Next Article in Journal
Use of Bioprinted Lipases in Microwave-Assisted Esterification Reactions
Next Article in Special Issue
Effect of Ce Content on the Chemical Looping Oxidative Dehydrogenation of Propane to Propylene over a VOx-CeO2/γ-Al2O3 Oxygen Carrier
Previous Article in Journal
Catalytic Distillation of Atmospheric Residue of Petroleum over HY-MCM-41 Micro-Mesoporous Materials
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Catalysts
Volume 13
Issue 2
10.3390/catal13020298
catalysts-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

A One-Pot Hydrothermal Preparation of High Loading Ni/La2O3 Catalyst for Efficient Hydrogenation of Cinnamaldehyde

by
Haoting Yan
1,
Yongwang Ren
1,
Renkun Zhang
1,
Feixiang Chang
1,
Qinhong Wei
1,* and
Jing Xu
2,*
1
Department of Chemical Engineering, School of Petrochemical Engineering & Environment, Zhejiang Ocean University, Zhoushan 316022, China
2
National Engineering Research Center for Marine Aquaculture, Zhejiang Ocean University, Zhoushan 316022, China
*
Authors to whom correspondence should be addressed.
Catalysts 2023, 13(2), 298; https://doi.org/10.3390/catal13020298
Submission received: 21 December 2022 / Revised: 24 January 2023 / Accepted: 26 January 2023 / Published: 28 January 2023
(This article belongs to the Special Issue Catalytic Transformation of Low-Carbon Resources)
Browse Figures
Review Reports Versions Notes

Abstract

It is a challenging task for selective hydrogenation of cinnamaldehyde (CAL) to hydrocinnamaldehyde (HCAL) without additional by-product formation. In this work, a La2O3 supported high Ni content nanoparticle catalyst was prepared for CAL selective hydrogenation. Meanwhile, Co-La2O3 catalysts were used as a reference catalyst. XRD, TEM, STEM-HAADF, XPS, and H2-TPR measurements were used to investigate the physicochemical properties of Ni-La2O3 catalysts. The experimental results confirmed that the CAL conversion and HCAL selectivity were effectively promoted with the increase of Ni loading amounts. At a Ni/La molar ratio of four, a high HCAL selectivity of 87.4% was obtained at a CAL conversion of 88.1% under mild reaction conditions. The catalyst was recycled five times without activity loss. Combined with various characterizations, it could be inferred that the good hydrogen adsorption and dissociation capacity of Ni and the presence of a certain amount of oxygen vacancies on the La2O3 support have a positive effect on the improvement of HCAL selectivity. This work provided an effective path to design transition-metal-based supported oxide catalyst for the cinnamaldehyde hydrogenation to hydrocinnamaldehyde.

1. Introduction

α, β-unsaturated aldehydes containing C=C and C=O bonds are important raw materials and intermediates in organic synthesis and the chemical industry [1]. Moreover, the hydrogenation products of such aldehydes have high application values in fragrance, pharmaceutical, and fine chemical industries [2]. For example, cinnamaldehyde, which is one of the α, β-unsaturated aldehydes families, has two hydrogenation products, namely, the cinnamyl alcohol (COL) from the C=O group hydrogenation and the hydrocinnamaldehyde (HCAL) from the C=C group hydrogenation. These two products can be used in the formulation of fragrance and cosmetic flavors [3], and in the development of novel anti-AIDS (Acquired Immune Deficiency Syndrome) drugs [4]. Currently, the main route for the production of HCAL is based on the hydrolysis method of toluene chlorination, in which the benzylidene chloride is generated by side chain methyl dichloro reaction of toluene and then hydrolyzed in acid or alkaline to form HCAL. Despite the high yield of this method, the waste stream (acidic) is difficult to be handled, meanwhile, the HCl produced tends to corrode the reaction equipment. In contrast, adopting hydrogenation of CAL to prepare HCAL could be effective to avoid the production of corrosive by-products or wastes. Therefore, the study of selective hydrogenation of cinnamaldehyde is of important significance. For cinnamaldehyde hydrogenation, the C=C bond, due to its lower energy at 615 kJ/mol, is more likely to be thermodynamically hydrogenated to HCAL as compared to that of the C=O bond with a relatively high energy at 715 kJ/mol [5]. Although the C=C bond is more easily hydrogenated, achieving a high selectivity in target products (HCAL or COL) undoubtedly encounters some difficulties. Consequently, more studies of catalysts have been devoted to the selective hydrogenation of cinnamaldehyde.
In the hydrogenation reaction, noble metals usually present excellent catalytic activities [6,7,8]. Moreover, some studies were also focused on metal introduction, aiming to improve COL selectivity. The alloy catalyst prepared by some synthetic methods is an effective measure for the hydrogenation reaction of cinnamaldehyde. For example, a Pt-Co bimetallic nanocatalyst [9] was used for the hydrogenation of cinnamaldehyde, and the result exhibited an excellent COL selectivity of 89.3%, which was mainly ascribed to the preferential adsorption of the C=O group over the synergistic effect between Pt nanoparticles and an amorphous Co-Aspartic acid polymer. Furthermore, zhang and his co-workers [10] prepared an Al2O3-supported Pt-Fe bimetallic catalyst and obtained 96.6% CAL conversion and 77.2% COL selectivity, respectively. Based on the results, the introduction of Fe could change the electronic and surface properties of the active Pt sites. Another way to obtain high selectivity is to design catalysts with specific structures, which may improve metal dispersion and limit the adsorption of the functional groups of substrate molecules. Han et al. [11] reported a highly dispersed Pd nanocatalyst confined in ZSM-5 zeolite crystals using a “secondary growth” synthesis strategy. The results showed that under the confining effect of the zeolite structure, the selectivity of HCAL was 73.3% over Pd@SG-ZSM-5. Furthermore, catalysts with a core-shell structure were also employed for the hydrogenation reaction of cinnamaldehyde. Zhang [12] et al. reported a kind of Pt nanocatalyst encapsulated in a hollow-flower-like Zr-MOFs double shell micro-reactor, which maintained high stability and improved the selectivity of COL due to the restriction effect of UiO-66 channels. By contrasting the catalytic efficiency of the samples, it was proved that the double-shell not only served as a stabilizer to restrict Pt nanoparticles with a high dispersion, but also as a sieve to regulate the contact direction of cinnamaldehyde to Pt site in light of the medium-sized channel formed on the outer shell.
However, considering the high cost of noble metal catalysts, it is desirable to develop inexpensive, non-noble metal catalysts with good catalytic activities. One widely used strategy is to prepare oxide supported transition metal catalysts, which have been applied in chemical synthesis and energy conversion process [13]. Pecchi et al. [14] prepared a SiO2 encapsulated cobalt core-shell catalyst using a solvothermal method for the core and a modified Stöber method for the shell. They adjusted the reduction temperature to improve Co/CoO surface distribution and, thus, enhanced both the dissociation of dissolved hydrogen and adsorption the C=O bond, obtaining the selectivity of more than 60% over Co-CoO@SiO2-500 °C sample. In addition to Co, some transition metals, like Ni [15], Fe, and Cu are also commonly used as hydrogenation catalysts, usually being designed in the form of monometal [16], alloys [17,18], intermetallic compounds [19], and so on. In the same way, oxide supports also play important roles in improving catalytic stability and selectivity. They may have some differences in morphology, specific surface area, acidity and alkalinity, electronic structure and geometry, and some of them also have catalytic activity. For example, ceria, which has good oxygen storage capacity, is often used as the catalyst support [20]. In addition, SiO2 [21], Al2O3 [22], and La2O3 [23] are also commonly considered as supports. Generally, based on these supports, high dispersion and low metal loaded capacity are the conventional ideas for the preparation of metal-based supported catalysts [24]. Recently, an inverse ZrO2/Cu catalyst, composed of 10% of ZrO2 supported over 90% of Cu, was reported by Ma and his co-worker to use for CO2 hydrogenation, exhibiting the high hydrogenation conversion to methanol [25]. Under optimal condition, the catalyst composed by 10% of ZrO2 supported over 90% of Cu exhibited the highest methanol formation rate of 524 gMeOHkgcat−1 h−1 at 220 °C, 3.3 times higher than the activity of traditional Cu/ZrO2 catalysts (159 gMeOHkgcat−1 h−1). Despite making many attempts, an inverse loading idea to design catalysts for cinnamaldehyde hydrogenation has not yet been developed.
Herein, a transition-metal-based supported oxide catalyst was prepared for the highly selective hydrogenation of cinnamaldehyde to hydro-cinnamaldehyde using a high loading strategy. A one-pot hydrothermal approach via mixed metal salt solution was employed to achieve the controllable synthesis of La2O3 supported Ni catalysts with different metal loading. At the same time, we also used cobalt nitrate to prepare corresponding Co-La2O3 catalysts as the reference sample for the performance test. Through performance tests, the Ni-La2O3 catalyst with an Ni/La molar ratio of four could simultaneously accomplish a high HCAL selectivity of 87.4% at a CAL conversion of 88.1%, verifying the idea of using inverse oxide/nickel focusing on a simple design of available catalysts for the cinnamaldehyde hydrogenation conversion.

2. Results and Discussion

2.1. Characterization of the Catalysts

The XRD patterns of the prepared catalysts are shown in Figure 1a. It is clear that the diffraction peaks corresponding to the La2O2(CO3) phase (PDF#84-1963) were observed in the calcined samples. Furthermore, NiO peaks were also detected in Ni4-La2O3, while there were no obvious NiO peaks in Ni1-La2O3. After reduction, characteristic peaks at 44.6°, 51.9°, and 76.5° were indexed in Ni4-La2O3, which were attributed to the (111), (200), and (220) lattice planes of metallic Ni0 species (PDF#70-0989), respectively. However, the Ni1-La2O3 presented the absence of Ni0 peaks, mainly due to the low Ni content compared to that of Ni4-La2O3. In addition, the remaining peaks at different positions were assigned to La2O3 (PDF#83-1344). Based on the XRD results, the La2O2(CO3) phases were formed on the calcined samples, which originated from the low-temperature calcination of the hydrothermal precursors (≤500 °C) [26]. HRTEM images of Ni4-La2O3 and Ni1/4-La2O3 are shown in Figure 1b,c. The lattice spacings measured at 0.175 nm and 0.203 nm were attributed to (200) and (111) crystal planes of Ni0, respectively. Although the reduced Ni1-La2O3 displayed the absence of Ni0 peaks, the TEM image gave a clear indication for the presence of Ni0. Furthermore, element mappings showed the uniform distribution of La, Ni, and O elements on the Ni4-La2O3 framework. Clearly, the point density of the Ni mapping image is higher than that of the La mapping image, indicating the higher Ni ratio over La in the Ni4-La2O3 sample.
The chemical state and surface composition of the prepared catalysts were obtained with XPS. Figure 2a showed Ni 2p spectra of Ni1/4-La2O3, Ni1-La2O3 and Ni4-La2O3, where two obvious peaks at 851.7 eV and 855.5 eV were attributed to the Ni0 and Ni2+ [27]. This result indicated that, after the reduction of samples, the majority of the Ni species were in the form of metallic Ni, with part of the Ni2+ species remaining [28]. In addition, the concentration of Ni in Ni1/4-La2O3, Ni1-La2O3, and Ni4-La2O3 were 4.21 wt%, 14.25 wt%, and 40.90 wt%, respectively. The spectra of La 3d were shown in Figure 2c, and the four peaks detected were assigned to La 3d5/2 (at 838.5 and 834.8 eV) and La 3d3/2 (at 855.5, 851.7 eV). The O 1s spectra were divided into three peaks, meaning various oxygen species related to oxygen vacancy. The first one at 529.1 eV was ascribed to lattice oxygen (O2-); the middle one at 530.9 eV was due to the oxygen species (O-/O22-) adsorbed on oxygen vacancies; and the final peak at 531.8 eV was accorded with carbonate species (CO32-). The above characterization observations illustrated the presence of a certain amount of oxygen vacancies and trace amounts of unreduced La2O2(CO3) species on Nix-La2O3 catalysts [26]. The existence of oxygen vacancies on Nix-La2O3 catalysts provided the possibility for adsorption of C=O bonds [29].
To discuss the reduction behavior of the calcined catalysts, Figure 3 exhibits H2-TPR data for the calcined samples. As shown in Figure 3, the oxide precursors of the Nix-La2O3 samples display two sets of reduction peaks. The reduction peak between 300–400 °C could be assigned to the reduction of NiO species. Regarding the peak at around 350–370 °C, it was caused by weak interaction between the NiO and La2O3 support. At the same time, the H2-TPR profiles also show reduction peaks at 400 °C, meaning that the higher the reduction temperature, the stronger the interaction between Ni nanoparticles and support might be [30]. However, for the La2O3 sample without loaded Ni nanoparticles, no reduction peaks were found below 700 °C, while one peak observed at around 750 °C was attributed to the reduction of the La-O bond. In light of the oxide precursors of Nix-La2O3, especially of those on Ni4-La2O3 and Ni1-La2O3, the reduction temperature was lower compared to that of La2O3, indicating that the La-O bond of the oxide precursors of Nix-La2O3 was more readily reduced in the presence of the active metal, thus resulting in more oxygen vacancies upon H2 reduction [31].

2.2. Catalytic Selective Hydrogenation of Cinnamaldehyde

In order to further investigate the synergistic effect of metal and support in the reaction process, the catalytic performance tests were evaluated in the selective hydrogenation of cinnamaldehyde (CAL) over Nix-La2O3 and Cox-La2O3 catalysts (x represented the molar ratio of Ni/Co and La), as shown in Figure 4.
The CAL could be hydrogenated to form HCAL and COL with selective hydrogenation of C=C and C=O bonds, respectively. Meanwhile, the obtained HCAL and COL could be further hydrogenated to hydrocinnamyl alcohol (HCOL). Therefore, designing an effective catalyst was critical for improving the selectivity of key products. The catalytic performance of Nix-La2O3 and Cox-La2O3 catalysts are shown in Figure 4b. As the metal content increased, the conversion of CAL for Ni1/4-La2O3, Ni1-La2O3, and Ni4-La2O3 catalysts was respectively increased from 71.2% to 88.1%, along with the selectivity of HCAL obtained from 20.9% to 87.4%. In particular, the Ni4-La2O3 exhibited not only the highest CAL conversion but also the largest selectivity to HCAL. Different from the results over Nix-La2O3 catalysts, the Cox-La2O3 catalysts exhibited distinctive catalytic behaviors. The conversion of CAL increased from 76.2% to 93.6% by gradually increasing Co loading amounts on Cox-La2O3 samples, whereas the highest HCAL selectivity was only 33.5% over the Co4-La2O3 catalyst. These results showed that the Nix-La2O3 catalyst preferred to perform the hydrogenation for the C=C group, while the Cox-La2O3 catalysts showed over-hydrogenation for CAL conversion.
The influence of reaction temperature and H2 pressure on CAL hydrogenation over Ni4-La2O3 had also been investigated (Figure 4c,d). Firstly, to determine the suitable reaction temperature, the catalytic hydrogenation of CAL was carried out at different temperatures with 2MPa of H2 pressure. Figure 4c displays that the reaction temperature had a remarkable influence on CAL hydrogenation reaction, especially for the process of C=C hydrogenation to HCAL. In addition, the optimal reaction temperature was determined to be 90 °C, as either higher or lower reaction temperatures resulted in comparatively lower HCAL selectivity, due to the formation of HCOL. It might be interpreted that the low reaction temperature was insufficient to obtain high CAL conversion, and the high reaction temperature was prone to over-hydrogenation of CAL to HCOL. Figure 4d shows the distribution of products at 90 °C with different H2 pressures over the representative Ni4-La2O3 catalyst sample. The effect of H2 pressure on catalytic performance was evaluated in the range of 1–4 MPa H2. The highest HCAL selectivity was achieved at 2 MPa H2 pressure with 87.4%. As the H2 pressure gradually increased to 4 MPa, the CAL conversion was almost unchanged, but the selectivity of HCAL decreased to 4.07%. This indicated that the excessive reaction pressure led to the over-hydrogenation of CAL to HCOL. Through exploring the reaction conditions, high CAL conversion and HCAL selectivity were obtained over Ni4-La2O3 at 90 °C with 2 MPa of H2 pressure.
Besides reaction temperature and H2 pressure, reaction time is also another essential factor in measuring catalytic activity and selectivity of Ni4-La2O3 for the CAL hydrogenation reaction. As shown in Table 1, it is obvious that the process of cinnamaldehyde hydrogenation required the participation of a catalyst (entry 1) [32]. Meanwhile, the results (entry 2) were obtained by examining the effect of reaction time on the CAL conversion. With the increase in reaction time, the conversion of CAL approached to 100%, while the selectivity of HCAL was gradually decreased. Notably, the HCAL selectivity was only at 3.8% in a 4 h reaction, which was attributed to the over-hydrogenation of CAL. It has been proposed that oxygen vacancies can be used as active sites for activation of C=O bonds [29]. Furthermore, based on the characterization of XPS and H2-TPR, as well as the above catalytic performances, it was determined that the dissociative adsorption of the C=C and C=O bonds was carried out on the metallic nickel active sites and oxygen vacancies of La2O3 support. Meanwhile, hydrogenation of the C=C bond was more accessible in comparison to that of C=O bond, both thermodynamically and kinetically [33]. When the nickel content increased, the hydrogenation of the C=C bonds over Ni4-La2O3 was more readily realized, which might be the reason for the high selectivity of HCAL. However, after 3–4 h of the hydrogenation reaction, an uncontrollable over-hydrogenation occurred, leading to the formation of HCOL.
Additionally, the solvent might play an important role in the CAL hydrogenation reaction, mostly reflected in the effective diffusion of hydrogen at the gas-liquid and liquid–solid interfaces. The CAL hydrogenation reactions were performed under different solvents over the Ni4-La2O3 catalyst, as shown in entry 3, and corresponded, in turn, to methanol, isopropanol, N-hexane. With Methanol and N-hexane as solvents, the high CAL conversion was obtained but with low HCAL selectivity. In contrast, the conversion of isopropanol was lower, while achieving higher HCAL selectivity. By comparison, ethanol was selected as the most suitable solvent for CAL hydrogenation. In order to illustrate the catalytic activity of the as-prepared Ni4-La2O3 catalyst, a commercial Pd/C catalyst was also tested for cinnamaldehyde hydrogenation, with results shown in entry 4. An excellent conversion was exhibited when 10% Pd/C was used as the catalyst, but the selectivity of HCAL was relatively lower, which was attributed to the strong hydrogenation activity of Pd.
As displayed in Figure 5, the recycling tests were recorded by carrying out the CAL hydrogenation reaction where the reusability of Ni4-La2O3 was investigated for five runs, including the fresh one and four repeat experiments. After each run reaction, the sample was recovered with centrifugation to remove the reaction substances. Subsequently, the recovered sample was washed several times with water and ethanol to remove substrate residues and was dried overnight at 60 °C under vacuum before the next cycle. For the first run reaction, the catalyst reached 68.1% conversion of CAL and 85.4% selectivity to HCAL at 90 °C and 2 MPa H2 pressure after 2 h. After five cycles, the sample still kept good catalytic activity with 85.46% selectivity to HCAL at 66.37% CAL conversion, and no activity loss was observed. These results demonstrated that the Ni4-La2O3 catalyst sample has achieved acceptable reaction stability of cinnamaldehyde hydrogenation.

3. Materials and Methods

3.1. Materials

Ni(NO3)2·6H2O (AR grade, >99%), La(NO3)3·6H2O (AR grade, >99%), Co(NO3)2·4H2O (AR grade, >99%), Urea (AR grade, >99%), absolute ethanol (AR grade, >99%), and Cinnamic aldehyde (AR grade, 99%) were purchased from Aladdin Reagent Co., Ltd. in Shanghai, China. All of the above reagents were used directly without any treatment. All gases (H2, N2) used for catalyst preparation and reaction processes were of ultrahigh purity (>99%).

3.2. Synthesis of Nix-La2O3

Nix-La2O3 catalysts were prepared using a hydrothermal synthesis method in sealed Teflon-lined autoclaves. Typically, 8.14 g Ni(NO3)2·6H2O (as nickel source), 3.03 g La(NO3)3·6H2O, and 4.62 g urea were dissolved in 100 mL of deionized water with rigorous stirring. After being dissolved completely, the above solution was added into a Teflon-lined autoclave and then heated to 120 °C for 20 h. The obtained precipitations were centrifugally washed with deionized water several times, dried at 100 °C overnight, and calcined at 500 °C (5 °C/min) for 2 h in air. Finally, the resulting powders were reduced under H2 (10 vol% H2/N2) at 600 °C for 2 h to gain the Nix-La2O3 catalysts (x represented the molar ratio of Ni and La). These prepared samples were designated as Ni1/4-La2O3, Ni1-La2O3 and Ni4-La2O3, respectively. Similarly, the Cox-La2O3 catalysts were also synthesized as that of Nix-La2O3 above, using the same steps, just replacing Ni(NO3)2·6H2O with Co(NO3)2·4H2O.

3.3. Catalyst Characterization

The X-ray diffraction (XRD) spectra were recorded using a DX-2700 diffractometer (Haoyuan Corporation, Dandong, China) with CuKα source (λ = 1.5406 Ȧ) at the condition of 40 kV, 30 mA and a scan rate of 0.02°/s. Diffraction patterns were recorded from 2 θ as 10° to 80°. The transmission electron microscopy (TEM) images and scanning transmission electron microscopy images with a high-angle annular dark field scanning pattern (STEM-HAADF) equipped with an energy-diffusive spectroscopy (FlatQuad 5060 F, EDS) were filmed on a JEM-2100 (JEOL, Tokyo, Japan). Prior to the measurement, the samples were dispersed in ethanol using ultrasound and the resulting suspension was dropped on a copper grid coated with a carbon film. X-ray photoelectron spectroscopy (XPS) spectra were carried out using an Axis Ultra DLD (Kratos Analytical, Manchester, UK) with a monochromatic Al Kα X-ray source and the pass energy was 100.0 eV with an energy step of 1.000 eV. All of the binding energies (BEs) were calibrated with using that of C 1s (284.8 eV). Hydrogen temperature programmed reduction (H2-TPR) experiments were carried out on a TP-5080 chemical adsorption analyzer (Xianquan, Tianjin, China). Before the H2-TPR measurement, 0.05 g of the catalyst was loaded to a fixed-bed quartz tube and pretreated in an Ar flow of 15 ml/min at 300 °C for 1 h. After being cooled at the same atmosphere to 30 °C, the pretreated sample was reduced from 30 °C to 800 °C in a flow (15 mL/min) of 5 % H2/Ar at a ramp of 10 °C/min.

3.4. Catalytic Reaction

The hydrogenation reaction of CAL was carried out in a sealed Teflon-lined stainless steel automatic high-pressure autoclave. In a typical test, 70 μL (0.55 mmol) of CAL dispersed in 6 ml of absolute alcohol was put into an autoclave (20 mL). Then, 50 mg of the prepared catalyst sample was added into the autoclave above. Then, after sealing the reactor, hydrogen was first purged three times to remove the air inside before 2 MPa of hydrogen was introduced as the reaction gas. After that, the reaction temperature was heated to 90 °C to carry out the reaction for a certain period of time, with the heating mantle stirring at a rate of 600 rpm. After the reaction, the obtained product was analyzed with gas chromatography equipped with a HP-5 MS column. The conversion of the reactant and the selectivity of the target product were calculated using the following Formulas (1) and (2):
Conversion (%) = [CAL feed (mol) − CAL residue (mol)] × 100% / CAL feed (mol)
Selectivity (%) = target product (mol) × 100% / [CAL feed (mol) − CAL residue (mol)]

4. Conclusions

In summary, a La2O3 oxide supported high Ni loading amount catalyst has been prepared successfully with a one-pot hydrothermal synthesis method. In the performance test of cinnamaldehyde hydrogenation reaction, a Ni4-La2O3 catalyst displayed excellent catalytic performance with a high CAL conversion of 88.1% and superior HCAL selectivity of 87.4% at 90 °C and 2 MPa H2 pressure, which was better than that of the Cox-La2O3 catalysts under the same reaction conditions. Moreover, combined with XRD, XPS and TPR characterization results, this outstanding catalytic performance could be attributed to the excellent adsorption and dissociation of metallic Ni on C=C bonds and hydrogen molecules along with the adsorption of C=O bonds by oxygen vacancies occurring simultaneously on the Ni/La2O3 support. Finally, the optimal Ni4-La2O3 catalyst also maintain excellent catalytic repeatability and chemical stability after five consecutive recycling tests. Overall, the catalyst design consisting of oxide support with oxygen vacancy and high metal loading also provided a new idea for chemoselective hydrogenation of α, β-unsaturated aldehydes.

Author Contributions

Conceptualization, H.Y. and Y.R.; methodology, H.Y. and R.Z.; formal analysis, H.Y. and F.C.; data curation, H.Y.; writing—original draft preparation, H.Y.; supervision, Q.W. and J.X. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Natural Science Foundation of China (grant number 22202180) and the Natural Science Foundation of Zhejiang Province of China (grant number LQ20B030010).

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Farrar-Tobar, R.A.; Dell’Acqua, A.; Tin, S.; de Vries, J.G. Metal-catalysed selective transfer hydrogenation of α, β-unsaturated carbonyl compounds to allylic alcohols. Green Chem. 2020, 22, 3323–3357. [Google Scholar] [CrossRef]
  2. Zahid, M.; Li, J.; Ismail, A.; Zaera, F.; Zhu, Y. Platinum and cobalt intermetallic nanoparticles confined within MIL-101 (Cr) for enhanced selective hydrogenation of the carbonyl bond in α, β-unsaturated aldehydes: Synergistic effects of electronically modified Pt sites and Lewis acid sites. Catal. Sci. Technol. 2021, 11, 2433–2445. [Google Scholar] [CrossRef]
  3. Iqbal, Z.; Sadiq, M.; Sadiq, S.; Saeed, K. Selective hydrogenation of cinnamaldehyde to cinnamyl alcohol over palladium/zirconia in microwave protocol. Catal. Today 2022, 397, 389–396. [Google Scholar] [CrossRef]
  4. Sreenavya, A.; Mallannavar, C.N.; Sakthivel, A. Functional group hydrogenation of cinnamaldehyde to hydrocinnamyl alcohol over nickel-ruthenium containing hydrotalcite. Mater. Today Proc. 2021, 46, 3152–3157. [Google Scholar] [CrossRef]
  5. Zhao, J.; Yuan, H.; Gui, Y.; Li, X.; Qin, X.; Wei, C.; Liu, Y.; Wang, G.; Zhou, L.; Fang, S. Engineering the interface of Au nanocatalysts with FeOx for enhanced selective hydrogenation of cinnamaldehyde. J. Mater. Sci. 2021, 56, 5760–5771. [Google Scholar] [CrossRef]
  6. Li, Z.J.; Wei, W.; Li, H.H.; Li, S.H.; Leng, L.P.; Zhang, M.Y.; Horton, J.H.; Wang, D.S.; Sun, W.W.; Guo, C.M.; et al. Low-Temperature Synthesis of Single Palladium Atoms Supported on Defective Hexagonal Boron Nitride Nanosheet for Chemoselective Hydrogenation of Cinnamaldehyde. ACS Nano 2021, 15, 10175–10184. [Google Scholar] [CrossRef] [PubMed]
  7. Das, T.K.; Remanan, S.; Ghosh, S.; Das, N.C. An environment friendly free-standing cellulose membrane derived for catalytic reduction of 4-nitrophenol: A sustainable approach. J. Environ. Chem. Eng. 2021, 9, 104596. [Google Scholar] [CrossRef]
  8. Das, T.K.; Das, N.C. Advances on catalytic reduction of 4-nitrophenol by nanostructured materials as benchmark reaction. Int. Nano Lett. 2022, 23, 1–20. [Google Scholar] [CrossRef]
  9. Tang, Y.; Li, H.K.; Cui, K.C.; Xia, Y.D.; Yuan, G.Y.; Feng, J.; Xiong, W. Chemoselective hydrogenation of cinnamaldehyde over amorphous coordination polymer supported Pt-Co bimetallic nanocatalyst. Chem. Phys. Lett. 2022, 801, 8. [Google Scholar] [CrossRef]
  10. Zhang, Y.; Su, J.F.; Chen, J.N.; Dai, C.S.; Zhang, B.S. Insight into the role of iron in platinum-based bimetallic catalysts for selective hydrogenation of cinnamaldehyde. Chin. Chem. Lett. 2022, 33, 3757–3761. [Google Scholar] [CrossRef]
  11. Alfilfil, L.; Ran, J.S.; Chen, C.L.; Dong, X.L.; Wang, J.J.; Han, Y. Highly dispersed Pd nanoparticles confined in ZSM-5 zeolite crystals for selective hydrogenation of cinnamaldehyde. Microporous. Mesoporous. Mat. 2022, 330, 5. [Google Scholar] [CrossRef]
  12. Zhang, B.; Li, M.; Lei, H.; Chen, J.; Wang, S.; Chen, C. Combining shell confinement and outside decoration to boost the selectivity of Pt nanocatalysts in hollow-flower like Zr-MOFs double shell micro-reactor for hydrogenation cinnamaldehyde to unsaturated alcohol. Appl. Surf. Sci. 2022, 599, 153899. [Google Scholar] [CrossRef]
  13. Wei, X.J.; Rang, X.D.; Zhu, W.H.; Xiang, M.; Deng, Y.Y.; Jiang, F.H.; Mao, R.; Zhang, Z.W.; Kong, X.Q.; Wang, F. Morphology effect of CeO2 on Ni/CeO2 catalysts for selective hydrogenation of cinnamaldehyde. Chem. Phys. 2021, 542, 6. [Google Scholar] [CrossRef]
  14. Bustamante, T.M.; Fraga, M.A.; Fierro, J.L.G.; Campos, C.H.; Pecchi, G. Cobalt SiO2 core-shell catalysts for chemoselective hydrogenation of cinnamaldehyde. Catal. Today 2020, 356, 330–338. [Google Scholar] [CrossRef]
  15. Patil, K.N.; Manikanta, P.; Srinivasappa, P.M.; Jadhav, A.H.; Nagaraja, B.M. Exploring the confined space and active sites of Ni@ OCNTs catalyst for chemoselective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde. J. Environ. Chem. Eng. 2022, 10, 108208. [Google Scholar] [CrossRef]
  16. Gryglewicz, S.; Sliwak, A.; Cwikla, J.; Gryglewicz, G. Performance of Carbon Nanofiber and Activated Carbon Supported Nickel Catalysts for Liquid-Phase Hydrogenation of Cinnamaldehyde into Hydrocinnamaldehyde. Catal. Lett. 2014, 144, 62–69. [Google Scholar] [CrossRef]
  17. Pei, A.; Ruan, L.N.; Liao, J.H.; Fu, H.; Zeng, L.; Liu, J.; Li, M.; Chen, B.H.; Zhu, L.H. Platinum Island-on-Copper-Nickel Alloy Nanoparticle/Carbon Trimetallic Nanocatalyst for Selective Hydrogenation of Cinnamaldehyde. Catal. Lett. 2021, 151, 559–572. [Google Scholar] [CrossRef]
  18. Jia, A.Z.; Yao, X.F.; Feng, L.; Ma, Z.X.; Li, F.; Wang, Y.J. Synthesis of Hierarchically Porous Amorphous Alloy Hollow Sphere with High Surface Area as Effective and Selective Catalysts for Cinnamaldehyde Hydrogenation. Eur. J. Inorg. Chem. 2020, 2020, 1184–1191. [Google Scholar] [CrossRef]
  19. Liu, P.; Zhu, Y.L.; Zhou, L.; Zhang, W.H.; Li, Y.X. Amorphous Nickel Phosphide Nanoparticles for Selective Hydrogenation of Cinnamaldehyde. Catal. Lett. 2020, 150, 2695–2702. [Google Scholar] [CrossRef]
  20. Li, Z.; Dong, X.; Zhang, M.; Leng, L.; Chen, W.; Horton, J.H.; Wang, J.; Li, Z.; Wu, W. Selective hydrogenation on a highly active single-atom catalyst of palladium dispersed on ceria nanorods by defect engineering. ACS Appl. Mater. Interfaces 2020, 12, 57569–57577. [Google Scholar] [CrossRef]
  21. Wang, H.; Shu, Y.; Zheng, M.; Zhang, T. Selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde over SiO2 supported nickel phosphide catalysts. Catal. Lett. 2008, 124, 219–225. [Google Scholar] [CrossRef]
  22. Wang, H.; Liu, B.; Liu, F.; Wang, Y.; Lan, X.; Wang, S.; Ali, B.; Wang, T. Transfer hydrogenation of cinnamaldehyde catalyzed by Al2O3 using ethanol as a solvent and hydrogen donor. ACS Sustain. Chem. Eng. 2020, 8, 8195–8205. [Google Scholar] [CrossRef]
  23. Cifuentes, B.; Valero, M.F.; Conesa, J.A.; Cobo, M. Hydrogen production by steam reforming of ethanol on Rh-Pt catalysts: Influence of CeO2, ZrO2, and La2O3 as supports. Catalysts 2015, 5, 1872–1896. [Google Scholar] [CrossRef]
  24. Dragoi, B.; Mazilu, I.; Chirieac, A.; Ciotonea, C.; Ungureanu, A.; Marceau, E.; Dumitriu, E.; Royer, S. Highly dispersed copper (oxide) nanoparticles prepared on SBA-15 partially occluded with the P123 surfactant: Toward the design of active hydrogenation catalysts. Catal. Sci. Technol. 2017, 7, 5376–5385. [Google Scholar] [CrossRef]
  25. Wu, C.; Lin, L.; Liu, J.; Zhang, J.; Zhang, F.; Zhou, T.; Rui, N.; Yao, S.; Deng, Y.; Yang, F.; et al. Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation. Nat. Commun. 2020, 11, 5767. [Google Scholar] [CrossRef]
  26. Dai, Y.H.; Xu, M.; Wang, Q.J.; Huang, R.; Jin, Y.Y.; Bian, B.; Tumurbaatar, C.; Ishtsog, B.; Bold, T.; Yang, Y.H. Enhanced activity and stability of Ni/La2O2CO3 catalyst for CO2 methanation by metal-carbonate interaction. Appl. Catal. B-Environ. 2020, 277, 10. [Google Scholar] [CrossRef]
  27. Shafiee, P.; Alavi, S.M.; Rezaei, M. Mechanochemical synthesis method for the preparation of mesoporous Ni–Al2O3 catalysts for hydrogen purification via CO2 methanation. J. Energy Inst. 2021, 96, 1–10. [Google Scholar] [CrossRef]
  28. Wang, N.; Yu, X.; Shen, K.; Chu, W.; Qian, W. Synthesis, characterization and catalytic performance of MgO-coated Ni/SBA-15 catalysts for methane dry reforming to syngas and hydrogen. Int. J. Hydrog. Energy 2013, 38, 9718–9731. [Google Scholar] [CrossRef]
  29. Zhang, J.; Gao, Z.; Wang, S.; Wang, G.; Gao, X.; Zhang, B.; Xing, S.; Zhao, S.; Qin, Y. Origin of synergistic effects in bicomponent cobalt oxide-platinum catalysts for selective hydrogenation reaction. Nat. Commun. 2019, 10, 4166. [Google Scholar] [CrossRef]
  30. Niu, L.; An, Y.; Yang, X.; Bian, G.; Wu, Q.; Xia, Z.; Bai, G. Highly dispersed Ni nanoparticles encapsulated in hollow mesoporous silica spheres as an efficient catalyst for quinoline hydrogenation. Mol. Catal. 2021, 514, 111855. [Google Scholar] [CrossRef]
  31. Ebrahimi, P.; Kumar, A.; Khraisheh, M. Combustion synthesis of lanthanum oxide supported Cu, Ni, and CuNi nanoparticles for CO2 conversion reaction. Int. J. Hydrog. Energy, 2022; in press. [Google Scholar] [CrossRef]
  32. Liu, H.; Li, Z.; Li, Y. Chemoselective hydrogenation of cinnamaldehyde over a Pt-Lewis acid collaborative catalyst under ambient conditions. Ind. Eng. Chem. Res. 2015, 54, 1487–1497. [Google Scholar] [CrossRef]
  33. Hao, C.-H.; Guo, X.-N.; Pan, Y.-T.; Chen, S.; Jiao, Z.-F.; Yang, H.; Guo, X.-Y. Visible-light-driven selective photocatalytic hydrogenation of cinnamaldehyde over Au/SiC catalysts. J. Am. Chem. Soc. 2016, 138, 9361–9364. [Google Scholar] [CrossRef]
Catalysts 13 00298 g001
Figure 1. (a) XRD pattern of Nix-La2O3 samples, (b) HRTEM images of Ni4-La2O3 and Ni1/4-La2O3, (c) STEM-HAADF image, and (d) element mappings of the Ni4-La2O3 sample.
Figure 1. (a) XRD pattern of Nix-La2O3 samples, (b) HRTEM images of Ni4-La2O3 and Ni1/4-La2O3, (c) STEM-HAADF image, and (d) element mappings of the Ni4-La2O3 sample.
Catalysts 13 00298 g001
Catalysts 13 00298 g002
Figure 2. XPS spectra of Nix-La2O3 catalysts with different nickel capacities: (a) Ni 2p; (b) O 1s; (c) La 3d.
Figure 2. XPS spectra of Nix-La2O3 catalysts with different nickel capacities: (a) Ni 2p; (b) O 1s; (c) La 3d.
Catalysts 13 00298 g002
Catalysts 13 00298 g003
Figure 3. H2-TPR profiles of oxide precursors of Nix-La2O3 catalysts.
Figure 3. H2-TPR profiles of oxide precursors of Nix-La2O3 catalysts.
Catalysts 13 00298 g003
Catalysts 13 00298 g004
Figure 4. The process for selective hydrogenation of CAL (a), catalytic performance over various Nix-La2O3 and Cox-La2O3 catalysts (b), reaction conditions: 0.55 mmol CAL, 50 mg catalyst, 6 mL absolute ethanol as solvent, 2 MPa H2, reaction temperature 90 °C, reaction time 2 h. Influence of reaction temperature (c) and hydrogenation pressure (d) on the selective hydrogenation of CAL over Ni4-La2O3.
Figure 4. The process for selective hydrogenation of CAL (a), catalytic performance over various Nix-La2O3 and Cox-La2O3 catalysts (b), reaction conditions: 0.55 mmol CAL, 50 mg catalyst, 6 mL absolute ethanol as solvent, 2 MPa H2, reaction temperature 90 °C, reaction time 2 h. Influence of reaction temperature (c) and hydrogenation pressure (d) on the selective hydrogenation of CAL over Ni4-La2O3.
Catalysts 13 00298 g004
Catalysts 13 00298 g005
Figure 5. Recycling tests of selective hydrogenation of cinnamaldehyde over Ni4-La2O3 catalyst. Reaction conditions: 0.8 mmol CAL, 50 mg catalyst, 6 mL absolute ethanol as solvent, 2 MPa H2, reaction temperature 90 °C, reaction time 2 h.
Figure 5. Recycling tests of selective hydrogenation of cinnamaldehyde over Ni4-La2O3 catalyst. Reaction conditions: 0.8 mmol CAL, 50 mg catalyst, 6 mL absolute ethanol as solvent, 2 MPa H2, reaction temperature 90 °C, reaction time 2 h.
Catalysts 13 00298 g005
Table 1. Catalytic hydrogenation of CAL over different reaction conditions.
Table 1. Catalytic hydrogenation of CAL over different reaction conditions.
EntrySampleTime (h)SolventConv.
(%)		Selectivity (%)
COLHCALHCOL
entry 1 1Blank2Ethanol0000
entry 2 1Ni4-La2O31Ethanol79.720.5183.1616.33
399.920.5114.9584.54
499.280.43.895.8
entry 3 1Ni4-La2O32Methanol77.650.2839.7659.96
Isopropanol47.071.2780.1618.57
N-hexane99.620.0637.3562.59
entry 4 110% Pd/C2Ethanol1004.069.226.8
1 Reaction conditions: 0.55 mmol CAL, 50 mg catalyst, 6 mL solvent, 2 MPa H2, reaction temperature 90 °C.
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Yan, H.; Ren, Y.; Zhang, R.; Chang, F.; Wei, Q.; Xu, J. A One-Pot Hydrothermal Preparation of High Loading Ni/La2O3 Catalyst for Efficient Hydrogenation of Cinnamaldehyde. Catalysts 2023, 13, 298. https://doi.org/10.3390/catal13020298

AMA Style

Yan H, Ren Y, Zhang R, Chang F, Wei Q, Xu J. A One-Pot Hydrothermal Preparation of High Loading Ni/La2O3 Catalyst for Efficient Hydrogenation of Cinnamaldehyde. Catalysts. 2023; 13(2):298. https://doi.org/10.3390/catal13020298

Chicago/Turabian Style

Yan, Haoting, Yongwang Ren, Renkun Zhang, Feixiang Chang, Qinhong Wei, and Jing Xu. 2023. "A One-Pot Hydrothermal Preparation of High Loading Ni/La2O3 Catalyst for Efficient Hydrogenation of Cinnamaldehyde" Catalysts 13, no. 2: 298. https://doi.org/10.3390/catal13020298

APA Style

Yan, H., Ren, Y., Zhang, R., Chang, F., Wei, Q., & Xu, J. (2023). A One-Pot Hydrothermal Preparation of High Loading Ni/La2O3 Catalyst for Efficient Hydrogenation of Cinnamaldehyde. Catalysts, 13(2), 298. https://doi.org/10.3390/catal13020298

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop