Topotactic Transformation of Metal-Organic Frameworks to Graphene-Encapsulated Transition-Metal Nitrides as Efficient Fenton-like Catalysts

被引：280

作者：

Li, Xuning ^{[1
,2
]}

Ao, Zhimin ^{[3
]}

Liu, Jiayi ^{[1
,2
]}

Sun, Hongqi ^{[4
]}

Rykov, Alexandre I. ^{[1
]}

Wang, Junhu ^{[1
]}

机构：

[1] Chinese Acad Sci, Dalian Inst Chem Phys, Mossbauer Effect Data Ctr, Dalian 116023, Peoples R China

[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

[3] Guangdong Univ Technol, Inst Environm Hlth & Pollut Control, Sch Environm Sci & Engn, Guangzhou 510006, Guangdong, Peoples R China

[4] Edith Cowan Univ, Sch Engn, Joondalup, WA 6027, Australia

来源：

ACS NANO | 2016年 / 10卷 / 12期

基金：

中国国家自然科学基金;

关键词：

graphene encapsulated; Mn4N; sulfate radicals; activation mechanism; DFT calculation; NITROGEN-DOPED GRAPHENE; BISPHENOL-A; HETEROGENEOUS ACTIVATION; PHENOL DEGRADATION; SULFATE RADICALS; CARBON NANOTUBES; FACILE SYNTHESIS; PRUSSIAN BLUE; PEROXYMONOSULFATE; OXIDATION;

D O I：

10.1021/acsnano.6b07522

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Innovation in transition-metal nitride (TMN) preparation is highly desired for realization of various functionalities. Herein, series of graphene-encapsulated TMNs (FexMn6-xCo4-N@C) with well-controlled morphology have been synthesized through topotactic transformation of metal-organic frameworks in an N-2 atmosphere. The as-synthesized FexMn6-xCo4-N@C nanodices were systematically characterized and functionalized as Fenton-like catalysts for catalytic bisphenol A (BPA) oxidation by activation of peroxymonosulfate (PMS). The catalytic performance of FexMn6-xCo4-N@C was found to be largely enhanced with increasing Mn content. Theoretical calculations illustrated that the dramatically reduced adsorption energy and facilitated electron transfer for PMS activation catalyzed by Mn4N are the main factors for the excellent activity. Both sulfate and hydroxyl radicals were identified during the PMS activation, and the BPA degradation pathway mainly through hydroxylation, oxidation, and decarboxylation was investigated. Based on the systematic characterization of the catalyst before and after the reaction, the overall PMS activation mechanism over FexMn6-xCo4-N@C was proposed. This study details the insights into versatile TMNs for sustainable remediation by activation of PMS.

引用

页码：11532 / 11540

页数：9

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