载流子对聚苯胺可见光催化苄胺氧化性能的影响

doi:10.16085/j.issn.1000-6613.2019-2079

化工进展 ›› 2020, Vol. 39 ›› Issue (10): 4041-4050.DOI: 10.16085/j.issn.1000-6613.2019-2079

载流子对聚苯胺可见光催化苄胺氧化性能的影响

孔鹏¹^,²(), 葛振宇², 汪杰², 王瑞义², 李忠¹(), 郑占丰²()

^1.太原理工大学煤科学与技术教育部和山西省重点实验室，山西太原 030024
^2.中国科学院山西煤炭化学研究所煤转化国家重点实验室，山西太原 030001

出版日期:2020-10-05 发布日期:2020-10-09
通讯作者: 李忠,郑占丰
作者简介:孔鹏（1986—），男，博士研究生，研究方向为聚合物光催化有机合成。E-mail：kongpeng@sxicc.ac.cn。
基金资助:
国家自然科学基金(21773284)

Effects of carriers on the photocatalytic performance of polyaniline for the benzylamine oxidation reaction under visible-light irradiation

Peng KONG¹^,²(), Zhenyu GE², Jie WANG², Ruiyi WANG², Zhong LI¹(), Zhanfeng ZHENG²()

^1.Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China

Online:2020-10-05 Published:2020-10-09
Contact: Zhong LI,Zhanfeng ZHENG

摘要/Abstract

摘要：

使用不同浓度的盐酸对本征态聚苯胺进行再掺杂处理，制备了一系列不同载流子（极化子和双极化子）含量的聚苯胺，通过FTIR、XRD、XPS和EPR等表征分析了极化子和双极化子结构的形成及变化过程，探究了载流子含量对能带结构、苄胺吸附活化、导电性以及光生电子-空穴分离效率的影响，考察了极化子和双极化子结构对聚苯胺光催化苄胺氧化的影响。结果表明：HCl掺杂过程中会有极化子和双极化子结构的形成，极化子和双极化子均能吸附苄胺形成表面复合物，拓展了可见光的吸收范围。极化子结构介导光生电子转移过程，促进光生电子-空穴分离，进而提高光催化苄胺氧化活性，而双极化子的存在对光催化苄胺高效转化不利。

关键词: 聚合物, 极化子, 双极化子, 催化, 活化, 苄胺氧化

Abstract:

Polyanilines (PANIs) with different contents of carriers (polarons and bipolarons) were prepared by doping the emeraldine base form of polyaniline with different concentrations of HCl. The formation processes of polaron and bipolaron were characterized by FTIR, XRD, XPS and EPR spectra. The influences of the carriers on the energy band structure, the adsorption and activation of benzylamine, the conductivity, and the separation efficiency of photogenerated electron-hole pairs were analyzed. In addition, the photocatalytic performance of PANIs towards the selective benzylamine oxidation reaction under visible light were investigated. The results showed that the polaron and bipolaron were formed during the doping process of PANIs and they both interacted with benzylamine to form the surface complex, which enhanced the absorption of visible light. The polaron-mediated electron transfer process was beneficial to the separation efficiency of photo-generated electron-hole pairs, and thus improved the activity of benzylamine oxidation. However, the presence of bipolaron was unfavorable for high photocatalytic activity.

Key words: polymers, polarons, bipolarons, catalysis, activation, benzylamine oxidization

中图分类号:

O643.3

孔鹏, 葛振宇, 汪杰, 王瑞义, 李忠, 郑占丰. 载流子对聚苯胺可见光催化苄胺氧化性能的影响[J]. 化工进展, 2020, 39(10): 4041-4050.

Peng KONG, Zhenyu GE, Jie WANG, Ruiyi WANG, Zhong LI, Zhanfeng ZHENG. Effects of carriers on the photocatalytic performance of polyaniline for the benzylamine oxidation reaction under visible-light irradiation[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4041-4050.

参考文献

1	CHEN J, CEN J, XU X, et al. The application of heterogeneous visible light photocatalysts in organic synthesis[J]. Catalysis Science & Technology, 2016, 6(2): 349-362.
2	NICOLAOU K C, MATHISON C J N, MONTAGNON T. New reactions of IBX: oxidation of nitrogen- and sulfur-containing substrates to afford useful synthetic intermediates[J]. Angewandte Chemie International Edition, 2003, 42(34): 4077-4082.
3	MUKAIYAMA T, KAWANA A, FUKUDA Y, et al. Oxidation of various secondary amines to imines with N-tert-butylphenylsulfinimidoyl chloride[J]. Chemistry Letters, 2001, 30(5): 390-391.
4	FURUKAWA S, OHNO Y, SHISHIDO T, et al. Selective amine oxidation using Nb₂O₅ photocatalyst and O₂[J]. ACS Catalysis, 2011, 1(10): 1150-1153.
5	KONG P, LIU P, GE Z, et al. Conjugated HCl-doped polyaniline for photocatalytic oxidative coupling of amines under visible light[J]. Catalysis Science & Technology, 2019, 9(3): 753-761.
6	JIANG W, LUO W, ZONG R, et al. Polyaniline/carbon nitride nanosheets composite hydrogel: a separation-free and high-efficient photocatalyst with 3D hierarchical structure[J]. Small, 2016, 12(32): 4370-4378.
7	NEELGUND G M, BLIZNYUK V N, OKI A. Photocatalytic activity and NIR laser response of polyaniline conjugated graphene nanocomposite prepared by a novel acid-less method[J]. Applied Catalysis B: Environmental, 2016, 187: 357-366.
8	LIU L, DING L, LIU Y, et al. A stable Ag₃PO₄@PANI core@shell hybrid: enrichment photocatalytic degradation with π-π conjugation[J]. Applied Catalysis B: Environmental, 2017, 201: 92-104.
9	LI J, ZHU L, WU Y, et al. Hybrid composites of conductive polyaniline and nanocrystalline titanium oxide prepared via self-assembling and graft polymerization[J]. Polymer, 2006, 47(21): 7361-7367.
10	FRISCH M J, TRUCKS G W, SCHLEGEL H B, et al. Gaussian 09 Revision D.01[CP]. Gaussian Inc., Wallingford CT, 2013.
11	CAO Y, LI S, XUE Z, et al. Spectroscopic and electrical characterization of some aniline oligomers and polyaniline[J]. Synthetic Metals, 1986, 16(3): 305-315.
12	TANG J, JING X, WANG B, et al. Infrared spectra of soluble polyaniline[J]. Synthetic Metals, 1988, 24(3): 231-238.
13	ZENG X, KO T. Structures and properties of chemically reduced polyanilines[J]. Polymer, 1998, 39(5): 1187-1195.
14	TURSUN A, ZHANG X, RUXANGUL J. Comparative studies of solid-state synthesized polyaniline doped with inorganic acids[J]. Materials Chemistry and Physics, 2005, 90(2): 367-372.
15	SANCHES E A, SOARES J C, MAFUD A C, et al. Structural characterization of chloride salt of conducting polyaniline obtained by XRD, SAXD, SAXS and SEM[J]. Journal of Molecular Structure, 2013, 1036: 121-126.
16	SANCHES E A, SILVA J M S DA, FERREIRA J M D O, et al. Nanostructured polyaniline emeraldine-base form (EB-PANI): a structural investigation for different neutralization times[J]. Journal of Molecular Structure, 2014, 1074: 732-737.
17	KUMAR S N, GAILLARD F, BOUYSSOUX G, et al. High-resolution XPS studies of electrochemically synthesized conducting polyaniline films[J]. Synthetic Metals, 1990, 36(1): 111-127.
18	WEI X L, FAHLMAN M, EPSTEIN A J. XPS study of highly sulfonated polyaniline[J]. Macromolecules, 1999, 32(9): 3114-3117.
19	WAN M, YANG J. Mechanism of proton doping in polyaniline[J]. Journal of Applied Polymer Science, 1995, 55(3): 399-405.
20	MACDIARMID A G, CHIANG J C, RICHTER A F, et al. Polyaniline: a new concept in conducting polymers[J]. Synthetic Metals, 1987, 18 (1/2/3): 285-290.
21	BHADRA S, SINGHA N K, KHASTGIR D. Polyaniline by new miniemulsion polymerization and the effect of reducing agent on conductivity[J]. Synthetic Metals, 2006, 156(16): 1148-1154.
22	JIANG R, DONG S, SONG S. Spectroscopy and electrochemistry of polyaniline in non-aqueous solution[J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1989, 85(7): 1575-1584.
23	DMITRIEVA E, HARIMA Y, DUNSCH L. Influence of phenazine structure on polaron formation in polyaniline: in situ electron spin resonance-ultraviolet/visible-near-infrared spectroelectrochemical study[J]. The Journal of Physical Chemistry B, 2009, 113(50): 16131-16141.
24	WANG Z H, JAVADI H H S, RAY A, et al. Electron localization in polyaniline derivatives[J]. Physical Review B, 1990, 42(8): 5411-5413.
25	BOUDREAUX D S, CHANCE R R, WOLF J F, et al. Theoretical-studies on polyaniline[J]. Journal of Chemical Physics, 1986, 85(8): 4584-4590.
26	STAFSTR?M S, BRéDAS J L, EPSTEIN A J, et al. Polaron lattice in highly conducting polyaniline: theoretical and optical studies[J]. Physical Review Letters, 1987, 59(13): 1464-1467.
27	ALMASI M J, FANAEI SHEIKHOLESLAMI T, NAGHDI M R. Band gap study of polyaniline and polyaniline/MWNT nanocomposites with in situ polymerization method[J]. Composites Part B: Engineering, 2016, 96: 63-68.
28	TAUC J, GRIGOROVICI R, VANCU A. Optical properties and electronic structure of amorphous germanium[J]. Physical Status Solidi, 1966, 15(2): 627-637.
29	ABDULLA H S, ABBO A I. Optical and electrical properties of thin films of polyaniline and polypyrrole[J]. International Journal of Electrochemical Science, 2012, 7(2012): 10666-10678.
30	SHAFIEE A, SALLEH M M, YAHAYA M. Determination of HOMO and LUMO of [6,6]-phenyl C61-butyric acid 3-ethylthiophene ester and poly(3-octyl-thiophene-2,5-diyl) through voltametry characterization[J]. Sains Malaysiana, 2011, 40(2): 173-176.
31	WANG Z, GARTH K, GHASIMI S, et al. Conjugated microporous poly(benzochalcogenadiazole)s for photocatalytic oxidative coupling of amines under visible light[J]. ChemSusChem, 2015, 8(20): 3459-3464.
32	KONG P, TAN H, LEI T, et al. Oxygen vacancies confined in conjugated polyimide for promoted visible-light photocatalytic oxidative coupling of amines[J]. Applied Catalysis B: Environmental, 2020, 272: 118964.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.
[7]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[8]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[9]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[10]	许友好, 王维, 鲁波娜, 徐惠, 何鸣元. 中国炼油创新技术MIP的开发策略及启示[J]. 化工进展, 2023, 42(9): 4465-4470.
[11]	耿源泽, 周俊虎, 张天佑, 朱晓宇, 杨卫娟. 部分填充床燃烧器中庚烷均相/异相耦合燃烧[J]. 化工进展, 2023, 42(9): 4514-4521.
[12]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[13]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[14]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[15]	高彦静. 单原子催化技术国际研究态势分析[J]. 化工进展, 2023, 42(9): 4667-4676.

载流子对聚苯胺可见光催化苄胺氧化性能的影响

Effects of carriers on the photocatalytic performance of polyaniline for the benzylamine oxidation reaction under visible-light irradiation

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价