基于限域空间内原位形成的碳层构筑铁单原子催化剂用于高效芬顿反应

doi:10.1016/S1872-2067(26)65114-5

催化学报 ›› 2026, Vol. 88: 432-441.DOI: 10.1016/S1872-2067(26)65114-5

基于限域空间内原位形成的碳层构筑铁单原子催化剂用于高效芬顿反应

王洋^a^,^b, 范存冯^a^,^b, 刘洋^a^,^b, 郑晓芹^a^,^b, 刘譞懿^a^,^b, 张凯^a^,^b, 寇佳慧^a^,^c^,^*(), 黄亨明^a^,^c^,^*(), 孙林兵^a^,^b^,^*()

^a 南京工业大学材料化学工程全国重点实验室, 江苏南京 211816
^b 南京工业大学化工学院, 江苏南京 211816
^c 南京工业大学材料科学与工程学院, 江苏南京 211816

收稿日期:2025-11-07 接受日期:2026-02-08 出版日期:2026-09-18 发布日期:2026-09-05
通讯作者: *电子信箱: jhkou@njtech.edu.cn (寇佳慧),
h.huang@njtech.edu.cn (黄亨明),
lbsun@njtech.edu.cn (孙林兵).
基金资助:
国家自然科学基金(22125804);国家自然科学基金(U24A20534);江苏省自然科学基金(BK20253005);苏州实验室开放基金(SZLAB-1308-2024-ZD005);材料化学工程全国重点实验室基金(SKL-MCE-24A01)

Iron single-atom catalysts created in constrained space with in-situ-formed carbon layers for efficient Fenton reaction

Yang Wang^a^,^b, Cun-Feng Fan^a^,^b, Yang Liu^a^,^b, Xiao-Qin Zheng^a^,^b, Xuan-Yi Liu^a^,^b, Kai Zhang^a^,^b, Jiahui Kou^a^,^c^,^*(), Hengming Huang^a^,^c^,^*(), Lin-Bing Sun^a^,^b^,^*()

^a State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^b College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^c College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China

Received:2025-11-07 Accepted:2026-02-08 Online:2026-09-18 Published:2026-09-05
Supported by:
The National Natural Science Foundation of China(22125804);The National Natural Science Foundation of China(U24A20534);The Natural Science Foundation of Jiangsu Province(BK20253005);The Open Research Fund of Suzhou Laboratory(SZLAB-1308-2024-ZD005);The State Key Laboratory of Materials-Oriented Chemical Engineering(SKL-MCE-24A01)

摘要/Abstract

摘要：

苯酚是工业废水中常见的有机污染物, 必须严格控制并实现达标排放, 以防范其对生态系统和人体健康的潜在风险. 然而, 传统芬顿(Fenton)技术在实际应用中仍面临诸多挑战, 包括铁基催化剂活性位利用率低、金属铁位点流失以及反应pH适应范围有限等. 单原子催化剂通过实现金属与载体间的强效相互作用及原子级分散特性, 有效克服了传统芬顿催化剂在活性与稳定性方面的局限性. 尽管已有研究报道开发出适用于芬顿反应的铁单原子催化剂, 但其存在制备过程复杂、反应条件苛刻且性能欠佳等问题. 因此, 开发一种较为简单的策略制备出具有高效苯酚降解性能的铁单原子催化剂具有一定的研究意义.
本研究提出一种基于固相研磨结合热处理的单原子催化剂合成策略. 该策略以含模板剂的SBA-15(TLS)为载体, 利用其硅壁与模板剂之间形成的限域空间, 通过固相研磨将Fe(NO₃)₃前驱体引入该空间. 在后续热处理过程中, 铁原子被锚定于模板剂原位生成的碳层中, 成功构建出新型单原子催化剂Fe₁@C-TLS. 作为对比, 采用不含模板剂的SBA-15(TRS)通过类似的策略制备了参比样品(Fe@TRS). 实验结果与理论计算结果表明, 该限域空间有效抑制了铁原子的迁移与团聚, 形成了独特的Fe-C₃配位构型. 而不具有限域空间的催化剂Fe@TRS中产生了纳米颗粒. 在Fenton降解反应中, Fe₁@C-TLS表现出优异的催化活性 (k = 0.102 min⁻¹), 显著优于Fe@TRS (k = 0.0115 min⁻¹)以及目前报道的大多数铁基及其他过渡金属基催化剂. 此外, 在不同反应条件下, Fe₁@C-TLS均可实现高效降解苯酚, 且反应后金属位点仍以单原子形式存在, 表明该催化剂具有良好的循环稳定性. 结合反应过程计算与实验验证, Fe-C₃配位构型能够有效促进反应物H₂O₂向•OH转化, 进而攻击苯酚实现高效降解.
综上, 本工作通过简单的固相研磨与热处理结合的策略, 成功制备了锚定于原位形成的碳层上的铁单原子催化剂. 该催化剂在苯酚降解反应中表现出优异的降解性能与循环稳定性, 为功能性单原子催化剂的简易合成提供了新的思路.

关键词: 单原子催化剂, 铁, 限域空间, 碳层, 苯酚降解

Abstract:

Phenol is a common organic pollutant in industrial wastewater and must be strictly controlled and discharged to meet standards to prevent ecological health risks. Traditional Fenton method faces challenges such as low utilization of active sites in iron-based catalysts, leaching of metallic iron, and limited pH adaptability. In this work, we introduce a solid-grinding followed by heat-treatment (SH) method for the synthesis of iron single-atom catalysts (SACs). This approach leverages the unique constrained space which is between the silica walls and the template within template-loaded SBA-15 (TLS). The precursor Fe(NO₃)₃ is able to penetrate the constrained space through solid-grinding. During the following heat treatment process, iron single atoms are formed and stabilized in the in-situ carbon layers formed by the template, resulting in the formation of a novel SAC, named as Fe₁@C-TLS. Experiments and theoretical calculations reveal that the constrained space effectively inhibits the migration and agglomeration of iron atoms to form a unique Fe-C₃ coordination structure. The Fe₁@C-TLS catalyst exhibits excellent activity (k = 0.102 min⁻¹) in the Fenton reaction for the degradation of phenol, significantly outperforming the Fe@TRS nanoparticle catalyst prepared without constrained space (k = 0.0115 min⁻¹), as well as reported iron and other transition metals-based catalysts.

Key words: Single-atom catalysts, Iron, Constrained space, Carbon layers, Phenol degradation

王洋, 范存冯, 刘洋, 郑晓芹, 刘譞懿, 张凯, 寇佳慧, 黄亨明, 孙林兵. 基于限域空间内原位形成的碳层构筑铁单原子催化剂用于高效芬顿反应[J]. 催化学报, 2026, 88: 432-441.

Yang Wang, Cun-Feng Fan, Yang Liu, Xiao-Qin Zheng, Xuan-Yi Liu, Kai Zhang, Jiahui Kou, Hengming Huang, Lin-Bing Sun. Iron single-atom catalysts created in constrained space with in-situ-formed carbon layers for efficient Fenton reaction[J]. Chinese Journal of Catalysis, 2026, 88: 432-441.

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https://www.cjcatal.com/CN/Y2026/V88/I9/432

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Fig. 1. A schematic representation illustrating the synthesis process of catalysts comprising individual iron atoms and iron nanoparticles. (a) Synthesis of single iron atoms anchored on in-situ-generated carbon layers within constrained space in TLS by the SH method. (b) Synthesis of aggregated Fe2O3 in a traditional carrier TRS with no constrained space.

Fig. 2. Materials characterization. (a) Low-angle XRD patterns for the samples TLS, Fe1@C-TLS, C-TLS, Fe@TRS, and TRS. (b) Nitrogen adsorption-desorption isotherms for TLS, before and after the incorporation of Fe(NO3)3, with the corresponding pore size distribution shown in the inset. (c) DTG curves for Fe(NO3)3@TLS, Fe(NO3)3@TRS, C-TLS, and TLS. (d) TG-MS analysis for Fe(NO3)3@TLS. (e) HAAFD-STEM image for Fe1@C-TLS. Red circles indicate the locations of single-atom bright spots. (f) HAAFD-STEM image for Fe@TRS. The nanoparticles are indicated by yellow circles.

Fig. 3. Investigation of local chemical environment and valence. (a) XPS spectra of Fe 2p for Fe1@C-TLS and Fe@TRS. (b) XPS spectra of C 1s for Fe1@C-TLS and C-TLS. (c) Normalized Fe K-edge XANES spectra of Fe1@C-TLS, Fe@TRS, Fe2O3, and Fe foil. (d) Fourier transform k3-weighted EXAFS spectra for Fe1@C-TLS, Fe@TRS, Fe2O3, and Fe foil. (e) Fitted EXAFS curve in R-space for Fe1@C-TLS. (f) Fitted EXAFS curve in k-space for Fe1@C-TLS. (g) WT image of Fe2O3. (h) WT image of Fe@TRS. (i) WT image of Fe1@C-TLS.

Fig. 4. Catalytic performance on Fenton phenol degradation. (a) The degradation of phenol by different catalysts (reaction conditions: pH = 3.0 ± 0.2, [catalyst] = 0.1 g·L?1, [phenol] = 20 mg·L?1, [H2O2] = 1000 ppm, T = 40 °C). (b) The corresponding kinetic curves for phenol degradation by Fe@TRS and Fe1@C-TLS at 40 °C. (c) A comparative study of the performance of typical catalysts on the degradation kinetics of organic pollutants. (d) The degradation of phenol by Fe1@C-TLS at different H2O2 concentrations (reaction conditions: pH = 3.0 ± 0.2, [Catalyst] = 0.1 g·L?1, [phenol] = 20 mg·L?1, T = 40 °C). (e) The degradation of phenol by Fe1@C-TLS at different pH values. (Reaction conditions: [Catalyst] = 0.1 g·L?1, [phenol] = 20 mg·L?1, [H2O2] = 1000 ppm, T = 40 °C). (f) The degradation of phenol by Fe1@C-TLS at different temperatures (reaction conditions: pH = 3.0 ± 0.2, [Catalyst] = 0.1 g·L?1, [phenol] = 20 mg·L?1, [H2O2] = 1000 ppm).

Fig. 5. Examination of phenol degradation mechanism. (a) Degradation performance of the catalyst Fe1@C-TLS and the leaching situation of Fe1@C-TLS at 20 min. (b) CV curves of Fe1@C-TLS and Fe@TRS. (c) EIS spectra of Fe1@C-TLS and Fe@TRS. (d) EPR spectra of the Fenton reaction catalyzed by Fe1@C-TLS at different pH values. (e) Schematic diagram of the Fe1@C-TLS catalytic mechanism for phenol degradation. (f) The effect of TBA on the degradation of phenol in Fe1@C-TLS.

Fig. 6. Theoretical calculations. (a) Relative energy change for the conversion of H2O2 to •OH by Fe-C3 (A), Fe-C3 (B), Fe-C4 and Fe2O3. Charge transfer between metal atoms and carriers of (b) Fe-C3 (A), (c) Fe-C3 (B) and (d) Fe-C4.

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基于限域空间内原位形成的碳层构筑铁单原子催化剂用于高效芬顿反应

Iron single-atom catalysts created in constrained space with in-situ-formed carbon layers for efficient Fenton reaction

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