Photocatalytic Oxidation of 5-Hydroxymethylfurfural Selectively into 2,5-Diformylfuran with CdS Nanotube

doi:10.6023/A22010018

Abstract

Conversion of 5-hydroxymethylfurfural (HMF) into high value-added chemicals to take place of carbon resources relying on non-renewable fossil reserves has attracted much attention in recent years. Besides, in a system of water splitting for hydrogen production, HMF oxidation can be incorporated to provide electrons instead of the kinetically sluggish water oxidation. In this paper, hollow ZnS@CdS/Ni nanotubes were prepared for photocatalytic oxidation of HMF coupled by catalytic hydrogen generation. ZnO was employed as template to form ZnO@ZnS@CdS first. The ZnO template was removed in the presence of strong basic solution. Due to the excess of S^2- used, ZnS defect state exsited in ZnS@CdS, which was confirmed by ultraviolet-visible (UV-Vis) spectroscopy and X-ray photoelectron spectroscopy (XPS). The ZnS defect state had no effect on the conduction band edge potential of ZnS but reduced the band gap of ZnS. In combination of the absorption edge and the electrochemical measurements, the potentials for valence band edges of CdS and ZnS defect state were determined, respectively. Under light irradiation, the photogenerated electrons could be accumulated on the surface of CdS, and the photogenerated holes could migrate from CdS to ZnS defect, reducing the carrier recombination and improving the photocatalytic performance. With further deposition of Ni nanoparticles on the surface of CdS nanotube, the ZnS@CdS/Ni structure could accomplish the oxidation of HMF into 2,5-diformylfuran (DFF) selectively and hydrogen production at the both reaction sites. Under optimal amount of the Ni deposition, conversion of 36% for HMF oxidation was accomplished by ZnS@CdS/Ni-30 after 1 h photo reaction. At this stage, DFF as the main product with selectivity of 99% was obtained. Besides, H₂ was detected in the head space of the reaction system, suggesting that HMF can be functioned as electron donor in stead of an H₂O molecule in photo water splitting. The photo-generated holes were found to be the active species for the conversion of HMF into DFF. Under optimal photo reaction time (1 h), the prepared catalyst can be recycled three times without obvious decrease in catalytic activity. And the X-ray diffraction (XRD) pattern for the catalyst after photo reaction kept similar to that before reaction.

Key words: biomass, 5-hydroxymethylfurfural, 2,5-diformylfuran, photocatalysis, cadmium sulfide

Cite this article

Heng Shu, Yide-Rigen Bao, Yong Na. Photocatalytic Oxidation of 5-Hydroxymethylfurfural Selectively into 2,5-Diformylfuran with CdS Nanotube[J]. Acta Chimica Sinica, 2022, 80(5): 607-613.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 12

Figure 1. X-ray diffraction (XRD) pattern of ZnS@CdS

Figure 2. (a) UV-vis spectra of CdS, ZnS and ZnS@CdS; (b) Kubelka-Munk curves of CdS and ZnS

Figure 3. Mott-Schottky curves of (a) CdS and (b) ZnS

Figure 4. SEM images of (a) ZnS@CdS and (b) ZnS@CdS/Ni

Figure 5. (a) HRTEM image of ZnS@CdS/Ni; (b) HRTEM image correlating to the interplanar crystal spacings of ZnS (111), CdS (002) and Ni (002)

Figure 6. XPS spectra of ZnS@CdS/Ni. (a) survey spectra, (b) Cd 3d, (c) Zn 2p, (d) S 2p and (e) Ni 2p

Figure 7. HMF oxidation catalyzed by ZnS@CdS/Ni with various deposition times of Ni

Figure 8. Conversion of HMF versus reaction time catalyzed by ZnS@CdS/Ni-30

Figure 9. Conversion of HMF in the presence of EDTA

Figure 10. Energy diagram of ZnS@CdS/Ni

Figure 11. The catalytic stability of recycled ZnS@CdS/Ni-30

Figure 12. The XRD patterns of ZnS@CdS/Ni-30 before and after reaction

References 20

[1]	Corma, A.; Iborra, S.; Velty, A. Chem. Rev. 2007, 107, 2411. doi: 10.1021/cr050989d
[2]	Lanzafame, P.; Centi, G.; Perathoner, S. Chem. Soc. Rev. 2014, 43, 7562. doi: 10.1039/c3cs60396b pmid: 24577063
[3]	Sajid, M.; Zhao, X.; Liu, D. Green Chem. 2018, 20, 5427. doi: 10.1039/C8GC02680G
[4]	Li, K.; Sun, Y. Chem. Eur. J. 2018, 24, 18258. doi: 10.1002/chem.201803319
[5]	Brandolese, A.; Ragno, D.; Di Carmine, G.; Bernardi, T.; Bortolini, O.; Giovannini, P. P.; Pandoli, O. G.; Altomare, A.; Massi, A. Org. Biomol. Chem. 2018, 16, 8955. doi: 10.1039/c8ob02425a pmid: 30403257
[6]	Werpy, T.; Petersen, G.; Aden, A.; Bozell, J.; Holladay, J.; White, J.; Manheim, A.; Eliot, D.; Lasure, L.; Jones, S. Top value added chemicals from biomass. Volume 1-Results of screening for potential candidates from sugars and synthesis gas, U.S. Department of Energy, Washington, DC, 2004.
[7]	Zhang, Z.; Deng, K. ACS Catal. 2015, 5, 6529. doi: 10.1021/acscatal.5b01491
[8]	Butburee, T.; Chakthranont, P.; Phawa, C.; Faungnawakij, K. ChemCatChem 2020, 12, 1873. doi: 10.1002/cctc.201901856
[9]	Li, C.; Na, Y. ChemPhotoChem 2021, 5, 502. doi: 10.1002/cptc.202000261
[10]	Fujishima, A.; Honda, K. Nature 1972, 238, 37. doi: 10.1038/238037a0
[11]	Kudo, A.; Miseki, Y. Chem. Soc. Rev. 2009, 38, 253. doi: 10.1039/B800489G
[12]	Cheng, L.; Xiang, Q.; Liao, Y.; Zhang, H. Energ. Environ. Sci. 2018, 11, 1362. doi: 10.1039/C7EE03640J
[13]	Chang, K.; Mei, Z.; Wang, T.; Kang, Q.; Ouyang, S.; Ye, J. ACS Nano 2014, 8, 7078. doi: 10.1021/nn5019945 pmid: 24923678
[14]	Qiu, B.; Zhu, Q.; Du, M.; Fan, L.; Xing, M.; Zhang, J. Angew. Chem. Int. Ed. 2017, 56, 2684. doi: 10.1002/anie.201612551
[15]	Feng, H.; Tang, L.; Zeng, G.; Zhou, Y.; Deng, Y.; Ren, X.; Song, B.; Liang, C.; Wei, M.; Yu, J. Adv. Colloid Interface Sci. 2019, 267, 26. doi: 10.1016/j.cis.2019.03.001
[16]	You, B.; Sun, Y. Acc. Chem. Res. 2018, 51, 1571. doi: 10.1021/acs.accounts.8b00002
[17]	Wang, W.; Wen, Q.; Liu, Y.; Zhai, T. Acta Chim. Sinica 2020, 78, 1185. (in Chinese) doi: 10.6023/A20060265
	(王文彬, 温群磊, 刘友文, 翟天佑, 化学学报, 2020, 78, 1185.) doi: 10.6023/A20060265
[18]	Xin, Y.; Huang, Y.; Lin, K.; Yu, Y.; Zhang, B. Sci. Bull. 2018, 63, 601. doi: 10.1016/j.scib.2018.03.015
[19]	Hao, X.; Wang, Y.; Zhou, J.; Cui, Z.; Wang, Y.; Zou, Z. Appl. Catal. B 2018, 221, 302. doi: 10.1016/j.apcatb.2017.09.006
[20]	Gai, Q.; Ren, S.; Zheng, X.; Liu, W.; Dong, Q. Catal. Sci. Technol. 2021, 11, 5579. doi: 10.1039/D1CY00811K

CdS基纳米管光催化氧化5-羟甲基糠醛选择性生成2,5-呋喃二甲醛