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

doi:10.6023/A22010018

摘要/Abstract

将生物质转化为高附加值化学品以替代传统化石能源衍生的碳资源不可再生能源已经引起了人们的广泛关注. 本工作制备了内部中空的ZnS@CdS/Ni纳米管催化剂用于光催化氧化5-羟甲基糠醛(HMF). 通过X射线光电子能谱表征了催化剂内部存在ZnS缺陷态使得ZnS能带带隙降低. 光照条件下, 光生空穴能够从CdS迁移至ZnS缺陷态, 抑制了ZnS@CdS内部的载流子复合, 提高了光催化性能. 中空的纳米管表面负载Ni催化剂可以参与质子还原产氢的反应, 而ZnS@CdS内部产生的空穴可以催化氧化HMF选择性生成2,5-呋喃二甲醛(DFF). 光反应1 h后, HMF的转化率达到36%, 产物DFF选择性为99%, 并且催化剂可以重复利用三次而不降低催化效果.

关键词: 生物质, 5-羟甲基糠醛, 2,5-二甲酰基呋喃, 光催化, 硫化镉

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

引用此文

舒恒, 包义德日根, 那永. 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[J]. 化学学报, 2022, 80(5): 607-613.

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.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 12

图1. ZnS@CdS的XRD图

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

图2. (a) CdS、ZnS及ZnS@CdS的紫外-可见吸收光谱; (b) CdS、ZnS的Kubelka-Munk曲线

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

图3. (a) CdS和(b) ZnS的莫特肖特基曲线

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

图4. ZnS@CdS (a)和ZnS@CdS/Ni (b)的SEM图

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

图5. (a) ZnS@CdS/Ni的HRTEM图; (b) HRTEM图中显示的ZnS (111), CdS (002)和Ni (002)晶格间隙

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)

图6. ZnS@CdS/Ni的XPS谱图. (a) 全谱, (b) Cd 3d, (c) Zn 2p, (d) S 2p, (e) Ni 2p

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

图7. 沉积Ni不同时长的ZnS@CdS/Ni氧化HMF结果

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

图8. ZnS@CdS/Ni-30光催化氧化HMF的转化率随时间变化图

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

图9. 加入EDTA后的HMF转化率对比图

Figure 9. Conversion of HMF in the presence of EDTA

图10. ZnS@CdS/Ni能带结构图

Figure 10. Energy diagram of ZnS@CdS/Ni

图11. ZnS@CdS/Ni-30的光催化循环稳定性

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

图12. 光反应前后ZnS@CdS/Ni-30的XRD谱图对比

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

参考文献 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