表面硫原子优化NiFe层状双氢氧化物活性位提高尿素氧化效率

doi:10.1016/S1872-2067(26)64992-3

催化学报

表面硫原子优化NiFe层状双氢氧化物活性位提高尿素氧化效率

邓喆^a,1, 马贤迪^a,1, 王宁^a,1, 焦梦改^a,c, 万浩^a, 张利利^a,*, 马炜^a,b,*, 周震^a,d

^a郑州大学化工学院, 新能源科学与工程交叉研究中心(IRC4SE2), 河南郑州 450001;
^b中南大学粉末冶金国家重点实验室, 湖南长沙 410083;
^c南开大学先进能源材料化学教育部重点实验室, 天津 300071;
^d南开大学材料科学与工程学院, 新能源材料化学研究所, 新能源转化与存储交叉科学中心, 天津 300350

收稿日期:2025-09-12 接受日期:2025-11-13
通讯作者: *电子信箱: llzhang@zzu.edu.cn (张利利); mawei@zzu.edu.cn (马炜).
作者简介:¹共同第一作者.
基金资助:
河南省自然科学基金(242300421230); 国家自然科学基金(U21A20281和22208322); 河南省高等教育机构重点研究项目(24A530009); 郑州大学青年教师专项基金(JC23257030); 郑州大学青年骨干教师发展基金(2024ZDGGJS008); 粉末冶金国家重点实验室专项资金(Sklpm-KF-021).

Superficial S atom optimized active sites in NiFe layered double hydroxides for electrocatalytic urea oxidation

Zhe Deng^a,1, Xiandi Ma^a,1, Ning Wang^a,1, Menggai Jiao^a,c, Hao Wan^a, Li-Li Zhang^a,*, Wei Ma^a,b,*, Zhen Zhou^a,d

^aInterdisciplinary Research Center for Sustainable Energy Science and Engineering (IRC4SE2), School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China;
^bState Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, Hunan, China;
^cKey Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China;
^dSchool of Materials Science and Engineering, Institute of New Energy Material Chemistry, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300350, China

Received:2025-09-12 Accepted:2025-11-13
Contact: * E-mail: llzhang@zzu.edu.cn (L.-L. Zhang), mawei@zzu.edu.cn (W. Ma).
About author:¹ Contributed equally to this work.
Supported by:
Natural Science Foundation of Henan (242300421230), the National Natural Science Foundation of China (U21A20281, 22208322), the Key Research Projects of Higher Education Institutions of Henan Province (24A530009), the Special Fund for Young Teachers from Zhengzhou University (JC23257030), the Zhengzhou University Young Faculty Development Fund (2024ZDGGJS008), and the fund from State Key Laboratory of Powder Metallurgy (Sklpm-KF-021).

摘要/Abstract

摘要： 工业社会的快速发展加剧了能源危机与环境污染, 电解水制氢作为清洁能源载体展现出替代化石燃料的巨大潜力. 然而, 阳极析氧反应(OER)的缓慢动力学严重制约了电解效率. 尿素氧化反应(UOR)因其热力学平衡电位低、尿素来源广泛等优势, 可替代OER以突破效率瓶颈. 因此, 开发高效UOR催化剂对提升制氢效率、降低能耗及协同净化环境具有重要战略意义. 镍基催化剂因成本优势在UOR领域受到广泛关注, 但其复杂的六电子转移过程导致过电位高、稳定性差, 且高价态NiOOH活性中心的转化机制尚不明确. 镍铁层状氢氧化物(NiFe-LDH)虽具备高比表面积和独特结构优势, 但羟基与Fe的强配位抑制了活性Ni³⁺-O物种的形成, 提高了起始电位. 此外, 在UOR过程中于分子尺度识别并追踪NiFe-LDH的活性位点仍面临巨大挑战. 因此, 通过结构重构促进Ni³⁺-O生成, 并借助分子尺度原位技术揭示活性位点演化路径, 是提升本征催化活性的核心.
本文通过引入低电负性S元素取代NiFe-LDH中的O元素以调控催化剂的电子结构, 构建S-NiFe-LDH催化剂, 成功探究了UOR过程中活性位点的演化路径并实现了高效UOR过程. 原位Raman结果表明, 相较于NiFe-LDH, S-NiFe-LDH在更低的电位下检测到Ni³⁺-O的特征峰, 说明S掺杂促进了Ni位点重构(Ni²⁺-O → Ni³⁺-O)的过程, 从而提高了尿素氧化效率. 此外, 毒化实验表明, 低电位下NiFe-LDH的活性位点为Ni²⁺和Fe³⁺, S掺杂促进了低电位下的活性位点由Ni²⁺/Fe³⁺向高价Ni³⁺的转化过程, 而高电位下二者活性位点均为Ni³⁺. X-射线光电子能谱和X-射线吸收精细结构结果表明, 催化剂晶格中的O^2‒被S^2‒取代增强了Ni‒S共价键并扩展了Ni原子的3d电子云, 从而使Ni元素d带中心上移, 最终促成Ni³⁺在更低电位下形成, 从而优化了本征活性与反应动力学. 得益于此, S-NiFe-LDH在100 mA cm^‒2电流密度下仅需1.36 V即可实现高效UOR, 并展现出优异的长期稳定性. 理论计算进一步证实, S掺杂提升了Ni-S键的共价性, 促进了电子传输过程, 有效降低了决速步(CONH₂NH* → CONH₂N*)的脱氢能垒, 增强了表面Ni位点在UOR过程中的活性, 这与实验的结果相一致.
综上, 本研究采用水热法构建了S-NiFe-LDH催化剂, 通过优化活性金属电子结构提高了碱性条件下的UOR活性, 利用原位表征技术阐明了UOR过程中活性位点的转化路径, 为开发高性能UOR催化剂提供了新思路.

关键词: 尿素氧化反应, 硫掺杂, NiFe层状双氢氧化物, 表面重构, 活性位

Abstract: Developing efficient electrocatalysts for the urea oxidation reaction (UOR) is a promising strategy for purifying urea-laden wastewater and promoting energy-efficient hydrogen production. However, the strong binding of the hydroxyl group to Fe sites in the NiFe layered double hydroxide (NiFe-LDH) impedes the generation of active Ni³⁺-O, thus raising the onset potential of UOR. Moreover, identifying and tracking the active sites in NiFe-LDH at the molecular level remains a considerable challenge during the UOR process. Herein, we modified NiFe-LDH by incorporating the low-electronegativity S element to create S-NiFe-LDH, thereby optimizing the electron structure and facilitating the transfer of active sites from Ni²⁺ and Fe³⁺ in the original NiFe-LDH to high-valence Ni intermediates in S-NiFe-LDH at a low applied potential. Moreover, the incorporation of S into NiFe-LDH significantly reduces the thermodynamic barrier of the Ni active sites, advancing the intrinsic activity and kinetic process of the active sites for the decomposition of urea by facilitating the Ni³⁺-O formation because of the facile dehydrogenation steps at the Ni sites. As a result, the S-NiFe-LDH achieved excellent electrochemical UOR activity, with a low potential of 1.36 V and long-term durability at 100 mA cm^‒2, demonstrating promising prospects for practical application. Overall, this work unscrambles the immediate active sites during electrocatalysis and paves a new avenue for the electronic engineering of NiFe-based catalysts in the UOR process.

Key words: Urea oxidation reaction, S doping, NiFe layered hydroxide, Surface reconstruction, Active sites

邓喆, 马贤迪, 王宁, 焦梦改, 万浩, 张利利, 马炜, 周震. 表面硫原子优化NiFe层状双氢氧化物活性位提高尿素氧化效率[J]. 催化学报, DOI: 10.1016/S1872-2067(26)64992-3.

Zhe Deng, Xiandi Ma, Ning Wang, Menggai Jiao, Hao Wan, Li-Li Zhang, Wei Ma, Zhen Zhou. Superficial S atom optimized active sites in NiFe layered double hydroxides for electrocatalytic urea oxidation[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)64992-3.

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