Zirconium-Based Amphoteric Metal–Organic Framework Membrane for Blue Energy Harvesting

Rockson Kwesi Tonnah , Milton Chai , Mohammad Khedri , Milad Razbin , Yasaman Boroumand , Reza Maleki , Huan Xiao , Amir Razmjou , Mohsen Asadnia

Carbon Energy ›› 2025, Vol. 7 ›› Issue (11) : e70050

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Carbon Energy ›› 2025, Vol. 7 ›› Issue (11) :e70050 DOI: 10.1002/cey2.70050
RESEARCH ARTICLE
Zirconium-Based Amphoteric Metal–Organic Framework Membrane for Blue Energy Harvesting
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Abstract

Salination of solutions of salinity gradient releases large-scale clean and renewable energy, which can be directly and efficiently transformed into electrical energy using ion-selective nanofluidic channel membranes. However, conventional ion-selective membranes are typically either cation- or anion-selective. A pH-switchable system capable of dual cation and anion transport along with salt gradient energy harvesting properties has not been demonstrated in ion-selective membranes. Here, we constructed an amphoteric heterolayer metal–organic framework (MOF) membrane with subnanochannels modified with carboxylic and amino functional groups. The amphoteric MOF-composite membrane, AAO/aUiO-66-(COOH)2/UiO-66-NH2, exhibits pH-tuneable ion conduction and achieves osmotic energy conversion of 7.4 and 5.7 W/m2 in acidic and alkaline conditions, respectively, using a 50-fold salt gradient. For different anions but the same cation diffusion transport, the amphoteric membrane produces an outstanding I/CO32− selectivity of ~4160 and an osmotic energy conversion of ~133.5 W/m2. The amphoteric membrane concept introduces a new pathway to explore the development of ion transport and separation technologies and their application in osmotic energy-conversion devices and flow batteries.

Keywords

amphoteric membrane / blue energy generator / carboxylic and amino functional groups / MOF-composite membrane / pH-tuneable ion transport

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Rockson Kwesi Tonnah, Milton Chai, Mohammad Khedri, Milad Razbin, Yasaman Boroumand, Reza Maleki, Huan Xiao, Amir Razmjou, Mohsen Asadnia. Zirconium-Based Amphoteric Metal–Organic Framework Membrane for Blue Energy Harvesting. Carbon Energy, 2025, 7(11): e70050 DOI:10.1002/cey2.70050

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References

[1]

B. Zhang, W. Xu, L. Peng, Y. Li, W. Zhang, and Z. Wang, “Nature-Inspired Interfacial Engineering for Energy Harvesting,” Nature Reviews Electrical Engineering 1, no. 4 (2024): 218–233.

[2]

L. Li, J. Lin, N. Wu, et al., “Review and Outlook on the International Renewable Energy Development,” Energy and Built Environment 3, no. 2 (2022): 139–157.

[3]

N. Sezer and M. Koç, “Development and Performance Assessment of a New Integrated Solar, Wind, and Osmotic Power System for Multigeneration, Based on Thermodynamic Principles,” Energy Conversion and Management 188 (2019): 94–111.

[4]

H. Xie, Z. Zhao, T. Liu, et al., “A Membrane-Based Seawater Electrolyser for Hydrogen Generation,” Nature 612, no. 7941 (2022): 673–678.

[5]

Q. Ren, H. Hu, Q. Zeng, Q. Jiang, and P. Wang, “Hybrid Solar Photovoltaic and Salinity-Gradient Based Osmotic Energy Conversion System With Synergistic Performance Enhancement,” Energy Conversion and Management 283 (2023): 116898.

[6]

W. Chen, Y. Xiang, X. Y. Kong, and L. Wen, “Polymer-Based Membranes for Promoting Osmotic Energy Conversion,” Giant 10 (2022): 100094.

[7]

Z. Wu, T. Zhang, B. Wang, et al., “Scalable Bacterial Cellulose Biofilms With Improved Ion Transport for High Osmotic Power Generation,” Nano Energy 88 (2021): 106275.

[8]

S. Zhou, L. Xie, X. Li, et al., “Interfacial Super-Assembly of Ordered Mesoporous Carbon-Silica/AAO Hybrid Membrane With Enhanced Permselectivity for Temperature-and pH-Sensitive Smart Ion Transport,” Angewandte Chemie 133, no. 50 (2021): 26371–26380.

[9]

Z. Zhang, L. He, C. Zhu, Y. Qian, L. Wen, and L. Jiang, “Improved Osmotic Energy Conversion in Heterogeneous Membrane Boosted by Three-Dimensional Hydrogel Interface,” Nature Communications 11, no. 1 (2020): 875.

[10]

F. Zhang, J. Yu, Y. Si, and B. Ding, “Meta-Aerogel Ion Motor for Nanofluid Osmotic Energy Harvesting,” Advanced Materials 35, no. 38 (2023): 2302511.

[11]

W. Xin, Z. Zhang, X. Huang, et al., “High-Performance Silk-Based Hybrid Membranes Employed for Osmotic Energy Conversion,” Nature Communications 10, no. 1 (2019): 3876.

[12]

Z. Ding, T. Gu, R. Zhang, et al., “Plasma-Oxidized 2D Mxenes Subnanochannel Membrane for High-Performance Osmotic Energy Conversion,” Carbon Energy 6, no. 8 (2024): e509.

[13]

M. Chen, K. Yang, J. Wang, H. Sun, X. Xia, and C. Wang, “In Situ Growth of Imine-Bridged Anion-Selective COF/AAO Membrane for Ion Current Rectification and Nanofluidic Osmotic Energy Conversion,” Advanced Functional Materials 33, no. 36 (2023): 2302427.

[14]

Y. Fu, X. Guo, Y. Wang, X. Wang, and J. Xue, “An Atomically-Thin Graphene Reverse Electrodialysis System for Efficient Energy Harvesting From Salinity Gradient,” Nano Energy 57 (2019): 783–790.

[15]

J. hong, T. Xu, H. Qi, et al., “Permeability and Selectivity Synergistically Enhanced Nanofluidic Membrane for Osmotic Energy Harvesting,” Carbon Energy 6, no. 8 (2024): e458.

[16]

Y. Liu, J. Ping, and Y. Ying, “Anion-Selective Layered Double Hydroxide Composites-Based Osmotic Energy Conversion for Real-Time Nutrient Solution Detection,” Advanced Science 9, no. 6 (2022): 2103696.

[17]

F. F. Liu, X. P. Zhao, B. Kang, X. H. Xia, and C. Wang, “Non-Linear Mass Transport in Confined Nanofluidic Devices for Label-Free Bioanalysis/Sensors,” TrAC, Trends in Analytical Chemistry 123 (2020): 115760.

[18]

C. Wang, X. P. Zhao, F. F. Liu, Y. Chen, X. H. Xia, and J. Li, “Dendrimer-Au Nanoparticle Network Covered Alumina Membrane for Ion Rectification and Enhanced Bioanalysis,” Nano Letters 20, no. 3 (2020): 1846–1854.

[19]

M. Abdollahzadeh, M. Chai, E. Hosseini, et al., “Designing Angstrom-Scale Asymmetric MOF-on-MOF Cavities for High Monovalent Ion Selectivity,” Advanced Materials 34, no. 9 (2022): 2107878.

[20]

R. K. Tonnah, M. Chai, M. Abdollahzadeh, et al., “Bioinspired Angstrom-Scale Heterogeneous MOF-on-MOF Membrane for Osmotic Energy Harvesting,” ACS Nano 17, no. 13 (2023): 12445–12457.

[21]

C. Wang, F. F. Liu, Z. Tan, Y. Chen, W. Hu, and X. Xia, “Fabrication of Bio-Inspired 2D MOFs/PAA Hybrid Membrane for Asymmetric Ion Transport,” Advanced Functional Materials 30, no. 9 (2020): 1908804.

[22]

A. R. Fauziah and L. H. Yeh, “Engineered Heterogenous Subnanochannel Membranes With a Tri-Continuous Pore Structure of Large Geometry Gradient for Massively Enhanced Osmotic Power Conversion From Organic Solutions,” Advanced Functional Materials 34, no. 7 (2024): 2306834.

[23]

R. K. Tonnah, M. Chai, M. Khedri, et al., “Bilayer Asymmetric-Based Metal-Organic Frameworks Membrane for Blue Energy Conversion,” Desalination 591 (2024): 117968.

[24]

K. Catania, “The Shocking Predatory Strike of the Electric Eel,” Science 346, no. 6214 (2014): 1231–1234.

[25]

T. B. H. Schroeder, A. Guha, A. Lamoureux, et al., “An Electric-Eel-Inspired Soft Power Source From Stacked Hydrogels,” Nature 552, no. 7684 (2017): 214–218.

[26]

L. Yang and L. Wen, “Bio-Inspired Ion Transport/Extraction Systems Toward Future Energy Demand,” Cell Reports Physical Science 3, no. 12 (2022): 101167.

[27]

Y. Hu, Y. Teng, Y. Sun, et al., “Bioinspired Poly (Ionic Liquid) Membrane for Efficient Salinity Gradient Energy Harvesting: Electrostatic Crosslinking Induced Hierarchical Nanoporous Network,” Nano Energy 97 (2022): 107170.

[28]

H. Furukawa, K. E. Cordova, M. O'Keeffe, and O. M. Yaghi, “The Chemistry and Applications of Metal-Organic Frameworks,” Science 341, no. 6149 (2013): 1230444.

[29]

B. Seoane, J. Coronas, I. Gascon, et al., “Metal–Organic Framework Based Mixed Matrix Membranes: A Solution for Highly Efficient CO2 Capture?,” Chemical Society Reviews 44, no. 8 (2015): 2421–2454.

[30]

R. Freund, O. Zaremba, G. Arnauts, et al., “The Current Status of MOF and COF Applications,” Angewandte Chemie International Edition 60, no. 45 (2021): 23975–24001.

[31]

L. Fu, Z. Yang, Y. Wang, R. Li, and J. Zhai, “Construction of Metal-Organic Frameworks (MOFs)–Based Membranes and Their Ion Transport Applications,” Small Science 1, no. 2 (2021): 2000035.

[32]

J. Hou, H. Wang, and H. Zhang, “Zirconium Metal–Organic Framework Materials for Efficient Ion Adsorption and Sieving,” Industrial & Engineering Chemistry Research 59, no. 29 (2020): 12907–12923.

[33]

T. Xu, F. Sheng, B. Wu, et al., “Ti-Exchanged UiO-66-NH2–Containing Polyamide Membranes With Remarkable Cation Permselectivity,” Journal of Membrane Science 615 (2020): 118608.

[34]

J. Lu, G. Jiang, H. Zhang, et al., “An Artificial Sodium-Selective Subnanochannel,” Science Advances 9, no. 4 (2023): eabq1369.

[35]

Y. C. Liu, L. H. Yeh, M. J. Zheng, and K. C. W. Wu, “Highly Selective and High-Performance Osmotic Power Generators in Subnanochannel Membranes Enabled by Metal-Organic Frameworks,” Science Advances 7, no. 10 (2021): eabe9924.

[36]

T. Xu, M. A. Shehzad, X. Wang, B. Wu, L. Ge, and T. Xu, “Engineering Leaf-Like UiO-66-SO3H Membranes for Selective Transport of Cations,” Nano-Micro Letters 12 (2020): 51.

[37]

J. Lu, H. Zhang, J. Hou, et al., “Efficient Metal Ion Sieving in Rectifying Subnanochannels Enabled by Metal–Organic Frameworks,” Nature Materials 19, no. 7 (2020): 767–774.

[38]

H. Xiao, M. Chai, M. Abdollahzadeh, et al., “A Lithium Ion Selective Membrane Synthesized From a Double Layered Zrvbased Metalorganic Framework (MOF-on-MOF) Thin Film,” Desalination 532 (2022): 115733.

[39]

J. Hou, H. Zhang, H. Wang, A. W. Thornton, and K. Konstas, “Amphoteric Metal–Organic Framework Subnanochannels With pH-Tuneable Cation and Anion Sieving Properties,” Journal of Materials Chemistry A 11, no. 25 (2023): 13223–13230.

[40]

L. Yao, Q. Li, S. Pan, J. Cheng, and X. Liu, “Bio-Inspired Salinity-Gradient Power Generation With UiO-66-NH2 Metal-Organic Framework Based Composite Membrane,” Frontiers in Bioengineering and Biotechnology 10 (2022): 901507.

[41]

Y. Su, J. Hou, C. Zhao, Q. Han, J. Hu, and H. Zhang, “Flexible UiO-66-(COOH)2 Metal–Organic Framework Membranes for Salinity Gradient Power Generation,” Chemical Engineering Journal 476 (2023): 146649.

[42]

X. Li, G. Jiang, M. Jian, et al., “Construction of Angstrom-Scale Ion Channels With Versatile Pore Configurations and Sizes by Metal-Organic Frameworks,” Nature Communications 14, no. 1 (2023): 286.

[43]

M. Mohammad, A. Razmjou, K. Liang, M. Asadnia, and V. Chen, “Metal–Organic-Framework-Based Enzymatic Microfluidic Biosensor Via Surface Patterning and Biomineralization,” ACS Applied Materials & Interfaces 11, no. 2 (2018): 1807–1820.

[44]

M. Chai, A. Razmjou, and V. Chen, “Metal-Organic-Framework Protected Multi-Enzyme Thin-Film for the Cascade Reduction of CO2 in a Gas-Liquid Membrane Contactor,” Journal of Membrane Science 623 (2021): 118986.

[45]

Y. Luan, Y. Qi, Z. Jin, X. Peng, H. Gao, and G. Wang, “Synthesis of a Flower-Like Zr-Based Metal–Organic Framework and Study of Its Catalytic Performance in the Mannich Reaction,” RSC Advances 5, no. 25 (2015): 19273–19278.

[46]

E. Binaeian, Y. Li, H. A. Tayebi, and D. Yuan, “Enhancing Toxic Gas Uptake Performance of Zr-Based MOF Through Uncoordinated Carboxylate and Copper Insertion; Ammonia Adsorption,” Journal of Hazardous Materials 416 (2021): 125933.

[47]

Y. Cao, H. Zhang, F. Song, et al., “UiO-66-NH2/GO Composite: Synthesis, Characterization and CO2 Adsorption Performance,” Materials 11, no. 4 (2018): 589.

[48]

Z. Zhang, P. Zhang, S. Yang, et al., “Oxidation Promoted Osmotic Energy Conversion in Black Phosphorus Membranes,” Proceedings of the National Academy of Sciences of the United States of America 117, no. 25 (2020): 13959–13966.

[49]

C. W. Chu, A. R. Fauziah, and L. H. Yeh, “Optimizing Membranes for Osmotic Power Generation,” Angewandte Chemie 135, no. 26 (2023): e202303582.

[50]

W. Xin, H. Xiao, X. Y. Kong, et al., “Biomimetic Nacre-Like Silk-Crosslinked Membranes for Osmotic Energy Harvesting,” ACS Nano 14, no. 8 (2020): 9701–9710.

[51]

J. Zhou, J. Hao, R. Wu, et al., “Maximizing Ion Permselectivity in Mxene/MOF Nanofluidic Membranes for High-Efficient Blue Energy Generation,” Advanced Functional Materials 32, no. 49 (2022): 220976.

[52]

L. Ding, D. Xiao, Z. Lu, et al., “Oppositely Charged Ti3C2Tx Mxene Membranes With 2D Nanofluidic Channels for Osmotic Energy Harvesting,” Angewandte Chemie 132, no. 22 (2020): 8798–8804.

[53]

X. Wang, M. Li, Y. Xiong, et al., “Cellulose Nanocrystal Composite Membrane Enhanced With in Situ Grown Metal–Organic Frameworks for Osmotic Energy Conversion,” Small 21, no. 3 (2025): 2408695.

[54]

K. T. Huang, W. H. Hung, Y. C. Su, et al., “Zwitterionic Gradient Double-Network Hydrogel Membranes With Superior Biofouling Resistance for Sustainable Osmotic Energy Harvesting,” Advanced Functional Materials 33, no. 19 (2023): 2211316.

[55]

Z. J. Yang, L. H. Yeh, Y. H. Peng, Y. Chuang, and K. Wu, “Frontispiz: Enhancing Ionic Selectivity and Osmotic Energy by Using an Ultrathin Zr-MOF-Based Heterogeneous Membrane With Trilayered Continuous Porous Structure,” Angewandte Chemie 136, no. 35 (2024): e202408375.

[56]

L. Ding, M. Zheng, D. Xiao, et al., “Frontispiece: Bioinspired Ti3C2Tx MXene-Based Ionic Diode Membrane for High-Efficient Osmotic Energy Conversion,” Angewandte Chemie International Edition 61, no. 41 (2022): e202206152.

[57]

A. Esfandiar, B. Radha, F. C. Wang, et al., “Size Effect in Ion Transport Through Angstrom-Scale Slits,” Science 358, no. 6362 (2017): 511–513.

[58]

K. P. Gregory, G. R. Elliott, H. Robertson, et al., “Understanding Specific Ion Effects and the Hofmeister Series,” Physical Chemistry Chemical Physics 24, no. 21 (2022): 12682–12718.

[59]

K. P. Gregory, E. J. Wanless, G. B. Webber, V. Craig, and A. J. Page, “The Electrostatic Origins of Specific Ion Effects: Quantifying the Hofmeister Series for Anions,” Chemical Science 12, no. 45 (2021): 15007–15015.

[60]

R. Wei, X. Liu, L. Cao, et al., “Zeolite Membrane With Sub-Nanofluidic Channels for Superior Blue Energy Harvesting,” Nature Communications 15, no. 1 (2024): 10489.

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