镧掺杂诱导晶格膨胀NiSe催化剂用于高效尿素氧化辅助电解水制氢

doi:10.1016/S1872-2067(26)65054-1

催化学报

镧掺杂诱导晶格膨胀NiSe催化剂用于高效尿素氧化辅助电解水制氢

张权^a, 马鹤津^a, 韩若冰^a, 杨统林^d, 陈真会^a, 祝淼洋^a, 时佳维^c,*, 蔡卫卫^c,*, 杨方麒^d,*, 杨泽惠^b,*

^a湖北师范大学化学化工学院, 污染物分析与资源化技术湖北省重点实验室, 湖北黄石 435002;
^b三峡大学材料与化工学院, 湖北宜昌 443002;
^c昆明理工大学材料科学与工程学院, 云南昆明 650093;
^d南京邮电大学柔性电子全国重点实验室&先进材料研究所, 江苏南京 210023

收稿日期:2025-11-10 接受日期:2025-11-10
通讯作者: *电子信箱: 1132411710@qq.com (时佳维), willcai1985@gmail.com (蔡卫卫), iamfqyang@njupt.edu.cn (杨方麒), yeungzehui@gmail.com (杨泽惠).
基金资助:
国家自然科学基金(22302062, 22302097, 52562032); 南京邮电大学自然科学研究创业人才引进基金(NY223180, NY223068).

Lattice-expanded NiSe catalyst via lanthanum incorporation for accelerating urea electrooxidation in assisting water electrolysis

Quan Zhang^a, Hejin Ma^a, Ruobing Han^a, Tonglin Yang^d, Zhenhui Chen^a, Miaoyang Zhu^a, Jiawei Shi^c,*, Weiwei Cai^c,*, Fangqi Yang^d,*, Zehui Yang^b,*

^aHubei Key Laboratory of Pollutant Analysis and Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi 435002, Hubei, China;
^bCollege of Materials and Chemical Engineering, China Three Gorges University, Yichang 443002, Hubei, China;
^cFaculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China;
^dState Key Laboratory of Flexible Electronics (LoFE) & Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications, Nanjing 210023, Jiangsu, China

Received:2025-11-10 Accepted:2025-11-10
Contact: *E-mail: 1132411710@qq.com (J. Shi), willcai1985@gmail.com (W. Cai), iamfqyang@njupt.edu.cn (F. Yang), yeungzehui@gmail.com (Z. Yang).
Supported by:
National Natural Science Foundation of China (22302062, 22302097, 52562032) and the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (NY223180, NY223068).

摘要/Abstract

摘要： 氢能作为清洁能源体系的核心, 其高效制取对实现“双碳”目标具有重要意义. 相比于传统的电解水析氧反应(OER), 尿素氧化反应(UOR)具有更低的理论电位, 将其与析氢反应(HER)耦合不仅能有效降低制氢能耗, 还能兼顾含尿素废水的净化处理. 然而, 开发低成本、高活性且性能稳定的UOR和HER双功能电催化剂仍面临反应动力学缓慢和活性位点暴露不足的巨大挑战. 针对这一挑战, 通过元素掺杂调控材料的晶格结构与电子性质, 已成为提升催化性能的有效策略. 本研究聚焦于稀土元素镧(La)的掺杂效应, 诱导晶格膨胀并优化电子结构, 从而构建高性能的双功能电催化剂, 以突破现有尿素辅助电解水技术的瓶颈.
本研究通过水热法成功合成了镧掺杂的NiSe系列催化剂, 系统研究了La掺杂量对NiSe催化剂性能的影响. X-射线衍射和高分辨透射电镜分析表明, La³⁺取代较小的Ni²⁺导致晶格膨胀, La-NiSe-2的(101)面间距从0.26增加到0.29 nm, 证实了La掺杂引起的NiSe晶格膨胀. X-射线光电子能谱分析证实La成功掺入NiSe结构, Ni 2p峰正移约0.3 eV, 表明电子从La转移到Se, 进而改变了Ni的电子密度. La-NiSe-2催化剂在UOR测试中表现出卓越性能: 在1.6 V vs. RHE时电流密度达到213 mA cm^‒2, 是未掺杂NiSe的两倍; Tafel斜率仅为44.3 mV dec^‒1, 远低于NiSe的73.7 mV dec^‒1, 表明La掺杂显著提高了UOR反应动力学. EIS图谱揭示La掺杂显著降低了电荷转移电阻, 促进了Ni²⁺/Ni³⁺氧化生成活性NiOOH物种. 经过5000次CV循环后性能无明显衰减, 50 h恒电位测试保持稳定, 证实了其优异的稳定性. 在HER测试中, La-NiSe-2在‒10 mA cm^‒2时过电位仅135 mV, Tafel斜率为78 mV dec^‒1, 显著优于未掺杂NiSe. 此外, La-NiSe-2在5000次CV循环和20 h连续运行后保持稳定, 也证明了其优异稳定性, 表现出优异的双功能特性. DFT计算进一步分析了UOR反应过程: La掺杂使得NiSe尿素吸附能从‒1.03增至‒1.31 eV, 同时将电位决定步骤的能垒从1.54降至0.88 eV. 差分电荷密度分析证实La向Se转移0.16 e^‒, 增加了Ni活性中心的电子密度. CO₂程序升温脱附测试显示La-NiSe的CO₂脱附峰温(112 ºC)低于NiSe(131 ºC), 进一步证实La-NiSe-2上吸附物种CO₂更容易脱附. 在尿素辅助电解水测试中, 该催化剂仅需1.52 V即可达到10 mA cm^‒2, 显著降低了电解水产氢系统能耗. 基于以上结果, 本文提出La诱导NiSe的作用机制: La³⁺取代Ni²⁺引起晶格膨胀, 增加活性位点暴露; 电子转移优化了Ni-Se相互作用, 稳定了Ni³⁺活性物种; 同时增强了尿素吸附并降低反应能垒, 最终实现UOR/HER性能的双重提升, 为尿素辅助电解水技术提供了高效双功能催化剂设计策略.
综上, 本研究通过稀土镧掺杂调控晶格结构和电子性质, 为开发高效和低成本的尿素辅助电解水体系提供了新思路. 该镧掺杂方法可拓展至其他稀土元素或过渡金属硒化物体系, 有望推动氢能与环境治理的协同发展.

关键词: 镧掺杂, 硒化镍, 双功能电催化剂, 尿素电氧化, 电解水

Abstract: Developing bifunctional electrocatalysts for energy-efficient urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) is critical for sustainable hydrogen production and wastewater remediation, yet hindered by sluggish kinetics and insufficient active sites. Herein, we propose demonstrate that lanthanum (La) doping effectively activates nickel selenide (NiSe) by inducing lattice expansion—substituting smaller Ni²⁺ (0.69 Å) with larger La³⁺ ion (1.16 Å)—thereby modulating its electronic structure. The optimized La-NiSe-2 catalyst exhibits markedly enhanced UOR and HER performance: it achieves a UOR current density of 213 mA cm^‒2 at 1.6 V vs. RHE (twice that of pristine NiSe) and requires only 135 mV overpotential for HER at ‒10 mA cm^‒2, with a Tafel slope of 78 mV dec^‒1. Operando electrochemical impedance spectroscopy and density functional theory calculations reveal that La incorporation enhances charge transfer and strengthens urea adsorption. This work highlights rare-earth-mediated electronic modulation as a viable strategy for designing high-performance bifunctional catalysts for urea-assisted energy and environmental applications.

Key words: Lanthanum doping, Nickelous selenide, Bifunctional electrocatalyst, Urea electrooxidation, Water electrolysis

张权, 马鹤津, 韩若冰, 杨统林, 陈真会, 祝淼洋, 时佳维, 蔡卫卫, 杨方麒, 杨泽惠. 镧掺杂诱导晶格膨胀NiSe催化剂用于高效尿素氧化辅助电解水制氢[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65054-1.

Quan Zhang, Hejin Ma, Ruobing Han, Tonglin Yang, Zhenhui Chen, Miaoyang Zhu, Jiawei Shi, Weiwei Cai, Fangqi Yang, Zehui Yang. Lattice-expanded NiSe catalyst via lanthanum incorporation for accelerating urea electrooxidation in assisting water electrolysis[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65054-1.

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