Polyporphyrin/MXene-based Self-supporting Composite Films and Photocatalytic Degradation of Pollutants

doi:10.11901/1005.3093.2024.050

Chinese Journal of Materials Research

2024, Vol. 38

Issue (12): 950-960 DOI: 10.11901/1005.3093.2024.050

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Polyporphyrin/MXene-based Self-supporting Composite Films and Photocatalytic Degradation of Pollutants

HUO Zhaohui(

), WU Haojie, HE Yongqi, ZHENG Mingxiu, ZHAN Manzi, ZHANG Qitong, LIAO Xiaolin

School of Chemistry and Materials Science, GuangDong University of Education, Guangzhou 510303, China

Cite this article:

HUO Zhaohui, WU Haojie, HE Yongqi, ZHENG Mingxiu, ZHAN Manzi, ZHANG Qitong, LIAO Xiaolin. Polyporphyrin/MXene-based Self-supporting Composite Films and Photocatalytic Degradation of Pollutants. Chinese Journal of Materials Research, 2024, 38(12): 950-960.

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Abstract

Herein, photocatalyst composite films of polyporphyrin/MXene were prepared via anodic oxidation method with octaethyl porphyrin zinc and 4,4-bipyridine as monomers, and multi-layered Ti₃C₂ as MXene self-supporting film, with the aim to prepare a novel material with high-photocatalysis efficiency for degradation of dyestuffs wastewaters. The prepared catalyst was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, photoelectrochemical testing etc. The photocatalytic degradation effect of the synthesized self-supporting composite film photocatalyst on methylene blue was assessed through photocatalytic degradation testing. The results indicate that loading polyporphyrin onto MXene thin films can promote the separation of photo generated electron pairs, improve the efficiency of polyporphyrin photocatalysis, and achieve reusable recycling of materials. The increase in interlayer spacing of MXene was achieved by loading polyporphyrin onto the MXene through anodic oxidation, effectively solving the problem related with restacking and increasing the porosity of MXene. When the area of the polyporphyrin/MXene based composite film is 1 cm² and the initial concentration of methylene blue is 10 mg/L, the degradation rate of methylene blue by the composite material reaches 98% after 80 minutes of illumination. The capture experiment shows that the main free radical playing a role in the photocatalytic degradation of methylene blue is h⁺.

Key words: composite material porphyrin MXene self-supporting membrane anodic oxidation method photocatalytic Methylene blue

Received: 22 January 2024

ZTFLH:

O643.36

Fund: Guangdong Basic and Applied Basic Research Fund (Guangdong Guangzhou Joint Fund) Project(2023A1515111132);Guangzhou Basic and Applied Basic Project(202102020424);College Student Innovation and Entrepreneurship Training Program Project(202414278081);Guangdong Province Key Field Special Project for Ordinary Universities(2023ZDZX4043)

Corresponding Authors: HUO Zhaohui, Tel: 13422197623, E-mail: huozhaohui@gdei.edu.cn

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	HUO Zhaohui
	WU Haojie
	HE Yongqi
	ZHENG Mingxiu
	ZHAN Manzi
	ZHANG Qitong
	LIAO Xiaolin

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https://www.cjmr.org/EN/10.11901/1005.3093.2024.050 OR https://www.cjmr.org/EN/Y2024/V38/I12/950

Fig.1 Schematic diagram of synthesis of the ZnOEP/MXene films

Fig.2 SEM diagram of Ti₃AlC₂ (a), Ti₃C₂ (b, c), Section diagram of MXene film (Ti₃C₂) (d), Section diagram of the ZnOEP/MXene films (e, f)

Fig.3 FT-IR profiles of the ZnOEP/MXene films

Fig.4 XRD spectrum of the ZnOEP/MXene films

Fig.5 XPS spectra of specific regions (a) Ti 2p, (b) O 1s, (c) N 1s, (d) C 1s and (e) Zn 2p

Fig.6 EIS profiles of the ZnOEP/MXene films (a) and the photocurrent curves of the ZnOEP/MXene films (b)

Table 1 Fitting data of adsorption kinetics of methylene blue on porphyrin/MXene based composite films

Fig.7 Adsorption dynamics fitting curve and expression

Fig.8 Methylene blue standard curve (a) and self-degradation diagram (b)

Fig.9 Effect of H₂O₂ on degradation of photocatalyst (a), photocatalytic degradation rates of methylene blue by different materials (b), photocatalytic degradation properties of methylene blue by different materials (c) and degradation rates (d) of the ZnOEP/MXene films for methylene blue in the presence of different free radical trapping agents

Fig.10 Mechanism of the photocatalytic degradation of methylene blue by the ZnOEP/MXene films

Fig.11 Cyclic service life of the ZnOEP/MXene films

1	Afkhami A, Saber-Tehrani M, Bagheri H. Modified maghemite nanoparticles as an efficient adsorbent for removing some cationic dyes from aqueous solution [J]. Desalination, 2010, 263(1-3): 240
2	Wang Z H, Wu Z K, Zhi X J, et al. TiO₂/CTS/ATP adsorbent modification and its application in adsorption-ultrafiltration process for dye wastewater purification [J]. Environ. Sci. Pollut. Res., 2021, 28(42): 59963
3	Khataee A, Karimi A, Arefi-Oskoui S, et al. Sonochemical synthesis of Pr-doped ZnO nanoparticles for sonocatalytic degradation of Acid Red 17 [J]. Ultrason. Sonochem., 2015, 22: 371
4	Liu Z H, Yue Y C, Qiu Y F, et al. Preparation of g-C₃N₄/Ag/BiOBr composite and photocatalytic reduction of nitrate [J]. Chin. J. Mater. Res., 2023, 37(10): 781
	刘志华, 岳远超, 丘一帆等. g-C₃N₄/Ag/BiOBr复合材料的制备及其光催化还原硝酸盐氮 [J]. 材料研究学报, 2023, 37(10): 781
5	Chen Y F, Qiu G, Xie S D. Application of TiO₂/graphene photocatalysis technology in pollution control of Fengjiang River [J]. Environ. Prot. Technol., 2023, 29(3): 1
	陈宜菲, 邱罡, 谢树德. TiO₂/石墨烯光催化技术在枫江污染治理中的应用研究 [J]. 环保科技, 2023, 29(3): 1
6	Hou J, Yang P Z, Zheng Q H, et al. Preparation and performance of Graphite/TiO₂ composite photocatalyst [J]. Chin. J. Mater. Res., 2021, 35(9): 703
	侯静, 杨培志, 郑勤红等. 石墨/TiO₂复合光催化剂的制备和性能 [J]. 材料研究学报, 2021, 35(9): 703
7	Ge R Y, Li X Q, Kang S Z, et al. Highly efficient graphene oxide/porphyrin photocatalysts for hydrogen evolution and the interfacial electron transfer [J]. Appl. Catal., 2016, 187B: 67
8	Wang J M, Zheng Y, Peng T Y, et al. Asymmetric Zinc Porphyrin derivative-Sensitized graphitic carbon nitride for efficient visible-light-driven H₂production [J]. ACS Sustain. Chem. Eng., 2017, 5(9): 7549
9	Zhu K, Zhang M Q, Feng X Y, et al. A novel copper-bridged graphitic carbon nitride/porphyrin nanocomposite with dramatically enhanced photocatalytic hydrogen generation [J]. Appl. Catal., 2020, 268B: 118434
10	Da Silva E S, Moura N M M, Neves M G P M S, et al. Novel hybrids of graphitic carbon nitride sensitized with free-base meso-tetrakis(carboxyphenyl) porphyrins for efficient visible light photocatalytic hydrogen production [J]. Appl. Catal., 2018, 221B: 56
11	Wang L, Fan H Y, Bai F. Porphyrin-based photocatalysts for hydrogen production [J]. MRS Bull., 2020, 45(1): 49
12	Li Z, Jing Z Q, Xia C G. Review on application of metalloporphyrins in catalytic oxidation reactions [J]. Chin. J. Org. Chem., 2007, 27(1): 34
	李臻, 景震强, 夏春谷. 金属卟啉配合物的催化氧化应用研究进展 [J]. 有机化学, 2007, 27(1): 34
13	Sprick R S, Jiang J X, Bonillo B, et al. Tunable organic photocatalysts for visible-light-driven hydrogen evolution [J]. J. Am. Chem. Soc., 2015, 137(9): 3265
14	Germain J, Fréchet J M J, Svec F. Nanoporous polymers for hydrogen storage [J]. Small, 2009, 5(10): 1098
15	Zhang Y G, Riduan S N. Functional porous organic polymers for heterogeneous catalysis [J]. Chem. Soc. Rev., 2012, 41(6): 2083
16	Kaur P, Hupp J T, Nguyen S B T. Porous organic polymers in catalysis: opportunities and challenges [J]. ACS Catal., 2011, 1(7): 819
17	Li Y J, Wang L M, Gao Y, et al. Porous metalloporphyrinic nanospheres constructed from metal 5,10,15,20-tetraksi (4′-ethynylphenyl) porphyrin for efficient catalytic degradation of organic dyes [J]. RSC Adv., 2018, 8(14): 7330
18	Shah N, Wang X Y, Tian J. Recent advances in MXenes: a promising 2D material for photocatalysis [J]. Mater. Chem. Front., 2023, 7(19): 4184
19	Nan J X, Guo X, Xiao J, et al. Nanoengineering of 2D MXene-based materials for energy storage applications [J]. Small, 2021, 17(9): 1902085
20	Wu Z T, Shang T X, Deng Y Q, et al. The assembly of MXenes from 2D to 3D [J]. Adv. Sci., 2020, 7(7): 1903077
21	Tang J Y, Huang X, Qiu T F, et al. Interlayer space engineering of MXenes for electrochemical energy storage applications [J]. Chem. Eur. J., 2021, 27(6): 1921
22	Li Z J, Dai J, Li Y R, et al. Intercalation-deintercalation design in MXenes for high-performance supercapacitors [J]. Nano Res., 2022, 15: 3213
23	Yang K, Luo M, Zhang D T, et al. Ti₃C₂T _x /carbon nanotube/porous carbon film for flexible supercapacitor [J]. Chem. Eng. J., 2022, 427: 132002
24	Lian S H, Li G H, Song F, et al. Surfactant-free self-assembled MXene/carbon nanotubes hybrids for high-rate sodium- and potassium-ion storage [J]. J. Alloys Compd., 2022, 901: 163426
25	Wang R C, Luo S H, Xiao C, et al. MXene-carbon nanotubes layer-by-layer assembly based on-chip micro-supercapacitor with improved capacitive performance [J]. Electrochim. Acta, 2021, 386: 138420
26	Zhou Z H, Liu J Z, Zhang X X, et al. Ultrathin MXene/calcium alginate aerogel film for high-performance electromagnetic interference shielding [J]. Adv. Mater. Interfaces, 2019, 6(6): 1802040
27	Deng Y Q, Shang T X, Wu Z T, et al. Fast gelation of Ti₃C₂T _x MXene initiated by metal ions [J]. Adv. Mater., 2019, 31(43): 1902432
28	Fan Q, Zhao R Z, Yi M J, et al. Ti₃C₂-MXene composite films functionalized with polypyrrole and ionic liquid-based microemulsion particles for supercapacitor applications [J]. Chem. Eng. J., 2022, 428: 131107
29	Li T, Ding B, Wang J, et al. Sandwich-structured ordered mesoporous polydopamine/MXene hybrids as high-performance anodes for lithium-ion batteries [J]. ACS Appl. Mater. Interfaces, 2020, 12(13): 14993
30	Liu H, Zhang X, Zhu Y F, et al. Electrostatic self-assembly of 0D-2D SnO₂ quantum dots/Ti₃C₂T _x MXene hybrids as anode for lithium-ion batteries [J]. Nano-Micro Lett., 2019, 11: 65
31	Liu Y T, Zhang P, Sun N, et al. Self-assembly of transition metal oxide nanostructures on MXene nanosheets for fast and stable lithium storage [J]. Adv. Mater., 2018, 30(23): 1707334
32	Mao X Q, Zou Y J, Xu F, et al. Three-dimensional self-supporting Ti₃C₂ with MoS₂ and Cu₂O nanocrystals for high-performance flexible supercapacitors [J]. ACS Appl. Mater. Interfaces, 2021, 13(19): 22664
33	Zhang T Z, Wang R, Xiao J P, et al. CoS nanowires grown on Ti₃C₂T _x are promising electrodes for supercapacitors: high capacitance and remarkable cycle capability [J]. J. Colloid Interface Sci., 2021, 602: 123
34	Li J F, Han L, Li Y Q, et al. MXene-decorated SnS₂/Sn₃S₄ hybrid as anode material for high-rate lithium-ion batteries [J]. Chem. Eng. J., 2020, 380: 122590
35	Li C Y, Zhang D D, Cao J, et al. Ni₃S₂ nanoparticles anchored on d-Ti₃C₂ nanosheets with enhanced sodium storage [J]. ACS Appl. Energy Mater., 2021, 4(3): 2593
36	Wang H Q, Zhao Y X, Gou L, et al. Rational construction of densely packed Si/MXene composite microspheres enables favorable sodium storage [J]. Rare Met., 2022, 41(5): 1626
37	Zhu X D, Xie Y, Liu Y T. Exploring the synergy of 2D MXene-supported black phosphorus quantum dots in hydrogen and oxygen evolution reactions [J]. J. Mater. Chem., 2018, 6A(43): 21255
38	Guo X, Zhang W X, Zhang J Q, et al. Boosting sodium storage in two-dimensional phosphorene/Ti₃C₂T _x MXene nanoarchitectures with stable fluorinated interphase [J]. ACS Nano, 2020, 14(3): 3651

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