{"title":"界面化学键对schwertmanite电子结构的调制增强光- fenton催化活性","authors":"Xuqian Wang, Zhe Wang, Tianyu Wang, Anqi Wang, Jiepeng Wang, Yongkui Zhang, Yabo Wang","doi":"10.1016/j.jcat.2025.116426","DOIUrl":null,"url":null,"abstract":"<div><div>The rational design of Fe-based catalysts with optimized electronic structures remains critical for achieving efficient pollutant degradation in photo-Fenton systems. This study presents a facile biomineralization approach to structurally modulate biogenic schwertmannite (Sch, Fe<sub>8</sub>O<sub>8</sub>(OH)<sub>8-2x</sub>(SO<sub>4</sub>)<sub>x</sub>, 1 ≤ x ≤ 1.75) through xanthan gum (XG) addition. The abundant carboxyl group on XG provided well-dispersed nucleation sites, which modulated the growth of Sch crystal clusters and effectively transformed aggregated Sch particles into nanowhisker-embedded hybrid network (Sch-XG) with 9.6-fold increased specific surface area. Moreover, strong interfacial chemical-bonded of Fe-O-C bridge was proved to exist between surface iron species of Sch and carboxyl group of XG, which further changed the energy band and electronic structure of Sch. Eventually, such modification facilitated photogenerated electron transfer, Fe(III)/Fe(II) cycling and enhanced adsorption-activation of H<sub>2</sub>O<sub>2</sub> by Sch-XG hybrid, which demonstrated good photo-Fenton performance, achieving complete sulfamethoxazole (SMX) removal within 20 min (<em>k</em> = 0.179 min<sup>−1</sup>) through synergistic radical-nonradical pathways dominated by surface-bound •OH. Notably, the Sch-XG hybrid exhibited broad pH adaptability (3.0–9.0), low iron leaching (<0.37 mg L<sup>−1</sup>), and >99 % SMX degradation efficiency after fourth cycles. After degradation products identification and ROS attack sites analysis, three primary SMX transformation routes via hydroxylation, ring opening and S-N bond cleavage were proposed, while effective detoxification of SMX was achieved through toxicity prediction and bio-toxicity assessment. This work provided a feasible interfacial engineering strategy to enhance catalytic potential of natural iron minerals for sustainable water remediation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116426"},"PeriodicalIF":6.5000,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Electronic structure modulation of schwertmannite by interfacial chemical bond for enhanced photo-Fenton catalytic activity\",\"authors\":\"Xuqian Wang, Zhe Wang, Tianyu Wang, Anqi Wang, Jiepeng Wang, Yongkui Zhang, Yabo Wang\",\"doi\":\"10.1016/j.jcat.2025.116426\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The rational design of Fe-based catalysts with optimized electronic structures remains critical for achieving efficient pollutant degradation in photo-Fenton systems. This study presents a facile biomineralization approach to structurally modulate biogenic schwertmannite (Sch, Fe<sub>8</sub>O<sub>8</sub>(OH)<sub>8-2x</sub>(SO<sub>4</sub>)<sub>x</sub>, 1 ≤ x ≤ 1.75) through xanthan gum (XG) addition. The abundant carboxyl group on XG provided well-dispersed nucleation sites, which modulated the growth of Sch crystal clusters and effectively transformed aggregated Sch particles into nanowhisker-embedded hybrid network (Sch-XG) with 9.6-fold increased specific surface area. Moreover, strong interfacial chemical-bonded of Fe-O-C bridge was proved to exist between surface iron species of Sch and carboxyl group of XG, which further changed the energy band and electronic structure of Sch. Eventually, such modification facilitated photogenerated electron transfer, Fe(III)/Fe(II) cycling and enhanced adsorption-activation of H<sub>2</sub>O<sub>2</sub> by Sch-XG hybrid, which demonstrated good photo-Fenton performance, achieving complete sulfamethoxazole (SMX) removal within 20 min (<em>k</em> = 0.179 min<sup>−1</sup>) through synergistic radical-nonradical pathways dominated by surface-bound •OH. Notably, the Sch-XG hybrid exhibited broad pH adaptability (3.0–9.0), low iron leaching (<0.37 mg L<sup>−1</sup>), and >99 % SMX degradation efficiency after fourth cycles. After degradation products identification and ROS attack sites analysis, three primary SMX transformation routes via hydroxylation, ring opening and S-N bond cleavage were proposed, while effective detoxification of SMX was achieved through toxicity prediction and bio-toxicity assessment. This work provided a feasible interfacial engineering strategy to enhance catalytic potential of natural iron minerals for sustainable water remediation.</div></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":\"452 \",\"pages\":\"Article 116426\"},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2025-09-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951725004920\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951725004920","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
合理设计具有优化电子结构的铁基催化剂对于实现光- fenton系统中污染物的高效降解至关重要。本研究提出了一种简单的生物矿化方法,通过黄原胶(XG)添加来结构调节生物源schwertmannite (Sch, Fe8O8(OH)8-2x(SO4)x, 1 ≤ x ≤ 1.75)。XG上丰富的羧基提供了分散良好的成核位点,调节了Sch晶体团簇的生长,有效地将聚集的Sch粒子转化为比表面积增加9.6倍的纳米晶须嵌入混合网络(Sch-XG)。此外,Sch表面铁种与XG的羧基之间存在Fe- o- c桥的强界面化学键,进一步改变了Sch的能带和电子结构。最终,这种修饰促进了Sch-XG杂化物的光生电子转移和Fe(III)/Fe(II)循环,增强了Sch-XG对H2O2的吸附活化,表现出良好的光- fenton性能。在20 min (k = 0.179 min−1)内通过表面结合•OH主导的自由基-非自由基协同途径完全去除磺胺甲新唑(SMX)。值得注意的是,Sch-XG杂种具有广泛的pH适应性(3.0-9.0),低铁浸出(<0.37 mg L−1),第四次循环后SMX降解效率>;99 %。通过降解产物鉴定和ROS攻击位点分析,提出了羟化、开环和S-N键切割三种SMX的主要转化途径,并通过毒性预测和生物毒性评估实现SMX的有效解毒。本研究为提高天然铁矿物对水的可持续修复催化潜力提供了可行的界面工程策略。
Electronic structure modulation of schwertmannite by interfacial chemical bond for enhanced photo-Fenton catalytic activity
The rational design of Fe-based catalysts with optimized electronic structures remains critical for achieving efficient pollutant degradation in photo-Fenton systems. This study presents a facile biomineralization approach to structurally modulate biogenic schwertmannite (Sch, Fe8O8(OH)8-2x(SO4)x, 1 ≤ x ≤ 1.75) through xanthan gum (XG) addition. The abundant carboxyl group on XG provided well-dispersed nucleation sites, which modulated the growth of Sch crystal clusters and effectively transformed aggregated Sch particles into nanowhisker-embedded hybrid network (Sch-XG) with 9.6-fold increased specific surface area. Moreover, strong interfacial chemical-bonded of Fe-O-C bridge was proved to exist between surface iron species of Sch and carboxyl group of XG, which further changed the energy band and electronic structure of Sch. Eventually, such modification facilitated photogenerated electron transfer, Fe(III)/Fe(II) cycling and enhanced adsorption-activation of H2O2 by Sch-XG hybrid, which demonstrated good photo-Fenton performance, achieving complete sulfamethoxazole (SMX) removal within 20 min (k = 0.179 min−1) through synergistic radical-nonradical pathways dominated by surface-bound •OH. Notably, the Sch-XG hybrid exhibited broad pH adaptability (3.0–9.0), low iron leaching (<0.37 mg L−1), and >99 % SMX degradation efficiency after fourth cycles. After degradation products identification and ROS attack sites analysis, three primary SMX transformation routes via hydroxylation, ring opening and S-N bond cleavage were proposed, while effective detoxification of SMX was achieved through toxicity prediction and bio-toxicity assessment. This work provided a feasible interfacial engineering strategy to enhance catalytic potential of natural iron minerals for sustainable water remediation.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.