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Applied Catalysis A: General 292 (2005) 223–228 www.elsevier.com/locate/apcata Catalytic oxidation of cyclohexane to
Applied Catalysis A: General 292 (2005) 223–228 www.elsevier.com/locate/apcata Catalytic oxidation of cyclohexane to

Applied Catalysis A: General 292 (2005) 223–228

Applied Catalysis A: General 292 (2005) 223–228 www.elsevier.com/locate/apcata Catalytic oxidation of cyclohexane to

www.elsevier.com/locate/apcata

Catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone over Co 3 O 4 nanocrystals with molecular oxygen

Lipeng Zhou, Jie Xu * , Hong Miao, Feng Wang, Xiaoqiang Li

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Graduate School of the Chinese Academy of Sciences, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, PR China

Received 7 April 2005; received in revised form 27 May 2005; accepted 11 June 2005 Available online 8 August 2005

Abstract

Co 3 O 4 nanocrystals with average particle sizes of 30 and 50 nm were synthesized using cobalt nitrate as precursor, and were characterized by X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), and Fourier transform infrared (FT-IR) spectroscopy. Catalytic oxidation of cyclohexane with molecular oxygen was studied over Co 3 O 4 nanocrystals. These catalysts showed obviously higher activities as compared to Co 3 O 4 prepared by the conventional methods, Co 3 O 4 /Al 2 O 3 , or homogeneous cobalt catalyst under comparable reaction conditions. The 89.1% selectivity to cyclohexanol and cyclohexanone at 7.6% conversion of cyclohexane was realized over 50 nm sized Co 3 O 4 nanocrystals at 393 K for 6 h. # 2005 Elsevier B.V. All rights reserved.

Keywords: Nanocrystals; Co 3 O 4 ; Cyclohexane; Oxidation

1. Introduction

Oxidation of cyclohexane is one of the important bulk processes for the production of polyamide fibers and plastics, such as nylon-6 and nylon-6,6. More than 10 6 tonnes of cyclohexanone and cyclohexanol (K/A oil) are produced worldwide per annum [1]. Industrially, the process for cyclohexane oxidation is carried out at 423–433 K in the presence of cobalt-based homogeneous catalyst, resulting in about 4% conversion and 70–85% selectivity to K/A oil [2]. This process is low in energy efficiency, and generates plenty of by-products and waste. Increasing environmental concerns in recent years, as well as great demands for these products call for a more effective catalytic process using environmen- tally friendly oxidant, such as molecular oxygen [3,4]. Catalysts, such as TS-1, Ti-MCM-41, and metal containing aluminophosphate molecular sieve, have been employed for the cyclohexane oxidation, using molecular oxygen as oxidant [5–8]. MnAPO-36 was found to be the most active

* Corresponding author. Tel.: +86 411 84379245; fax: +86 411 84379245. E-mail address: xujie@dicp.ac.cn (J. Xu).

0926-860X/$ – see front matter # 2005 Elsevier B.V. All rights reserved.

doi:10.1016/j.apcata.2005.06.018

one, and 13% conversion of cyclohexane and 62% selectivity to K/A oil were obtained at 403 K for 24 h under 1.5 MPa air pressure [9]. However, most of these systems show relatively low selectivity to the desired products, or exhibit low activity. As Schuchardt et al. have acknowledged, although many attempts have been made in the cyclohexane oxidation, it continues to be a challenge [10]. Nanostructured materials have attracted great interest in recent years due to their particular physical and chemical properties [11,12]. The properties of these materials mainly depend on their shape, size, and structure, which are strongly determined by the synthetic processes. Nanostructured catalysts, such as Fe 2 O 3 , Co 3 O 4 , and mixed Fe–Co oxide, have been employed in the cyclohexane oxidation [13–15]. Unfortunately, these catalysts are unstable during the reaction. For example, employing Fe 2 O 3 nanoparticles as catalyst in cyclohexane oxidation, the conversion in the second run was decreased to about 70% of that in the first run [15]. The poor recyclability may attribute to the fact that the particles are amorphous and thus easy to leach into solution during reaction [15]. Although there are several reports on the preparation of cobalt oxide nanoparticles [16–19],

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L. Zhou et al. / Applied Catalysis A: General 292 (2005) 223–228

synthesis of Co 3 O 4 nanocrystals with a sharp distribution of particle size is still a difcult task, since the precipitation of cobalt in solution is very fast under basic conditions, and the particles agglomerate to form congeries of random shape in synthetic process. In this paper, we demonstrated a convenient method for synthesizing the stable Co 3 O 4 nanocrystals from the commercially available inorganic cobalt salt. N-Cetyl- N,N,N-trimethyl ammonium bromide (CTAB) and in situ generated triethylamine salt were applied as stabilizers to prevent the agglomeration of the particles during the preparation process, and Co 3 O 4 nanocrystals with narrow size distribution were successfully obtained. The nanopar- ticles of Co 3 O 4 could effectively catalyze the oxidation of cyclohexane to K/A oil under mild conditions with molecular oxygen as oxidant. The heterogeneity of the reaction, the stability and the recyclability of the catalyst make this system attractive for potential industry applica- tions.

2. Experimental

2.1. Catalyst preparation

All chemicals were of analytic grade without any purication. Co(NO 3 ) 2 6H 2 O (99%), N-cetyl-N,N,N-tri- methyl ammonium bromide (99%), Na 2 CO 3 (99%), and (CH 3 CH 2 ) 3 N (TEA, 99%) were purchased from Tianjin Kermel Chemical Reagent Development Center. Co 3 O 4 nanocrystals were prepared by precipitation method using cobalt nitrate as the precursor in the presence of CTAB. In a typical synthesis, 124.5 mmol of Co(N- O 3 ) 2 6H 2 O and 25.0 mmol of CTAB were dissolved in 750 mL deionized water, in a 1000 mL round bottom ask, giving a pink solution. After stirring for 20 min, 249.0 mmol of triethylamine was rapidly added into the pink solution under vigorous agitation, giving a blue mixture. Then, the blue mixture was stirred at 348 K for 8 h, and the color of the mixture changed into black. The as-synthesized cobalt oxide was obtained by centrifugation and then dried at 353 K for 48 h. The dried material was treated by Soxhlet extraction over ethanol for 48 h to remove stabilizers. The obtained solid referred to as Catalyst 1 was calcined at 573 K under owing air for 2 h after drying at 373 K for 8 h. Catalyst 2 was prepared by the following procedure: 12.5 mmol of Co(NO 3 ) 2 6H 2 O and 2.5 mmol of CTAB were used with the same molar ratio of Co/TEA, while the other experimental conditions were same with Catalyst 1. For comparison, Co 3 O 4 was prepared by conventional method adapted from literature [17]. A solution of Na 2 CO 3 was added into a solution of cobalt nitrate under agitation, and then the mixture was stirred for 8 h at 348 K. The precipitate was ltrated and washed with deionized water for three times, and then the solid was calcined at 573 K under owing air for 2 h after it was dried at 373 K for 8 h. This

sample was designated as Catalyst 3. Co 3 O 4 was also prepared by air-calcination of cobalt nitrate at 673 K for 2 h. Supported catalyst loading 5 wt% Co 3 O 4 was prepared by impregnation of g-Al 2 O 3 (BET surface area: 233 m 2 /g and pore volume: 0.389 cm 3 /g) with an aqueous solution of cobalt nitrate. After impregnation for 48 h, the materials were dried at 393 K overnight, and nally calcined at 673 K for 2 h (XRD analysis indicates cobalt oxide was in the cubic structure of Co 3 O 4 ).

2.2. Characterization of catalysts

X-ray diffraction (XRD) patterns were recorded on a PANalytical XPert PRO instrument with Cu Ka (0.154 nm) radiation at 40 kVand 40 mA in the range of 1070 8 . A scan rate of 0.208891 8 /s with a step size of 0.016711 8 was used for data collection. BET surface area of the samples was determined by nitrogen adsorption at 77 K using a Quantachrome NOWA 4000 apparatus. Fourier transform infrared (FT-IR) spectroscopy was performed on a Bruker Tensor 27 FT-IR spectrometer with 32 scans for a resolution of 4 cm 1 in KBr media at room temperature. The microstructures of the catalysts were examined by transmission electron microscopy (TEM) on a JEOL JEM- 2000EX electron microscope at an accelerating voltage of 100 kV. For elemental analysis, the ICP analysis was carried out using a TJA Advantage ICP-AES instrument.

2.3. Catalytic tests

The liquid-phase oxidation of cyclohexane was performed in a 100 mL autoclave reactor with a Teon insert inside. Typically, 15 g cyclohexane, 0.1 g (65 wt%) tert-butyl hydroperoxide (TBHP), and 0.2 g catalyst were added into the reactor. Then, the reactor was heated to the reaction temperature after sealing, while agitation was realized by means of a magnetic stirrer. Upon heating to the reaction temperature, the reactor was charged with 1.0 MPa of O 2 . During reaction, oxygen was fed continuously to maintain constant pressure at 1.0 MPa. When the reaction was stopped, the reaction mixture was diluted with 15 g ethanol to dissolve the by-products. The reaction products were identied by comparison with authentic products and by GCMS analysis. After the quantitative decomposition of cyclohexyl hydro- peroxide (CHHP) to cyclohexanol by adding excess triphenylphosphine to the reaction mixture, the quantitative analyses of cyclohexanol and cyclohexanone were carried out by an Agilent 4890D gas chromatography, which was equipped with an OV-1701 column (30 m 0.25 mm 0.3 mm), using toluene as the internal standard. The concentrations of CHHP were determined by iodometric titration, and the acid and ester by acidbase titration. Typically, CHHP was analyzed by following procedure:

L. Zhou et al. / Applied Catalysis A: General 292 (2005) 223228

225

/ Applied Catalysis A: General 292 (2005) 223 – 228 225 Fig. 1. XRD patterns of

Fig. 1. XRD patterns of Catalysts 13.

20 mL acetic acid was added to 510 g reaction mixture, 10 mL saturated KI solution was added, and the mixture was stored for 20 min in darkness and then titrated with 0.1 M Na 2 S 2 O 3 solution. Acids and esters were analyzed as follows:

0.2 g triphenylphosphine was added to 510 g reaction mixture to decompose CHHP, the solution was kept for 30 min before diluting with 25 mL acetone, and 25 mL deionized water and then titrated with 0.1 M NaOH. The solution was reuxed for 1 h after adding 20 mL 0.1 M NaOH and then titrated with 0.1 M HCl.

3. Results and discussion

3.1. Preparation and characterization

Cobalt oxide nanoparticles was prepared from cobalt nitrate in the presence of CTAB and in situ generated triethylamine salt. The BET surface area of Catalysts 13 was 21, 57, and 79 m 2 /g, respectively. Fig. 1 summarizes the XRD patterns of the calcined catalysts prepared by the present method and its comparison with that prepared by the conventional method. Within these peaks, eight peaks at 36.88, 65.38, 59.48, 31.38, 44.88, 18.98, 38.58, and 55.78 in

59.4 8 , 31.3 8 , 44.8 8 , 18.9 8 , 38.5 8 , and

Fig. 3. FT-IR spectra of Catalyst 1: (a) after calcinations, (b) as-synthesized after, and (c) before extraction of stabilizers.

decreasing order of peak height of the three samples can be assigned to the cubic structure of Co 3 O 4 with Fd3m space group as compared to a data le JCPDS-43-1003, which gives eight peaks at 36.88, 65.28, 59.38, 31.38, 44.88, 19.08, 38.58, and 55.78 in decreasing order of peak height. The value of the cell constant (a = 0.8082) is very near to the published data for Co 3 O 4 powder (a = 0.8084). This indicates that these catalysts had highly crystallized cubic structure. The particle sizes of Catalysts 13 calculated from the (3 1 1) plane using the Sherrer equation were 33, 24, and 19 nm, respectively. The microstructure of Co 3 O 4 nanocrystals prepared by present method is given in Fig. 2. TEM analysis had revealed evidence that the particles exhibited platelet morphologies with minor particle agglomeration and a relatively narrow particle size distribution. The average particle diameters of Catalysts 1 (Fig. 1a) and 2 (Fig. 1b) were 50 and 30 nm, respectively. This result was coincident with the particle sizes calculated from the Sherrer equation. It implies that the secondary particles were not formed and the samples were highly crystalline. Fig. 3 shows the FT-IR spectra of Catalyst 1 after calcination (trace a), and those of as-synthesized Catalyst 1

(trace a), and those of as-synthesized Catalyst 1 Fig. 2. TEM photographs of (a) Catalyst 1

Fig. 2. TEM photographs of (a) Catalyst 1 and (b) Catalyst 2.

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L. Zhou et al. / Applied Catalysis A: General 292 (2005) 223228

before (trace c) and after (trace b) extraction of the stabilizers. The bands at 2915 and 2848 cm 1 in trace c were the CH stretching modes attributed to CTAB and triethylamine salt. After extraction of the stabilizers by ethanol, the peaks attribute to CH stretches almost disappeared, which suggested that CTAB and triethylamine salt were mostly removed from samples. Two bands at 668 and 579 cm 1 could be assigned to the vibration of CoO due to Co 3 O 4 [20], as indicated that Co 3 O 4 were formed in the aging process. After addition of triethylamine, at rst the color of the mixture was blue and then it slowly turned into black, showing the color of Co 3 O 4 , in the aging process. The color change provided another evidence that Co 3 O 4 nanoparticles were formed during the aging. CTAB and triethylamine salt stabilized the particles by capping the surface of nanoparticles with organic ligands. The formation of nanoparticles was proposed through inorganicorganic layered particles model. Because the surface of metal oxide particles was polar, and the organic cations of in situ generated triethylamine salt and CTAB were adsorbed on the surface of metal oxide particles. The organic shells can keep the nanoparticles apart from each other by presenting a strong steric hindrance to overcome van der Waals interactions between the nanoparticles [21]. It promoted the formation of nanoparticles with narrow size and shape distribution [2123]. Analogous adsorptions of surfactants on the surface of mica, silica, and metal oxide have also been reported [24,25].

3.2. Catalytic performance

Metal oxide nanoparticles can exhibit unique chemical properties due to their limited size and a high density of corner or edge surface sites [26]. Herein, the activity of the Co 3 O 4 nanocrystals catalysts is compared with the conventionally prepared catalyst and homogeneous cobalt catalyst for the liquid phase oxidation of cyclohexane using molecular oxygen as oxidant. Since the reaction had an induction period, a small amount of TBHP that acted as a radical initiator was added to the reaction system to eliminate the induction period [27]. The products obtained were cyclohexanol, cyclohexanone, CHHP, acid (mainly adipic acid), and ester (dicyclohexyl adipate, hexanolac- tone, and the other esters). CHHP could decompose totally in the chromatograph to produce mainly cyclohexanol and cyclohexanone, so it could not be detected by GC [28,29]. The acid, such as adipic acid, would easily decompose in the GC analyses, hence it could not be exactly determined by GC. The components of esters were quite complicated and some of them also could not be detected by GC [30]. In this study, quantitative analyses of CHHP, acids, and esters were carried out by titration, and cyclohexanol and cyclohexanone by GC. The analytical results of a solution of cyclohexane oxidation from an industrial operation by our method were in accordance with the separated yields, which proved that our analytical method for

Table 1 Oxidation of cyclohexane with different catalysts a

Entry

Catalyst

Conversion

Product distribution (mol%)

 
 

(mol%)

A

K

CHHP

Acid

Ester

1

Blank

1.2

7.3

35.9

53.6

2.3

0.9

2

1

7.6

39.6

49.5

0.8

4.8

5.3

3

2

7.3

33.9

41.7

1.1

14.5

8.8

4

3

1.3

60.4

33.7

2.9

3.0

0

5

1 b

2.8

51.1

33.3

9.8

3.3

2.5

6

1 c

0.2

79.8

20.2

––

7

Co d

4.7

32.6

28.7

0.8

22.5

15.4

8

Co 3 O 4 e

3.5

38.3

31.4

10.7

14.6

5.0

9

Co/Al 2 O 3

2.3

41.0

35.7

12.4

5.4

5.5

10 CoAPO-5

f

1.6

35.0

21.7

44.1

11 CoAPO-5

g

5.8

36.5

41.2

14.2

4.4

3.5

12 MnAPO-5 f

2.7

36.9

56.0

0

5.9

1.2

13 MnAPO-5 g

9.6

26.7

59.8

0

9.0

4.6

a Reaction time: 6 h and reaction temperature: 393 K. A: cyclohexanol, K: cyclohexanone, acid: mainly adipic acid, ester: dicyclohexyl adipate, hexanolactone, and other ester.

b Reaction without TBHP.

c Add 5 wt% 2,6-di-tert-butyl-4-methylphenol (BHT). CHHP, acid, and ester were not analyzed.

d Co(OAc) 2 4H 2 O as catalyst, [Co] = 100 ppm.

e Co 3 O 4 was prepared by air-calcination cobalt nitrate at 673 K for 2 h. XRD analysis indicated Co 3 O 4 had highly crystallized cubic structure.

f Results from Ref. [27]. Reactions were carried at 403 K for 8 h.

g Results from Ref. [27]. Reactions were carried using a free-radical initiator TBHP (0.7 wt% of cyclohexane) at 403 K for 8 h.

the

believable.

reaction

mixture

of

cyclohexane

oxidation

was

3.2.1. Oxidation of cyclohexane over different catalysts As shown in Table 1, the conversions of cyclohexane over Catalyst 3 and Co 3 O 4 prepared by air-calcination of cobalt nitrate, which were prepared by the conventional method, were 1.3% and 3.5%, respectively. Co 3 O 4 /Al 2 O 3 showed a cyclohexane conversion of 2.3%. Further, the reaction was carried out in the absence of catalyst (entry 1) and a low conversion was noted. On the other hand, Co 3 O 4 nanocrys- tals showed obviously higher conversion as compared to Co 3 O 4 prepared by the conventional method or Co 3 O 4 / Al 2 O 3 under same reaction conditions. For example, Catalyst 1 exhibited the best performance, with a cyclo- hexane conversion of 7.6%, 89.1% selectivity, and a yield of 6.7% to K/A oil, which was higher than those obtained using metal substituted AlPO-n, or MCM-41 as catalyst [68,27]. Addition of TBHP, which acts as a free-radical initiator, decreased the induction period and the conversion was increased (entries 2 and 5). Similar phenomenon was also observed in cyclohexane oxidation with MeAlPO-5, such as CoAPO-5 and MnAPO-5 (entries 1013), as catalysts. It should be noted that the homogeneous cobalt catalyst showed a cyclohexane conversion of only 4.7% and a selectivity of 61.3% to K/A oil under comparable reaction conditions (entry 7). The conversion over Catalysts 1 and 2 were comparable, which suggests that particle sizes range from 30 to 50 nm had slight effect on the conversion of

L. Zhou et al. / Applied Catalysis A: General 292 (2005) 223228

227

/ Applied Catalysis A: General 292 (2005) 223 – 228 227 F i g . 4

Fig. 4. Inuence of reaction temperature on Catalyst 1 performance.

t a l y s t 1 p e r f o r m a n

Fig. 5. Inuence of reaction time on cyclohexane oxidation over Catalyst 1.

cyclohexane. However, the selectivity to K/A oil on the Catalyst 1 was higher than that of Catalyst 2. One of the possible reasons may be attributed to that smaller particles have stronger surface energy, which will lead to the over- reaction of cyclohexanol and cyclohexanone to by-products. As Catalyst 1 was the most active catalyst in this work, we have chosen this catalyst for the more detailed study.

3.2.2. Effect of reaction temperature Fig. 4 shows the effect of the reaction temperature on cyclohexane oxidation at reaction time of 6 h. As expected, the conversion of cyclohexane increased with reaction temperature. On the other hand, at initial stage, the selectivity to K/A oil went up with increasing temperature and reached a maximum of 89.1% at 393 K, and then decreased remarkably with further increasing of tempera- ture. The distribution of cyclohexanone also reached its maximum 49.5% at 393 K and the change trend was similar with that of selectivity to K/A oil. However, as reaction temperature increases, the distribution of cyclohexanol decreased all along. At rst the change was very small, and then cyclohexanol distribution decreased sharply. In addi- tion, the molar ratio of K/A oil went up when the temperature was increased, which suggests that cyclohex- anol was continuously oxidized to cyclohexanone [1]. The change trend of CHHP distribution was like that of cyclohexanol, and there was very small quantity of CHHP in the reaction mixture when the reaction temperature was above 393 K. For example, the CHHP distribution was only 0.8% at 393 K. The selectivity to K/A oil increased while the distribution of CHHP decreased at high reaction tempera- ture, and this show that CHHP is an unstable intermediate and it could decompose to cyclohexanol, cyclohexanone [1]. Generally, the acid and ester were the products of deep oxidation of K/A oil. The distributions of these by-products increased with increasing of the reaction temperature, which indicates that, at higher temperature, the rate of oxidizing the substrate to desired products was slower than that of oxidizing K/A oil to form by-products. Thus, reaction

temperature is an important reaction parameter to maintain a high selectivity to the desired products. For this reason, 393 K was the most proper reaction temperature and thus selected as reaction temperature for the subsequent studies.

3.2.3. Effect of reaction time The effect of reaction time on cyclohexane conversion and products distributions at reaction temperature of 393 K is shown in Fig. 5. It can be seen the cyclohexane conversion steadily increased with increasing reaction time. In addition, the selectivity to K/A oil rose to its maximum 90.4% at 4 h, and decreased with further increase reaction time. At initial 4 h, the distribution of alcohol changed slightly, but it decreased with further increasing reaction time. On the other hand, the selectivity of cyclohexanone increased during the initial 8 h and reached a maximum of 55.4% at reaction time of 8 h, and then decreased with further increasing reaction time. The distribution of CHHP decreased sharply during the initial 6 h period, and thereafter the amount of CHHP became very little (<1%). The distribution of acid and ester increased with increasing reaction time. However, the highest yield of K/A oil was obtained at the reaction time of 6 h. We chose 6 h for the subsequent studies.

time of 6 h. We chose 6 h for the subsequent studies. Fig. 6. Catalytic performance

Fig. 6. Catalytic performance of the fresh and recycled Catalyst 1.

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L. Zhou et al. / Applied Catalysis A: General 292 (2005) 223228

3.2.4. The stability of catalyst

In order to check the recyclability of the catalyst, six

reaction runs were carried out. After each reaction the catalyst was separated by ltration and washed with water and ethanol for several times, then the catalyst was dried at 393 K for 8 h to remove water and ethanol. The regenerated catalyst was used for the recycling study under the same reaction conditions. The results on the fresh and recycled catalyst are shown in Fig. 6. It can be seen that the conversion of cyclohexane on the recycled catalyst was slightly lower than that on fresh catalyst. The selectivity of K/A oil on recycled catalyst was almost equal with that over fresh catalyst. These results disclose that the catalyst is stable or could be recycled after the reaction. Analyzing the reaction mixture with ICP mass spectrometry, only a small amount of cobalt (0.1 ppm) was observed, which

could be attributed to leaching of cobalt ions or the nanoparticles not removable by ltration. To study whether the catalytic reaction was via heterogeneous catalysis, the solution of reaction mixtures was ltered after reaction for 4 h, and then was reacted at 393 K for another 2 h under stirring. It was found that the conversion of the ltrate changed from 4.5% to 5.3%, which would attribute to the autoxidation or the cobalt in the ltrate. These evidences proved that the reaction was a heterogeneous process, because the amount of dissolved cobalt is much lower than in the homogeneous catalysis and the contribution from homogeneous cobalt is neglectable [7]. The oxidation of cyclohexane is believed to be a free- radical mechanism. It is evidenced by the following facts: the reaction was terminated by the addition of 5 wt% 2,6-di-tert- butyl-4-methylphenol, which was a free-radical scavenger (see Table 1, entry 6). Moreover, addition of a free radical (TBHP) decreased the induction period and increased the rate of the reaction, while the selectivity remained unchanged (see Table 1, entries 2 and 5). Another fact is that the CHHP existing in the initial stage of the reaction could decompose to cyclohexanol and cyclohexanone (see Fig. 5).

4. Conclusions

A new method for preparing Co 3 O 4 nanocrystals from

inorganic cobalt salt is established. Co 3 O 4 nanocrystals with average particle size of 30 and 50 nm were successfully synthesized using cobalt nitrate as precursor. CTAB and in situ generated triethylamine salt acted as stabilizers to prevent the nanocrystals agglomerate in the process.

Co 3 O 4 nanocrystals are effective catalysts in cyclohexane

oxidation to cyclohexanol and cyclohexanone using molecular oxygen as oxidant. Co 3 O 4 with an average particles size of 50 nm showed a better activity and selectivity to the desired products, and the conversion of cyclohexane was 7.6% while the selectivity to K/A oil was 89.1% for a reaction time of 6 h. The catalyst was recyclable and was reused ve times with only a slight lost of the activity, and exhibited practically the same selectivity as that

of the fresh catalyst. The oxidation of cyclohexane is considered to undergo via a free-radical mechanism.

Acknowledgments

We gratefully acknowledge the National Natural Science Foundation of China (Grant: 20233040) and the National High Technology Research and Development Program of China (Grant: 2004AA32G020) for nancial supports. We also thank Prof. Ryuichiro Ohnishi for helpful discussions on preparation the paper.

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