oligomerization. High ethylene

© 2024 American Chemical Society https://doi.org/10.1021/acs.iecr.4c01435

13025 Ind. Eng. Chem. Res. 2024, 63, 13025−13036
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

acid sites contribute more and more to the product formation, from TianDa Chemical Reagent Co., Ltd. and used without
and the LAO product rate decreases sharply.37 The Brønsted further purification. Polymerization-grade ethylene (99.95%)
acid sites promote the oligomerization of ethylene, while was obtained from Dalian GuangMing Special Gas Products
causing further alkylation, isomerization, and β-splitting of the Co., Ltd., which was subsequently purified by activated Al2O3,
olefinic substances, especially at higher reaction temper- 3 Å molecular sieve, and a Ag catalyst (Dalian Zhonghuida
atures.38,39 It appears that byproduct formation can be avoided Scientific Instrument Co. LTD).
by the nickel center acting alone on the ethylene The fresh and spent catalysts were characterized by XRD on
oligomerization, but according to previous research results, a Rigaku Corporation SmartLab 9KW diffractometer using Cu
the activity of loaded catalysts containing only nickel is low Kα radiation in a scanning range of 5−70° at 10°/min. The
because their sites require an activation process.15,40,41 Usually, SEM images were taken on a FEI NOVA Nano SEM 450
the nickel salt can have good catalytic activity after the microscope, and TEM images were obtained using a JEM-
activation via the cocatalyst.42 In summary, changing the F2000 field-emission transmission electron microscope to
cocatalyst to activate the nickel catalyst seems to be a research determine the morphology of the solid samples. The nickel
path to promote ethylene oligomerization. contents were determined by ICP (PerkinElmer AVIO 500).
In previous studies, researchers attempted to carry out the XPS was performed on a Thermo SCIENTIFIC ESCALAB
ethylene oligomerization/polymerization reaction by changing 250Xi instrument. Spectral treatment was performed using
the type of cocatalyst.43−45 LiAlH4 is relatively cheaper and XPSPEAK41 software, and the binding energies (BE) were
more readily available than alkyl-aluminum cocatalysts, and the referenced to the C 1s peak at 284.8 eV. In situ FT-IR was
reaction does not require strict anhydrous and oxygen-free recorded on a Bruker VERTEX 80v infrared spectrometer and
conditions, which can effectively simplify the process. acquisition at 4 cm−1 resolution. When the sample was loaded,
However, a higher reaction temperature of 230 °C is required. it was dehydrated in a vacuum at 130 °C for 4 h, and a
Therefore, a catalyst that is resistant to high temperature and spectrum of the dehydrated sample was obtained. Then, the
tends to generate LAO products is needed for the reaction catalyst was cooled to 30 °C and exposed to pure CO from 5−
with LiAlH4. Versailles/Santa Barbara-5 (VSB-5), one of the 20 min (H2 direct adsorption for 20 min). The temperature
porous nickel phosphate prepared by Gérard Férey’s group, was ramped to 220 °C in pure gas at a rate of 6.5 °C/min,
which has a large surface area (500 m2 g−1) and a crystal while spectra were collected every 15 min. All spectra reported
structure that could remain intact at 450 °C,46 came into our here were baseline-corrected, and the spectra shown are
view recently. The material has a one-dimensional pore system difference spectra with those of the dehydrated catalyst
that extends along the [001] direction with the octahedral subtracted from those of the treated catalysts.
hexa-coordinated nickel centers, which have been used as 2.2. Catalyst Preparation. 2.2.1. VSB-5-H3PO4. The
catalysts for olefin hydrogenation after heat treatment at 350 procedure to synthesize VSB-5-H3PO4 was similar to the
°C (aimed to evacuate the pores and to form unsaturated previously reported literature.46 6.0 g of NiCl2·6H2O was
coordinated Ni2+).46−48 However, there are still no studies on dissolved in 60 mL of deionized water, followed by the
the use of VSB-5 in ethylene oligomerization despite its addition of H3PO4 (6.2 g). Subsequently, 1,3-propylenedi-
excellent catalytic potential.48 amine (9.8 g) was added dropwise with stirring to pH = 9. A
In this work, we synthesize two different forms of VSB-5 large amount of green precipitate appeared in the solution at
(VSB-5-H3PO4 and VSB-5-NaH2PO2) using a one-pot method this time. Thereafter, the mixed solution was transferred into a
and apply them as catalysts in the oligomerization of ethylene. Teflon-lined autoclave (120 mL) and crystallized at 180 °C for
In contrast to other nonhomogeneous MOF catalytic systems, 5 d. The product was cooled to ambient temperature, washed
the catalytic process of this work was effectively simplified due repeatedly with deionized water and ethanol, and then dried at
to the absence of alkyl-aluminum cocatalysts. The fresh and 70 °C for 4 h and stored in an airtight manner. The amounts of
used catalysts are characterized by inductively coupled plasma nickel and phosphorus determined by ICP were 34.69 and
spectrometry (ICP), X-ray diffraction (XRD), Fourier trans- 12.79 wt %, respectively.
form infrared spectroscopy (FT-IR), X-ray photoelectron 2.2.2. VSB-5-NaH2PO2. The procedure to synthesize VSB-5-
spectroscopy (XPS), scanning electron microscopy (SEM), NaH2PO2 was similar to the previously reported literature.47
and transmission electron microscopy (TEM). In addition, we 0.61 g of NiCl2·6H2O, 3.6 g of HMT, and 4.1 g of NaH2PO2·
conducted in situ IR-CO/H2 at different temperatures to H2O were dissolved in 64 mL of deionized water. Then, NH3·
investigate the active centers in the catalysts. Combined with H2O (1 mol/L) was used to adjust the pH to 9, and the mixed
the results of the catalytic reaction, it is found that the catalysts solution was transferred into a Teflon-lined autoclave (100
need to interact with LiAlH4 to form active centers involved in mL) and crystallized at 140 °C for 6 h. The product was
the reaction. Furthermore, a probable Cossee−Arlman-type cooled to ambient temperature and washed repeatedly with
mechanism is proposed. deionized water and ethanol and then dried at 70 °C for 4 h
and stored in an airtight manner. The amounts of nickel and
2. EXPERIMENTAL SECTION phosphorus determined by ICP were 26.36 and 10.43 wt %,
2.1. Materials and Characterization. H3PO4 (85%, respectively.
Tianjin Fuyu Fine Chemical Co., Ltd.), NaH2PO2·H2O 2.3. Catalytic Test. Ethylene oligomerization was
(99%), and methyl tert-butyl ether (MTBE, 99%) were performed in a 200 mL stainless-steel autoclave with
purchased from Tianjin jingdongtianzheng Precision Chemical mechanical stirring (850 rpm). A 40 mL portion of undecane
Reagent Factory. NiCl2·6H2O (98%), HCl (36.5%), and n- as a solvent was added with 0.05 g of catalyst (activated for 4 h
heptane (98.5%) were purchased from Damao Chemical under different conditions) and a certain amount of LiAlH4 as
Reagent Factory. LiAlH4 (97%), 1,3-Propanediamine (98%), a cocatalyst. After purging with 5 bar of N2 (3 times) and 10
hexamethyltetramine (HMT, 99%), and undecane (99%) were bar of ethylene (once), a certain amount of ethylene was
purchased from Aladdin. Anhydrous ethanol was purchased flushed into the reactor at room temperature, and then, the
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time was started after heating up to the reaction temperatures

(160−240 °C). After a limited reaction time, the heating was
stopped, and the autoclave was brought to an ice water bath for
rapid cooling to 30 °C. The gas mixture was collected with gas
bags and quantified by gas chromatography (GC) (Techcomp
7890F, FID) equipped with a TM-Al2O3/S column (50 m ×
0.53 mm × 25 μm), and the analysis conditions were an initial
temperature of 80 °C and then direct ramping up to 180 °C.
The liquid phase was separated from the catalyst by
centrifugation, and a 1 mL portion was combined with 20
μL of n-heptane as an external standard. The sample was
analyzed by GC (Agilent 6890, FID) equipped with a HP-5
column (30 m × 0.32 mm × 0.25 μm) with the temperature of
the column maintained at 35 °C for 5 min and ramped at 10
°C/min until the temperature reached 280 °C. The categories
of products using VSB-5-H3PO4 as examples of catalyst were
determined by GC-mass spectrometry (GC-MS) (EXACTIVE
GC, FID), and the spectra are shown in Figures S5 and S6. All
data were repeated at least twice, and the error limit of data
was about ±5%.
To facilitate calculations and comparisons, the average
activity of catalysts (activity) and the selectivity of products (S)
in this work were calculated according to the following
equation as other studies of ethylene oligomeriza-
tion;18,25,27,49,50 the mass of products with different carbon
numbers is marked by mCx (x = 2, 4, 6, 8, ≥ 10).
d

mCx (g)
activity (g pro./gcat. × h 1) =
mcat.(g) × t(h)

mCx (g)
SCx% = × 100%
mCx (g)

Further, the selectivities of 1-Cx (LAOs) in Cx products (eq 1)

and all products (eq 2) are marked according to the following
equations
m1 Cx (g)
S1 Cx in all %= × 100% Figure 1. (a) XRD patterns of VSB-5s and (b) FT-IR spectra of VSB-
mCx(g) (1) 5s.

m1 Cx (g)
S1 Cx in Cx % = × 100% The TEM images of VSB-5-H3PO4 also show that the particles
mCx (g) (2) are rod-like structures, while no nickel oxide particles are
visible, whereas VSB-5-NaH2PO2 particles exhibit a distinct
filamentary structure (Figure 2g−i) with a diameter range of
3. RESULTS AND DISCUSSION 0.05−0.13 μm, mostly in the range of 0.06−0.09 μm. It is
3.1. Preparation and Characterization of Catalysts. shown that the morphology of VSB-5 particles changes when it
The XRD patterns of the VSB-5s are shown in Figure 1a, is synthesized with different phosphorus and base sources even
which exhibit the characteristic diffraction peaks at about 5.6 at the same pH.
and 11.2° corresponding to (100) and (200) reflections, The typical XPS survey spectra of VSB-5s are exhibited in
respectively.51 The patterns of VSB-5-H3PO4 and VSB-5- Figure 3a, in which there are three obvious peaks at 133.0 (P
NaH2PO2 are in good agreement with the simulated patterns. 2p), 531.0 (O 1s), and 856.0 (Ni 2p). Six different peaks are
The IR spectra in Figure 1b demonstrate five characteristic observed in the high-resolution Ni 2p spectra (Figure 3b).
peaks of VSB-5s, the stretching vibration peaks of the O−H Two major peaks centered at 856.0 and 873.5 eV could be
bond (3537 cm−1), the vibration peaks of the P−O bond in the ascribed to Ni 2p1/2 and Ni 2p3/2, respectively, which are
tetrahedra of PO4 (1116 and 1050 cm−1), the Ni−O bond attributed to Ni2+ in the skeleton.53,54 The subpeaks located at
(522 cm−1), and the vibrational peak of the Ni−O−H bond 857.2 and 875.1 eV, from which a spin energy separation of
(447 cm−1). The above absorption peaks are essentially the 17.9 eV can be calculated, may be attributed to the formation
same as previously reported.47,51−53 of Ni3+ in amorphous NiOOH by hydration and oxidation of
The morphologies of the two materials are shown by SEM the embedded ions in the VSB-5.53−56 In addition, the broad
images in Figure 2a−f. Among them, VSB-5-H3PO4 particles peaks located at 862.2 and 880.0 eV are the satellite peaks of
have a rod-like structure (Figure 2a−c) with a diameter range Ni 2p1/2 and Ni 2p3/2, respectively. Figure 3c shows the
of 0.30−0.75 μm. The average diameter is about 0.468 μm. spectrum of P 2p with the main peak at 133.4 eV (P−O) for
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Figure 2. (a−c) SEM images and (d−f) TEM images of VSB-5-H3PO4 and (g−i) SEM images of VSB-5-NaH2PO2.

both materials, which is in perfect agreement with the bonding material does not require a high heat treatment temperature
pattern of P in VSB-5. The O 1s core-level XPS peak to effectively catalyze the reaction to proceed. We further
deconvoluted into Ni−O and P−O binding. Their correspond- characterize the structure of the materials after calcination at
ing binding energies are found to be 531.4 and 532.1 eV for 350 °C under N2. XRD patterns (Figure S1a) show that the
VSB-5s in Figure 3d. crystallinity of both materials decreased, but the crystal
3.2. Ethylene Oligomerization. The catalytic perform- structure of both VSB-5s remains. The SEM images (Figure
ance of VSB-5-H3PO4 under different reaction conditions is S1b,c) show that the VSB-5-H3PO4 particles have very slight
shown in Figure 4. Combined with the treatment temperatures defects after heat treatment, but the overall structure is intact,
reported in previous studies,46−48 three conditions such as 30 while the structure of the VSB-5-NaH2PO2 particles is
°C without any treatment, 130 °C (first weight loss end point completely unchanged. Further TEM photographs of VSB-5-
of the TGA curve46) vacuum treatment for 4 h, and N2 H3PO4 (Figure S 1d,e) are obtained and confirm that its
treatment at 350 °C for 4 h are used for catalysts, and their structure is not changed. In addition, the XPS spectra of Ni 2p
oligomerization performances are shown in Figure 4a. and P 2p of the two VSB-5s under different temperature
Surprisingly, the catalytic activity 107.6 gpro./(gcat.·h) is treatments (Figure S2) reveal that the valence state of metal Ni
obtained under vacuum treatment at 130 °C and no further is basically unchanged, but the peak position of P migrated 0.5
increase in activity is observed by increasing the pretreatment eV toward the high-energy direction, which should be caused
temperature. An activity of 98.2 gpro./(gcat.·h) is obtained even by the detachment of some free hydroxyls from P. All of the
under untreated conditions. It indicates that the VSB-5 above suggest that high-temperature treatment can change
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Figure 3. XPS spectra of the VSB-5s: (a) survey; (b) Ni 2p; (c) P 2p, and (d) O 1s.

their structure to some extent, but it does not substantially 67.6 to 179.0 gpro./(gcat.·h) (Figure 4d), indicating that the
increase the reactivity. VSB-5s may have intrinsic active centers higher pressure within the operating range of the instrument is
that can sufficiently catalyze the reaction when activated at 130 always favorable. Finally, the optimal reaction conditions 130
°C. The effect of the Al/Ni molar ratio on the catalytic °C vacuum treatment for 4 h, an Al/Ni molar ratio of 20, and a
performance is shown in Figure 4b. With the increase in the temperature of 220 °C under 20 bar are obtained based on the
Al/Ni molar ratio from 5 to 25, the catalytic activity first above.
increases and then decreases. The reasons may be that the As shown in Table 1 Entry 1, the oligomerization hardly
excessive amount of cocatalyst still leads to over-reduction of occurs in the absence of the cocatalyst, displaying that the
the active center. Unlike conventional catalysts using alkyl- reaction must be carried out in the presence of a cocatalyst,
aluminum cocatalysts, increasing the amount of LiAlH4 does which is basically the same as the previous research results.44
not result in a higher carbon number product, but the Then, we carry out the ethylene oligomerization in toluene
selectivity of the LAO product does not decrease, which is an solution using the VSB-5-H3PO4-Et2AlCl system at room
advantage of VSB-5-H3PO4. The effects of different temper- temperature according to our previously studied optimal
atures on the catalytic activity of VSB-5-H3PO4 are shown in conditions.19 The results show that the activity using the
Figure 4c. The reactivity rises gradually with the increase of alkyl-aluminum cocatalyst is significantly lower than that in the
temperature from 160 to 240 °C, reaching a maximum of 109.8 LiAlH4 system, while the product is biased toward dimerization
gpro./(gcat.·h). However, a significant decrease in the selectivity (Table 1 Entry 2). It indicates that LiAlH4 as a cocatalyst
of the LAO product was observed at 240 °C, which indicates seems to be more helpful to increase the activity of the
that excessively high temperatures are not favorable for the oligomerization.
generation of linear α-olefins. When the pressure of the Under the optimal conditions, we compare the activity of
reaction increases from 8 to 20 bar, the activity increases from VSB-5-H3PO4 and VSB-5-NaH2PO2. The reactivity of VSB-5-
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Figure 4. Effect of (a) heat treatment; (b) Al/Ni; (c) reaction temperature, and (d) pressure on the catalytic activity and the product distribution.
Reaction conditions: 0.5 h, 850 rpm, 40 mL of undecane as a solvent, VSB-5-H3PO4 as a catalyst, and LiAlH4 as a cocatalyst. V.T: vacuum heat
treatment.

Table 1. Ethylene Oligomerization with VSB-5sa

selectivity (%)
treatment temperature activity 1-C4 in all (in 1-C6 in all (in 1-C8 in all (in
entry catalyst (°C) gpro./(gcat.·h) C2 % C4) % C6) % C8) % ≥C10 %
b
1 VSB-5-H3PO4 130 3.80 0 100(100) 0 0 0
2c VSB-5-H3PO4 130 138.3 0 89.6(93.7) 0 0 0
3 VSB-5-H3PO4 130 179.0 1.5 52.0(89.3) 18.3(63.8) 6.9(73.5) 2.1
4 VSB-5-NaH2PO2 200 178.1 1.5 51.8(87.6) 17.3(62.1) 6.8(73.1) 2.1
a
Reaction conditions: mcat. = 0.05 g, LiAlH4 as a cocatalyst, Al:Ni = 20, 220 °C, 20 bar, 0.5 h, 40 mL of undecane as a solvent. bNo cocatalysts in
the reaction. cReaction conditions: mcat. = 0.005 g, Et2AlCl as a cocatalyst, Al:Ni = 200, 20 °C, 50 mL of toluene as a solvent. This system produced
0.015 g of C6 product but not the 1-C6 product.

NaH2PO2 after 4 h of vacuum heat treatment at 200 °C (its products continued to decrease owing to their further reaction
first weight loss end point of the TGA curve47) is shown in to other by-products. Thus, prolonging the reaction time is not
Table 1 Entry 4. While the Ni content of VSB-5-NaH2PO2 is favorable for the preparation of LAOs.
relatively low, the catalytic activity and selectivity of LAOs are In a further study, we find that if the reaction is terminated
very close to those of VSB-5-H3PO4, which may illustrate that halfway to take a sample, the original solution cannot continue
the rod structure of VSB-5-NaH2PO2 possesses high outer to react (black line in Figure 6a,b, even below that of the
specific surface area visualized by narrower rods in SEM original 30 min due to loss of the gas products). Only with the
images, and visibly smaller diameters resulted in larger lateral addition of new LiAlH4, the oligomerization of ethylene will be
surface area, which may help improve mass transfer. ongoing again (blue line in Figure 6a,b). It indicates that
The mass of products keeps increasing with the prolonged exposure to air may deactivate the catalytic centers that have
time in the presence of both catalysts (Figure 5). The catalyst been formed and adding new cocatalysts can recover these
is still active to conduct the reaction, but the selectivity of LAO active centers. To determine the stability of the catalyst, we
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Figure 6. Leaching test of (a) VSB-5-H3PO4 and (b) VSB-5-

NaH2PO2. Reaction conditions: mcat. = 0.05 g, LiAlH4 as a cocatalyst,
Al:Ni = 20, 220 °C, 20 bar, and 40 mL of undecane as a solvent.

Figure 5. Effect of reaction time using (a) VSB-5-H3PO4 and (b) after Run 1 (Figure S3a−f). Both materials are covered by
VSB-5-NaH2PO2. Reaction conditions: mcat. = 0.05 g, LiAlH4 as a other amorphous substances. Subsequently, the FT-IR spectra
cocatalyst, Al/Ni = 20, 220 °C, 20 bar, and 40 mL of undecane as a of the two spent catalysts (Figure S3g,h) show that the
solvent. After 40 min of reaction, the subsequent pressure was kept
always at 20 bar.
absorption peaks of [AlH6]3+ and Al appeared in both reused
materials compared to the fresh material, while the absorption
peaks at 3000−2800 cm−1 attributed to alkanes do not appear.
added a fresh batch of LiAlH4 to the reaction filtrate (red line This suggests that there seems to be no heavy carbon product
in Figure 5a,b). It is found that the reaction essentially does attached to the catalyst, and the amorphous material should be
not occur. These results demonstrate that there is no loss of Ni a mixture of Li3AlH6 and Al, which are decomposition
active species on the catalyst. products of LiAlH4. Further, XRD characterization of both
The results of catalyst reuse are shown in Figure 7. The materials (Figure S4) shows that their crystal structure
recovered catalysts are fully washed with MTBE, dried, and gradually disappears but does not convert into nickel
further tested after being reactivated. The activity of both phosphate. The corresponding peaks of Li3AlH6 and Al appear
catalysts decreased during Run 2, with VSB-5-H 3 PO 4 in the patterns, and the peaks of Al become stronger with the
decreasing to 50.4% of the original activity and VSB-5- increase of the reuse time. The above study basically indicates
NaH2PO2 decreasing to 64.7%. We assume that it should be that it is the decomposition products of LiAlH4 that affect the
caused by the decomposition products of LiAlH4 covering the reusability of the catalyst. Even so, the reuse activity of VSB-5s,
catalyst surface or the generated high-carbon product blocking especially using acid treatment, is higher than that of previous
the pores.16 As a result, we washed the catalyst after Run 2 studies (43%).44 However, VSB-5s are unstable in acid, so they
with MTBE, calcined it at 350 °C in N2 for 4 h (marked as cannot be acid-treated multiple times to increase the activity.
3C), or washed it with 2.5% (v/v) HCl/EtOH (marked as Overcoming this problem is still the main direction of our
3H), and then tested them in Run 3. The results show that future research.
both methods can improve the reuse performance of VSB-5- We compare these catalysts with other reported heteroge-
H3PO4, but the acid treatment is better, in which the activity neous Ni-catalysts for ethylene oligomerization, as shown in
reaches 63.8% of the original. However, the reuse performance Table 2. Ni-ZIF-8 and Ni-MOF-5 exhibit extremely high
for VSB-5-NaH2PO2 showed a decline in calcination at 350 °C catalytic activity in the presence of an alkyl-aluminum
under N2 (48.0% of the origin). It suggests that the coverage of cocatalyst. In both of them, the anomalous coordination
the decomposition products of LiAlH4 is the main reason for environment gives the Ni centers unique null coordination
the decrease in the activity of recovered catalysts. To further sites, which can effectively facilitate the onset of ethylene
verify this conclusion, we obtain SEM images of the catalysts oligomerization. However, the carbon chain length of the
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Figure 7. Ethylene oligomerization with the recovered catalyst. (a)

VSB-5-H3PO4 and (b) VSB-5-NaH2PO2. Reaction conditions: mcat. =
0.05 g, LiAlH4 as a cocatalyst, Al:Ni = 20, 220 °C, 20 bar, and 40 mL
of undecane as a solvent.

product cannot be extended, so they are only outstanding Figure 8. In situ FTIR spectra of (a) CO and (b) H2 for VSB-5-
dimerization catalysts. Among other types of catalysts, Ni- H3PO4 at a constant pressure of 0.1 mbar.
AlSBA-15 possesses high activity without any cocatalysts, but
the selectivity of LAO products is very low, which is caused by 3.3. Exploration of the Reaction Mechanism. 3.3.1. Ex-
its acidic catalytic centers. The previous studies have shown ploration of the Active Site. To explore the state of the active
that high ethylene oligomerization activity and more LAO center, we further characterize the catalysts by in situ IR-CO. It
products with higher carbon numbers are difficult to obtain is known that the active centers of ethylene oligomerization
without an alkyl-aluminum cocatalyst. Herein, VSB-5s present catalysts can effectively bind with CO to form Ni2+−CO or
an impressive result. Ni+−CO species.33,34,58−61 In the IR spectra, the absorption

Table 2. Comparison of Heterogeneous Ni-Catalysts for Ethylene Oligomerization

selectivity (%)
Al/Ni molar activity
catalyst cocatalyst ratio gpro./(gcat.·h) 1-C4 in all (in C4) % 1-C6 in all (in C6) % 1-C8 in all (in C8) % refs
Ni-ZIF-8 (0.40 wt %) MAO 4640 2130 85.1(87.7) 26
Ni-MOF-5 (5.32 wt %) MAO 1000 9040 81.1(84.2) 27
Ni@MOF DEAC 800 43.5 43.7(64.3) 19.0(63.2) 0.8a 57
Ni (1%)-MFU-4l MAO 500 198.0 92.0(94.5) 20
Ni-AlSBA-15 175.0 6.82(16.8) 1.71(4.6) 14.8a 25
13Ni2P/ASA LiAlH4 13.7 49.4 18.0a 36.0a 24.0a 44
16Ni2P/SiO2 LiAlH4 15.2 68.3 26.8a 40.0a 17.7a 43
VSB-5-H3PO4 LiAlH4 20 179.0 52.0(89.3) 18.3(63.8) 6.9(73.5) this work
VSB-5-NaH2PO2 LiAlH4 20 178.1 51.8(87.6) 17.3(62.1) 6.8(73.1) this work

a
Selectivity of Cx in all products (x = 4,6,8).

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Figure 9. Probable mechanism of ethylene oligomerization catalyzed by VSB-5.

peaks of Ni2+−CO are observed at 2200−2180 cm−1 and the vacuum heat treatment at 130 °C. Ni2+−H2 species (3926
peaks of Ni+−CO are characterized by υs(CO) at 2145−2131 cm−1) do not appear at the same time, which further proves
cm−1 as well as υas(CO) at 2100−2081 cm−1.62−64 In a that there is no unsaturated Ni2+ site in VSB-5s to bind to the
previous study, Chen et al. observed the adsorption peak at gas molecules. The aforementioned phenomenon shows that
2194 cm−1 after heat treatment of VSB-5 at 250 °C, suggesting the formation of the active Ni−H centers may not be reacting
that high-temperature treatment could obtain Ni2+ active with the H2 from the decomposition of LiAlH4 and VSB-5 and
sites.65 In this work, VSB-5-H3PO4 is treated under vacuum at does not seem to involve the olefin hydrogenation process. In
130 °C for 4 h and then is cooled to 30 °C. After the CO gas order to explore the formation process of the active center, we
(0.1 mbar) is adsorbed for 20 min, the temperature rises from carried out ethylene oligomerization at 140 °C, below the
30 to 220 °C at 6.5 °C/min and each temperature point is temperature of 150 °C67 where LiAlH4 begins to melt and
maintained for 15 min, as shown in Figure 8a. Two major decompose. The results showed that no product is generated.
peaks at 2120 and 2170 cm−1 appear at 5 min of adsorption, This basically indicates that only when LiAlH4 undergoes
and the intensity of these peaks gradually increases with the fusion or decomposition can the active center of the reaction
extension of adsorption time. As the temperature increases, the be generated. Therefore, we speculate that the molten lithium
positions of these peaks remained unchanged throughout the aluminum hydride is the key to forming active centers.
above process. These two peaks should be attributed to the 3.3.2. Potential Reaction Mechanisms. By summarizing the
region of the P and Q rotation branches of gaseous CO.58,59,66 above studies, VSB-5 is liable to have no active site to directly
The changes in the intensity of these adsorption peaks may be catalyze ethylene oligomerization. However, according to the
caused by an increase in the amount of ambient CO. In order previous study in the Al2O3−LiAlH4 system,43 the activity of
to exclude the factors, we treated the catalyst under vacuum at the reaction was extremely low at 12.5 gpro./(gcat.·h) in the
220 °C for 15 min. The intensity of the two peaks decreased absence of Ni sites, proving that the reaction requires the
clearly, but the peak position is equally unchanged. The participation of active Ni centers. Therefore, a probable
residual peaks may be generated by the CO entering the pores mechanism is shown in Figure 9. First, the LiAlH4 forms the
of the material. Therefore, combined with the above- active component [AlH4]− in the ionized state during
mentioned results, it indicates that VSB-5s do not form Ni2+ melting;68,69 then, H on [AlH4]− can react with the OH of
or Ni+ centers involved in the ethylene oligomerization after the catalyst and the unsaturated Ni site forms. Thereafter,
treatment at 130 °C. another [AlH4]− binds to the Ni site and the Al−H bond is
To further validate the above conclusions, we tested the broken to form the active Ni−H center with temperatures
catalyst with in situ IR-H2 as shown in Figure 8b. The continuing to rise.70,71 The H2 generated directly from LiAlH4
adsorption peak at 3430 cm−1 attributed to Ni+−H2 never combines with ethylene to form ethane at the same time.
appears,63 proving that there is no Ni+ generated directly after Ethylene can be coordinated to the active nickel center.
13033 https://doi.org/10.1021/acs.iecr.4c01435
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Accompanying the further insertion of ethylene, an alkyl Dalian 116024, China; orcid.org/0000-0003-0741-
catalyst intermediate is formed in the reaction and 1-butene is 8023; Email: [email protected]
subsequently obtained via a β-hydrogen elimination step. The
generation of 1-hexene and 1-octene is essentially the same as Authors
that of 1-butene, and then, the catalyst is reverted to the Ni−H Cong Wang − State Key Laboratory of Fine Chemicals, School
active center. In addition, analyzing the product categories of Chemical Engineering, Dalian University of Technology,
plays an important role in understanding the catalytic Dalian 116024, China
mechanism.19,25 According to the characterization results of Zheng Huang − State Key Laboratory of Fine Chemicals,
GC-MS, in the exception of the LAO products, the other School of Chemical Engineering, Dalian University of
byproducts are endo-olefins (cis-2-butene, trans-2-butene, and Technology, Dalian 116024, China
3-decene), branched olefins (2-ethyl-1-butene, 2-ethyl-1- Anfeng Peng − State Key Laboratory of Fine Chemicals,
hexene) and alkanes. All of the above byproducts are School of Chemical Engineering, Dalian University of
consistent with those generated via the Cossee−Arlman Technology, Dalian 116024, China
mechanism15,25 and the amounts of them are relatively small. Complete contact information is available at:
The reason that VSB-5s can make the reaction more inclined https://pubs.acs.org/10.1021/acs.iecr.4c01435
to generate LAOs may be the higher valence state of Ni in their
structure compared with N2P catalysts, which will not be easily Author Contributions
overreduced to the deactivated state. Meanwhile, there are C.W.: conceptualization, methodology, investigation, and
fewer empty coordination sites in the Ni centers of VSB-5s, writing�original draft. G.L.: project administration, writ-
which effectively reduce the frequency of the generated ing�review and editing, and supervision. Z.H.: conceptualiza-
product reinserting into the Ni center to continue to tion and investigation, A.P.: investigation.
participate in the branching reaction, thus maintaining the
selectivity of the LAO product.72 Notes
The authors declare no competing financial interest.
4. CONCLUSIONS
Two VSB-5s (VSB-5-H3PO4 and VSB-5-NaH2PO2) are
synthesized and used as catalysts in ethylene oligomerization.
■ ABBREVIATIONS
LAOs, linear α-olefins; LLDPE, linear low-density poly-
They do not require 350 °C heat treatment as in the olefin ethylene; HDPE, high-density polyethylene; MOFs, metal−
hydrogenation process and maintain a wider distribution of organic frameworks; VSB-5, Versailles/Santa Barbara-5; ICP,
LAO products at a relatively high activity compared to other inductively coupled plasma spectrometry; XRD, X-ray
Ni-MOFs and Ni silica aluminate catalysts in ethylene diffraction; FT-IR, Fourier transform infrared spectroscopy;
oligomerization. Meanwhile, the selectivity of LAOs decreases XPS, X-ray photoelectron spectroscopy; SEM, scanning
with prolonging the reaction time. The catalyst can be reused electron microscopy; MTBE, methyl tert-butyl ether; HMT,
in the reaction by adding new LiAlH4. The decomposition hexamethyltetramine
product of LiAlH4 may cover the surface of the catalyst, which
can be removed by acid. Furthermore, studies of in situ IR
demonstrated that active centers for ethylene oligomerization
may form in VSB-5 assisted by LiAlH4. Combined with the
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