Translator Disclaimer
3 November 2020 Temperature effect on green-synthesized Co3O4 nanoparticle as photocatalyst for overall water splitting
Author Affiliations +
Abstract

Co3O4 nanoparticles were synthesized by a green synthesis method using bread fungus and cobalt nitrate hexahydrate as the precursors. The effects of the calcination temperature on the structure and properties of nanoparticles, and the ambient temperature on the photocatalytic reaction are discussed. The cubic structure of Co3O4 nanoparticles was obtained, and the grain size was between 14 and 19 nm at different calcination temperatures. Co3O4 calcined at 500°C shows good photocatalytic performance. Without adding any sacrificial agent and cocatalyst, the amount of hydrogen and oxygen released in 5 h were 259.4 and 135.7  μmolg  −  1, respectively. The results show that, with the increase of ambient temperature, the evolution rate of hydrogen and oxygen is accelerated, and the atomic ratio of hydrogen to oxygen is close to 2:1. In addition, the Co3O4 photocatalyst has good stability. Our study provides an environmentally friendly, low-cost, and efficient method for the preparation of cobalt oxide photocatalysts with excellent performance.

1.

Introduction

With the serious energy crisis and increasing environmental concerns, development of better energy storage materials is urgently needed.1,2 Photocatalytic water splitting is an environmentally friendly and promising way to store unexploited solar energy in the form of hydrogen because of its high energy density.35 The photocatalyst is one of the key factors in the photocatalytic water splitting.69 The major challenge in this area is to create a sustainable and efficient photocatalyst that can work well with visible light, which is the major component (i.e., 50%) of the solar spectrum.10 Nanostructured metal oxides (such as TiO2, SnO2, Co3O4, Fe2O3, CuO, and WO3) are novel materials for photocatalytic water splitting under visible light irradiation.1115 Among them, Co3O4 as a p-type semiconductor is particularly attractive in this area because of its suitable bandgap of 3.95 to 2.13 eV.16

Synthesis of Co3O4 nanoparticles has been reported using various methods, such as thermal decomposition,17 template method,18 hydrothermal method,19 microwave-assisted,20 and chemical spray pyrolysis.21 These methods usually consume more energy, are capital intensive, and use toxic chemicals in the preparation process.16,22 As an alternative to these traditional methods, green synthesis is considered to be a safe, economic, and ecological method for the preparation of nanoparticles.23 Green synthesis by naturally derived materials, including plant extract and components and microorganisms, has been studied for mass production to detoxify and degrade hazardous pollutants.24,25 For example, Abukhadra et al.26 reported MCM-41/Co3O4 nanocomposite was synthesized from rice husk silica gel and peach leaves, for enhanced photocatalytic degradation of acephate pesticide. Salam et al.27 prepared organo-bentonite/Co3O4 green nanocomposite and investigated it as a potential eco-friendly, low-cost adsorbent and photocatalyst for promising removal of both malachite green dye and Cr(VI) ions.

Therefore, developing an efficient and stable photocatalyst by an environmentally friendly, low-cost, and efficient green-synthesis method to accomplish the overall water splitting without using sacrificial agents, noble metals, and external bias is still a challenge. In this paper, we report on the green synthesis, characterization, and catalytic effect of the green-synthesized Co3O4 nanoparticles on overall water splitting. The effects of the calcination temperature on the structure and properties, and the ambient temperature on the photocatalytic process, have also been reported.

2.

Experimental

2.1.

Green Synthesis of Co3O2 Nanoparticles

All reagents were of analytical reagent grade and used as received from Sinopharm Chemical Reagent Co., Ltd. Co3O4 nanoparticles were synthesized using bread fungus as a green material. Initially, fungus was grown on bread by putting it in dark for more than 10 days. Cobalt nitrate [Co(No3)2·6H2O] was put into distilled water to form a 0.2 M reddish solution. Then fungus from bread was added until the red solution turned green. The green mixture was stirred for 3 h and kept the temperature at 50°C. After stirring for 3 h, the mixture was left in the dark overnight. The resulting mixture is then filtered, and the filtered solution was stored in an oven at 70°C to obtain a dark red, jelly-like mixture, which was calcined in a muffle furnace at different temperatures.

2.2.

Characterization

The morphology of the Co3O4 nanoparticles was determined via scanning electron microscopy (SEM) (JEOL JSM-7800F). X-ray diffraction (XRD) patterns were obtained from a PANalytical X’pert Pro MPD diffractometer operated at 40 kV and 40 mA using Ni-filtered Cu Kα irradiation (λ=1.5406  ). A FEI Tecnai G2 F30 transmission electron microscope (TEM) was used to characterize the structure of Co3O4 nanoparticles. UV–Vis absorption spectra were measured on a Hitachi U-4100 instrument equipped with a diffuse reflectance accessory.

2.3.

Photocatalytic Reaction

The photocatalytic overall water splitting was carried out under visible light irradiation by using 300-W Xe lamp equipped with a 420-nm cutoff filter. 10 mg of Co3O4 nanoparticles was added into 80 ml of water in a Pyrex cell with a side window for external-light incidence. The evolved gas was analyzed on a gas chromatograph (thermal conductivity detector, TDX-01 column, N2 as carrier gas) every 60 min. N2 was bubbled into the cell for 15 min before the photocatalytic reaction to remove O2. The different ambient temperature for photocatalytic reaction was kept by thermostatic water bath.

3.

Results and Discussion

To investigate the morphology of Co3O4 nanoparticles, SEM was employed, and the results are shown in Fig. 1. As shown in Fig. 1(a), the nanoparticles calcined at 700°C show the hexagonal structure, some of which are very large in size. As can be seen from Figs. 1(b)1(d), the nanoparticles calcined at 600°C, 500°C, and 400°C have spherical structure, and the distribution is very uniform. On the other hand, the nanoparticles calcined at 400°C are very large and agglomerated as shown in Fig. 1(e), which are not suitable for use as photocatalysts.

Fig. 1

SEM images of Co3O4 nanoparticles calcined at the different temperature: (a) 700°C, (b) 600°C, (c) 500°C, (d) 450°C, and (e) 400°C.

JPE_10_4_042006_f001.png

Figure 2 presents the XRD pattern of Co3O4 nanoparticles calcined at different temperatures. The peaks at 2θ values [19.1 deg, 31.2 deg, 36.9 deg, 38.5 deg, 44.8 deg, 55.6 deg, 59.4 deg, 65.3 deg, 74.1 deg, and 77.3 deg corresponding to (111), (200), (311), (222), (400), (422), (511), (440), (620), and (533) planes of Co3O4, respectively] are indexed to the cubic Co3O4 (JCPDS42-1467).28,29 It can be seen from Fig. 2, there is no other impurity peak, indicating high purity of Co3O4. At the same time, the diffraction peak is sharp, suggesting that the crystallinity of Co3O4 is relatively high. But with the increase in temperature, the small peaks according to (222), (422), (620), or (533) planes of Co3O4 appeared, which may be due to the morphology of Co3O4 as shown in Fig. 1. By using Sheerer formula D=0.94λ/βcosθ, the size of Co3O4 nanoparticles according to the diffraction peak of (311) crystal plane is 15, 14, 19, and 18 nm for the calcination temperature at 450°C, 500°C, 600°C, and 700°C, respectively.

Fig. 2

XRD spectrum of Co3O4 calcined at different temperatures.

JPE_10_4_042006_f002.png

To verify the micro-structure of Co3O4, the TEM image of Co3O4 nanoparticles calcined at 500°C is shown in Fig. 3. From Fig. 3(a), it can be seen that Co3O4 nanoparticles are uniformly dispersed and their size is less than 20 nm. As shown in Fig. 3(b), the lattice fringes of Co3O4 can be observed clearly. The fringes with spacing of 0.46 nm correspond to (111) lattice plane (JCPDS42-1467) of the cubic Co3O4, suggesting Co3O4 nanoparticles exhibit good crystallinity.

Fig. 3

TEM images of Co3O4 nanoparticles calcined at 500°C: (a) low magnification and (b) high magnification.

JPE_10_4_042006_f003.png

The UV–Vis spectra of Co3O4 nanoparticles are shown in Fig. 4. As can be seen from Fig. 4, there are two broad peaks in the wavelength range of 300 to 450 nm and 600 to 750 nm. The first peak can be assigned to O2 to Co2+ charge transfer, and the second one can be assigned to O2 to Co3+ charge transfer.30 The peak intensity of Co3O4 nanoparticles calcined at 500°C is the highest, which indicates that Co3O4 nanoparticles calcined at 500°C can absorb more light. When the temperature is higher than 500°C, the peak intensity decreases gradually. As discussed by XRD, the size of Co3O4 nanoparticles calcined at 500°C is the smallest, and the nanoparticles size increases with the increase of temperature. This suggests that the calcination temperature not only affects the grain size but also the light absorption.

Fig. 4

UV–Vis spectrum of Co3O4 calcined at different temperatures.

JPE_10_4_042006_f004.png

Figure 5 shows the amount of the hydrogen and oxygen evolution under visible irradiation over Co3O4 calcined at 450°C and 500°C as the function of the irradiation time. From Fig. 5(a), the evolution of the hydrogen is 247.1  μmolg1 and that of the oxygen is 109.5  μmolg1 for Co3O4 photocatalyst calcined at 450°C in 5 h without use of any cocatalyst and sacrificial agent. Moreover, the ratio of the hydrogen to the oxygen is almost 2:1. Co3O4 calcined at 500°C also showed the same trend. For overall water splitting, the amount of the hydrogen evolution is 259.4  μmolg1 and that of the oxygen is 135.7  μmolg1 in 5 h using Co3O4 calcined at 500°C as shown in Fig. 5(b). Obviously, Co3O4 photocatalyst calcined at 500°C shows the better photocatalytic activity than that of Co3O4 calcined at 450°C and is chosen for further photocatalytic experiments by controlling the ambient temperature.

Fig. 5

Reaction time courses of the hydrogen and the oxygen evolution under visible irradiation over Co3O4 calcined at different temperatures: (a) 450°C and (b) 500°C.

JPE_10_4_042006_f005.png

To study the effect of the ambient temperature on the photocatalytic process, the reaction temperature was controlled at 40°C, 50°C, and 60°C, and the results about the amount of the hydrogen and the oxygen evolution are shown in Fig. 6. With the increase of temperature, the evolution of hydrogen and oxygen also increases. The increase of the evolution may be due to the increase in kinetics of the reaction. The increase of temperature effect may increase the mobility of carriers. These charge carriers then move on to the surface with less recombination rate and react fast to produce hydrogen and oxygen. As shown in Fig. 6, the amount of hydrogen at 40°C, 50°C, and 60°C is 268.9, 284.6, and 310.7  μmolg1, respectively, while the amount of oxygen is 133.1, 146.4, and 175.3  μmolg1, respectively. Obviously, the ratio of the hydrogen to oxygen is near 2:1 in all experiments, which means that Co3O4 photocatalyst can completely split pure water without using any cocatalyst and sacrificial agent.

Fig. 6

Amount of the hydrogen and the oxygen evolution under visible irradiation in 5 h over Co3O4 calcined at 500°C as the function of the ambient temperature.

JPE_10_4_042006_f006.png

The photocatalytic stability of Co3O4 nanoparticles was evaluated under visible light irradiation at room temperature for 12 h. The experiment was done in three cycles. After 4 h of each cycle, the photocatalyst was recovered by centrifugation and drying and used in the next cycle. Figure 7 shows the stability performance of Co3O4 over three cycles. It can be seen from Fig. 7 that the hydrogen and the oxygen evolution of the latter cycle is only slightly lower than that of the previous cycle, and the reduction rate is less than 9%, which suggests that the Co3O4 for overall water splitting is stable.

Fig. 7

Reaction time courses of the hydrogen and the oxygen evolution under the visible irradiation over Co3O4 calcined at 500°C at room temperature.

JPE_10_4_042006_f007.png

4.

Conclusion

Through this environmentally friendly and inexpensive method, Co3O4 nanoparticles were successfully synthesized using the bread fungus as green materials. These nanoparticles calcined at 500°C had the smallest grain size, the uniform distribution, and the best light absorption. Furthermore, Co3O4 nanoparticles were used as a photocatalyst for overall water splitting under visible light irradiation without any cocatalyst and sacrificial agent. The evolution rates of the hydrogen and the oxygen increased by increasing the photocatalytic temperature, and the ratio of the hydrogen to oxygen is close to 2:1. In addition, Co3O4 photocatalyst had a good stability. Especially, Co3O4 calcined at 500°C showed a good photocatalytic performance. Within 5 h, the amount of hydrogen and oxygen is 259.4 and 135.7  μmolg1, respectively. Therefore, the green synthesis of cobalt oxide is a promising method for overall water splitting.

Acknowledgments

This work was supported by the Natural Science Foundation of China (Nos. 21878242 and 21828802), Fundamental Research Funds for the Central Universities of China (No. xzd012020045), and Key Research and Development Projects of Shaanxi Province (Nos. 2018GY097 and 2018SF383).

References

1. 

X. J. Guan et al., “Making of an industry-friendly artificial photosynthesis device,” ACS Energy Lett., 3 (9), 2230 –2231 (2018). https://doi.org/10.1021/acsenergylett.8b01377 Google Scholar

2. 

X. H. Liu et al., “In situ synthesis of ultrafine metallic MoO2/carbon nitride nanosheets for efficient photocatalytic hydrogen generation: a prominent cocatalytic effect,” Catal. Sci. Technol., 10 4053 –4060 (2020). https://doi.org/10.1039/D0CY00421A Google Scholar

3. 

T. Takata et al., “Photocatalytic water splitting with a quantum efficiency of almost unity,” Nature, 581 411 –414 (2020). https://doi.org/10.1038/s41586-020-2278-9 Google Scholar

4. 

X. J. Guan et al., “Efficient unassisted overall photocatalytic seawater splitting on GaN-based nanowire arrays,” J. Phys. Chem. C, 122 (25), 13797 –13802 (2018). https://doi.org/10.1021/acs.jpcc.8b00875 JPCCCK 1932-7447 Google Scholar

5. 

Q. Wang et al., “Particulate photocatalysts for light-driven water splitting: mechanisms, challenges, and design strategies,” Chem. Rev., 120 919 –985 (2020). https://doi.org/10.1021/acs.chemrev.9b00201 CHREAY 0009-2665 Google Scholar

6. 

S. Cao et al., “Emerging photocatalysts for hydrogen evolution,” Trends Chem., 2 57 –70 (2020). https://doi.org/10.1016/j.trechm.2019.06.009 Google Scholar

7. 

Z. Hu et al., “An elemental phosphorus photocatalyst with a record high hydrogen evolution efficiency,” Angew. Chem. Int. Ed., 55 9580 –9585 (2016). https://doi.org/10.1002/anie.201603331 Google Scholar

8. 

C. M. Wolff et al., “All-in-one visible-light-driven water splitting by combining nanoparticulate and molecular co-catalysts on CdS nanorods,” Nat. Energy, 3 862 –869 (2018). https://doi.org/10.1038/s41560-018-0229-6 Google Scholar

9. 

M. A. Sayed et al., “Photocatalytic hydrogen generation from raw water using zeolite/polyaniline @Ni2O3 nanocomposite as a novel photo-electrode,” Energy, 187 115943 (2019). https://doi.org/10.1016/j.energy.2019.115943 ENGYD4 0149-9386 Google Scholar

10. 

D. Y. Chen et al., “Construction of Ni-doped SnO2-SnS2 heterojunctions with synergistic effect for enhanced photodegradation activity,” J. Hazard. Mater., 368 204 –213 (2019). https://doi.org/10.1016/j.jhazmat.2019.01.009 JHMAD9 0304-3894 Google Scholar

11. 

Z. Wang et al., “Phosphorus-doped Co3O4 nanowire array: a highly efficient bifunctional electrocatalyst for overall water splitting,” ACS Catal., 8 (3), 2236 –2241 (2018). https://doi.org/10.1021/acscatal.7b03594 Google Scholar

12. 

M. Mishra and D.-M. Chun, “α-Fe2O3 as a photocatalytic material: a review,” Appl. Catal. A: Gen., 498 (5), 126 –141 (2015). https://doi.org/10.1016/j.apcata.2015.03.023 Google Scholar

13. 

Z. Wang et al., “Identifying copper vacancies and their role in the CuO based photocathode for water splitting,” Angew. Chem. Int. Ed., 58 17604 –17609 (2019). https://doi.org/10.1002/anie.201909182 Google Scholar

14. 

Z. W. Chen et al., “Recent advances in tin dioxide materials: some developments in thin films, nanowires, and nanorods,” Chem. Rev., 114 7442 –7486 (2014). https://doi.org/10.1021/cr4007335 CHREAY 0009-2665 Google Scholar

15. 

R. T. Huang et al., “Environmentally benign synthesis of Co3O4-SnO2 heteronanorods with efficient photocatalytic performance activated by visible light,” J. Colloid. Interf. Sci., 542 460 –468 (2019). https://doi.org/10.1016/j.jcis.2019.01.089 Google Scholar

16. 

A. Jelinska et al., “Enhanced photocatalytic waters splitting on very thin WO3 films activated by high-temperature annealing,” ACS Catal., 8 (11), 10573 –10580 (2018). https://doi.org/10.1021/acscatal.8b03497 Google Scholar

17. 

S. Farhadi, K. Pourzare and S. Sadeghinejad, “Simple preparation of ferromagnetic Co3O4 nanoparticles by thermal dissociation of the [CoII(NH3)6](NO3)2 complex at low temperature,” J. Nanostruct. Chem., 3 (16), 1 –7 (2013). https://doi.org/10.1186/2193-8865-3-16 Google Scholar

18. 

G. Kwak et al., “Preparation method of Co3O4 nanoparticles using ordered mesoporous carbons as a template and their application for Fischer–Tropsch synthesis,” J. Phys. Chem. C, 117 (4), 1773 –1779 (2013). https://doi.org/10.1021/jp3106698 JPCCCK 1932-7447 Google Scholar

19. 

H.-P. Cong and S.-H. Yu, “Shape control of cobalt carbonate particles by a hydrothermal process in a mixed solvent: an efficient precursor to nanoporous cobalt oxide architectures and their sensing property,” Cryst. Growth Des., 9 (1), 210 –217 (2009). https://doi.org/10.1021/cg8003068 CGDEFU 1528-7483 Google Scholar

20. 

S. Q. Chen and Y. Wang, “Microwave-assisted synthesis of a Co3O4-graphene sheet-on-sheet nanocomposite as a superior anode material for Li-ion batteries,” J. Mater. Chem., 20 (43), 9735 –9739 (2010). https://doi.org/10.1039/c0jm01573c JMACEP 0959-9428 Google Scholar

21. 

R. C. Ambare, S. R. Bharadwaj and B. J. Lokhande, “Non-aqueous route spray pyrolyzed Ru:Co3O4 thin electrodes for supercapacitor application,” Appl. Surf. Sci., 349 887 –896 (2015). https://doi.org/10.1016/j.apsusc.2015.04.175 ASUSEE 0169-4332 Google Scholar

22. 

J. K. Sharma et al., “Green synthesis of Co3O4 nanoparticles and their applications in thermal decomposition of ammonium perchlorate and dye-sensitized solar cells,” Mater. Sci. Eng. B, 193 181 –188 (2015). https://doi.org/10.1016/j.mseb.2014.12.012 Google Scholar

23. 

N. O. M. Dewi et al., “Green synthesis of Co3O4 nanoparticles using Euphorbia heterophylla L. leaves extract: characterization and photocatalytic activity,” IOP Conf. Ser.: Mater. Sci. Eng, 509 012105 (2019). https://doi.org/10.1088/1757-899X/509/1/012105 Google Scholar

24. 

R. Sathyavathi, M. Krishna and D.N. Rao, “Biosynthesis of silver nanoparticles using Moringa oleifera leaf extract and its application to optical limiting,” J. Nanosci. Nanotechnol., 11 2031 –2035 (2011). https://doi.org/10.1166/jnn.2011.3581 JNNOAR 1533-4880 Google Scholar

25. 

J. Osuntokun, D. C. Onwudiwe and E. E. Ebenso, “Green synthesis of ZnO nanoparticles using aqueous Brassica oleracea L. var. italica and the photocatalytic activity,” Green Chem. Lett. Rev., 12 (4), 444 –457 (2019). https://doi.org/10.1080/17518253.2019.1687761 Google Scholar

26. 

M. R. AbuKhadra et al., “Enhanced photocatalytic degradation of acephate pesticide over MCM-41/Co3O4 nanocomposite synthesized from rice husk silica gel and peach leaves,” J. Hazard. Mater., 389 122129 (2020). https://doi.org/10.1016/j.jhazmat.2020.122129 JHMAD9 0304-3894 Google Scholar

27. 

M.A. Salam et al., “Insight into the adsorption and photocatalytic behaviors of an organo-bentonite/Co3O4 green nanocomposite for malachite green synthetic dye and Cr(VI) metal ions: application and mechanisms,” ACS Omega, 5 2766 –2778 (2020). https://doi.org/10.1021/acsomega.9b03411 Google Scholar

28. 

J. Chen et al., “An ultrafast supercapacitor built by Co3O4 with tertiary hierarchical architecture,” Vacuum, 174 109219 (2020). https://doi.org/10.1016/j.vacuum.2020.109219 VACUAV 0042-207X Google Scholar

29. 

T. Chang et al., “Post-plasma-catalytic removal of toluene using MnO2-Co3O4 catalysts and their synergistic mechanism,” Chem. Eng. J., 348 15 –25 (2018). https://doi.org/10.1016/j.cej.2018.04.186 Google Scholar

30. 

M. K. Uddin and U. Baig, “Synthesis of Co3O4 nanoparticles and their performance towards methyl orange dye removal: characterization, adsorption and response surface methodology,” J. Clean. Prod., 211 1141 –1153 (2019). https://doi.org/10.1016/j.jclepro.2018.11.232 Google Scholar

Biography

Qing-Yun Chen is a professor in State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University. She obtained her PhD from Nara Women’s University of Japan in 2007. She joined Xi'an Jiaotong University in 2008 and her research interests have focused on photocatalysis for water splitting.

Biographies of the other authors are not available.

© 2020 Society of Photo-Optical Instrumentation Engineers (SPIE)
Qing-Yun Chen, Sajjad U. Haq, Zhong-Hang Xing, and Yun-Hai Wang "Temperature effect on green-synthesized Co3O4 nanoparticle as photocatalyst for overall water splitting," Journal of Photonics for Energy 10(4), 042006 (3 November 2020). https://doi.org/10.1117/1.JPE.10.042006
Received: 5 August 2020; Accepted: 23 October 2020; Published: 3 November 2020
JOURNAL ARTICLE
8 PAGES


SHARE
Advertisement
Advertisement
Back to Top