溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

doi:10.3866/PKU.WHXB201611102

物理化学学报 >> 2017, Vol. 33 >> Issue (3): 611-619.doi: 10.3866/PKU.WHXB201611102

溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

白金,陈鑫,奚兆毅,王翔,李强,胡绍争*()

辽宁石油化工大学化学化工与环境学部,辽宁抚顺113001

收稿日期:2016-09-23 发布日期:2017-03-07
通讯作者: 胡绍争 E-mail:hushaozhenglnpu@163.com
基金资助:
国家自然科学基金(41571464);辽宁省教育厅项目(L2014145);辽宁省自然科学基金(201602467)

Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C₃N₄ Catalyst

Jin BAI,Xin CHEN,Zhao-Yi XI,Xiang WANG,Qiang LI,Shao-Zheng HU*()

College of Chemistry, Chemical Engineering, and Environmental Engineering, Liaoning Shihua University, Fushun 113001, Liaoning Province, P. R. China

Received:2016-09-23 Published:2017-03-07
Contact: Shao-Zheng HU E-mail:hushaozhenglnpu@163.com
Supported by:
the National Natural Science Foundation of China(41571464);Education Department of Liaoning Province, China(L2014145);Natural Science Foundation of Liaoning Province, China(201602467)

摘要/Abstract

摘要：

采用离子液体[Bmim]Br为溶剂,溶剂热后处理法制备了具有大比表面积和氮空穴的石墨相氮化碳催化剂.采用X射线衍射(XRD)光谱、扫描电镜(SEM)、氮气吸附、紫外-可见(UV-Vis)光谱、X射线光电子能谱(XPS)、荧光光谱(PL)、电子顺磁共振谱(EPR)、程序升温脱附(TPD)等分析手段对制备的催化剂进行了表征.结果表明经过溶剂热后处理的催化剂形貌由无规则的层状结构变为尺寸为30-40 nm的纳米颗粒,导致比表面积从8.6 m²·g^-1增加到37.9 m²·g^-1.从N₂-TPD、荧光光谱及密度泛函理论(DFT)模拟计算的结果得出,氮空穴不仅能捕获光生电子促进电子空穴的有效分离,还能吸附并活化反应物氮气分子.溶剂热处理后,增加的比表面积导致更多的氮空穴作为反应活性位暴露在催化剂表面,是固氮活性显著提高.本文还探讨了可能的反应机理.

关键词: 石墨相氮化碳, 离子液体, [Bmim]Br, 光催化固氮

Abstract:

In this work, graphitic carbon nitride (g-C₃N₄) with large surface area and many nitrogen vacancies was synthesized by introducing ionic liquid[Bmim]Br as a solvent into the solvothermal post-treatment. X-ray diffraction (XRD), N₂ adsorption, scanning electron microscopy (SEM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), temperature-programmed desorption of N₂ (N₂-TPD), and photoluminescence (PL) spectroscopy were used to characterize the prepared catalysts. The morphology of the as-prepared g-C₃N₄ was markedly changed from an orderless layered structure to nanoparticles with a uniform size distribution of around 30-40 nm after the introduction of[Bmim]Br, leading an increase in surface area from 8.6 to 37.9 m²·g^-1. N₂-TPD, photoluminescence spectra, and density functional theory (DFT) simulations indicated that the nitrogen vacancies not only trapped the photogenerated electrons to enhance their separation rate, but also served as active sites for the adsorption and activation of N₂ molecules. The increased surface area of the as-prepared g-C₃N₄ meant that more nitrogen vacancies were exposed on the surface, leading to a markedly promoted nitrogen photofixation ability. The possible reaction mechanism is proposed.

Key words: Graphitic carbon nitride, Ionic liquid, [Bmim]Br, Nitrogen photofixation

白金,陈鑫,奚兆毅,王翔,李强,胡绍争. 溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响[J]. 物理化学学报, 2017, 33(3), 611-619. doi: 10.3866/PKU.WHXB201611102

Jin BAI,Xin CHEN,Zhao-Yi XI,Xiang WANG,Qiang LI,Shao-Zheng HU. Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C₃N₄ Catalyst[J]. Acta Phys. -Chim. Sin. 2017, 33(3), 611-619. doi: 10.3866/PKU.WHXB201611102

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201611102

https://www.whxb.pku.edu.cn/CN/Y2017/V33/I3/611

参考文献

1	Vol'pin M. E. ; Shur V. B. ; Berkovich E. G. Inorg. Chim. Acta 1998, 280, 264.
2	Leigh G. J. Science 1998, 279, 506.
3	Tamelen E. E. ; Akermark B. J. Am. Chem. Soc. 1968, 90, 4492.
4	Dickson C. R. ; Nozik A. J. J. Am. Chem. Soc. 1978, 100, 8007.
5	Hu S. Z. ; Li Y. M. ; Li F. Y. ; Fan Z. P. ; Ma H. F. ; Li W. ; Kang X. X. ACS. Sus. Chem. Eng 2016, 4, 2269.
6	Ranjit K. T. ; Viswanathan B. Indian J. Chem. Sect. A 1996, 35, 443.
7	Schrauzer G. N. ; Guth T. D. J. Am. Chem. Soc. 1977, 99, 7189.
8	Ranjit K. T. ; Varadarajan T. K. ; Viswanathan B. J. Photochem.Photobiol. A:Chem. 1996, 96, 181.
9	Rusina O. ; Linnik O. ; Eremenko A. ; Kisch H. Chem. Eur. J. 2003, 9, 561.
10	Hoshino K. Chem. Eur. J. 2001, 7, 2727.
11	Hoshino K. ; Inui M. ; Kitamura T. ; Kokado H. Angew. Chem.Int. Ed. 2000, 39, 2509.
12	Zhao W. R. ; Zhang J. ; Zhu X. ; Zhang M. ; Tang J. ; Tan M. ; Wang Y. Appl. Catal. B:Environ. 2014, 144, 468.
13	Liang Y. T. ; Vijayan B. K. ; Gray K. A. ; Hersam M. C. Nano Lett. 2011, 11, 2865.
14	Walter M. G. ; Warren E. L. ; McKone J. R. ; Boettcher S.W. ; Mi Q. ; Santori E. A. ; Lewis N. S. Chem. Rev. 2010, 110, 6446.
15	Britto P. J. ; Santhanam K. S. V. ; Rubio A. ; Alonso J. A. ; Ajayan P. M. Adv. Mater. 1999, 11, 154.
16	Zhu D. ; Zhang L. ; Ruther R. E. ; Ruther R. J. Nat. Mater. 2013, 12, 836.
17	Wang X. C. ; Maeda K. ; Thomas A. ; Takanabe K. ; Xin G. ; Carlsson J. M. ; Domen K. ; Antonietti M. Nat. Mater. 2009, 8, 76.
18	Zhao Z.W. ; Sun Y. J. ; Dong F. Nanoscale 2015, 7, 15.
19	Zheng Y. ; Liu J. ; Liang J. ; Jaroniec M. ; Qiao S. Energy Environ. Sci 2012, 5, 6717.
20	Zheng Y. ; Jiao Y. ; Chen J. ; Liu J. ; Liang J. ; Du A. ; Zhang W. ; Zhu Z. ; Jaroniec M. ; Smith S. C. ; Lu G. ; Qiao S. J. Am.Chem. Soc. 2011, 133, 20116.
21	Xu J. ; Wu H. T. ; Wang X. ; Xue B. ; Li Y. X. ; Cao Y. Phys. Chem. Chem. Phys. 2013, 15, 4510.
22	Li Q. ; Yang J. ; Feng D. ; Wu Z. ; Wu Q. ; Park S. S. ; Ha C. S. ; Zhao D. Nano Res. 2010, 3, 632.
23	Park S. S. ; Chu S.W. ; Xue C. ; Zhao D. ; Ha C. S. Mater. J.Chem. 2011, 21, 10801.
24	Welton T. Chem. Rev 1999, 99, 2071.
25	Keim W. Angew. Chem. Int. Ed. 2000, 39, 3772.
26	Kubisa P. Prog. Polym. Sci 2004, 29, 3.
27	Paramasivam I. ; Macak J. M. ; Selvam T. ; Schmuki P. Electrochim. Acta 2008, 54, 643.
28	Yoo K. S. ; Lee T. G. ; Kim J. Microporous Mesoporous Mat 2005, 84, 211.
29	Ding K. L. ; Miao Z. J. ; Liu Z. M. ; Zhang Z. F. ; Han B. X. ; An G. M. ; Miao S. D. ; Xie Y. J. Am. Chem. Soc. 2007, 129, 6362.
30	Liu Y. ; Li J. ; Wang M. J. ; Li Z. Y. ; Liu H. T. ; He P. ; Yang X.R. ; Li J. H. Cryst. Growth Des. 2005, 5, 1643.
31	Xu L. ; Xia J. X. ; Xu H. ; Yin S. ; Wang K. ; Huang L. Y. ; Wang L. G. ; Li H. M. J. Power Sources 2014, 245, 866.
32	Di J. ; Xia J. X. ; Yin S. ; Xu H. ; Xu L. ; He M. Q. ; Li H. M. ; Xu L. ; Jiang Y. P. RSC Adv 2013, 3, 19624.
33	Xiao D. L. ; Li S. Q. ; Liu S. B. ; He H. ; Lu J. R. New J. Chem 2016, 40, 320.
34	Di J. ; Xia J. X. ; Yin S. ; Xu H. ; Xu L. ; Xu Y. G. ; He M. Q. ; Li H. M. J. Mater. Chem. A 2014, 2, 5340.
35	Dong G. H. ; Ho W. K. ; Wang C. Y. J. Mater. Chem. A 2015, 3, 23435.
36	Li H. ; Shang J. ; Ai Z. H. ; Zhang L. Z. J. Am. Chem. Soc. 2015, 137, 6393.
37	Hong Z. H. ; Shen B. ; Chen Y. L. ; Lin B. Z. ; Gao B. F. J. Mater. Chem. A 2013, 1, 11754.
38	Hu S. Z. ; Li F. Y. ; Fan Z. P. ; Gui J. Z. J. Power Sources 2014, 250, 30.
39	Yang R. C. ; Lu X. J. ; Huang X. ; Chen Z. M. ; Zhang X. ; Xu M. D. ; Song Q.W. ; Zhu L. T. Appl. Catal. B:Environ. 2015, 170-171, 225.
40	Wang Z. H. ; Ma W. H. ; Chen C. C. ; Ji H.W. ; Zhao J. C. Chem. Eng. J. 2011, 170, 353.
41	Wang X. C. ; Chen X. F. ; Thomas A. ; Fu X. Z. ; Antonietti M. Adv. Mater. 2009, 21, 1609.
42	Oregan B. ; Gr?tzel M. Nature 1991, 353, 737.
43	Yan S. C. ; Li Z. S. ; Zou Z. G. Langmuir 2009, 25, 10397.
44	Hu S. Z. ; Ma L. ; Xie Y. ; Li F. Y. ; Fan Z. P. ; Wang F. ; Wang Q. ; Wang Y. J. ; Kang X. X. ; Wu G. Dalton Trans 2015, 44, 20889.
45	Lei W. ; Portehault D. ; Dimova R. ; Antoniettit M. J. Am.Chem. Soc 2011, 133, 7121.
46	Zhang Y.W. ; Liu J. H. ; Wu G. ; Chen W. Nanoscale 2012, 4, 5300.
47	Hu S. Z. ; Ma L. ; Li F. Y. ; Fan Z. P. ; Wang Q. ; Bai J. ; Kang X. X. ; Wu G. RSC Adv 2015, 5, 90750.

[1]	任书霞, 杨铮, 安帅领, 孟婕, 刘晓敏, 赵晋津. 高效光电调控钙钛矿量子点阻变存储性能[J]. 物理化学学报, 2023, 39(12): 2301033 - .
[2]	沈荣晨, 郝磊, 陈晴, 郑巧清, 张鹏, 李鑫. 高分散Co_0.2Ni_1.6Fe_0.2P助催化剂改性P掺杂g-C₃N₄纳米片高效光催化析氢的研究[J]. 物理化学学报, 2022, 38(7): 2110014 - .
[3]	周亮, 李云锋, 张永康, 秋列维, 邢艳. 具有高效界面电荷转移的0D/2D Bi₄V₂O₁₁/g-C₃N₄梯形异质结的设计合成及抗生素降解性能研究[J]. 物理化学学报, 2022, 38(7): 2112027 - .
[4]	王薇, 黄宇, 王震宇. 缺陷工程调控石墨相氮化碳及其光催化空气净化应用进展[J]. 物理化学学报, 2021, 37(8): 2011073 - .
[5]	王欢, 吴云雁, 赵燕飞, 刘志敏. 离子液体介导CO₂化学转化研究进展[J]. 物理化学学报, 2021, 37(5): 2010022 - .
[6]	陈文琼, 关永吉, 张姣, 裴俊捷, 张晓萍, 邓友全. 外电场作用下离子液体振动光谱变化的分子动力学模拟研究[J]. 物理化学学报, 2021, 37(10): 2001004 - .
[7]	吴智伟, 丁伟璐, 张雅琴, 王艳磊, 何宏艳. 咪唑类离子液体与酪氨酸相互作用及机理的密度泛函理论研究[J]. 物理化学学报, 2021, 37(10): 2002021 - .
[8]	王亦清,沈少华. 非金属掺杂石墨相氮化碳光催化的研究进展与展望[J]. 物理化学学报, 2020, 36(3): 1905080 - .
[9]	惠淑荣, 赵丽薇, 刘青山, 宋大勇. [C₃mim][NTf₂]/DEC/[Li][NTf₂]体系的基础性质[J]. 物理化学学报, 2020, 36(11): 1910067 - .
[10]	刘璐, 徐玉萍, 陈霞, 洪梅, 佟静. 1-烷基-3-甲基咪唑氯化物焓变的热重分析[J]. 物理化学学报, 2020, 36(11): 2004014 - .
[11]	胡益民, 韩杰, 郭荣. 非离子表面活性剂Brij 30诱导离子液体型表面活性剂C₁₆imC₈Br蠕虫状胶束向凝胶的转变[J]. 物理化学学报, 2020, 36(10): 1909049 - .
[12]	杨康,帅骁睿,杨化超,严建华,岑可法. 基于室温离子液体的活化石墨烯粉末超级电容储能性能[J]. 物理化学学报, 2019, 35(7): 755 -765 .
[13]	潘明光,赵永升,曾小勤,邹建新. 偶氮苯基型离子液体溶液对空气中湿度的变色响应[J]. 物理化学学报, 2019, 35(6): 624 -629 .
[14]	龚燕燕,刘海春,张朵,佟静. 醚基功能化离子液体[MOEMIm]Cl和[EOEMIm]Cl热力学性质[J]. 物理化学学报, 2019, 35(11): 1224 -1231 .
[15]	陈文琼,关永吉,张晓萍,邓友全. 分子动力学模拟研究外电场对咪唑类离子液体振动谱的影响[J]. 物理化学学报, 2018, 34(8): 912 -919 .

溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C₃N₄ Catalyst

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0

溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C3N4 Catalyst

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0

Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C₃N₄ Catalyst