Fe(III)螯合掺杂对g-C<sub>3</sub>N<sub>4</sub>光催化性能和活性位的影响

引用本文: 刘桂梅, 董国辉, 曾玉彬, 王传义. Fe(III)螯合掺杂对g-C₃N₄光催化性能和活性位的影响[J]. 催化学报, 2020, 41(10): 1564-1572. doi: S1872-2067(19)63518-7 shu

Citation: Guimei Liu, Guohui Dong, Yubin Zeng, Chuanyi Wang. The photocatalytic performance and active sites of g-C₃N₄ effected by the coordination doping of Fe(III)[J]. Chinese Journal of Catalysis, 2020, 41(10): 1564-1572. doi: S1872-2067(19)63518-7 shu

Fe(III)螯合掺杂对g-C₃N₄光催化性能和活性位的影响

a 武汉大学动力与机械学院, 湖北武汉 430072;
b 陕西科技大学环境科学与工程学院, 陕西西安 710021
基金项目:
国家自然科学基金（21876104，21603271，U1703129）.

摘要: 元素掺杂是一种简单有效的光催化剂改性方法.已有诸多文献报道采用非金属元素（B、P、S）或金属元素（Na⁺，Ni³⁺，Co³⁺，Cu²⁺）对g-C₃N₄进行掺杂改性，但目前对金属掺杂的模型和影响机理尚不清晰.g-C₃N₄作为层状材料，它的表面和边缘有大量的胺基，它对光生载流子的传输起到重要作用.此外，胺基可以与金属通过配位键形成螯合物；与胺基螯合的金属由于其功函数较小，可以捕获半导体的光生电子，并有利于降低光生载流子的复合.本文选用Fe（III）对g-C₃N₄进行掺杂改性，SEM-EDS表明，C和N元素均匀分布在g-C₃N₄整个骨架上，而Fe元素主要分布在g-C₃N₄边缘部分；FTIR结果发现，掺杂Fe后，N-H_x伸缩振动峰强度随着掺杂量的增加而降低，证明Fe（III）与g-C₃N₄表面胺基之间形成配位键，即Fe（III）掺杂为螯合掺杂.Fe（III）螯合掺杂后的g-C₃N₄光催化氧化RhB和光催化还原Cr（VI）的性能都得到显著提升.这是因为螯合掺杂Fe（III）后，g-C₃N₄不仅产生了更多的光生电子，而且由于产生的Fe（II）的芬顿效应产生了更多的羟基自由基，极大地提升了g-C₃N₄光催化氧化还原性能.但是Fe（III）螯合掺杂后却抑制了g-C₃N₄光催化去除NO的性能，NO去除性能随着Fe（III）掺杂量的增加而下降，这与Fe（III）的螯合掺杂模型有密切关系.NO-TPD实验结果表明，Fe掺杂降低了g-C₃N₄对NO的吸附；但脱氨基实验证明胺基对NO吸附并无作用.通过EPR表征发现，掺杂Fe后C的Lorentzian线强度降低了2/3，说明C上的未成对电子减少.同时通过固体NMR（¹H谱）中发现掺杂后N-H₂减少、但C-H数量增多的规律.说明Fe（III）与表面胺基（N-H₂）螯合后，质子占据C活性位，而C活性位却是NO在g-C₃N₄表面的吸附位点.所以Fe（III）的螯合掺杂会降低g-C₃N₄光催化去除NO的性能.
综上，Fe（III）螯合掺杂可以提高g-C₃N₄的氧化还原能力，但是并不适用于所有的光催化反应.同时，关注不理想的活性变化有助于进一步挖掘改性方法对材料结构的影响，指导改性材料的使用，并可能为其它相关研究带来启发.

关键词:

English

The photocatalytic performance and active sites of g-C₃N₄ effected by the coordination doping of Fe(III)

a Hubei Key Laboratory of Accoutrement Technique in Fluid Machinery and Power Engineering, Wuhan University, Wuhan 430072, Hubei, China;
b School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, Shaanxi, China
Received Date: 09 September 2019
Revised Date: 27 September 2019
Fund Project:
This work was supported by the National Nature Science Foundation of China (21876104, 21603271, U1703129) are gratefully appreciated.

Abstract: Element doping is a simple and effective method to improve photocatalytic activity of g-C₃N₄. However, the doping model and mechanism of metal elements are still uncharacterized. In this study, we found that Fe(III) can be doped into g-C₃N₄ through the coordination between amidogen and Fe(III). After activity tests, it was found that this coordination doping of Fe(III) could enhance the RhB oxidation and Cr(VI) reduction activities of g-C₃N₄ in interesting ways, but it is not helpful for the NO-removal performance of g-C₃N₄. Characterization and calculation results show that the coordination of Fe(III) can not only improve the transfer of photogenerated electrons, but it also can passivate the carbon site of triazine rings, which is the active site of NO-removal. This study revealed some doping mechanisms and effect mechanisms of elemental metal in photocatalysis.

Key words:

Doping
/ g-C₃N₄
/ Photocatalysis
/ Fe ion
/ NO removal

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Fe(III)螯合掺杂对g-C₃N₄光催化性能和活性位的影响

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The photocatalytic performance and active sites of g-C₃N₄ effected by the coordination doping of Fe(III)

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Fe(III)螯合掺杂对g-C3N4光催化性能和活性位的影响

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