Citation: Shiyu Wei, Xiang Li, Chao Huang, Dongmei Chen, Shunlin Zhang, Bixue Zhu. Enhanced PFOA removal via defect engineering in NH₂-UiO-66[J]. Chinese Chemical Letters, ;2026, 37(5): 111858. doi: 10.1016/j.cclet.2025.111858 shu

Enhanced PFOA removal via defect engineering in NH₂-UiO-66

Guizhou Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang 550025, China

zhangsl@gzu.edu.cn

Received Date: 27 March 2025
Revised Date: 30 July 2025
Accepted Date: 17 September 2025
Available Online: 18 September 2025

Figures(4)

Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH₂-UiO-66 derivatives with gradient defect densities (NH₂-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH₂-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO^- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH₃⁺), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
- PFASs,
- PFOA,
- NH₂-UiO-66,
- Defect engineering,
- MOFs
1. [1]
  M.G. Evich, M.J.B. Davis, J.P. McCord, et al., Science 375 (2022) 9065. doi: 10.1126/science.abg9065
2. [2]
  C. Sonne, M.S. Bank, B.M. Jenssen, et al., Science 379 (2023) 887–888. doi: 10.1126/science.adh0934
3. [3]
  J. Hu, X. Yang, X. Song, et al., J. Hazard. Mater. 480 (2024) 136283. doi: 10.1016/j.jhazmat.2024.136283
4. [4]
  R. Li, N.N. Adarsh, H. Lu, M. Wriedt, Matter 5 (2022) 3161–3193. doi: 10.1016/j.matt.2022.07.028
5. [5]
  W. Ji, L. Xiao, Y. Ling, et al., J. Am. Chem. Soc. 140 (2018) 12677–12681. doi: 10.1021/jacs.8b06958
6. [6]
  Z. Chen, Y.L. Lu, L. Wang, et al., J. Am. Chem. Soc. 145 (2023) 260–267. doi: 10.1021/jacs.2c09866
7. [7]
  A. Román Santiago, S. Yin, J. Elbert, et al., J. Am. Chem. Soc. 145 (2023) 9508–9519. doi: 10.1021/jacs.2c10963
8. [8]
  Y. Fang, P. Meng, C. Schaefer, D.R.U. Knappe, Water Res. 230 (2023) 119522. doi: 10.1016/j.watres.2022.119522
9. [9]
  S. Sinha, A. Chaturvedi, R.K. Gautam, J.J. Jiang, J. Am. Chem. Soc. 145 (2023) 27390–27396. doi: 10.1021/jacs.3c08352
10. [10]
  Y. Wen, Á. Rentería-Gómez, G.S. Day, et al., J. Am. Chem. Soc. 144 (2022) 11840–11850. doi: 10.1021/jacs.2c04341
11. [11]
  C. Zhang, K. Yan, C. Fu, et al., Chem. Rev. 122 (2022) 167–208. doi: 10.1021/acs.chemrev.1c00632
12. [12]
  N. Kim, J. Elbert, E. Shchukina, X. Su, Nat. Commun. 15 (2024) 8321. doi: 10.1038/s41467-024-52630-w
13. [13]
  J. Fang, S. Li, T. Gu, et al., J. Environ. Chem. Eng. 12 (2024) 111833. doi: 10.1016/j.jece.2023.111833
14. [14]
  S. Li, J. Ma, J. Cheng, et al., Langmuir 40 (2024) 2815–2829. doi: 10.1021/acs.langmuir.3c02939
15. [15]
  P.S. Pauletto, T.J. Bandosz, J. Hazard. Mater. 425 (2022) 127810. doi: 10.1016/j.jhazmat.2021.127810
16. [16]
  L.I. FitzGerald, J.F. Olorunyomi, R. Singh, C.M. Doherty, ChemSusChem 15 (2022) 202201136. doi: 10.1002/cssc.202201136
17. [17]
  H. Shan, J. Xiao, G. Duan, et al., Univ. Nat. Sci. Ed. 36 (2023) 43–52. doi: 10.1007/s11802-023-5076-9
18. [18]
  N. Ilić, K. Tan, F. Mayr, et al., Adv. Mater. 37 (2024) 2413120.
19. [19]
  M. Endoh, H. Konno, Chem. Lett. 50 (2021) 1592–1596. doi: 10.1246/cl.210233
20. [20]
  Q. Li, S. Zhu, F. Chen, C. Guo, Environ. Res. 211 (2022) 113083. doi: 10.1016/j.envres.2022.113083
21. [21]
  S. Zhang, Y. Xie, R.J. Somerville, et al., Small 19 (2023) 2206999. doi: 10.1002/smll.202206999
22. [22]
  G. Luo, S. Zhang, S.L. Zhang, et al., J. Mol. Struct. 1299 (2024) 137145. doi: 10.1016/j.molstruc.2023.137145
23. [23]
  R.R. Liang, Y. Yang, Z. Han, et al., Adv. Mater. 36 (2024) 2407194. doi: 10.1002/adma.202407194
24. [24]
  C. Zhao, Y. Xu, F. Xiao, et al., Chem. Eng. J. 406 (2021) 126852. doi: 10.1016/j.cej.2020.126852
25. [25]
  R.R. Liang, S. Xu, Z. Han, et al., J. Am. Chem. Soc. 146 (2024) 9811–9818. doi: 10.1021/jacs.3c14487
26. [26]
  Z. Fang, B. Bueken, D.E. De Vos, R.A. Fischer, Angew. Chem. Int. Ed. 54 (2015) 7234–7254. doi: 10.1002/anie.201411540
27. [27]
  N.S. Portillo-Vélez, J.L. Obeso, J.A. de los Reyes, et al., Commun. Mater. 5 (2024) 247. doi: 10.1038/s43246-024-00691-1
28. [28]
  J. Ren, M. Ledwaba, N.M. Musyoka, et al., Coord. Chem. Rev. 349 (2017) 169–197. doi: 10.1016/j.ccr.2017.08.017
29. [29]
  Y. Bai, Y. Dou, L.H. Xie, et al., Chem. Soc. Rev. 45 (2016) 2327–2368. doi: 10.1039/C5CS00837A
30. [30]
  S. Yuan, L. Feng, K. Wang, et al., Adv. Mater. 30 (2018) 1704303. doi: 10.1002/adma.201704303
31. [31]
  X. Miao, S. Chen, C. Peng, et al., Int. J. Hydrogen Energy 71 (2024) 121–130. doi: 10.1016/j.ijhydene.2024.05.224
32. [32]
  R. Han, K. Wang, Q. Jiang, et al., J. Colloid Interface Sci. 671 (2024) 680–691. doi: 10.1016/j.jcis.2024.05.206
33. [33]
  X. Zhao, M. Liu, Z. Shang, et al., Energy Fuels 38 (2024) 17939–17947. doi: 10.1021/acs.energyfuels.4c03204
34. [34]
  X. Huang, Z. Shang, X. Zhao, et al., J. Energy Storage 102 (2024) 114054. doi: 10.1016/j.est.2024.114054
35. [35]
  G. Luo, J. Jiang, S. Wei, et al., Sep. Purif. Technol. 343 (2024) 127133. doi: 10.1016/j.seppur.2024.127133
36. [36]
  L. Xiao, Y. Ling, A. Alsbaiee, et al., J. Am. Chem. Soc. 139 (2017) 7689–7692. doi: 10.1021/jacs.7b02381
37. [37]
  X. Li, H. Zhao, X. Quan, et al., J. Hazard. Mater. 186 (2011) 407–415. doi: 10.1016/j.jhazmat.2010.11.012
38. [38]
  D. Shettć, I. Jahovic, T. Skorjanc, et al., ACS Appl. Mater. Interfaces 12 (2020) 43160–43166. doi: 10.1021/acsami.0c13400
39. [39]
  D. Zhang, Q. Luo, B. Gao, et al., Chemosphere 144 (2016) 2336–2342. doi: 10.1016/j.chemosphere.2015.10.124
40. [40]
  M. Van den Bergh, A. Krajnc, S. Voorspoels, et al., Angew. Chem. Int. Ed. 59 (2020) 13666-13666. doi: 10.1002/anie.202007703
41. [41]
  J. Wang, Z. Li, N. Hu, et al., J. Mater. Chem. A 5 (2017) 22506–22511. doi: 10.1039/C7TA08598B
42. [42]
  L. Piai, J.E. Dykstra, M.G. Adishakti, et al., Water Res. 162 (2019) 518–527.
43. [43]
  L. Ding, H. Deng, C. Wu, X. Han, Chem. Eng. J. 181 (2012) 360–370.
44. [44]
  M.J. Chen, A.C. Yang, N.H. Wang, et al., Microp. Mesop. Mater. 236 (2016) 202–210.
45. [45]
  A. Dhakshinamoorthy, M. Alvaro, P. Horcajada, et al., ACS Catal. 2 (2012) 2060–2065. doi: 10.1021/cs300345b
46. [46]
  D.W. Kim, H.G. Kim, D.H. Cho, Catal. Commun. 73 (2016) 69–73.
1. [1]
  Baker Rhimi , Zheyang Liu , Jing Li , Min Zhou , Qiang Ma , Zhifeng Jiang . The potential of diatomic-site catalysts for CO2 photoreduction to multi-carbon products. Chinese Journal of Structural Chemistry, 2026, 45(2): 100791-100791. doi: 10.1016/j.cjsc.2025.100791
2. [2]
  Fei Jin , Bolin Yang , Xuanpu Wang , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Facilitating efficient photocatalytic hydrogen evolution via enhanced carrier migration at MOF-on-MOF S-scheme heterojunction interfaces through a graphdiyne (CnH2n-2) electron transport layer. Chinese Journal of Structural Chemistry, 2023, 42(12): 100198-100198. doi: 10.1016/j.cjsc.2023.100198
3. [3]
  Guoqiang Peng , Xiuyan Li , Min Li , Zhibo Su , Falu Hu , Guowei Zhou . Engineering efficient metal-organic frameworks for photocatalytic CO₂ reduction. Acta Physico-Chimica Sinica, 2026, 42(2): 100164-0. doi: 10.1016/j.actphy.2025.100164
4. [4]
  Tengjia Ni , Xianbiao Hou , Huanlei Wang , Lei Chu , Shuixing Dai , Minghua Huang . Controllable defect engineering based on cobalt metal-organic framework for boosting oxygen evolution reaction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100210-100210. doi: 10.1016/j.cjsc.2023.100210
5. [5]
  Malaika Arshad , Zia Ul Haq Khan , Swera Talib , Sana Sabahat , Noor Samad Shah , Huma Ajab , Farooq Ahmad , Syed Khasim , M. A. Diab , Heba A. El-Sabban . A comprehensive review: MOFs and their derivatives as high-performance supercapacitor electrodes. Chinese Journal of Structural Chemistry, 2025, 44(9): 100676-100676. doi: 10.1016/j.cjsc.2025.100676
6. [6]
  Xiaoyu Song , Lei Xu , Xiangyu Meng , Yuening Wang , Mingjian Zhang , Aochi Liu , Jie Lin , Xiaotian Wang . TMO-based SERS: Dual enhancement mechanisms and multi-functional analytical applications. Chinese Journal of Structural Chemistry, 2026, 45(2): 100797-100797. doi: 10.1016/j.cjsc.2025.100797
7. [7]
  Xingyan Liu , Yue Li , Kaili Wu , Panpan Li , Yonggang Xu , Xiaowei Li , Junhao Zhou , Youzhou He , Min Fu , Guangming Jiang , Siping Wei . In-situ confined up-conversion Pt/CQDs within linker-defective NH₂-MIL-125 to integrate photosensitivity and conductivity for hydrogen production and NO oxidation. Chinese Chemical Letters, 2025, 36(11): 110853-. doi: 10.1016/j.cclet.2025.110853
8. [8]
  Ying Hou , Zhen Liu , Xiaoyan Liu , Zhiwei Sun , Zenan Wang , Hong Liu , Weijia Zhou . Laser constructed vacancy-rich TiO_2-x/Ti microfiber via enhanced interfacial charge transfer for operando extraction-SERS sensing. Chinese Chemical Letters, 2024, 35(9): 109634-. doi: 10.1016/j.cclet.2024.109634
9. [9]
  Zhemi Xu , Haolin Cui , Shule Zhang , Peiyuan Guan , Tianhao Ji , Jin Yan , Qianyu Li , Dewei Chu , Yunxuan Weng , Zhimin Ao , Yang Liu , Jian Jin . Facet engineering of metal-organic frameworks enables high piezoelectricity and piezocatalysis: A case study of ZIF-8. Chinese Chemical Letters, 2026, 37(4): 111667-. doi: 10.1016/j.cclet.2025.111667
10. [10]
  Lingxiang Bao , Jing-Hong Li , Rui-Biao Lin , Jianyuan Wu , Zhenhong Tan , Wu Xie , Wenhai Ji , Dong Zhang , Anucha Koedtruad , Jingjing Ma , Wang Hay Kan , Feng Pan , Toru Ishigaki , Takashi Kamiyama , Ping Miao . Elucidation of the CO₂ adsorption mechanism of [Zn₂(mtz)₂(ox)] using neutron powder diffraction. Chinese Chemical Letters, 2026, 37(5): 110864-. doi: 10.1016/j.cclet.2025.110864
11. [11]
  Shujun Ning , Zhiyuan Wei , Zhening Chen , Tianmin Wu , Lu Zhang . Curvature and defect formation synergistically promote the photocatalysis of ZnO slabs. Chinese Chemical Letters, 2025, 36(7): 111057-. doi: 10.1016/j.cclet.2025.111057
12. [12]
  Yaxin Sun , Huiyu Li , Shiquan Guo , Congju Li . Metal-based cathode catalysts for electrocatalytic ORR in microbial fuel cells: A review. Chinese Chemical Letters, 2024, 35(5): 109418-. doi: 10.1016/j.cclet.2023.109418
13. [13]
  Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO₃₋_x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753
14. [14]
  Erzhuo Cheng , Yunyi Li , Wei Yuan , Wei Gong , Yanjun Cai , Yuan Gu , Yong Jiang , Yu Chen , Jingxi Zhang , Guangquan Mo , Bin Yang . Galvanostatic method assembled ZIFs nanostructure as novel nanozyme for the glucose oxidation and biosensing. Chinese Chemical Letters, 2024, 35(9): 109386-. doi: 10.1016/j.cclet.2023.109386
15. [15]
  Shenghui Tu , Anru Liu , Hongxiang Zhang , Lu Sun , Minghui Luo , Shan Huang , Ting Huang , Honggen Peng . Oxygen vacancy regulating transition mode of MIL-125 to facilitate singlet oxygen generation for photocatalytic degradation of antibiotics. Chinese Chemical Letters, 2024, 35(12): 109761-. doi: 10.1016/j.cclet.2024.109761
16. [16]
  Ying Zhao , Yin-Hang Chai , Meng-Meng Zhai , Qin-Ying Jin , Xiaoyan Lu , Yi-Dan Qiao , Lu-Fang Ma . New functional metal–organic framework (MOF) based optical thermometer by the post-synthesis doping rare earth ions into MOF. Chinese Chemical Letters, 2026, 37(1): 111085-. doi: 10.1016/j.cclet.2025.111085
17. [17]
  Xueqi Yang , Juntao Zhao , Jiawei Ye , Desen Zhou , Tingmin Di , Jun Zhang . 调节NNU-55(Fe)的d带中心以增强CO₂吸附和光催化活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100074-0. doi: 10.1016/j.actphy.2025.100074
18. [18]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
19. [19]
  Yangrui Xu , Yewei Ren , Xinlin Liu , Hongping Li , Ziyang Lu . NH₂-UIO-66 Based Hydrophobic Porous Liquid with High Mass Transfer and Affinity Surface for Enhancing CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(11): 2403032-0. doi: 10.3866/PKU.WHXB202403032
20. [20]
  Ziruo Zhou , Wenyu Guo , Tingyu Yang , Dandan Zheng , Yuanxing Fang , Xiahui Lin , Yidong Hou , Guigang Zhang , Sibo Wang . Defect and nanostructure engineering of polymeric carbon nitride for visible-light-driven CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100245-100245. doi: 10.1016/j.cjsc.2024.100245

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(7)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Enhanced PFOA removal via defect engineering in NH2-UiO-66

Metrics

通讯作者: 陈斌, bchen63@163.com

Enhanced PFOA removal via defect engineering in NH₂-UiO-66