Efficient conversion of benzylalcohol on a mesoporous Co3O4

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Efficient conversion of benzylalcohol on a mesoporous Co3O4 Qiaoqiao Zhang, Xiaoran Fu, Qiubin Kan, and Jingqi Guan Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.9b00075 • Publication Date (Web): 05 Mar 2019 Downloaded from http://pubs.acs.org on March 10, 2019

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Industrial & Engineering Chemistry Research

Efficient conversion of benzylalcohol on a mesoporous Co3O4

Qiaoqiao Zhang, Xiaoran Fu, Qiubin, Kan, and Jingqi Guan*

College of Chemistry, Jilin University, JieFang Road 2519, Changchun 130023, PR China *E-mail: [email protected] (J. Guan)

1

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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ABSTRACT High-efficiency conversion of benzylalcohol to benzaldehyde on heterogeneous catalysts using oxygen as oxidant is important in industrial catalysis due to economic and environmentally friendly superiority. Herein, an ordered mesoporous Co3O4 was fabricated

by

copying

hexagonally

mesoporous

silica

SBA-15.

Various

characterization technologies show that the prepared cobalt oxide has ordered mesoporous structure. The mesoporous Co3O4 can partially oxidize benzylalcohol with 93.6% of conversion by using air as an oxidant, much higher than that achieved on commercial cobalt oxide under the same condition. The mesopore in Co3O4 can facilitate the adsorption of substrate and oxidant to the active centers and diffusion of product and hence improve the catalytic performance.

KEYWORDS: Benzylalcohol; Selective oxidation; SBA-15; Mesoporous cobalt oxide; Hard template

1. INTRODUCTION Benzaldehyde is widely applied as the intermediate to produce medicine, dyestuff, and perfume in the chemical industry.1-4 In general, the hydrolysis of benzylidene chloride can produce benzaldehyde in traditional industries,5 in which induction of chloride is unavoidable, which does great harm to the environment. Benzylalcohol as a vital raw material is a kind of extremely popular chemical reactant in many catalytic reactions, which can be converted into various products, such as aldehydes6, esters7, amines8. In fact, it has been demonstrated that benzaldehyde could 2


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be obtained by selectively oxidizing benzylalcohol with some oxidants such as H2O2, KMnO4, CrO3, and O2.1,6,9-13 Among them, O2 is an optimal choice due to environmental and energy crisis, which is a cheap and environmentally friendly oxidant.14 However, there are still many challenges since high-efficiency, stable, and cheap catalysts are urgently needed.15 To date, some metal-based materials played a more and more important role in heterogeneous catalysis, such as Fe-based14, Co-based7, and Ni-based8 catalysts. It has been demonstrated that mesoporous metal-based materials possess widely applications owing to the large superficial area and porosity, which were widely used as microwave absorbers16, electrode materials17,18, sensors19,20, and catalysts21-26, etc. Over the course of the decades, lots of mesoporous silica materials were synthesized.27,28 Inspired by ordered mesoporous silica materials, some ordered mesoporous metal oxides were successfully synthesized even if huge challenges exist. For example, Stucky and coworkers synthesized some mesoporous metal oxides with semicrystalline fabric by soft template synthesis method.29 In addition, Zhu et al adopted a hard templating method to synthesize ordered mesoporous chromic oxide.30 Among several mesoporous metal oxides, mesoporous cobalt oxides possess the unique spinel structure and mixed valence of Co2+ and Co3+, which may perform great potential for the heterogeneous catalysis. Yue et al took advantage of FDU-12, KIT-6, and SBA-16 to synthesize mesoporous Co3O4 with different superficial areas.31 Over the last decade, mesoporous cobalt oxides have begun to gain great attention for applications in catalysis. Ordered mesoporous cobalt oxides with the cubic framework 3



have been synthesized, which exhibited excellent catalytic performances for CO oxidation.32 In addition to CO oxidation, a mesoporous cobalt oxide by copying KIT-6 can catalyze the oxidation of methanol and benzylalcohol.33,34 In this work, we synthesized a new mesoporous Co3O4 (meso-Co3O4) catalyst via copying SBA-15, which could facilitate conversion from benzylalcohol to benzaldehyde with air as an oxidant. The structure of meso-Co3O4 was investigated by several characterization techniques. The measurements of benzylalcohol oxidation reaction demonstrated that meso-Co3O4 possessed higher catalytic performance than commercial Co3O4 under the same condition.

2. EXPERIMENTAL SECTION 2.1. Catalyst preparation Mesoporous silica SBA-15 was prepared according to the previous literature.35 Typically, 1.0 g of SBA-15 was dispersed in 50 mL of toluene at 65 °C. Then, 2.0 g of cobalt nitrate was added into this mixture along with forceful stirring for 3 h. After filtrating, the obtained pink powders were calcined at 600 °C for 6 h. The SBA-15 template was removed by washing with 2 M of hot NaOH solution, and mesoporous Co3O4 without template was finally obtained, which was denoted as meso-Co3O4.

2.2. Characterization Small-angle XRD pattern was recorded by using a Riguku D/MAX2550 diffractometer, where the 2θ range is 0.5-5o. Transmission electron microscope 4


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(TEM) images were obtained by a Hitachi HT7700. Raman spectrum was recorded on a Renishaw Raman spectrometer. The infrared spectra (IR) of various samples were recorded on a NICOLET Impact 410 spectrometer. N2 adsorption-desorption isotherms were performed on a Micromeritics ASAP 2020. Scienta ESCA200 spectrometer with Al-Kα radiation was used to measure the XPS spectra.

2.3. Catalytic tests The benzylalcohol oxidation reaction was performed in a flask with the condenser and air pump. In this reaction, 1 mmol of benzylalcohol, 8 mL of solvent, and 120 mg of the catalyst were added, followed by flowing dry air at the rate of 80 mL min-1. The filtrate was analyzed by a Shimadzu GC-8A (Japan) gas chromatography (GC). The main product is benzaldehyde, while the main by-product is benzoic acid. The catalyst can be recycled and reused by filtering, washing, and drying. Small amount of benzoquinone and trace amount of benzyl benzoate are also detected. The turnover frequency

(TOF)

is

calculated

according

to

The number of moles of the target product (benzaldehyde)

.

𝑇ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑑 𝑜𝑓 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 ∗ 𝑡𝑖𝑚𝑒

3. RESULTS AND DISCUSSION 3.1. Structure characterization

5


the

equation:

TOF=


(110)

1

(200)

2 3 4 2 theta (degree)

(311)

b

SBA-15 meso-Co3O4

(100)

meso-Co3O4

Intensity (a.u.)

a Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

5

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(220)

(511)

(111)

(440)

(400) (222)

(422)

commercial Co3O4

10

20

30 40 50 2 theta (degree)

60

70

Figure 1. (a) Small-angle XRD patterns of SBA-15 and meso-Co3O4, and (b) wide-angle XRD patterns of commercial Co3O4 and meso-Co3O4.

Figure 1a shows the small-angle XRD patterns of SBA-15 and meso-Co3O4. The existence of three signals for SBA-15 can be indexed to (100), (110), and (200) diffraction planes. Compare with SBA-15, these peaks of meso-Co3O4 shift negatively, indicating ordered pore structure is formed.36 The wide-angle XRD pattern of meso-Co3O4 (Figure 1b) displays the similarity to that of the commercial Co3O4, which is the typical characteristic of spinel structure.37

6


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0

0.0

5

10 15 Pore size (nm)

20

0.2 0.4 0.6 0.8 Relative Pressure (P/P0)

b dV/dD (cm3g-1nm-1)

dV/dD (cm3g-1nm-1)

a

Quantity Adsorbed (cm3/g)

Figure 2. SEM (a) and TEM (b) images of meso-Co3O4.

Quantity Adsorbed (cm3/g)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.0

1.0

0

5

10 15 Pore size (nm)

20

0.2 0.4 0.6 0.8 Relative Pressure (P/P0)

1.0

Figure 3. N2 adsorption–desorption isotherms and pore size distributions of (a) SBA-15 and (b) meso-Co3O4.

The SEM and TEM image of meso-Co3O4 is exhibited in Figure 2. From Figure 2a, meso-Co3O4 shows similar morphology to the parent SBA-15.38-40 From Figure 2b, meso-Co3O4 displays a regular porous property with pores throughout the particles, and the pore diameter is approximately 2.0 nm, which is from the replication 7



of the walls of SBA-15.

a

A1g

Meso-Co3O4

Fg F2g F2g

200

b

Co-O

Absorbance (a.u.)

Commercial Co3O4

Intensity(a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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F2g

400 600 800 -1 Raman shift (cm )

1000 400

Co-O

Commercial Co3O4 Meso-Co3O4

600 800 Wavenumber (cm-1)

1000

Figure 4. (a) Raman spectra and (b) FT-IR spectra of meso-Co3O4 and commercial Co3O4.

N2 adsorption–desorption isotherms and pore size distribution of SBA-15 and meso-Co3O4 are demonstrated in Figure 3. Both samples demonstrate a typical IV isotherm, suggesting the existence of mesoporous structure. Figure 4a depicts the Raman spectra of meso-Co3O4 and commercial Co3O4. Five peaks are located in Raman shifts of about 194, 480, 522, 619, 686 cm-1, which can be attributed to Raman vibrations of cobalt oxide.41 Compared with commercial Co3O4, the peak position of meso-Co3O4 shifts positively and the peak intensity increases, indicating that smaller Co3O4 nanoparticles are formed in meso-Co3O4. FT-IR spectrum of meso-Co3O4 and commercial Co3O4 is displayed in Figure 4b. The two peaks located at 667 and 580 cm−1 are due to the vibration of Co-O bond.

8


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a

b

Co 2p3/2 Co 2p

Sat. Co2+ Sat.

810

O 1s

Ox-

Intensity (a.u.)

Co3+

Co 2p1/2

Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


540

800 790 780 Binding Energy (eV)

OLatt

535 530 Binding Energy (eV)

525

Figure 5. High-resolution XPS spectra of Co 2p (a) and O 1s (b) for meso-Co3O4.

The surface status of meso-Co3O4 was analyzed by XPS in Figure 5. Figure 5a shows Co 2p XPS spectrum, where the Co 2p3/2 and Co 2p1/2 are located at 781.2 eV and 796.3 eV, respectively. The Co 2p3/2 can be deconvolved into two peaks located at 782.5 eV and 781.1 eV, which represents the Co2+ and Co3+, respectively.42,43 For O 1s XPS spectrum (Figure 5b), it is deconvolved into two peaks located at 530.9 eV and 532.2 eV. The peak at 530.9 eV originates from the surface lattice oxygen species (OLatt), while the binding energy of 532.2 eV is characteristic of the surface adsorbed oxygen (Ox-).44,45

3.2. Catalytic performance The reaction performance of meso-Co3O4 and commercial Co3O4 for benzylalcohol oxidation is investigated under various experimental conditions. As shown in Table 1, a low benzylalcohol conversion of the blank reaction is manifested. Commercial Co3O4 shows low catalytic activity (Entry 2), while meso-Co3O4 displays 9



high activity (93.6%) and high selectivity (98.2%) at a suitable experimental condition (Entry 3). Experiments have been carried out under various solvents such as DMF, CH3CN, etc (Entries 6-8). The experimental result shows that the catalytic performance in DMF exhibits superiority for benzylalcohol oxidation, while it is extremely low in water (Entry 8). As shown in Table 1, the effect of temperature on this oxidation reaction with the catalysis of meso-Co3O4 has been studied. When the temperature decreases to 110 oC (Entry 9), the catalytic activity and selectivity become low. When the temperature increases to 130 oC (Entry 10), the activity improves, while the selectivity decreases. Therefore, the temperature of 120 oC should be the optimal temperature for selective oxidation of benzaldehyde on meso-Co3O4. The reactive time of benzylalcohol oxidation is extremely vital, which can influence the efficiency of a specific reaction. From Table 1, the conversion and selectivity rise as the reactive time increases until the reactive time is 8 h. The enhancement of time from 8 h to 10 h shows the rapid drop of benzaldehyde selectivity, which results from the rise of by-products with increasing reaction time.46 Therefore, the catalytic performance of benzylalcohol oxidation on meso-Co3O4 is applicable at the reactive time of 8 h. Compared with commercial Co3O4, the TOF value of meso-Co3O4 is 2.3 times, further demonstrating the enhanced catalytic activity of meso-Co3O4. In addition, the catalytic performance of meso-Co3O4 is compared with some Co-based catalysts reported previously (Table 2). Meso-Co3O4 shows higher activity than most cobalt-based catalysts. The high activity can be ascribed to the ordered mesoporous property and large superficial area, which can make the reactants adsorb 10


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and diffuse quickly.33

Table 1. Performance parameters for benzylalcohol oxidationa

En try

Catalyst

Tim e (h)

Solvent

1

Blank

8

120

18.9

2

Commercial Co3O4

DMF

8

120

49.5

3

meso-Co3O4

DMF

8

120

93.6

4

meso-Co3O4

DMF

6

120

5

meso-Co3O4

DMF

10

6

meso-Co3O4

Toluene

7

meso-Co3O4

8

Selectivity (%) TOF (h−1)

Benzaldehy Othe de rs >99

-

80.6

19.4

0.23

98.2

1.8

74.3

0.24

98.5

1.5

120

94.8

0.17

90.9

9.1

8

120

18.2

0.05

>99

-

CH3CN

8

120

37.5

0.09

>99

-

meso-Co3O4

Water

8

120

2.8

0.007

>99

-

9

meso-Co3O4

DMF

8

110

84.1

0.2

93.8

6.2

10

meso-Co3O4

DMF

8

130

94.8

0.21

89.5

10.5

aReaction

DMF

Tem pera Conver ture sion (oC) (%)

0.1

condition: catalyst 120 mg, benzylalcohol 1 mmol, solvent 8 mL, flow of air 80

mL·min-1.

Table 2. Performance parameters for benzylalcohol oxidation on some cobalt-based catalysts with air as the oxidant Benzaldehyde Catalyst

Temperature (°C )

Conversion (%)

Reference selectivity (%)

meso-Co3O4

120

93.6 11


98.2

This work


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3D-Co3O4

120

86.7

97.4

34

Co-ZIF-67

100

43

97

47

Co/C700

100

34

34

48

For evaluating the reaction stability of meso-Co3O4, leaching experiment is carried out. After the reaction of 2 h on meso-Co3O4, the meso-Co3O4 catalyst is filtered and the resulting solution without meso-Co3O4 is required to continue to react. The leaching result is depicted in Figure 6a, showing that the rate of benzylalcohol oxidation becomes obviously slow when the meso-Co3O4 catalyst is removed, while the benzylalcohol can be converted on meso-Co3O4 at a very quick rate, which demonstrates the excellent catalytic performance on meso-Co3O4 for benzylalcohol oxidation. Due to the significance of good stability in practical applications, the recycling experiment of meso-Co3O4 for benzylalcohol oxidation is implemented as depicted in Figure 6b. The experimental result shows that meso-Co3O4 possess high stability for benzylalcohol oxidation, which can still catalyze efficiently the reaction after 5 recycling times.

12


100

b

a

80 70 60 50 40 30 20

0

1

2

3

4 5 6 Time (h)

7

8

Benzylalcohol conversion (%) Benzaldehyde selectivity (%)

100

Benzylalcohol conversion (%)

Catalyst without interruption Catalyst was removed after 2 h

90 Conversion (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


100

80

80

60

60

40

40

20

20

0

9

1

2 3 4 Recycling times

0

5

Benzaldehyde selectivity (%)

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Figure 6. (a) Leaching experiment and (b) reuse experiment of the meso-Co3O4 catalyst for benzylalcohol oxidation.

OH O Co

Co O

-H2O

O2

OH OH

O*

O

OH

Co

Co

O Co

O O

O

Co O

O

OH

Figure 7. Proposed reaction mechanism for benzylalcohol oxidation on meso-Co3O4.

3.3. Catalytic mechanism According to some relevant literature about partial oxidation of alcohols on 13



Co-based catalysts,49,50 a reaction mechanism is proposed as shown in Figure 7. An oxygen molecule is first absorbed on the surface of meso-Co3O4, which is activated to form superoxide. This superoxide oxidizes benzylalcohol (tetra molecular) to produce benzaldehyde, and the meso-Co3O4 is regenerated to the original state.

4. CONCLUSIONS Ordered mesoporous cobalt oxide was synthesized through a hard templating strategy. The achieved meso-Co3O4 possesses a high superficial area and a regular porous structure. The meso-Co3O4 shows superior conversion (93.6%) and selectivity to benzaldehyde (98.2%) than commercial Co3O4 for benzylalcohol oxidation. Moreover, meso-Co3O4 exhibits good stability since the benzylalcohol conversion shows no obvious drop for benzylalcohol oxidation after 5 recycling times. Therefore, meso-Co3O4 shows great potential in industrial catalysis and the benzylalcohol oxidation on meso-Co3O4 has potential practical value.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (J. Guan) Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS 14


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This work was supported by the Natural Science Foundation of Jilin province (20180101291JC).

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O2

Mesoporous Co3O4


Efficient conversion of benzylalcohol on a mesoporous Co3O4

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