双金属Ni2P/Fe2P/Fe2O3@NF异质界面材料以耦合机制催化析氧反应并促进整体水分解

doi:10.11949/0438-1157.20251098

摘要/Abstract

摘要：

电解水是有潜力的规模化制备氢技术之一，而开发高活性低成本的氧析出反应（OER）和整体水分解催化剂是关键。本研究通过K₂FeO₄分解与Fe³⁺刻蚀泡沫镍（NF）制备了具有丰富异质界面的NiFe-LDH/Fe₂O₃@NF前驱体，经磷化后得到珊瑚状的双金属Ni₂P/Fe₂P/Fe₂O₃@NF复合材料。表征结果证实其结构中有丰富的异质界面和微米级通道。OER催化机制研究显示其为耦合的吸附演化机制（AEM）和晶格氧机制（LOM）。DFT计算表明磷化处理优化了活性氧中间体的吸附能，降低了决速步骤的能垒，并使Ni 3d轨道和Fe 3d轨道的态密度重叠程度增强，促进了双金属位点Ni²⁺®Fe³⁺之间的电子转移和Ni催化中心的形成，从而提升了材料的OER性能和稳定性。该材料在10和50 mA·cm^-2电流密度下的OER过电位仅分别为203和230 mV，且在10和500 mA·cm^-2的电流密度下均显示良好的稳定性。该材料同时展现出优异的氢析出反应（HER）活性，构建的全水解系统在1.58 V槽电压下即可驱动10 mA·cm^-2电流密度，展现出良好的双催化性能和稳定性。

关键词: 电解, 析氧反应, OER机理, 异质界面, 铁基过渡金属磷化物, 催化剂, 制氢

Abstract:

Water electrolysis is one promising technology for large-scale hydrogen production, in which developing high-activity and low-cost catalysts for oxygen evolution reaction (OER) and overall water splitting is the key. In this study, a NiFe-LDH/Fe₂O₃@NF precursor with rich heterointerfaces was synthesized via K₂FeO₄ decomposition and Fe³⁺ etching of nickel foam (NF), and coral-like bimetallic Ni₂P/Fe₂P/Fe₂O₃@NF was obtained after phosphidation. Material characterization confirmed the presence of abundant heterointerfaces and micrometer-scale channels in Ni₂P/Fe₂P/Fe₂O₃@NF. Study on the catalytic mechanism of OER reveals that is a coupled adsorption evolution mechanism (AEM) and lattice oxygen mechanism (LOM). Density functional theory (DFT) calculations indicate that the phosphating treatment optimizes the adsorption energy of reactive oxygen intermediates, lowers the energy barrier of the rate-determining step, and enhances the overlap between the density of states of Ni 3d and Fe 3d orbitals. This facilitates electron transfer across the bimetallic Ni²⁺–Fe³⁺ sites and promotes the formation of the Ni catalytic center, thereby improving both the oxygen evolution reaction (OER) performance and the structural stability of the material. The OER overpotential of this material is only 203 and 230 mV at current densities of 10 and 50 mA·cm^-2, respectively, and it also demonstrates good stability even at high current densities of up to 500 mA·cm^-2. This material also exhibits excellent hydrogen evolution reaction (HER) activity. When employed it as both anode and cathode, the overall electrolyzer only needs 1.58 V cell voltage to achieve 10 mA cm^-2 current density and without obvious degradation after 40 h test, highlighting its superior bifunctional performance and durability.

Key words: electrolysis, oxygen evolution reaction, OER mechanism, heterogeneous interface, iron-based transition metal phosphide, catalyst, hydrogen production

中图分类号:

TQ151.1

李佳润, 骆勇名, 韦思辰, 赵亚娟, 何盈盈. 双金属Ni₂P/Fe₂P/Fe₂O₃@NF异质界面材料以耦合机制催化析氧反应并促进整体水分解[J]. 化工学报, DOI: 10.11949/0438-1157.20251098.

Jiarun LI, Yongming LUO, Sichen WEI, Yajuan ZHAO, Yingying HE. Bimetallic Ni₂P/Fe₂P/Fe₂O₃@NF heterostructure catalyzes oxygen evolution reaction through coupled mechanism and promotes overall water splitting[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251098.

图/表 14

图1 Ni2P/Fe2P/Fe2O3@NF的制备过程

Fig.1 Preparation process of Ni2P/Fe2P/Fe2O3@NF

图2 材料的XRD谱图

Fig.2 XRD patterns of the as-prepared catalysts

图3 NiFe-LDH/Fe2O3@NF前驱体材料和Ni2P/Fe2P/Fe2O3@NF的SEM图

Fig. 3 SEM images of NiFe-LDH/Fe2O3@NF and Ni2P/Fe2P/Fe2O3@NF

图4 Ni2P/Fe2P/Fe2O3@NF的（a）TEM和（b）HRTEM图

Fig. 4 TEM (a) and HRTEM (b) images of Ni2P/Fe2P/Fe2O3@NF

图5 Ni2P/Fe2P/Fe2O3@NF的XPS谱图（a）总谱；（b）P 2p；（c）Ni 2p；（d）Fe 2p

Fig 5 XPS spectra of Ni2P/Fe2P/Fe2O3@NF (a) Overall spectrum; (b) P 2p; (c) Ni 2P; (d) Fe 2p

图6 材料的电化学性能测试结果（a）LSV曲线；（b）过电位比较；（c）Tafel曲线；（d）EIS图

Fig.6 The electrochemical performance of the catalysts (a) LSV curves; (b) Comparison of overpotentials; (c) The Tafel curves; (d) Nyquist diagrams of EIS

图7（a） 0.86 V电压时的电流密度与扫速的线性关系及相应的Cdl值；（b）ECSA归一化处理的LSV曲线；（c）转换频率；（d）Ni2P/Fe2P/Fe2O3@NF的稳定性测试

Fig.7 (a) The linear relationships between current density and scan rate at 0.86 V voltage and the corresponding Cdl values; (b) The LSV curves normalized by ECSA; (c) TOF curves; (d)Stability test of Ni2P/Fe2P/Fe2O3@NF

图8 (a~d) 1.0 M KOH和1.0 M TMAOH中的LSV曲线；（e）电解质溶液的pH对LSV曲线的影响；（f）1.5 V电位下的质子反应阶数ρ

Fig.8 (a~d) LSV curves in 1.0 M KOH and 1.0 M TMAOH; (e) Effect of pH values of the electrolyte on LSV curves; (f) Protonic reaction order ρ at 1.5 V

图9 甲醇探针对材料LSV曲线的影响

Fig. 9 Effect of methanol probe on LSV curves of catalysts

图10 Ni2P/Fe2P/Fe2O3@NF材料测试前后 XPS谱图（a）总谱；（b）P 2p谱；（c）Ni 2p；（d）Fe 2p

Fig.10 XPS spectra of Ni2P/Fe2P/Fe2O3@NF before and after test (a) Overall spectrum; (b) P 2p; (c) Ni 2p; (d) Fe 2p

图11 DFT计算 (a) 四种材料的模拟模型；(b) OER过程的自由能台阶图；(c) Ni、Fe的d带中心；模拟态密度PDOS：(d) NiFe-LDH/Fe2O3，(c) Ni2P/Fe2P/Fe2O3

Figure 11 DFT calculations: (a) Simulation models of four catalysts; (b) Free energy diagram for the OER process; (c) The d-band centers of Ni and Fe; Simulated projected density of states(PDOS): (d) NiFe-LDH/Fe2O3; (e) Ni2P/Fe2P/Fe2O3

图12 HER催化性能的电化学测试注:(a)LSV曲线;(b)过电位对比;(c)Tafel斜率;(d)奈奎斯特图

Fig.12 Electrochemical test for HER performance(a) LSV curves; (b) Comparison of overpotentials; (c) Tafel slopes; (d) Nyquist diagram

图13 DFT计算（a）HER过程中NiFe-LDH/Fe2O3和Ni2P/Fe2P/Fe2O3的各阶段模型；（b）HER过程的自由能台阶图

Figure 13 DFT calculations: (a) Simulation models of NiFe-LDH/Fe2O3 and Ni2P/Fe2P/Fe2O3 at each stepduring HER process; (b) Free energy diagram for HER process

图14（a） 双电极系统电解槽示意图；（b）整体水分解的LSV曲线；（c）稳定性测试

Fig.14 (a) Schematic diagram of the double-electrode system of the electrolytic cell; (b) LSV curves of the overall water splitting test; (c) Stability test

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双金属Ni₂P/Fe₂P/Fe₂O₃@NF异质界面材料以耦合机制催化析氧反应并促进整体水分解

Bimetallic Ni₂P/Fe₂P/Fe₂O₃@NF heterostructure catalyzes oxygen evolution reaction through coupled mechanism and promotes overall water splitting

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