Shape‐Controlled Reconstruction of Hollow Multimetallic Phosphosulfides Reveals an Activity–Stability Balance in Oxygen Evolution Catalysis
Journal
ChemCatChem
Journal Volume
18
Journal Issue
13
ISSN
1867-3880
1867-3899
Date Issued
2026-07
Author(s)
Abstract
Controlling precursor geometry offers a powerful yet underexplored route for regulating the structural evolution and catalytic behavior of multicomponent electrocatalysts. Herein, we report a shape-programmed strategy for constructing hollow multimetallic phosphosulfides from rhombic dodecahedral and cubic ZIF-67 precursors through sequential Ni2+-assisted reconstruction, Fe3+ incorporation, and phosphosulfidation. Both precursors undergo morphology-retained topochemical conversion into hollow NiCoFe phosphosulfide architectures, while the cubic pathway exhibits higher structural fidelity, more regular hollow frameworks, and superior morphology retention during multistep transformation and prolonged operation. In contrast, the rhombic-dodecahedral-derived catalyst shows slightly higher intrinsic oxygen evolution reaction (OER) activity, delivering an overpotential of 259 mV at 10 mA cm−2 and a Tafel slope of 41.1 mV dec−1 in 1.0 M KOH, whereas the cubic analogue combines high activity with enhanced structural robustness. Structural and spectroscopic analyses reveal that precursor geometry governs not only framework inheritance, but also the local reconstruction pathway, surface chemistry, and accessibility of electroactive sites. Operando Raman spectroscopy confirms the potential-induced generation of oxygen-containing surface species, while density functional theory identifies the *O to *OOH step as the potential-determining step. This work establishes precursor-shape-controlled topochemical evolution as an effective strategy for tuning the activity–stability balance of hollow phosphosulfide OER precatalysts.
Subjects
alkaline electrocatalysis
hollow nanocages
mixed-anion shell
morphology control
oxygen evolution reaction
Publisher
Wiley
Type
journal article