Article(id=1297161266146075462, tenantId=1146029695717560320, journalId=1296125381406982186, issueId=1297161216049308076, articleNumber=null, orderNo=null, doi=10.13550/j.jxhg.20250248, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1744214400000, receivedDateStr=2025-04-10, revisedDate=null, revisedDateStr=null, acceptedDate=1745769600000, acceptedDateStr=2025-04-28, onlineDate=1787196945939, onlineDateStr=2026-08-20, pubDate=1778774400000, pubDateStr=2026-05-15, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1787196945939, onlineIssueDateStr=2026-08-20, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1787196945939, creator=13701087609, updateTime=1787196945939, updator=13701087609, issue=Issue{id=1297161216049308076, tenantId=1146029695717560320, journalId=1296125381406982186, year='2026', volume='43', issue='5', pageStart='929', pageEnd='1184', issueExtLink='null', onlineDate='null', pubDate='1778774400000', pubDateStr='2026-05-15', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1787196933996, creator='13701087609', updateTime=1787202244949, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1297183491922354645, tenantId=1146029695717560320, journalId=1296125381406982186, issueId=1297161216049308076, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1297183491922354646, tenantId=1146029695717560320, journalId=1296125381406982186, issueId=1297161216049308076, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1087, endPage=1095, ext={EN=ArticleExt(id=1297161266330624839, articleId=1297161266146075462, tenantId=1146029695717560320, journalId=1296125381406982186, language=EN, title=Enzyme-inspired dye-incorporated iron-porphyrin metal organic framework for photocatalytic reduction of nitroarenes, columnId=null, journalTitle=Fine Chemicals, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Inspired by nitroreductase and the electron transfer process of its metabolite nitroaromatic or nitroheterocyclic compounds, dye 2,7-dichlorofluorescein, which was ring-opened through solvent-assisted ligand incorporation to form carboxylic acid ligand groups, was loaded into the channels of iron-porphyrin metal-organic framework PCN-222(Fe) for synthesis of -222(Fe). The -222(Fe) was characterized by 1HNMR, XRD, SEM, EDX, UV-Vis, fluorescence spectrometer and XPS, and evaluated for its electrochemical properties via cyclic voltammetry (CV). With -222(Fe) photo-catalyzing nitrobenzene reduction to aniline as a model reaction, the reaction conditions were optimized, the nitroaromatic hydrocarbon substrate was expanded and the cycling stability of the catalyst was evaluated. The results showed that -222(Fe) still maintained the PCN-222(Fe) parent framework with a molar ratio of DCF to iron porphyrin ligand 1.6∶1, with its formula speculated as C80H46.4Cl4.2FeN4O22.4Zr3 and a relative molecular mass of 1878.47. -222(Fe) exhibited UV-Vis absorption and fluorescence emission peaks at the same positions as DCF (532 and 556 nm, respectively), indicating electron transfer within the framework which can simulate the electron transfer process of nitroreductase. Under light irradiation, excited DCF transferred electrons to the iron-porphyrin center, from which the generated low-valent iron center transferred electrons to other electron acceptors, enabling the efficient reduction of nitrobenzene substrates. Under the optimal reaction conditions of room temperature, with 532 nm LED as light source, 2.5 μmol -222(Fe) as photocatalyst, 1 mL methanol as solvent, catalytic reduction of 0.1 mmol nitrobenzene for 2 h, the aniline yield was 82% and reduced to 77% when the catalyst was used continuously for three times. Under the optimum reaction conditions, the reduction of nitrobenzene substrates with different para substituents catalyzed by -222(Fe) showed yields from 64% to 91%.

, authors=Yang AN1, Xu ZHANG1, Renhai LIU1, Yusheng SHI2, Chunying DUAN3, Tiexin ZHANG1, *, authorsList=Yang AN, Xu ZHANG, Renhai LIU, Yusheng SHI, Chunying DUAN, Tiexin ZHANG, authorCompany=null, correspAuthors=Tiexin ZHANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1297161266712306505, articleId=1297161266146075462, tenantId=1146029695717560320, journalId=1296125381406982186, language=CN, title=酶启发2,7-二氯荧光素修饰铁卟啉金属有机框架的制备及光催化硝基芳烃还原, columnId=1297161266410316616, journalTitle=精细化工, columnName=催化与分离提纯技术, runingTitle=null, highlight=null, articleAbstract=

受硝基还原酶启发,模拟其代谢硝基芳香或者硝基杂环化合物的电子传递过程,通过溶剂辅助配体交换促使染料分子2,7-二氯荧光素(DCF)的内酯开环,并将暴露出来的羧酸基团配位负载于铁卟啉金属有机框架(MOFs)PCN-222(Fe)的锆氧簇节点上,设计、制备了基于MOFs的光催化材料-222(Fe)。采用1HNMR、XRD、SEM、EDX、UV-Vis、荧光光谱仪、XPS对-222(Fe)进行了表征。通过循环伏安(CV)测试了-222(Fe)的电化学性能。以-222(Fe)光催化硝基苯还原制备苯胺为模型反应,优化了反应条件,拓展硝基芳烃底物,考察了催化剂的循环稳定性。结果表明,-222(Fe)仍保持PCN-222(Fe)母体框架结构,其内部DCF与铁卟啉配体的物质的量比为1.6∶1,推测其化学式为C80H46.4Cl4.2FeN4O22.4Zr3,相对分子质量1878.47。-222(Fe)具有与DCF相同的最大紫外吸收峰(532 nm)和荧光发射峰(556 nm),其存在框架内电子转移,可模拟硝基还原酶的电子传递过程,光照下,DCF将电子传递给铁卟啉中心,生成的低价铁中心在厌氧条件下可将电子传递给硝基苯电子受体。-222(Fe)光催化硝基苯制备苯胺最佳反应条件为:室温下以532 nm LED为光源、2.5 μmol -222(Fe)为光催化剂、1 mL甲醇为溶剂、催化还原0.1 mmol硝基苯、反应时间2 h。在该条件下,苯胺产率为82%。催化剂连续使用3次后,苯胺产率降为77%。在最优反应条件下,-222(Fe)催化含有不同对位取代基的硝基苯底物的还原,产物产率64%~91%。

, authors=安洋1, 张旭1, 刘壬海1, 史雨生2, 段春迎3, 张铁欣1, *, authorsList=安洋, 张旭, 刘壬海, 史雨生, 段春迎, 张铁欣, authorCompany=null, correspAuthors=张铁欣, authorNote=

安洋(1992—),男,博士生,E-mail:

, correspAuthorsNote=
张铁欣(1983—),男,副教授,E-mail:
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酶启发2,7-二氯荧光素修饰铁卟啉金属有机框架的制备及光催化硝基芳烃还原
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安洋 1 , 张旭 1 , 刘壬海 1 , 史雨生 2 , 段春迎 3 , 张铁欣 1, *
精细化工 | 催化与分离提纯技术 2026,43(5): 1087-1095
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精细化工 |催化与分离提纯技术 2026 , 43 (5) : 1087 -1095
酶启发2,7-二氯荧光素修饰铁卟啉金属有机框架的制备及光催化硝基芳烃还原
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安洋(1992—),男,博士生,E-mail:

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安洋1 , 张旭1, 刘壬海1, 史雨生2, 段春迎3, 张铁欣1, *
作者信息
  • 1.大连理工大学 精细化工国家重点实验室,辽宁 大连 116024
  • 2.中国科学院 福建物质结构研究所,福建 福州 350002
  • 3.南京大学 配位化学全国重点实验室,江苏 南京 210023
通讯作者:
张铁欣(1983—),男,副教授,E-mail:
作者简介:

安洋(1992—),男,博士生,E-mail:

Enzyme-inspired dye-incorporated iron-porphyrin metal organic framework for photocatalytic reduction of nitroarenes
Yang AN1 , Xu ZHANG1, Renhai LIU1, Yusheng SHI2, Chunying DUAN3, Tiexin ZHANG1, *
Affiliations
  • 1.State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China
  • 2.State Key Laboratory of Structural Chemistry, Fujian Institute of Research on Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China
  • 3.State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, Jiangsu, China
出版时间: 2026-05-15 doi: 10.13550/j.jxhg.20250248
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受硝基还原酶启发,模拟其代谢硝基芳香或者硝基杂环化合物的电子传递过程,通过溶剂辅助配体交换促使染料分子2,7-二氯荧光素(DCF)的内酯开环,并将暴露出来的羧酸基团配位负载于铁卟啉金属有机框架(MOFs)PCN-222(Fe)的锆氧簇节点上,设计、制备了基于MOFs的光催化材料-222(Fe)。采用1HNMR、XRD、SEM、EDX、UV-Vis、荧光光谱仪、XPS对-222(Fe)进行了表征。通过循环伏安(CV)测试了-222(Fe)的电化学性能。以-222(Fe)光催化硝基苯还原制备苯胺为模型反应,优化了反应条件,拓展硝基芳烃底物,考察了催化剂的循环稳定性。结果表明,-222(Fe)仍保持PCN-222(Fe)母体框架结构,其内部DCF与铁卟啉配体的物质的量比为1.6∶1,推测其化学式为C80H46.4Cl4.2FeN4O22.4Zr3,相对分子质量1878.47。-222(Fe)具有与DCF相同的最大紫外吸收峰(532 nm)和荧光发射峰(556 nm),其存在框架内电子转移,可模拟硝基还原酶的电子传递过程,光照下,DCF将电子传递给铁卟啉中心,生成的低价铁中心在厌氧条件下可将电子传递给硝基苯电子受体。-222(Fe)光催化硝基苯制备苯胺最佳反应条件为:室温下以532 nm LED为光源、2.5 μmol -222(Fe)为光催化剂、1 mL甲醇为溶剂、催化还原0.1 mmol硝基苯、反应时间2 h。在该条件下,苯胺产率为82%。催化剂连续使用3次后,苯胺产率降为77%。在最优反应条件下,-222(Fe)催化含有不同对位取代基的硝基苯底物的还原,产物产率64%~91%。

酶启发  /  金属有机框架  /  铁卟啉  /  2,7-二氯荧光素  /  光致电荷转移  /  光催化技术

Inspired by nitroreductase and the electron transfer process of its metabolite nitroaromatic or nitroheterocyclic compounds, dye 2,7-dichlorofluorescein, which was ring-opened through solvent-assisted ligand incorporation to form carboxylic acid ligand groups, was loaded into the channels of iron-porphyrin metal-organic framework PCN-222(Fe) for synthesis of -222(Fe). The -222(Fe) was characterized by 1HNMR, XRD, SEM, EDX, UV-Vis, fluorescence spectrometer and XPS, and evaluated for its electrochemical properties via cyclic voltammetry (CV). With -222(Fe) photo-catalyzing nitrobenzene reduction to aniline as a model reaction, the reaction conditions were optimized, the nitroaromatic hydrocarbon substrate was expanded and the cycling stability of the catalyst was evaluated. The results showed that -222(Fe) still maintained the PCN-222(Fe) parent framework with a molar ratio of DCF to iron porphyrin ligand 1.6∶1, with its formula speculated as C80H46.4Cl4.2FeN4O22.4Zr3 and a relative molecular mass of 1878.47. -222(Fe) exhibited UV-Vis absorption and fluorescence emission peaks at the same positions as DCF (532 and 556 nm, respectively), indicating electron transfer within the framework which can simulate the electron transfer process of nitroreductase. Under light irradiation, excited DCF transferred electrons to the iron-porphyrin center, from which the generated low-valent iron center transferred electrons to other electron acceptors, enabling the efficient reduction of nitrobenzene substrates. Under the optimal reaction conditions of room temperature, with 532 nm LED as light source, 2.5 μmol -222(Fe) as photocatalyst, 1 mL methanol as solvent, catalytic reduction of 0.1 mmol nitrobenzene for 2 h, the aniline yield was 82% and reduced to 77% when the catalyst was used continuously for three times. Under the optimum reaction conditions, the reduction of nitrobenzene substrates with different para substituents catalyzed by -222(Fe) showed yields from 64% to 91%.

enzyme-inspiration  /  metal-organic frameworks  /  iron porphyrin  /  2,7-dichlorofluorescein  /  photo-induced-electron transfer  /  photocatalysis technology
安洋, 张旭, 刘壬海, 史雨生, 段春迎, 张铁欣. 酶启发2,7-二氯荧光素修饰铁卟啉金属有机框架的制备及光催化硝基芳烃还原. 精细化工, 2026 , 43 (5) : 1087 -1095 . DOI: 10.13550/j.jxhg.20250248
Yang AN, Xu ZHANG, Renhai LIU, Yusheng SHI, Chunying DUAN, Tiexin ZHANG. Enzyme-inspired dye-incorporated iron-porphyrin metal organic framework for photocatalytic reduction of nitroarenes[J]. Fine Chemicals, 2026 , 43 (5) : 1087 -1095 . DOI: 10.13550/j.jxhg.20250248
  • 国家自然科学基金项目(22472020; 22301028)
  • 国家外国专家项目(QN2023127001L)
  • 辽宁省科技计划联合计划项目(2023JH2/101700297)
  • 中央高校基本科研业务费项目(DUT24YG123)
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2026年第43卷第5期
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doi: 10.13550/j.jxhg.20250248
  • 接收时间:2025-04-10
  • 首发时间:2026-08-20
  • 出版时间:2026-05-15
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  • 收稿日期:2025-04-10
  • 录用日期:2025-04-28
基金
国家自然科学基金项目(22472020; 22301028)
国家外国专家项目(QN2023127001L)
辽宁省科技计划联合计划项目(2023JH2/101700297)
中央高校基本科研业务费项目(DUT24YG123)
作者信息
    1.大连理工大学 精细化工国家重点实验室,辽宁 大连 116024
    2.中国科学院 福建物质结构研究所,福建 福州 350002
    3.南京大学 配位化学全国重点实验室,江苏 南京 210023

通讯作者:

张铁欣(1983—),男,副教授,E-mail:
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
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