Effect of Oxygen on Photocatalytic Nitrogen Fixation Performance of N Vacancy-embedded Graphitic Carbon Nitride †

doi:10.7503/cjcu20190463

Abstract

Abstract:

N vacancy and oxygen co-doped g-C₃N₄ with outstanding N₂ photofixation ability was synthesized by dielectric barrier discharge plasma treatment. XRD, UV-Vis, N₂ adsorption, SEM, XPS, PL and TPD were used to characterize the as-prepared catalysts. The result shows that plasma treatment does not change the morphology of as-prepared catalyst but introduce nitrogen vacancies and oxygen into g-C₃N₄ lattice simultaneously. The as-prepared co-doped g-C₃N₄ displays the ammonium ion production rate as high as 5.9 mg·L ^-1·h ^-1· $g cat - 1$ , which is 2.2 and 20 times that of individual N vacancy-doped g-C₃N₄ and neat g-C₃N₄, as well as good catalytic stability. Experimental and density functional theory(DFT) calculation results indicate that, compared with individual N vacancies doping, the introduction of oxygen can promote the activation ability of N vacancies to N₂ molecule, leading to the promoted N₂ photofixation performance.

Key words: Graphitic carbon nitride, Nitrogen photofixation, Co-doping, Photocatalysis, Plasma treatment

CLC Number:

O644

ZHAO Yanfeng,SUN Xiaolong,HU Shaozheng,WANG Hui,WANG Fei,LI Ping. Effect of Oxygen on Photocatalytic Nitrogen Fixation Performance of N Vacancy-embedded Graphitic Carbon Nitride ^†[J]. Chemical Journal of Chinese Universities, 2020, 41(1): 132-139.

Figures/Tables 9

Fig.1 N2 photofixation ability over as-prepared catalysts(A), NH4+ production ability of OCN(VN) in aprotic solvent DMF or using AgNO3 as the electron scavenger(B), N2 photofixation ability of reused OCN(VN)(C) and comparison of NH4+ production rate over OCN(VN) and other catalysts(D)

Fig.2 Mass spectra of the indophenol prepared from different atmosphere

Fig.3 XRD patterns(A), UV-Vis spectra(B), plots of transformed Kubelka-Munk function vs. the energy of light(C) and N2 adsorption-desorption isotherms(D) of as-prepared catalysts

Fig.4 SEM and HRTEM(inset) images of NCN(A) and SEM images of CN(VN)(B), OCN(C) and OCN(VN)(D)

Fig.5 XPS spectra in the region of C1s(A), N1s(B), O1s(C) and VB XPS(D) of as prepared catalysts

Fig.6 Diagram of possible structure of OCN(VN)

Fig.7 N2-TPD curves of as-prepared NCN, CN(VN), OCN and OCN(VN)

Fig.8 EIS(A) and PL(B) spectra of NCN, CN(VN), OCN and OCN(VN) and comparison of their PL intensity under Ar and N2 atmospheres(C) and the possible electrons transfer route(inset)(C)

Fig.9 Optimal N2 adsorption model and the charge density difference of the N2 molecule adsorbed on CN(VN)(A) and OCN(VN)(B)

References 46

[1]	Fujishima A., Rao T. N ., Tryk D. A., J. Photochem. Photobiol. C: Photochem. Rev., 2000,1(1), 1— 21 doi: 10.1016/S1389-5567(00)00002-2 URL
[2]	Kamat P. V ., Chem. Rev., 1993,93(1), 267— 300 doi: 10.1021/cr00017a013 URL
[3]	Hoffmann M. R ., Martin S. T.,Choi W.,Bahnemann D. W., Chem. Rev., 1995,95(1), 69— 96 doi: 10.1021/cr00033a004 URL
[4]	Li X. B ., Xiong J.,Huang J. T.,Feng Z. J.,Luo J. M., J. Alloy. Compd., 2019,774, 768— 778 doi: 10.1016/j.jallcom.2018.10.034 URL
[5]	Li X. B ., Xiong J.,Xu Y.,Feng Z. J.,Huang J. T., Chinese J. Catal., 2019,40, 424— 433 doi: 10.1016/S1872-2067(18)63183-3 URL
[6]	Tian H. W ., Liu M.,Zhen W. T., Appl. Catal. B: Environ., 2018,225, 468— 476 doi: 10.1016/j.apcatb.2017.12.019 URL
[7]	Tian H. W ., Shen K.,Hu X. Y.,Qiao L.,Zheng W. T., J. Alloy. Compd., 2017,691, 369— 377 doi: 10.1016/j.jallcom.2016.08.261 URL
[8]	Shen K., Xue X., Wang X. Y ., Hu X. Y.,Tian H. W.,Zheng W. T., RSC Adv., 2017,7(38), 23319— 23327 doi: 10.1039/C7RA01856H URL
[9]	Luo W. J ., Chen X. J.,Wei Z.,Liu D.,Yao W. Q.,Zhu Y. F., Appl. Catal. B: Environ., 2019,255, 117761 doi: 10.1016/j.apcatb.2019.117761 URL
[10]	Hu S. Z., Qu X. Y.,Li P.,Wang F.,Li Q.,Song L. J.,Zhao Y. F.,Kang X. X., Chem. Eng. J., 2018,334, 410— 418 doi: 10.1016/j.cej.2017.10.016 URL
[11]	Guo S. E ., Deng Z. P.,Li M. X.,Jiang B. J.,Tian C. G.,Pan Q. J.,Fu H. G., Angew. Chem. Int. Ed., 2016,55(5), 1830— 1834 doi: 10.1002/anie.201508505 URL pmid: 26692105
[12]	Li G. L ., Guo C. S.,Yan M.,Liu S. Q., Appl. Catal B: Environ., 2016,183, 142— 148 doi: 10.1016/j.apcatb.2015.10.039 URL
[13]	Ansari M. B ., Jin H. L.,Parvin M. N.,Park S. E., Catal. Today, 2012,185(1), 211— 216 doi: 10.1016/j.cattod.2011.07.024 URL
[14]	Chen K., Zhang X. M ., Yang X. F.,Jiao M. G.,Zhou Z.,Zhang M. H.,Wang D. H.,Bu X. H., Appl. Catal B: Environ., 2018,238, 263— 273 doi: 10.1016/j.apcatb.2018.07.037 URL
[15]	Schrauzer G. N ., Guth T. D., J. Am. Chem. Soc., 1977,99(22), 7189— 7193 doi: 10.1021/ja00464a015 URL
[16]	Wang X. C ., Maeda K.,Chen X. F.,Takanabe K.,Domen K.,Hou Y. D.,Fu X. Z.,Antonietti M., J. Am. Chem. Soc. , 2009,131(5), 1680— 1681 doi: 10.1021/ja809307s URL pmid: 19191697
[17]	Li Q., Yang J., Feng D., Wu Z., Wu Q., Park S. S ., Ha C. S.,Zhao D., Nano Res., 2010,3(9), 632— 642 doi: 10.1007/s12274-010-0023-7 URL
[18]	Park S. S ., Chu S. W.,Xue C.,Zhao D.,Ha C. S., J. Mater. Chem., 2011,21, 10801— 10807 doi: 10.1039/c1jm10849b URL
[19]	Zheng Y., Liu J., Liang J., Jaroniec M., Qiao S., Energy Environ. Sci., 2012,5, 6717— 6731 doi: 10.1039/c2ee03479d URL
[20]	Zheng Y., Jiao Y., Chen J., Liu J., Liang J., Du A., Zhang W., Zhu Z., Smith S. C ., Jaroniec M.,Lu G.,Qiao S., J. Am. Chem. Soc., 2011,133(50), 20116— 20119 doi: 10.1021/ja209206c URL
[21]	Xiong T., Cen W. L ., Zhang Y. X.,Dong F., ACS Catal., 2016,6(4), 2462— 2472 doi: 10.1021/acscatal.5b02922 URL
[22]	Dong F., Zhao Z. W ., Sun Y. J.,Zhang Y. X.,Yan S.,Wu Z. B., Environ. Sci. Tech., 2015,49(20), 12432— 12440 doi: 10.1021/acs.est.5b03758 URL pmid: 26375261
[23]	Cao S. H ., Chen H.,Jiang F.,Wang X., Appl. Catal. B: Environ., 2018,224, 222— 229 doi: 10.1016/j.apcatb.2017.10.028 URL
[24]	Hu S. Z ., Qu X. Y.,Bai J.,Li P.,Li Q.,Wang F.,Song L. J., ACS Sus. Chem. Eng., 2017,5(8), 6863— 6872
[25]	Li X. M ., Sun X.,Zhang L.,Sun S. M.,Wang W. Z., J. Mater. Chem. A, 2018,6, 3005— 3011 doi: 10.1039/C7TA09762J URL
[26]	Dong G. H ., Ho W. K.,Wang C. Y., J. Mater. Chem. A, 2015,3, 23435— 23441 doi: 10.1039/C5TA06540B URL
[27]	Ma H. Q ., Shi Z. Y.,Li S.,Liu N., Appl. Surf. Sci., 2016,379, 309— 315 doi: 10.1016/j.apsusc.2016.04.085 URL
[28]	Hu S. Z ., Chen X.,Li Q.,Zhao Y. F.,Mao W., Catal. Sci. Technol., 2016,6, 5884— 5890 doi: 10.1039/C6CY00622A URL
[29]	Li H., Shang J., Ai Z. H ., Zhang L. Z., J. Am. Chem. Soc., 2015,137(19), 6393— 6399 doi: 10.1021/jacs.5b03105 URL pmid: 25874655
[30]	Li J. H ., Shen B.,Hong Z. H.,Lin B. Z.,Gao B. F.,Chen Y. L., Chem. Commun., 2012,48, 12017— 12019 doi: 10.1039/c2cc35862j URL pmid: 23133831
[31]	Qu X. Y ., Hu S. Z.,Bai J.,Li P.,Lu G.,Kang X. X., New J. Chem., 2018,42, 4998— 5004 doi: 10.1039/C7NJ04760F URL
[32]	Zhao W. R ., Zhang J.,Zhu X.,Zhang M.,Tang J.,Tan M.,Wang Y., Appl. Catal. B: Environ., 2014,144, 468— 477 doi: 10.1016/j.apcatb.2013.07.047 URL
[33]	Rusina O., Linnik O., Eremenko A., Kisch H., ., Chem. Eur. J 2003,9(2), 561— 565 doi: 10.1002/chem.200390059 URL pmid: 12532306
[34]	Hu S. Z ., Chen X.,Li Q.,Li F. Y.,Fan Z. P.,Wang H.,Wang Y. J.,Zheng B. H.,Wu G., Appl. Catal. B: Environ., 2017,201, 58— 69 doi: 10.1016/j.apcatb.2016.08.002 URL
[35]	Ding J., Xu W., Wan H., Yuan D., Chen C., Wang L., Guan G., Dai W. L ., Appl. Catal. B: Environ., 2018,221, 626— 634 doi: 10.1016/j.apcatb.2017.09.048 URL
[36]	Kim Y. I ., Atherton S. J.,Brigham E. S.,Mallouk T. E., J. Phys. Chem., 1993,97(45), 11802— 11810 doi: 10.1021/j100147a038 URL
[37]	Yuan B., Chu Z. Y ., Li G. Y.,Jiang Z. H.,Hu T. J.,Wang Q. H.,Wang C. H., J. Mater. Chem. C, 2014,2, 8212— 8215 doi: 10.1039/C4TC01421A URL
[38]	Wang K. Y., Gu G. Z.,Hu S. Z.,Zhang J.,Sun X. L.,Wang F.,Li P.,Zhao Y. F.,Fan Z. P.,Zou X., Chem. Eng. J., 2019,368, 896— 904 doi: 10.1016/j.cej.2019.03.037 URL
[39]	Li C., Yu S., Dong H., Wang Y., Wu H., Zhang X., Chen G., Liu C ., J. Colloid Interf. Sci., 2018,531, 331— 342 doi: 10.1016/j.jcis.2018.07.083 URL pmid: 30048886
[40]	Zhang Y. W ., Liu J. H.,Wu G.,Chen W.,. Nanoscale, 2012,4, 5300— 5303 doi: 10.1039/c2nr30948c URL
[41]	Fu J., Zhu B., Jiang C., Cheng B., You W., Yu J ., Small, 2017,13(15), 1603938 doi: 10.1002/smll.v13.15 URL
[42]	Qiu P., Xu C., Chen H., Jiang F., Wang X., Lu R., Zhang X., Appl. Catal. B: Environ.., 2017,206, 319— 327 doi: 10.1016/j.apcatb.2017.01.058 URL
[43]	Hoshino K., ., Chem. Eur. J 2001,7(13), 2727— 2731 doi: 10.1002/1521-3765(20010702)7:13&lt;2727::aid-chem2727&gt;3.0.co;2-4 URL pmid: 11486946
[44]	Lei W., Portehault D., Dimova R., Antoniettit M ., J. Am. Chem. Soc., 2011,133(18), 7121— 7127 doi: 10.1021/ja200838c URL
[45]	Qu X. Y ., Hu S. Z.,Bai J.,Li P.,Lu G.,Kang X. X., New J. Chem., 2018,42, 4998— 5004 doi: 10.1039/C7NJ04760F URL
[46]	Li S. J ., Chen X.,Hu S. Z.,Li Q.,Bai J.,Wang F., RSC Adv., 2016,6, 45931— 45937 doi: 10.1039/C6RA08817A URL