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Catalysts 2016, 6(5), 64; https://doi.org/10.3390/catal6050064

Article
Selective Aerobic Oxidation of Benzyl Alcohol Driven by Visible Light on Gold Nanoparticles Supported on Hydrotalcite Modified by Nickel Ion
1
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China
2
Department of Chemical Engineering, Inner Mongolia Chemical Engineering Professional College, Hohhot 010070, China
*
Author to whom correspondence should be addressed.
Academic Editors: Stuart H. Taylor and Keith Hohn
Received: 28 November 2015 / Accepted: 7 April 2016 / Published: 27 April 2016

Abstract

:
A series of hydrotalcite (HT) and hydrotalcite modified by the transition metal ion Ni(II) was prepared with a modified coprecipitation method before being loaded with gold nanoparticles. The gold supported on Ni3Al hydrotalcite with a Ni2+/Al3+ molar ratio of 3:1 was investigated. Different techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflection spectrum (UV-vis DRS) were applied to characterize the catalysts. A single-phase catalyst with high crystallinity, a layered structure and good composition was successfully fabricated. Good conversions and superior selectivities in the oxidation of benzyl alcohol and its derivatives were obtained with visible light due to the effect of localized surface plasmon resonance (LSPR) of gold nanoparticles and the synergy of the transition metal ion Ni(II). This reaction was proven to be photocatalytic by varying the intensity and wavelength of the visible light. The catalyst can be recycled three times. A corresponding photocatalytic mechanism of the oxidation reaction of benzyl alcohol was proposed.
Keywords:
Ni(II) ion; hydrotalcite; Au nanoparticles; photo-oxidation; benzyl alcohol

1. Introduction

Selective oxidations of alcohols to carbonyl compounds, such as aldehydes and ketones, have been very important organic synthesis processes in academic research and industrial production [1]. The carbonyl compounds, such as aldehydes and ketones, were key intermediates in perfumes, spices, flame retardants, pharmaceuticals and other fine chemicals [2]. However, alcohols have been traditionally oxidized by a stoichiometric oxidant, such as dichromate and permanganate, and a large number of toxic and harmful byproducts were produced in the reaction [3]. In recent years, in the interest of green chemistry and environmental protection, oxygen application as an oxidant has caught the attention of researchers; in the process, pollution-free and clean water was the byproduct [4,5]. In addition, the selection of a green, pollution-free catalyst was also very important. The metal catalysts such as Ru [6,7], Pd [8,9], Rh [10,11], Cu [12,13], Pt [14,15], Au−Pd [16,17], Au−Cu [18] and Au−Ag [19] were commonly applied using oxygen as the oxidant in the oxidation of alcohols to aldehyde or ketone compounds. However, most of these were used in a homogeneous complex catalysis, in applications with high temperatures and high pressures requiring the addition of alkali, making the reaction conditions harsh. Thus, choosing recyclable and highly efficient catalysts in line with green chemistry and environmental protection policies became a major challenge for the field.
Hydrotalcite (HT) was a new type of clay layered with double-hydroxyl anionic material in the general chemical formula of [M+21−x·M+3x·(OH)2]x+·[An]x/n·yH2O. It had broad applications in catalysis, ion exchange, as well as flame retardant, medicinal, gene storage and other fields. According to the ferromagnetic property of M2+, hydrotalcites were divided into ferromagnetic hydrotalcites and non-ferromagnetic hydrotalcites [20]. Currently, the use of MgAl hydrotalcite has been widely reported, whereas other types of hydrotalcite have their own useful characteristics. For example, the NiAl hydrotalcite has also had broad application in recent years. Choudary et al. initiated use of NiAl hydrotalcite as a catalyst by applying it in the selective oxidation of alcohols into ketones using oxygen. It can also be used as a precursor for new intercalated materials [21]. In this study, an Au catalyst was used with hydrotalcite as a carrier. Because of its double-hydroxyl layered structure, hydrotalcite can provide basic conditions for the reaction system and avoid the addition of extra alkaline substances in the reaction system [22]. Unlike traditional hydrotalcite, Mg2+ of MgAl hydrotalcite was transformed into Ni2+ in this study. If the Ni(II) ion species in the hydrotalcite can activate molecular oxygen, as suggested by Choudary et al., Al(III) as a Lewis acid will assist in the reduction of dioxygen, consequently accelerating the alcohol oxidation reaction [21]. As a result of the pluralism of the transitional metal valence state, the electron transfer became so important that it can promote the electron transfer in the organic molecules, thus accelerating the reaction.
Until now, the heterogeneous catalytic oxidation of alcohols has been widely studied, but high temperature, high pressure and alkali conditions in the reaction still cannot be avoided. In this study, gold nanoparticles were supported on Ni3Al HT (Au/Ni3Al HT) and applied in the catalytic oxidation of benzyl alcohol. Due to the LSPR effect of gold nanoparticles [23], which allowed for the strong absorption of visible light, they can be stimulated by visible light. Better activities on Au/Ni3Al HT by visible light and better recycling properties have occurred, compared with the results in other references [24,25,26,27]. The photocatalytic reaction can occur over Au supported on the hydrotalcite which can avoid the addition of alkaline substances. It can happen under normal temperature and atmospheric pressure. Therefore, it was a green and environmental friendly option.

2. Results and Discussion

2.1. Catalysts Characterization

2.1.1. X-ray Diffraction (XRD)

The structure and composition of the prepared samples have been studied by XRD. XRD with different supports are shown in Figure 1a. Peaks at 11.3, 22.7 and 34.5 degrees showed the support was a double-layer structure, and the growth of the crystal shape was satisfactory. With the increase of Ni(II) ion content, all the absorption peaks shifted to a smaller angular direction, due to the lattice expansion. A smaller peak at 32.3 degrees was the peak of Al(OH)3 [28]. The gold catalysts on different hydrotalcite supports are shown in Figure 1b; the peaks were the same as that of the hydrotalcite supports. Some changes appeared in the characteristic peak of Au (111) at 38.2 degrees. Its peak intensity was stronger and the peak shape was even sharper than that in Figure 1a, a result of the appearance of gold nanoparticles and the larger size of the gold nanoparticles [24]. The layer frame of the hydrotalcite support was not damaged. The peaks of the catalysts with different gold loadings are shown in Figure 1c. With an increase in gold loading, the intensity of the characteristic peaks of Au (111) increased gradually, but the layer frame of the hydrotalcite support was not yet damaged. The particle size of Au or hydrotalcite of x wt. % Au/Ni3Al HT (x = 0.5, 1, 2, 3, 4) was 2.33–2.35 nm.

2.1.2. X-ray Photoelectronic Spectra (XPS)

X-ray photoelectronic spectra (XPS) of the samples confirmed that gold existed in the metallic state on the HT. The corresponding Au 4f XPS spectrum for the 3 wt. % Au/Ni3Al HT is shown in Figure 2a. As shown in Figure 2a, the binding energies for the Au 4f7/2 (83.70 eV) and Au 4f5/2 (87.35 eV) were observed which demonstrated the appearance of Au(0) [25,29]. The Ni 2p and the Al 2p XPS spectra for the 3 wt. % Au/Ni3Al HT are shown in Figure 2b,c, and the appearance of Ni2+ and Al3+ can be proven by the results. Na 2s absorption peak appears in Figure 2c, because it was washed by sodium carbonate during the post-treatment.

2.1.3. Ultraviolet-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS)

The UV-vis diffuse reflection spectra of MgAl HT, NixMg1−xAl HT (x = 0.3, 0.5 and 0.7) and NixAl HT (x = 1, 3 and 5) are demonstrated in Figure 3a. No absorption peaks appeared on the MgAl HT in the case of no gold in the wavelength range of visible light. Two obvious absorption peaks occurred on NixMg1−xAl HT (x = 0.3, 0.5 and 0.7) and NixAl HT (x = 1, 3 and 5) at approximately 380 nm and 640 nm. The peak at approximately 640 nm occurred because the nickel-modified hydrotalcite itself was green.
The UV-vis diffuse reflection spectra of Au/MgAl HT, Au/NixMg1−xAl HT (x = 0.3, 0.5 and 0.7) and Au/NixAl HT (x = 1, 3 and 5) are shown in Figure 3b. Compared with Figure 3a, the absorption peak at approximately 640 nm disappeared gradually. A strong absorption peak appeared at approximately 530 nm, consistent with the absorption of gold nanoparticles between 515 and 535 nm in the visible light range [30].
The UV-vis diffuse reflection spectra of the catalysts with different gold loadings are shown in Figure 3c. When the gold loading (wt. %) was 0.5% or 1%, three obvious absorption peaks appeared at approximately 380 nm, 530 nm and 640 nm, possibly caused by the lower gold loading which allowed for the display of the absorption peak of the hydrotalcite support and Au. When increasing the gold loading to 2%, 3% and 4%, the absorption peak at approximately 380 nm and 640 nm decreased gradually.

2.1.4. Atomic Absorption Spectroscopy (AAS)

The result of AAS of the 3 wt. % Au/Ni3Al HT catalysts was analyzed in Table 1. The Ni2+ and Al3+ molar ratio was 3.3 on the hydrotalcite support; it was consistent with the theoretical mole ratio of 3 for Ni2+ and Al3+. The gold content was 2.6 wt. %, which was consistent with the theoretical value (3 wt. %) of gold content. As seen from the results, the catalyst has been prepared successfully.

2.2. Activity Test with Benzyl Alcohol

The conversion and selectivity of the oxidation of benzyl alcohol with different catalysts are summarized in Table 2. Benzyl alcohol was oxidized into benzaldehyde by using different catalysts. In Table 2’s entries 1–7, poor light activities are shown on MgAl HT, NixMg1−xAl HT (x = 0.3, 0.5 and 0.7) and NixAl HT (x = 1, 3 and 5). In Table 2, entries 8–14, for the 3 wt % gold supported on MgAl HT, NixMg1−xAl HT (x = 0.3, 0.5 and 0.7) and NixAl HT (x = 1, 3 and 5), the activities of the catalysts appear enhanced compared with those of entries 1–7. The conversion of benzyl alcohol increased from 3 to 30 times. The conversion of benzyl alcohol was the highest of all the catalysts, with the greatest difference in the Au/Ni3Al HT catalyst used in Table 2, entry 13. Table 2, entries 13 and 15–17, illustrate an increase in the gold loading as the oxidation activity of benzyl alcohol increased on Au/Ni3Al HT. However, in Table 2, entry 18, the oxidation activity of benzyl alcohol decreased with 4 wt. % Au/Ni3Al HT. The best catalytic activity occurred with 3 wt. % Au/Ni3Al HT (Table 2, entry13).
Then, experiments were conducted to determine the best solvent. The oxidation of benzyl alcohol on 3 wt % Au/Ni3Al HT in different solvents are shown in Table 3. In Table 3, entries 1–4, the conversion of benzyl alcohol to benzaldehyde was excellent in nonpolar solvents. When using benzotrifluoride as the solvent, the conversion occurred with the best result. In Table 3 entry 4, when using petroleum ether as the solvent, the selectivities for benzaldehyde decreased, and the other product was the corresponding benzyl benzoate [31]. As shown in Table 3 entries 5–8, the conversion of benzyl alcohol was lower in the other polar solvents except in ethanol. In Table 3, entry 8, when using methanol as the solvent, the selectivity for benzaldehyde has decreased, and the other product was the corresponding methyl benzoate. Because the hydroxyl group of methanol was activated, it would participate in this reaction quickly [31]. The results show that the conversion and selectivity of the oxidation of benzyl alcohol in benzotrifluoride was excellent.

2.3. Oxidation of Various Alcohols

Through the selection of the catalyst and solvent, the optimal conditions for the oxidation of benzyl alcohol were 3 wt. % Au/Ni3Al HT as the catalyst, benzotrifluoride as the solvent and oxygen as the oxidant with visible light irradiation.
Next, the conversion and selectivity of the oxidation of a broad range of alcohols with the proposed system are summarized in Table 4. The results of the oxidation of benzyl alcohol and its derivatives are shown in Table 4, entries 1–5. Excellent conversions and selectivities were found in all cases except with 4-nitro-benzyl alcohol [32]. Satisfactory conversions and selectivities were obtained in the oxidation of the other aromatic alcohols under the same conditions. Unfortunately, low conversion of the aliphatic alcohols can be found in Table 4, entries 8–9. Crotyl alcohol and n-octanol failed to be oxidized effectively resulting in less than 5% conversion of n-octanol. From these results, the oxidation of aliphatic alcohols proved to be unsatisfactory.

2.4. Effect of Light Intensity and Light Wavelength

To prove that the reaction was driven by visible light, the experiments of light intensity and light wavelength have been performed. The results are shown in Figure 4. With an increase in the light intensity, the conversion of the oxidation of benzyl alcohol increased (Figure 4a). With a decrease in the wavelength range, the conversion of benzyl alcohol reduced gradually. In particular, when the wavelength was controlled between 550–800 nm and 600–800 nm, the conversion of the oxidation of benzyl alcohol decreased substantially (Figure 4b). The results were consistent with the strong absorption of gold nanoparticles between 515 and 535 nm (Figure 3) [30]. These experiments illustrated that the reaction was photocatalytic.

2.5. Reaction Mechanism

On the basis of the results from the experiments above, a plausible reaction mechanism is shown in Scheme 1. The mechanism illustrates that when the catalyst surface was irradiated by visible light, it can excite the gold nanoparticles on the surface of catalysts, making the activated gold nanoparticles adsorb the H atoms in the OH group of the benzyl alcohol and form Au−H [33]. Thus, the charge of each atom in the benzyl alcohol molecules has changed. The O atoms of the OH group in the benzyl alcohol molecules (with their negative charge) were adsorbed by the Al3+ of the hydrotalcite. At the same time, the Ni2+ adsorbed the dissociated O atoms from O2 [21,26], which made the O atom adsorb the α-H of the benzyl alcohol. Then the α-H was fractured from the benzyl alcohol molecules, subsequently forming OH with the O atom on Ni2+. The H atom adsorbed on the gold particles was fractured and combined with the OH adsorbed by Al3+ to form water. Next, the OH on the Ni2+ surface transferred to the surface of Al3+, and the O atoms in the benzyl alcohol molecules adsorbed by Al3+ fell off, generating the final product benzaldehyde [28]. The catalyst can continue to participate in the reaction and complete the catalytic cycle.
The reaction mechanism over 3 wt. % Au/Ni3Al HT was different from that over Au/MgAl HT [27] because oxygen took part in the reaction over Au/Ni3Al HT at the beginning, whereas oxygen participated in the reaction after the production of benzaldehyde over Au/MgAl HT.

2.6. Recyclability Test

We tested the recyclability of the catalyst 3 wt. % Au/Ni3Al HT by the conversion of the oxidation of the benzyl alcohol driven by visible light. In the first run, the conversion of the oxidation of the benzyl alcohol was 74.7%, and in the third run, the conversion of the oxidation of the benzyl alcohol was 67.3%. A minor fluctuation occurred during the conversion of the oxidation of the benzyl alcohol, its catalytic activity decreased slightly but the catalyst did not lose its activity. Therefore, the catalyst that we prepared can be reused.

3. Experimental Section

3.1. The Preparation of the Catalyst

3.1.1. The Preparation of the Hydrotalcite

The various hydrotalcite supports, NixAl HT (x = 1, 3 and 5), were prepared by coprecipitation of Ni(NO3)2·6H2O/AlCl3·6H2O and NaOH/Na2CO3 solutions with a mechanical agitator by stirring at room temperature. They were then sedimented for 12 h at room temperature and washed five times in 0.1 mol·L−1 Na2CO3. Afterwards, they were dried at 80 °C for 20 h with a baking oven. Other hydrotalcite supports, such as MgAl HT (with MgCl2·6H2O) and NixMg1−xAl HT (x = 0.3, 0.5 and 0.7), were prepared with the same method [27,34]. Almost all reagents are purchased from J&K Technology Limited Company, Beijing, China. NaBH4 (≥98.0%, Sigma-Aldrich, St. Louis, MO, USA), HAuCl4·3H2O (≥49.0% Au, Sigma-Aldrich, St. Louis, MO, USA), L-Lysine (≥98.0%, J&K Technology Limited Company, Beijing, China). Benzyl alcohol (≥99.0%, Sigma-Aldrich, St. Louis, MO, USA). Trifluorotoluene (≥99.0%, J&K Technology Limited Company, Beijing, China).

3.1.2. The Preparation of Gold Nanoparticle Catalysts

A total of 3 wt. % Au/HT was supported by a NaBH4 reduction method using HAuCl4·3H2O as the gold precursor and NaBH4 as the reducing agent. The 3 wt. % Au/HT catalysts were prepared using a sequential deposition/reduction approach. HT (2.5 g) was dispersed in redistilled water (50 mL) and sonicated for 10 min. The pH value of the solution was adjusted to 10 using NaOH (0.5 mol·L−1) with stirring. Next, the HAuCl4·3H2O solution was added dropwise under sonication. Subsequently, lysine (20 mL) was added to the mixture. After stirring for 30 min, a fresh NaBH4 solution was added. This slurry was filtered before being washed with deionized water and ethanol, respectively. The resulting mixture was dried at 60 °C for 20 h. The catalysts of 3 wt. % Au/NixAl HT (x = 1, 3 and 5, Au/NixAl HT was the shortened form.), 3 wt. % Au/NixMg1−xAl HT (x = 0.3, 0.5 and 0.7, Au/NixMg1−xAl HT was the shortened form.), 3 wt. % Au/MgAl HT (Au/MgAl HT was the shortened form.), 0.5 wt. % Au/Ni3Al HT, 1 wt. % Au/Ni3Al HT, 2 wt. % Au/Ni3Al HT and 4 wt. % Au/Ni3Al HT were prepared with the same method [27,34].

3.2. Catalyst Characterization

The X-ray diffraction patterns (XRD) of the samples were recorded on a RIGAKU D/MAX-2500 (Rigaku Industrial Corporation, Osaka, Japan) X-ray diffractometer using CuKα radiation (λ = 1.5405 Å) at 40 kV and 100 mA. The diffraction data were collected from 5° to 80°. The X-ray photoelectron spectroscopy (XPS) measurements were performed on a Kratos XSAM800 (Kratos Company, Manchester, Britain) using AlKα radiation. The binding energy was calibrated using the C1s photoelectron peak at 284.8 eV as a reference. UV-visible diffuse reflectance spectra (UV-vis DRS) were detected on U-3900 made by Hitachi (Hitachi Limited Company, Tokyo, Japan). The gold contents of the samples and the molar ratios of Ni and Al were quantitated using atomic absorption spectroscopy (AAS) on a GBC AVANTA YX-05 instrument (GBC Scientific Instrument Company, Melbourne, Australia). The product was quantitatively analyzed with a Shimadzu gas chromatograph-2014C (GC-2014C) (Shimadzu Company, Kyoto, Japan). The identity of the product was confirmed via gas chromatography-mass spectrometry (GC-MS) on a Finnigan LCQ Advantage MAX instrument (Finnigan Company, Silicon valley, CA, USA).

3.3. Selective Oxidation of Benzyl Alcohol

The reactions were carried out in a 50 mL round-bottom flask with a magnetic stirrer. In a typical run, a mixture of benzyl alcohol (0.5 mmol), trifluorotoluene (5 mL), the catalyst (50 mg; 3 wt. %) and oxygen as the oxidant was transferred into the reactor. Then, the solution was intensively stirred at 313 K and 1 atm for the reported time with a 500 W halogen lamp. Aluminized paper was wrapped around the flask, and the reaction was run under the light in order to try to make the dark reaction occur in the same external environment as the light reaction. The reactions were followed by gas chromatography (GC) and the structures of the products were confirmed by GC-MS (Finnigan Company, Silicon valley, CA, USA). The catalyst and reactants were separated via centrifugation. Afterward, to do the recycling experiment, the catalyst was washed with Na2CO3 (0.1 mol·L−1) three times and ethanol once only. Finally, the catalyst was dried at 60 °C for 12 h. The recycled catalyst was reused in the next run under the same conditions.

4. Conclusions

In summary, it was demonstrated that the Ni-Al layered double hydroxides (LDHs) with a molar ratio of Ni2+ to Al3+ of 3 (Ni3Al HT) can be used as a support for the photocatalytic oxidation of alcohols under base-free conditions with visible light irradiation under atmospheric pressure using O2 as the sole oxidant. Through a series of characterization methods and experimental detections, the photocatalytic activity and selectivity were found to be excellent on 3 wt. % Au/Ni3Al HT. A relatively reasonable mechanism was proposed. The oxidation of aromatic alcohols was superior using this catalyst, although the oxidation of aliphatic alcohols was not satisfactory—a topic that should become the focus of future research. In a word, Au supported on the hydrotalcite modified by the transition metal Ni was successfully applied to the oxidation of alcohols and it could be applied to other organic processes in the future.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (NSFC, Nos. 20567002 and Nos. 21067007), the Education Department of Inner Mongolia Autonomous Region (NJ04093), Chunhui Plan of the Education Ministry (Z2004-2-15030 and Z2009-1-01005), the Natural Science Fund of Inner Mongolia (2010MS0203 and 2014MS0201), the 2013 Annual Grassland Talents Project of Inner Mongolia Autonomous Region and the 2013 Annual Inner Mongolia Talent Development Fund.

Author Contributions

D.G. carried out the catalyst preparation and their reaction activity studies and drafted the manuscript. Y.W., P.Z., M.B., H.X. and Z.G. participated in the design of the study and assisted in drafting the manuscript. All authors read and approved the final manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. (a) XRD patterns of the different supports; (b) XRD patterns of the Au catalysts with various supports; (c) XRD patterns of the Au/Ni3Al HT catalysts with different gold loadings.
Figure 1. (a) XRD patterns of the different supports; (b) XRD patterns of the Au catalysts with various supports; (c) XRD patterns of the Au/Ni3Al HT catalysts with different gold loadings.
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Figure 2. (a) XPS spectra of the Au 4f core level line for 3 wt. % Au/Ni3Al HT; (b) XPS spectra of the Ni 2p core level line for 3 wt. % Au/Ni3Al HT; (c) XPS spectra of the Al 2p core level line for 3 wt. % Au/Ni3Al HT.
Figure 2. (a) XPS spectra of the Au 4f core level line for 3 wt. % Au/Ni3Al HT; (b) XPS spectra of the Ni 2p core level line for 3 wt. % Au/Ni3Al HT; (c) XPS spectra of the Al 2p core level line for 3 wt. % Au/Ni3Al HT.
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Figure 3. (a) UV-visible diffuse reflection spectra of the different supports; (b) UV-visible diffuse reflection spectra of the Au catalysts with various supports; (c) UV-visible diffuse reflection spectra of the Au/Ni3Al HT catalysts with different gold loadings.
Figure 3. (a) UV-visible diffuse reflection spectra of the different supports; (b) UV-visible diffuse reflection spectra of the Au catalysts with various supports; (c) UV-visible diffuse reflection spectra of the Au/Ni3Al HT catalysts with different gold loadings.
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Figure 4. (a) Effect of light intensity on the photo-oxidation of benzyl alcohol; (b) Effect of the range of light wavelengths on the photo-oxidation of benzyl alcohol.
Figure 4. (a) Effect of light intensity on the photo-oxidation of benzyl alcohol; (b) Effect of the range of light wavelengths on the photo-oxidation of benzyl alcohol.
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Scheme 1. The mechanism for the photocatalytic aerobic oxidations of benzyl alcohol using 3 wt. % Au/Ni3Al HT.
Scheme 1. The mechanism for the photocatalytic aerobic oxidations of benzyl alcohol using 3 wt. % Au/Ni3Al HT.
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Table 1. Composition data obtained for 3 wt. % Au/Ni3Al HT catalysts a.
Table 1. Composition data obtained for 3 wt. % Au/Ni3Al HT catalysts a.
SampleChemical Composition (wt. %)
Au/Ni3Al HTNi2+Al3+AuNi2+:Al3+ molar ratio
40.55.82.63.3
a Determined by AAS.
Table 2. Oxidation of benzyl alcohol over the supported gold catalysts a.
Table 2. Oxidation of benzyl alcohol over the supported gold catalysts a.
EntryCatalystConversion (%) bSelectivity (%) b
LightDarkLightDark
1MgAl HT14.90.2>99>99
2Ni0.3Mg0.7Al HT4.72.6>99>99
3Ni0.5Mg0.5Al HT4.11.2>99>99
4Ni0.7Mg0.3Al HT7.70.4>99>99
5NiAl HT1.40.3>99>99
6Ni3Al HT6.54.5>99>99
7Ni5Al HT5.64.5>99>99
8Au/MgAl HT31.25.0>99>99
9Au/Ni0.3Mg0.7Al HT28.411.2>99>99
10Au/Ni0.5Mg0.5Al HT31.41.2>99>99
11Au/Ni0.7Mg0.3Al HT26.22.3>99>99
12Au/NiAl HT20.92.3>99>99
13Au/Ni3Al HT41.16.8>99>99
14Au/Ni5Al HT37.35.9>99>99
150.5 wt % Au/Ni3Al HT19.10.5>99>99
161 wt % Au/Ni3Al HT19.60.4>99>99
172 wt % Au/Ni3Al HT26.73.5>99>99
184 wt % Au/Ni3Al HT17.77.8>99>99
a Reaction conditions: 1, 4-dioxane (5 mL), benzyl alcohol (0.5 mmol), catalyst (50 mg), O2 (1 atm), exposure time (24 h). Light source: 500 W halogen lamp. The solution temperature during exposure was 313 K; b Conversion rate and selectivity were determined by GC.
Table 3. Effect of the solvent on the aerobic oxidation of benzyl alcohol over 3 wt. % Au/Ni3Al HT a.
Table 3. Effect of the solvent on the aerobic oxidation of benzyl alcohol over 3 wt. % Au/Ni3Al HT a.
EntrySolventConversion (%) bSelectivity (%) b
LightDarkLightDark
1toluene41.814.7>99>99
2benzotrifluoride74.5 (45.0) c21.7 (3.9) c>99>99
31, 4-dioxane68.6 (41.1) c24.8 (6.8) c>99>99
4petroleum ether47.720.359.2 d80.2 d
5DMSO5.91.8>99>99
6DMF23.611.6>99>99
7ethanol59.713.3>99>99
8methanol22.29.953.7 e34.7 e
a Reaction conditions: solvent (5 mL), benzyl alcohol (0.5 mmol), catalyst (50 mg), O2 (1 atm), exposure time (48 h). Light source: 500 W halogen lamp. The solution temperature during exposure was 313 K; b Conversion rate and selectivity were determined by GC; c Exposure time was 24 h; d The other product was benzyl benzoate; e The other product was methyl benzoate.
Table 4. Oxidation of different alcohols over 3 wt. % Au/Ni3Al HT a.
Table 4. Oxidation of different alcohols over 3 wt. % Au/Ni3Al HT a.
EntrySubstrateProductConversion (%) bSelectivity (%) b
LightDarkLightDark
1benzyl alcoholbenzaldehyde74.521.7>99>99
24-methyl benzyl alcohol4-methyl benzaldehyde60.127.2>99>99
34-methoxybenzylalcohol4-methoxy benzaldehyde77.834.4>99>99
4 c4-nitro benzyl alcohol4-nitrobenzaldehyde21.45.1>99>99
54-chloro benzyl alcohol4-chlorobenzaldehyde62.718.8>99>99
6phenylethanolacetophenone89.19.1>99>99
7cinnamyl alcoholcinnamyl aldehyde67.75.8>99>99
8crotyl alcoholcrotonaldehyde32.117.0>99>99
9n-octanoln-octanal4.80.3>99>99
a Reaction conditions: benzotrifluoride (5 mL), alcohol (0.5 mmol), catalyst (50 mg), O2 (1 atm), exposure time (48 h). Light source: 500 W halogen lamp. The solution temperature during exposure was 313 K; b Conversion rate and selectivity were determined by GC; c Reaction solvent was 1, 4-dioxane.
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