Facet-Dependent Water Clustering in ZIF-8 Enables High-Efficiency Methane Storage

TY - JOUR

T1 - Facet-Dependent Water Clustering in ZIF-8 Enables High-Efficiency Methane Storage

AU - Zhong, Keyi

AU - Jiang, Shuyi

AU - Duan, Jun

AU - Yao, Yuanxin

AU - Song, Zixuan

AU - Chen, Daoyi

AU - Liu, Kai

AU - Wang, Pengfei

AU - Zhu, Jinlong

AU - Feng, Xiao

AU - Zi, Mucong

N1 - Publisher Copyright: © 2025 Wiley-VCH GmbH.

PY - 2026/4/16

Y1 - 2026/4/16

N2 - Achieving high volumetric capacity for solid-state methane (CH4) storage under mild conditions remains a challenge for vehicular applications. While metal-organic frameworks (MOFs) demonstrate excellent CH4 physisorption kinetics, most fail to meet the U.S. Department of Energy (DOE)'s target of 263 v/v at pressures below 6.5 MPa. Here, we propose a strategy that engineers the exposed crystal facet of MOF to promote the clathrate formation on the surface, achieving an efficient combination of MOF adsorption and clathrate CH4 storage. We find that the exposed {100} facets of cubic ZIF-8 can induce polar water molecules to assemble into structured clusters and further encapsulate CH4 molecules, attributed to electrostatic interactions and the van der Waals effect. Finally, the cubic ZIF-8 boosts the massive generation of CH4 clathrate on the exposed facets and maintains the physical adsorption capacity for CH4 within the pores. In the fixed-bed system, pre-wetted cubic ZIF-8 can efficiently store CH4 with a recorded capacity of 343 v/v at 5 MPa, surpassing the DOE's target.

AB - Achieving high volumetric capacity for solid-state methane (CH4) storage under mild conditions remains a challenge for vehicular applications. While metal-organic frameworks (MOFs) demonstrate excellent CH4 physisorption kinetics, most fail to meet the U.S. Department of Energy (DOE)'s target of 263 v/v at pressures below 6.5 MPa. Here, we propose a strategy that engineers the exposed crystal facet of MOF to promote the clathrate formation on the surface, achieving an efficient combination of MOF adsorption and clathrate CH4 storage. We find that the exposed {100} facets of cubic ZIF-8 can induce polar water molecules to assemble into structured clusters and further encapsulate CH4 molecules, attributed to electrostatic interactions and the van der Waals effect. Finally, the cubic ZIF-8 boosts the massive generation of CH4 clathrate on the exposed facets and maintains the physical adsorption capacity for CH4 within the pores. In the fixed-bed system, pre-wetted cubic ZIF-8 can efficiently store CH4 with a recorded capacity of 343 v/v at 5 MPa, surpassing the DOE's target.

KW - facet engineering

KW - metal-organic frameworks

KW - methane clathrate

KW - methane storage

KW - water clusters

UR - https://www.scopus.com/pages/publications/105025552587

U2 - 10.1002/adfm.202527509

DO - 10.1002/adfm.202527509

M3 - Article

AN - SCOPUS:105025552587

SN - 1616-301X

VL - 36

JO - Advanced Functional Materials

JF - Advanced Functional Materials

IS - 31

M1 - e27509

ER -