Polyoxometalate Directional Etching for Fabricating Defect Hollow Metal–Organic Framework with Hierarchical Structure
Abstract
AbstractEncapsulating guests in metal–organic frameworks (MOFs) can widely expand their functionality, but usually reduces porosity, hindering reactant and product diffusion. Herein, a simple and rapid room temperature directional etching technique is developed to engineer MOFs with tailored hierarchical structures. With H3PMo12O40 (PMo12) as an etchant, classical cubic morphology of WNi@Z8, a ZIF‐8 MOF encapsulating SiW11NiO39 (WNi), can be transformed into various defect‐engineered hollow structures, and a comprehensive phase diagram is established by systematically adjusting etching parameters. Mechanistic studies reveal that PMo12 infiltrates ZIF‐8 preferentially through {111} facet, followed by controlled etching along {110} and {100} facets, enabling precise spatial control over cavity formation. The etched WNi@Z8 achieves an exceptional H2 evolution rate of 12,667 µmol g−1 h−1, nearly threefold enhancement over the non‐etched counterpart due to the enhanced exposure of encapsulated WNi clusters in the hollow structure. This work provides a generalizable strategy for engineering guest@MOFs to achieve high‐efficiency catalysis.
Article Details
Authors (7)
Wen‐Xiong Shi
Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 China
Heng‐Rui Fan
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 China
Wen‐Rui Liu
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 China
Ying‐Zhi Qi
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 China
Ming‐Yang Cui
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin 300384 China
Tong‐Bu Lu
State Key Laboratory of Crystal Materials Tianjin Key Laboratory of Functional Crystal Materials Institute of Functional Crystals Tianjin University of Technology Tianjin China
Zhi‐Ming Zhang
State Key Laboratory of Crystal Materials Institute for New Energy Materials and Low Carbon Technologies School of Materials Science and Engineering Tianjin University of Technology Tianjin China