Functionalized MOF lamellar membrane for efficient proton conduction

ZHANG Zhiyan; ZHANG Jie; WU Wenjia

doi:10.11949/0438-1157.20251340

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Functionalized MOF lamellar membrane for efficient proton conduction

Separation engineering | 更新时间：2026-08-13

- Functionalized MOF lamellar membrane for efficient proton conduction
- CIESC Journal Vol. 77, Issue 6, Pages: 3504-3512(2026)
- 作者机构：
  
  1.河南省化工研究所有限责任公司，河南郑州 450052
  2.郑州大学化工学院，河南郑州 450001
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20251340
  CLC： TQ 152;TQ 028.8
- Received：01 December 2025，
  
  Revised：2026-03-06，
  
  Online First：29 July 2026，
  
  Published：25 June 2026
- 稿件说明：
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张志岩, 张婕, 武文佳. 功能化MOF层状膜用于高效质子传导[J]. 化工学报, 2026, 77(6): 3504-3512

ZHANG Zhiyan, ZHANG Jie, WU Wenjia. Functionalized MOF lamellar membrane for efficient proton conduction[J]. CIESC Journal, 2026, 77(6): 3504-3512
张志岩, 张婕, 武文佳. 功能化MOF层状膜用于高效质子传导[J]. 化工学报, 2026, 77(6): 3504-3512 DOI： 10.11949/0438-1157.20251340.

ZHANG Zhiyan, ZHANG Jie, WU Wenjia. Functionalized MOF lamellar membrane for efficient proton conduction[J]. CIESC Journal, 2026, 77(6): 3504-3512 DOI： 10.11949/0438-1157.20251340.

摘要

通过后合成法制备两种具有不同功能基团的AlBDC-2X（—COOH和—SO

H）MOF纳米片并组装层状膜。结果表明，基团的成功引入有效降低MOF的孔径，从0.8 nm降到0.6 nm。同时，在低湿度下，共价连接的载体位点强化水吸收，在载体-水分子-载体间形成连续的质子传递路径，使得质子在低湿度下依然以跳跃机制低阻力传递。在80℃和20%相对湿度（RH）下，AlBDC-2SO

H和AlBDC-2COOH膜的质子传导率高达18.3和14.1 mS·cm

-1

，这些性能高于目前所报道的大部分MOF基质子传导材料。并且在80℃和100% RH下，AlBDC-2SO

H的质子传导率达到102.2 mS·cm

-1

。此外，共价连接的载体位点在不同湿度下提供了稳定的质子传导，45 h内没有显著下降。得益于高且稳定的质子传导能力，将该材产用于燃料电池电极中，最大功率密度和最大电流密度分别达到343.6 mW·cm

-2

和1183.1 mA·cm

-2

。

Abstract

Two AlBDC-2X (—COOH and —SO

H) MOF nanosheets with different functional groups were prepared by post-synthesis and assembled into layered membranes. The experimental results show that the successful introduction of the moieties effectively reduces the pore size of the MOF from 0.8 to 0.6 nm. Meanwhile

the covalently linked carrier sites enhance the water uptake at low humidity and form a continuous proton transfer path between carrier-water mol

ecules and carriers

which allows the protons to be transferred with a hopping mechanism and low resistance even at low humidity. At 80℃ and 20% relative humidity (RH)

the proton conductivities of AlBDC-2SO

H and AlBDC-2COOH membranes were 18.3 and 14.1 mS·cm

-1

which were higher than most of the MOF-based proton conducting materials reported so far. Moreover

the proton conductivity of AlBDC-2SO

H reaches 102.2 mS·cm

-1

at 80℃ and 100% RH. In addition

the covalently linked carrier sites ensure stable proton conductivity with no significant decrease over the 45 h test under varying RH. This high and stable proton conductivity also provided excellent fuel cell performance with maximum power density of 343.6 mW·cm

-2

and current density of 1183.1 mA·cm

-2

respectively.

关键词

Keywords

references

杨孝才 , 贾秋红 , 屈翔 , 等 . 操作参数对质子交换膜燃料电池冷却效果分析 [J ] . 郑州大学学报(工学版) , 2022 , 43 ( 4 ): 53 - 59 .

Yang X C , Jia Q H , Qu X , et al . Analysis of cooling effect of operating parameters on proton exchange membrane fuel cells [J ] . Journal of Zhengzhou University (Engineering Science) , 2022 , 43 ( 4 ): 53 - 59 .

Jiao K , Xuan J , Du Q , et al . Designing the next generation of proton-exchange membrane fuel cells [J ] . Nature , 2021 , 595 ( 7867 ): 361 - 369 .

韩启沃 , 刘永峰 , 裴普成 , 等 . 工作温度对PEMFC水分布、质子传输及性能影响分析 [J ] . 化工学报 , 2025 , 76 ( 1 ): 374 - 384 .

Han Q W , Liu Y F , Pei P C , et al . Analysis of influence of operating temperature on water distribution, proton transport and performance of PEMFC [J ] . CIESC Journal , 2025 , 76 ( 1 ): 374 - 384 .

Qian X T , Chen L , Yin L C , et al . CdPS 3 nanosheets-based membrane with high proton conductivity enab led by Cd vacancies [J ] . Science , 2020 , 370 ( 6516 ): 596 - 600 .

Cao L , Wu H , Cao Y , et al . Weakly humidity-dependent proton-conducting COF membranes [J ] . Advanced Materials , 2020 , 32 ( 52 ): 2005565 .

Wu W J , Li Y F , Liu J D , et al . Molecular-level hybridization of nafion with quantum dots for highly enhanced proton conduction [J ] . Advanced Materials , 2018 , 30 ( 16 ): 1707516 .

Shimizu G K H , Taylor J M , Kim S . Proton conduction with metal-organic frameworks [J ] . Science , 2013 , 341 ( 6144 ): 354 - 355 .

Lim D W , Kitagawa H . Rational strategies for proton-conductive metal-organic frameworks [J ] . Chemical Society Reviews , 2021 , 50 ( 11 ): 6349 - 6368 .

Lim D W , Kitagawa H . Proton transport in metal-organic frameworks [J ] . Chemical Reviews , 2020 , 120 ( 16 ): 8416 - 8467 .

Ramaswamy P , Wong N E , Shimizu G K H . MOFs as proton conductors-challenges and opportunities [J ] . Chemical Society Reviews , 2014 , 43 ( 16 ): 5913 - 5932 .

Trigg E B , Gaines T W , Maréchal M , et al . Self-assembled highly ordered acid layers in precisely sulfonated polyethylene produce efficient proton transport [J ] . Nature Materials , 2018 , 17 ( 8 ): 725 - 731 .

Surti P , Kailasa S K , Mungray A , et al . Vermiculite nanosheet augmented novel proton exchange membrane for microbial fuel cell [J ] . Fuel , 2024 , 357 : 130046 .

Xiong C Y , Ling Z W , Wang B , et al . Electrospinning-assisted construction of rapid proton conduction channels in halloysite nanotube-encapsulated ionic liquid-embedded sulfonated poly(ether ether ketone) proton exchange membranes [J ] . Fuel , 2024 , 362 : 130814 .

Tang H Y , Geng K , Wu L , et al . Fuel cells with an operational range of -20℃ to 200℃ enabled by phosphoric acid-doped intrinsically ultramicroporous membranes [J ] . Nature Energy , 2022 , 7 ( 2 ): 153 - 162 .

Tao S S , Zhai L P , Dinga Wonanke A D , et al . Confining H 3 PO 4 network in covalent organic frameworks enables proton super flow [J ] . Nature Communications , 2020 , 11 : 1981 .

Zhang Q Q , Zhang J , Qiu J J , et al . Detecting the conduction property of proton carriers at different relative humidity based on postsynthetic MOF nanosheets [J ] . ACS Applied Materials & Interfaces , 2024 , 16 ( 49 ): 67697 - 67705 .

Li X M , Dong L Z , Li S L , et al . Synergistic conductivity effect in a proton sources-coupled metal-organic framework [J ] . ACS Energy Letters , 2017 , 2 ( 10 ): 2313 - 2318 .

Liu M C , Weston P J , Hurt R H . Controlling nanochannel orientation and dimensions in graphene-based nanofluidic membranes [J ] . Nature Communications , 2021 , 12 : 507 .

Sadakiyo M , Yamada T , Kitagawa H . Rational designs for highly proton-conductive metal-organic frameworks [J ] . Journal of the American Chemical Society , 2009 , 131 ( 29 ): 9906 - 9907 .

Gao H X , Gao Z P , Ye C , et al . Free-standing polymer-metal-organic framework membrane with high proton conductivity and water stability [J ] . Nano Research , 2023 , 16 ( 5 ): 7950 - 7957 .

Cohen S M . The postsynthetic renaissance in porous solids [J ] . Journal of the American Chemical Society , 2017 , 139 ( 8 ): 2855 - 2863 .

Kang D W , Kang M , Hong C S . Post-synthetic modification of porous materials: superprotonic conductivities and membrane applications in fuel cells [J ] . Journal of Materials Chemistry A , 2020 , 8 ( 16 ): 7474 - 7494 .

Wang C , Yang Z R , Wu W J , et al . Two-dimensional acid-base hydrogen-bonded organic framework toward a highly conductive proton exchange membrane [J ] . Chemistry of Materials , 2024 , 36 ( 17 ): 8255 - 8263 .

Li Z X , Zhan D Y , Saeed A , et al . Fluoride sensing performance of fluorescent NH 2 -MIL-53(Al): 2D nanosheets vs . 3D bulk [J ] . Dalton Transactions , 2021 , 50 ( 24 ): 8540 - 8548 .

Phang W J , Jo H , Lee W R , et al . Superprotonic conductivity of a UiO-66 framework functionalized with sulfonic acid groups by facile postsynthetic oxidation [J ] . Angewandte Chemie International Edition , 2015 , 54 ( 17 ): 5142 - 5146 .

Eliasson K , Jiang F F , Åhlén M , et al . Scalable and versatile fabrication of free-standing covalent organic framework membranes with tunable microstructure for molecular separation [J ] . Journal of the American Chemical Society , 2025 , 147 ( 32 ): 29271 - 29281 .

Cusin L , Cieciórski P , van Gele S , et al . Synthesis of micrometre-thick oriented 2D covalent organic framework films by a kinetic polymerization pathway [J ] . Nature Synthesis , 2025 , 4 ( 5 ): 632 - 641 .

Yang Q , Zhang N , Zhang Q , et al . Band bending induced charge redistribution on the amorphous MIL-53(Al)/Co-LDH conjunction to boost the supercapacitive and oxygen evolution performance [J ] . Electrochimica Acta , 2022 , 429 : 141057 .

Chen H R , Liu Y R , Zheng M , et al . Water-retentive covalent organic framework membranes for efficient proton conduction in PEMFCs [J ] . Advanced Functional Materials , 2026 , 36 ( 18 ): e20568 .

Shi B B , Pang X , Li S N , et al . Short hydrogen-bond network confined on COF surfaces enables ultrahigh proton conductivity [J ] . Nature Communications , 2022 , 13 : 6666 .

Chen C C , Gao H X , Li H , et al . Adipic acid-mediated hydrogen bonding network allocation for efficient proton conduction in water-stabilized lamellar MOF membranes [J ] . Fuel , 2024 , 378 : 132855 .

Xue Y Q , Yuan X K , Chen C C , et al . Cross-layer alternating paired charge distribution to boost proton conductivity of COF lamellar membrane [J ] . Journal of Membrane Science , 2025 , 717 : 123556 .

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