Nano-MnO2 anchored on exfoliated MXene with exceptional and stable Fenton oxidation performance for organic micropollutants

doi:10.1016/S1872-2067(24)60041-0

Abstract

Abstract:

Peroxymonosulfate (PMS) Fenton-like systems have emerged as promising alternatives to hydrogen peroxide (H₂O₂). Fenton systems are currently used in the industry owing to their highly efficient utilization rate of oxidizing agents and wide operating pH ranges. Heterogeneous Fenton-like catalysts are promising candidates in this regard. However, self-aggregation and generation of ambiguous reactive oxygen species greatly restrict their broad application in practical settings. Herein, a redox reaction between exfoliated MXene and KMnO₄ facilitates the in-situ deposition of MnO₂ nanoparticles on the surface of Ti-deficient vacancies of MXene (MXene/MnO₂). Owing to the advantages of MXene with fast charge transfer and MnO₂ with strong PMS activation ability, the engineered MXene/MnO₂@PVDF catalytic membrane exhibited enhanced activity and excellent long-term stability for various refractory organic pollutants. Experimental observations, combined with density functional theory calculations, revealed that the exposed Mn sites effectively promoted the generation of ¹O₂. Interestingly, the widespread pathway for the direct generation of ¹O₂ via high-valent Mn-oxo phases has a high energy barrier (3.34 eV). In contrast, the pathway that uses the •OOH species as intermediates to produce ¹O₂ is energetically more viable (1.84 eV). This work offers insights into the in-situ engineering of transition metal-oxides on MXene-based membranes, facilitating their implementation in remediating micropollutant-contaminated environmental water.

Key words: MXene, MnO₂, Peroxymonosulfate, Singlet oxygen, Fenton-like reaction

Tao Wen, Sisheng Guo, Hengxin Zhao, Yuqi Zheng, Xinyue Zhang, Pengcheng Gu, Sai Zhang, Yuejie Ai, Xiangke Wang. Nano-MnO₂ anchored on exfoliated MXene with exceptional and stable Fenton oxidation performance for organic micropollutants[J]. Chinese Journal of Catalysis, 2024, 61: 215-225.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60041-0

https://www.cjcatal.com/EN/Y2024/V61/I6/215

Figures/Tables 6

Fig. 1. (a) Schematic illustrating for synthesizing ex-MXene/MnO2. XRD patterns (b,c), reaction rates and yield (d) for ex-MXene/MnO2 samples with different contact times. (Reaction conditions: [BPA] = 50 ppm, [catalyst] =1.0 g L-1, [PMS] = 2.0 g L-1; pH = 4.8).

Fig. 2. SEM (a) and TEM (b) images of MXene. SEM (c), TEM (d), HRTEM (inset: enlarged view of the selected area) (e), ring-like selected area electron diffraction (SAED) pattern (f), and corresponding element mappings (g) of MXene/MnO2.

Fig. 3. High-resolution XPS spectra comparisons of MXene and MXene/MnO2: C 1s (a), O 1s (b), Ti 2p (c), Mn 2p and Mn 3s (d). And (e) the proportion of various components comparisons of MXene and MXene/MnO2 by semi-quantitative method.

Fig. 4. The degradation curves of BPA with various systems (a), different activators (b) and their corresponding reaction rate constants (c). Factors influencing the BPA removal efficiency in the MXene/MnO2 + PMS system: PMS concentration (The inset present the corresponding pseudo-first-order reaction kinetic fitted curves) (d), catalyst dosage (e), reaction rate constant and reaction time (f) for MXene/MnO2 and other recently reported catalysts. (Reaction conditions: [BPA]= 50 ppm, [catalyst]= 1.0 g L-1, [PMS/PS/H2O2]= 2.0 g L-1; pH = 4.8).

Fig. 5. (a) k value and inhibition ratio of different quenchers towards MXene/MnO2 in BPA degradation process. ESR spectra for the activation of PMS by different systems obtained with (b) DMPO and (c) TEMP in an aqueous solution. (d-g) Four possible adsorption structures of PMS on MXene/MnO2 surface (The interatomic bond lengths in the diagram are in units of ?). (h) Differential charge densities of PMS-MXene/MnO2 for Type II configuration. (i,j) Possible reaction pathways of 1O2 generation. (k) Gibbs free energy comparisons of the two possible pathways (O, S, Mn, C, Ti and H atoms are in red, yellow, purple, brown, blue, and white color, respectively).

Fig. 6. (a) Schematic illustration of the device-level continuous flow Fenton-like reactor and details of the reactor. (b,c) MXene/MnO2/PVDF membrane. (d) SEM image of MXene/MnO2/PVDF membrane cross-section. (e) BPA removal in the device-level continuous flow Fenton-like reactor. (Experiment conditions: catalyst loading = 0.2 g, [BPA] = 10 ppm, [PMS] = 2.0 g L-1, flow rate = 120 mL h-1, initial pH = 4.8).

References

[1]	X. Nie, G. Y. Li, S. S. Li, Y. M. Luo, W. M. Luo, Q. Wan, T. C. An, Appl. Catal. B, 2022, 300, 120734.
[2]	W. H. M. Abdelraheem, M. N. Nadagouda, D. D. Dionysiou, Appl. Catal. B, 2020, 269, 118807.
[3]	X.-W. Zhang, M.-Y. Lan, F. Wang, C.-C. Wang, P. Wang, C. Ge, W. Liu, Chem. Eng. J., 2022, 450, 138082.
[4]	X. Chen, L. Liu, J. Environ. Chem. Eng., 2022, 10, 107449.
[5]	Y. Chen, C. J. Miller, R. N. Collins, T. D. Waite, Environ. Sci. Technol., 2021, 55, 13317-13325.
[6]	Y. Tian, N. Jia, L. Zhou, J. Lei, L. Wang, J. Zhang, Y. Liu, Chemosphere, 2022, 288, 132627.
[7]	K. Wang, C. Han, Z. P. Shao, J. S. Qiu, S. B. Wang, S.M. Liu, Adv. Funct. Mater., 2021, 31, 2102089.
[8]	F. Wang, Y. Gao, H. Chu, Y. Wei, C. Wang, S. Liu, G. Liu, H. Fu, P. Wang, C. Zhao, ACS EST Engg., 2024, 4, 153-165.
[9]	L. Xu, L. Qi, Y. Sun, H. Gong, Y. Chen, C. Pei, L. Gan, Chin. J. Catal., 2022, 41, 322-332.
[10]	S. O. Ganiyu, M. Arslan, M. Gamal El-Din, Chem. Eng. J., 2022, 433, 134579.
[11]	F. Qi, W. Chu, B. Xu, Chem. Eng. J., 2014, 235, 10-18.
[12]	D. Tang, G. Zhang, S. Guo, J. Colloid Interface Sci., 2015, 454, 44-51.
[13]	Z. Yang, C. Shan, B. Pan, J. J. Pignatello, Environ. Sci. Technol., 2021, 55, 8299-8308.
[14]	L. Pan, W. Shi, T. Sen, L. Wang, J. Zhang, Appl. Catal. B, 2021, 280, 119414.
[15]	E. T. Yun, J. H. Lee, J. Kim, H. D. Park, J. Lee, Environ. Sci. Technol., 2018, 52, 7032-7042.
[16]	W. Ren, C. Cheng, P. Shao, X. Luo, H. Zhang, S. Wang, X. Duan, Environ. Sci. Technol., 2022, 56, 78-97.
[17]	N. Li, J. H. Peng, W. J. Ong, T. T. Ma, Arramel, P. Zhang, J. Z. Jiang, X. F. Yuan, C. F. Zhang, Matter-Us, 2021, 4, 377-407.
[18]	X. Chen, X. Tong, J. Gao, L. Yang, J. Ren, W. Yang, S. Liu, M. Qi, J. Environ. Sci. Technol., 2022, 56, 4542-4552.
[19]	Z. Jiang, X. Y. Zhang, S. S. Guo, Y. Q. Zheng, J. Wang, T. Wen, X. K. Wang, Mater. Chem. Front., 2023, 7, 4658-4682.
[20]	L. Jin, S. You, N. Ren, B. Ding, Y. Liu, Environ. Sci. Technol., 2022, 56, 11750-11759.
[21]	L. Zhang, J. Chen, Y. Zhang, Z. Yu, R. Ji, X. Zhou, Appl. Catal. B, 2021, 297, 120475.
[22]	C. Li, C. Song, H. Li, L. Ye, Y. Xu, Y. Huang, G. Nie, R. Zhang, W. Liu, N. Huang, P. Wong, T. Ma, Chin. J. Catal., 2022, 43, 1927-1936.
[23]	Z. You, Y. Liao, X. Li, J. Fan, Q. Xiang, Nanoscale, 2021, 13, 9463.
[24]	C. Guan, X. Yue, J. Fan, Q. Xiang, Chin. J. Catal., 2022, 43, 2484-2499.
[25]	X. Guo, H. Zhang, Y. Y. Yao, C. M. Xiao, X. Yan, K. Chen, J. W. Qi, Y. J. Zhou, Z. G. Zhu, X. Y. Sun, J. S. Li, Appl. Catal. B, 2023, 323, 122136.
[26]	S. S. Luo, R. Wang, J. J. Yin, T. F. Jiao, K. Y. Chen, G. D. Zou, L. Zhang, J. X. Zhou, L. X. Zhang, Q. M. Peng, ACS Omega, 2019, 4, 3946-3953.
[27]	A. Fayyaz, K. Saravanakumar, K. Talukdar, Y. Kim, Y. Yoon, C. M. Park, Chem. Eng. J., 2021, 407, 127842.
[28]	P. Z. Yang, S. R. Li, X. F. Liang, X. J. An, D. F. Liu, W. L. Huang, Sep. Purif. Technol., 2022, 285, 120288.
[29]	Y. Zhou, S. Feng, X. Duan, W. Zheng, C. Shao, W. Wu, Z. Jiang, W. Lai, J. Solid State Chem., 2021, 300, 122231.
[30]	Z. Zhou, H. Dua, Z. Dai, Y. Mua, L. Tong, Q. Xing, S. Liu, Z. Ao, J. Zou, Chem. Eng. J., 2019, 374, 170-180.
[31]	J. Wang, X. Guo, R. Cui, H. Huang, B. Liu, Y. Li, D. Wang, D. Zhao, J. Dong, S. Li, B. Sun, ACS Appl. Nano Mater., 2020, 3, 11152-11159.
[32]	Q. Zhang, Y. Peng, F. Deng, M. Wang, D. Chen, Sep. Purif. Technol., 2020, 246, 116890.
[33]	M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. J. Niu, M. Heon, L. Hultman, Y. Gogotsi, M. W. Barsoum, Adv. Mater., 2011, 23, 4248-4253.
[34]	A. D. Becke, J. Chem. Phys., 1993, 98, 5648-5652.
[35]	X. Chen, S. Zhang, X. Qian, Z. Liang, Y. Xue, X. Zhang, J. Tian, Y. Han, M. Shao, Appl. Catal. B, 2022, 310, 121277.
[36]	Y. Ma, X. Lv, D. Xiong, X. Zhao, Z. Zhang, Appl. Catal. B, 2021, 284, 119720.
[37]	A. R. Khan, S. K. Awan, S. M. Husnain, N. Abbas, D. H. Anjum, N. Abbas, M. Benaissa, C. R. Mirza, S. Mujtaba-ul-Hassan, F. Shahzad, Ceram. Int., 2021, 47, 25951-25958.
[38]	F. He, B. Zhu, B. Cheng, J. Yu, W. Ho, W. Macyk, Appl. Catal. B, 2020, 272, 119006.
[39]	Z. Li, L. Wang, D. Sun, Y. Zhang, B. Liu, Q. Hu, A. Zhou, Mater. Sci. Eng, B, 2015, 191, 33-40.
[40]	Q. Xue, H. Zhang, M. Zhu, Z. Pei, H. Li, Z. Wang, Y. Huang, Y. Huang, Q. Deng, J. Zhou, S. Du, Q. Huang, C. Zhi, Adv. Mater., 2017, 29, 1604847.
[41]	H. Xia, J. Feng, H. Wang, M. O. Lai, L. Lu, J. Power Sources, 2010, 195, 4410-4413.
[42]	Z. Q. He, Y. H. Wang, Y. Li, J. J. Ma, Y. M. Song, X. X. Wang, F. P. Wang, J. Alloys Compd., 2022, 899, 163241.
[43]	W. Chen, G. Li, A. Pei, Y. Li, L. Liao, H. Wang, J. Wan, Z. Liang, G. Chen, H. Zhang, J. Wang, Y. Cui, Nat. Energy, 2018, 3, 428-435.
[44]	Y. Cao, T. Sheng, J. Mei, P. Qian, D. Huang, L. Sheng, G. Sheng, Appl. Catal. B, 2022, 319, 121892.
[45]	Y. Zou, J. Hu, B. Li, L. Lin, Y. Li, F. Liu, X.-Y. Li, Appl. Catal. B, 2022, 312, 121408.
[46]	S. Guo, Y. Zheng, X. Zhang, X. Lei, H. Sun, T. Wen, App. Catal. A, 2024, 670, 119543.
[47]	J. Yao, Y. Yu, R. Qu, J. Chen, Z. Huo, F. Zhu, Z. Wang, Environ. Sci. Technol., 2020, 54, 9052-9061.
[48]	X. Li, X. Huang, S. Xi, S. Miao, J. Ding, W. Cai, S. Liu, X. Yang, H. Yang, J. Gao, J. Wang, Y. Huang, T. Zhang, B. Liu, J. Am. Chem. Soc., 2018, 140, 12469-12475.
[49]	F. Wang, Y. Gao, H. Fu, S. Liu, Y. Wei, P. Wang, C. Zhao, J. Wang, C. Wang, Appl. Catal. B, 2023, 339, 123178.
[50]	Y. Li, C. Wang, F. Wang, W. Liu, L. Chen, C. Zhao, H. Fu, P. Wang, X. Duan, Appl. Catal. B, 2023, 331, 122699.
[51]	Y. Gao, T. W. Wu, C. D. Yang, C. Ma, Z. Y. Zhao, Z. H. Wu, S. J. Cao, W. Geng, Y. Wang, Y. Y. Yao, Y. N. Zhang, C. Cheng, Angew. Chem. In.t Ed., 2021, 60, 22513-22521.
[52]	B. K. Huang, X. Y. Ren, J. Zhao, Z. L. Wu, X. H. Wang, X. Y. Song, X. N. Li, B. Liu, Z. K. Xiong, B. Lai, Environ. Sci. Technol., 2023, 57, 14071-14081.

Nano-MnO₂ anchored on exfoliated MXene with exceptional and stable Fenton oxidation performance for organic micropollutants

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 6

References

Related Articles 15

Recommended Articles

Metrics

[1]	Cheng Cheng, Wei Ren, Hui Zhang, Xiaoguang Duan, Shaobin Wang. Single-atom iron catalysts for peroxymonosulfate-based advanced oxidation processes: Coordination structure versus reactive species [J]. Chinese Journal of Catalysis, 2024, 59(4): 15-37.
[2]	Junlei Zhang, Wencong Liu, Biao Liu, Xiaoguang Duan, Zhimin Ao, Mingshan Zhu. Is single-atom catalyzed peroxymonosulfate activation better? Coupling with metal oxide may be better [J]. Chinese Journal of Catalysis, 2024, 59(4): 137-148.
[3]	Jingyi Han, Jingqi Guan. Heteronuclear dual-metal atom catalysts for nanocatalytic tumor therapy [J]. Chinese Journal of Catalysis, 2023, 47(4): 1-31.
[4]	Ke Wang, Miao Cheng, Nan Wang, Qianyi Zhang, Yi Liu, Junwei Liang, Jie Guan, Maochang Liu, Jiancheng Zhou, Naixu Li. Inter-plane 2D/2D ultrathin La₂Ti₂O₇/Ti₃C₂ MXene Schottky heterojunctions toward high-efficiency photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2023, 44(1): 146-159.
[5]	Xue Bai, Jingqi Guan. MXenes for electrocatalysis applications: Modification and hybridization [J]. Chinese Journal of Catalysis, 2022, 43(8): 2057-2090.
[6]	Chun Zhu, Jin-Xia Liang, Yang-Gang Wang, Jun Li. Non-noble metal single-atom catalyst with MXene support: Fe₁/Ti₂CO₂ for CO oxidation [J]. Chinese Journal of Catalysis, 2022, 43(7): 1830-1841.
[7]	Xiu Qian, Yanjiao Wei, Mengjie Sun, Ye Han, Xiaoli Zhang, Jian Tian, Minhua Shao. Heterostructuring 2D TiO₂ nanosheets in situ grown on Ti₃C₂T_x MXene to improve the electrocatalytic nitrogen reduction [J]. Chinese Journal of Catalysis, 2022, 43(7): 1937-1944.
[8]	Neng Li, Jiahe Peng, Zuhao Shi, Peng Zhang, Xin Li. Charge transfer and orbital reconstruction of non-noble transition metal single-atoms anchored on Ti₂CT_x-MXenes for highly selective CO₂ electrochemical reduction [J]. Chinese Journal of Catalysis, 2022, 43(7): 1906-1917.
[9]	Yijing Gao, Shijie Zhang, Xiang Sun, Wei Zhao, Han Zhuo, Guilin Zhuang, Shibin Wang, Zihao Yao, Shengwei Deng, Xing Zhong, Zhongzhe Wei, Jian-guo Wang. Computational screening of O-functional MXenes for electrocatalytic ammonia synthesis [J]. Chinese Journal of Catalysis, 2022, 43(7): 1860-1869.
[10]	Junxian Bai, Rongchen Shen, Zhimin Jiang, Peng Zhang, Youji Li, Xin Li. Integration of 2D layered CdS/WO₃ S-scheme heterojunctions and metallic Ti₃C₂ MXene-based Ohmic junctions for effective photocatalytic H₂ generation [J]. Chinese Journal of Catalysis, 2022, 43(2): 359-369.
[11]	Huapeng Li, Bin Sun, Tingting Gao, Huan Li, Yongqiang Ren, Guowei Zhou. Ti₃C₂ MXene co-catalyst assembled with mesoporous TiO₂ for boosting photocatalytic activity of methyl orange degradation and hydrogen production [J]. Chinese Journal of Catalysis, 2022, 43(2): 461-471.
[12]	Yuhua Liu, Wei Zhang, Weitao Zheng. Surface chemistry of MXene quantum dots: Virus mechanism-inspired mini-lab for catalysis [J]. Chinese Journal of Catalysis, 2022, 43(11): 2913-2935.
[13]	Haoran Yu, Danxu Liu, Hengyi Wang, Haishuang Yu, Qingyun Yan, Jiahui Ji, Jinlong Zhang, Mingyang Xing. Singlet oxygen synergistic surface-adsorbed hydroxyl radicals for phenol degradation in CoP catalytic photo-Fenton [J]. Chinese Journal of Catalysis, 2022, 43(10): 2678-2689.
[14]	Lele Wang, Tao Yang, Lijie Peng, Qiqi Zhang, Xilin She, Hua Tang, Qinqin Liu. Dual transfer channels of photo-carriers in 2D/2D/2D sandwich-like ZnIn₂S₄/g-C₃N₄/Ti₃C₂ MXene S-scheme/Schottky heterojunction for boosting photocatalytic H₂ evolution [J]. Chinese Journal of Catalysis, 2022, 43(10): 2720-2731.
[15]	Chen Guan, Xiaoyang Yue, Jiajie Fan, Quanjun Xiang. MXene quantum dots of Ti₃C₂: Properties, synthesis, and energy-related applications [J]. Chinese Journal of Catalysis, 2022, 43(10): 2484-2499.