Unlocking Bimetallic Active Centers via Heterostructure Engineering for Exceptional Phosphate Electrosorption: Internal Electric Field-Induced Electronic Structure Reconstruction.

Abstract

Development of electrode materials exhibiting exceptional phosphate removal performance represents a promising strategy to mitigate eutrophication and meet ever-stricter stringent emission standards. Herein, we precisely designed a novel LaCeOx heterostructure-decorated hierarchical carbon composite (L8C2PC) for high-efficiency phosphate electrosorption. This approach establishes an internal electric field within the LaCeOx heterostructure, where the electrons transfer from Ce atoms to neighboring La atoms through superexchange interactions in La-O-Ce coordination units. The modulatory heterostructure endows a positive shift of the d band of La sites and the increase of electron density at Fermi level, promoting stronger orbital overlap and binding interactions. The introduction of oxygen vacancies during the in situ nucleation process reduces the kinetic barrier for phosphate-ion migration and supplies additional active centers. Moreover, the hierarchical carbon framework ensures electrical double-layer capacitance for phosphate storage and interconnected ion migration channels. Such synergistically multiple active centers grant the L8C2PC electrode with high-efficiency record in phosphate electrosorption. As expected, the L8C2PC electrode demonstrates the highest removal capability among the reported electrode materials with a saturation capacity of 401.31 mg P g-1 and a dynamic capacity of 91.83 mg P g-1 at 1.2 V. This electrochemical system also performs well in the dephosphorization in natural water samples with low concentration that enable effluent concentration to meet the first-class discharge standard for China (0.5 mg P L-1). This study advances efficient dephosphorization techniques to a new level and offers a deep understanding of the internal electric field that regulates metal orbitals and electron densities in heterostructure engineering.