Su Jian, Jiang Nan, Wang Yuanyuan, Jiang Bolong, Wang Xueqin, Song Hua
College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318 Heilongjiang, China.
College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318 Heilongjiang, China.
J Colloid Interface Sci. 2025 Dec;699(Pt 2):138177. doi: 10.1016/j.jcis.2025.138177. Epub 2025 Jun 16.
The strategic construction of built-in electric fields (BIEF) through heterostructure engineering has emerged as a promising avenue for enhancing the intrinsic catalytic activity in dual-functional water electrolysis. In this work, we develop an innovative in-situ topological reconstruction strategy to fabricate phosphorus-defect-enriched NiCoP@NiFe LDH p-n heterojunction architectures on nickel foam (denoted as NiCoP@NiFe LDH/NF), establishing a quantitative structure-activity relationship between BIEF intensity modulation and catalytic performance enhancement. The introduced phosphorus vacancies at the heterointerface synergistically amplify the BIEF strength compared to defect-free counterparts, as evidenced by advanced characterizations, which orchestrates three critical catalytic enhancements: (i) accelerated interfacial charge transfer kinetics (charge transfer resistance reduced by 48 %), (ii) optimized adsorption/desorption energetics for reactive intermediates (ΔG = -0.12 eV for HER), and (iii) precise tuning of transition metal d-band centers toward optimal positions. The resultant catalyst exhibits exceptional bifunctional activity with ultralow overpotentials of 36 mV (HER) and 220 mV (OER) at 10 mA∙cm, surpassing benchmark Pt/C (43 mV) and RuO (265 mV) catalysts. Remarkably, the assembled alkaline electrolyzer achieves a record-low cell voltage of 1.50 V at 10 mA∙cm with unprecedented durability (∼200 h). Through multiscale density functional theory (DFT) simulations, we systematically reveal that the BIEF amplification from defect-heterojunction synergy induces charge redistribution at the atomic level, thereby creating optimal dual-active sites with balanced H* and O-containing intermediate adsorption. This work establishes a novel paradigm for designing high-performance electrocatalysts through defect-mediated BIEF engineering while providing fundamental insights into the quantum-level regulation of catalytic processes.
通过异质结构工程策略构建内建电场（BIEF）已成为增强双功能水电解中本征催化活性的一条有前景的途径。在这项工作中，我们开发了一种创新的原位拓扑重构策略，在泡沫镍上制备富含磷缺陷的NiCoP@NiFe LDH p-n异质结结构（记为NiCoP@NiFe LDH/NF），建立了BIEF强度调制与催化性能增强之间的定量构效关系。与无缺陷的对应物相比，异质界面处引入的磷空位协同增强了BIEF强度，先进表征证明了这一点，这带来了三个关键的催化增强：（i）加速界面电荷转移动力学（电荷转移电阻降低48%），（ii）优化反应中间体的吸附/解吸能量（HER的ΔG = -0.12 eV），以及（iii）将过渡金属d带中心精确调整到最佳位置。所得催化剂表现出优异的双功能活性，在10 mA∙cm时具有36 mV（HER）和220 mV（OER）的超低过电位，超过了基准Pt/C（43 mV）和RuO（265 mV）催化剂。值得注意 的是，组装的碱性电解槽在10 mA∙cm时实现了创纪录的1.50 V低电池电压，且具有前所未有的耐久性（约200小时）。通过多尺度密度泛函理论（DFT）模拟，我们系统地揭示了缺陷-异质结协同作用引起的BIEF放大在原子水平上诱导电荷重新分布，从而创造出具有平衡的H*和含O中间体吸附的最佳双活性位点。这项工作建立了一种通过缺陷介导的BIEF工程设计高性能电催化剂的新范式，同时为催化过程的量子水平调控提供了基本见解。
