Acid-induced topological morphology modulation of graphitic carbon nitride homojunctions as advanced metal-free catalysts for OER and pollutant degradation

doi:10.1016/j.jmst.2021.01.030

Abstract

Abstract:

Topological morphology that dominates the surface electronic properties of nanostructures plays a key role in producing desired materials for versatile functions and applications in many fields, but its modulation for specific functions remains a big challenge. Herein, we report an acid-induced method to prepare S-doped graphitic carbon nitride/graphitic carbon nitride (S-CN/CN) homojunction by simply pyrolyzing a supramolecular precursor synthesized from melamine and H₂SO₄. The topological morphology and electronic structure of CN homojunction can be easily adjusted only by changing the ratio of raw materials. Moreover, the topological morphology of S-CN/CN homojunction can be further adjusted from hollow cocoon to 2D nanosheets by changing the annealing conditions. The optimized S-CN/CN homojunction shows highly efficient in charge transfer and separation and exhibits superior OER activity and high ability to degrade organic pollutants. Impressively, S-CN/CN nanosheets only demand low overpotential of 301 mV to drive a current density of 10 mAcm^-2 in 1 M KOH media, and the corresponding Tafel slope is only 57.71 mV/dec, which is superior to the most advanced precious metal IrO₂ catalyst. Moreover, under visible light irradiation, its photodegradation kinetic rate of RhB is 2.38, which is 47.6 times higher than that of bulk CN. This work provides useful guidance for designing and developing efficient multifunctional metal-free catalysts.

Key words: Topological morphology, Acid-induced, Molecular self-assembly, S-CN/CN homojunction, OER

Hua-Wei Zhang, Yi-Xin Lu, Bo Li, Gui-Fang Huang, Fan Zeng, Yuan-Yuan Li, Anlian Pan, Yi-Feng Chai, Wei-Qing Huang. Acid-induced topological morphology modulation of graphitic carbon nitride homojunctions as advanced metal-free catalysts for OER and pollutant degradation[J]. J. Mater. Sci. Technol., 2021, 86: 210-218.

Figures/Tables 6

Fig. 1. Illustration of the preparation procedure for supramolecular organic assemblies. The melamine solution without sulfuric acid will crystallize out perfect melamine crystals during cooling. The addition of sulfuric acid will hydrolyze part of the melamine molecules into cyanuric acid molecules, which are driven by multiple hydrogen bonds (green dotted lines) and counterion bridging (light blue solid lines) to assemble into MCA supramolecular organic assemblies with surrounding melamine molecules. When the amount of sulfuric acid added is less than 1 g, residual free melamine molecules remained in the solution will adsorb on the surface of the supramolecular organic assemblies and crystallize to form a “shell” during the cooling process. As the amount of sulfuric acid added is 1 g, the molar ratio of unhydrolyzed melamine to cyanuric acid and sulfate ions is cloes to 1:1, leading to the formation of rhombohedra MCA supramolecular assemblies. Further increasing the sulfuric acid added, melamine-cyanuric acid supramolecular complexes with an elongated rhombohedral structure will appear owing to the strong directional component of the interactions such as hydrogen bonds and counterion bridging.

Fig. 2. (a) The evolution process and conjectural mechanism of M-0.5 complex in the process of heating. The topological morphology of S-CN/CN homojunction can be easily adjusted from hollow cocoon to hierarchical architecture composed of 2D nanosheets only by changing the annealing conditions. (b) The XRD patterns and (c) the FTIR spectrum of the supramolecular precursor. (d) The XRD patterns and (e) the FTIR spectrum of MCN, RCN, CNS-0.25, CNS-0.5, CNS-1, and CNS-0.5 N.

Fig. 3. Acid-induced topological morphology modulation of graphitic carbon nitride junctions. The SEM images of (a) MCN, (b) RCN, (c) CNS-0.25, (d) CNS-0.5, (e) CNS-1, and (f) CNS-0.5 N with topological morphology. (g) EDS elemental mapping of CNS-0.5N.

Fig. 4. (a) UV/Vis light absorption spectra and plots of (αhν)2 versus energy (hν)2 for bandgap energy analysis, (b) Schematic band structures, (c) EIS Nyquist plots, (d) transient photocurrent response, (e) linear sweep voltammetry curves, and (f) Tafel plots of MCN, RCN, and CNS, respectively.

Fig. 5. (a) Photocatalytic activities and (b) apparent rate constants on the degradation of RhB. (c) Cycling runs for the photocatalytic degradation of RhB in the presence of CNS-0.5N under visible light irradiation. (d) The photocatalytic performance of CNS-0.5N in the presence of various quenchers.

Fig. 6. Schematic illustration of the band structures and the photogenerated charge transfer process of CNS-0.5N.

References 66

[1]	J. Song, C. Wei, Z.F. Huang, C. Liu, L. Zeng, X. Wang, Z.J. Xu, Chem. Soc. Rev. 49(2020) 2196-2214. DOI URL
[2]	K. Zhu, F. Shi, X. Zhu, W. Yang, Nano Energy 73 (2020), 104761. DOI URL
[3]	H. Xu, H. Shang, C. Wang, Y. Du, Coord. Chem. Rev. 418(2020), 213374. DOI URL
[4]	Y. Wu, C. Li, W. Liu, H. Li, Y. Gong, L. Niu, X. Liu, C. Sun, S. Xu, Nanoscale 11 (2019) 5064-5071. DOI URL
[5]	Z.P. Wu, X.F. Lu, S.Q. Zang, X.W. Lou, Adv. Funct. Mater. 30(2020), 1910274. DOI URL
[6]	W. Liu, H. Zhang, C. Li, X. Wang, J. Liu, X. Zhang. J. Energy Chem 47(2020) 333-345. DOI URL
[7]	K. Zeng, X. Zheng, C. Li, J. Yan, J.H. Tian, C. Jin, P. Strasser, R. Yang, Adv. Funct. Mater. 30(2020), 2000503. DOI URL
[8]	J. Yi, W. El-Alami, Y. Song, H. Li, P.M. Ajayan, H. Xu, Chem. Eng. J. 382(2020), 122812. DOI URL
[9]	X. Wu, D. Gao, H. Yu, J. Yu, Nanoscale 11 (2019) 9608-9616. DOI URL
[10]	Y. Li, M. Zhou, B. Cheng, Y. Shao, J. Mater. Sci 56(2020) 1-17. DOI URL
[11]	Q. Liu, J. Shen, X. Yu, X. Yang, W. Liu, J. Yang, H. Tang, H. Xu, H. Li, Y. Li, J. Xu, Appl. Catal. B 248 (2019) 84-94. DOI URL
[12]	M.G. Kim, W.K. Jo, J. Mater. Sci 40(2020) 168-175.
[13]	V. Balakumar, H. Kim, J.W. Ryu, R. Manivannan, Y.A. Son, J. Mater. Sci 40(2020) 176-184.
[14]	W. Zhang, Q. Yao, G. Jiang, C. Li, Y. Fu, X. Wang, A. Yu, Z. Chen, ACS Catal. 9(2019) 1603-11613.
[15]	Y. Zheng, Y. Liu, X. Guo, Z. Chen, W. Zhang, Y. Wang, X. Tang, Y. Zhang, Y. Zhao, J. Mater. Sci 41(2020) 117-126. DOI URL
[16]	Y. Li, F. Gong, Q. Zhou, X. Feng, J. Fan, Q. Xiang, Appl. Catal. B 268 (2020), 118381. DOI URL
[17]	S.N. Talapaneni, G. Singh, I.Y. Kim, K. AlBahily, A.H. Al-Muhtaseb, A.S. Karakoti, E. Tavakkoli, A. Vinu, Adv. Mater. 32(2020), 1904635. DOI URL
[18]	Q. Yan, G.F. Huang, D.F. Li, M. Zhang, A.L. Pan, W.Q. Huang, J. Mater. Sci 34(2018) 2515-2520.
[19]	T. Cea, N.R. Walet, F. Guinea, Nano Lett. 19(2019) 8683-8689. DOI URL
[20]	I. Cucchi, A. Marrazzo, E. Cappelli, S. Ricco, F.Y. Bruno, S. Lisi, M. Hoesch, T.K. Kim, C. Cacho, C. Besnard, E. Giannini, N. Marzari, M. Gibertini, F. Baumberger, A. Tamai, Phys. Rev. Lett. 124(2020), 106402. DOI PMID
[21]	J. Xu, Z. Wang, Y. Zhu, J. Mater. Sci 49(2020) 133-143.
[22]	R. Kamarudheen, G. Kumari, A. Baldi, Nat. Commun. 11(2020), 3957-3957. DOI PMID
[23]	Y. Lei, Y. Chen, R. Zhang, Y. Li, Q. Yan, S. Lee, Y. Yu, H. Tsai, W. Choi, K. Wang, Y. Luo, Y. Gu, X. Zheng, C. Wang, C. Wang, H. Hu, Y. Li, B. Qi, M. Lin, Z. Zhang, S.A. Dayeh, M. Pharr, D.P. Fenning, Y.H. Lo, J. Luo, K. Yang, J. Yoo, W. Nie, S. Xu, Nature 583 (2020) 790-795. DOI URL
[24]	Z. Jiang, J.W. Strzalka, D.A. Walko, J. Wang, Nat. Commun. 11(2020) 3197. DOI URL
[25]	X. Liu, Z. Hao, E. Khalaf, J.Y. Lee, Y. Ronen, H. Yoo, D.H. Najafabadi, K. Watanabe, T. Taniguchi, A. Vishwanath, P. Kim, Nature 583 (2020) 221-225. DOI URL
[26]	H. Xiong, H. Zhou, G. Sun, Z. Liu, L. Zhang, L. Zhang, F. Du, Z.-A. Qiao, S. Dai, Angew. Chem. Int. Ed. 59(2020) 11053-11060. DOI URL
[27]	H. He, J.-E. Ostwaldt, C. Hirschhaeuser, C. Schmuck, J. Niemeyer, Small 16 (2020), 2001044. DOI URL
[28]	A. Ibanez-Fonseca, D. Orbanic, F.J. Arias, M. Alonso, D.I. Zeugolis, J.C. Rodriguez-Cabello, Small 16 (2020), 2001244. DOI URL
[29]	J. Huang, H. Ren, R. Zhang, L. Wu, Y. Zhai, Q. Meng, J. Wang, Z. Su, R. Zhang, S. Dai, S.Z.D. Cheng, M. Huang, ACS Nano 14 (2020) 8266-8275. DOI URL
[30]	Y. Liu, J. Li, L. Kan, J. Li, M. Eddaoudi, Angew. Chem. Int. Ed. 59(2020) 19659-19662. DOI URL
[31]	S. Sun, S. Liang, Nanoscale 9 (2017) 10544-10578. DOI URL
[32]	N. Tian, H. Huang, X. Du, F. Dong, Y. Zhang, J. Mater. Chem. A Mater. Energy Sustain. 7(2019) 11584-11612. DOI URL
[33]	Q. Cao, B. Kumru, M. Antonietti, B.V.K.J. Schmidt, Mater. Horiz. 7(2020) 762-786. DOI URL
[34]	J. Xu, G. Wu, Z. Wang, X. Zhang, Chem. Sci. 3(2012) 3227-3230. DOI URL
[35]	Y.S. Jun, J. Park, S.U. Lee, A. Thomas, W.H. Hong, G.D. Stucky, Angew. Chem. Int. Ed. 52(2013) 11083-11087. DOI URL
[36]	B.X. Zhou, S.S. Ding, W. Wang, X.R. Wang, W.Q. Huang, K. Li, G.F. Huang, Nanoscale 12 (2020) 6037-6046. DOI URL
[37]	Y. Ishida, L. Chabanne, M. Antonietti, M. Shalom, Langmuir 30 (2014) 447-451. DOI PMID
[38]	H.L. Li, F.P. Li, Z.Y. Wang, Y.C. Jiao, Y.Y. Liu, P. Wang, X.Y. Zhang, X.Y. Qin, Y. Dai, B.B. Huang, Appl. Catal. B 229 (2018) 114-120. DOI URL
[39]	S. Dolai, J. Barrio, G. Peng, A. Grafmueller, M. Shalom, Nanoscale 11 (2019) 5564-5570. DOI URL
[40]	H. Wang, Y. Bian, J. Hu, L. Dai, Appl. Catal. B 238 (2018) 592-598. DOI URL
[41]	K. Wang, Q. Li, B. Liu, B. Cheng, W. Ho, J. Yu, Appl. Catal. B 176 (2015) 44-52.
[42]	M. Shalom, M. Guttentag, C. Fettkenhauer, S. Inal, D. Neher, A. Llobet, M. Antonietti, Chem. Mater. 26(2014) 5812-5818. DOI URL
[43]	Q. Liang, Z. Li, Y. Bai, Z.H. Huang, F. Kang, Q.H. Yang, Small 13 (2017), 1603182. DOI URL
[44]	Q. Qiao, W.Q. Huang, Y.Y. Li, B. Li, W. Hu, W. Peng, X. Fan, G.F. Huang, J. Mater. Sci. 53(2018) 15882-15894. DOI URL
[45]	Y.Y. Li, Y. Si, E.X. Han, W.Q. Huang, W.Y. Hu, A.L. Pan, G.F. Huang, J. Phys, D-Appl. Phys. 53(2020), 015502. DOI URL
[46]	Y. Li, X. Li, H. Zhang, J. Fan, Q. Xiang, J. Mater. Sci 56(2020) 69-88.
[47]	J. Cao, C. Pan, Y. Ding, W. Li, K. Lv, H. Tang. J. Environ. Chem. Eng. 7(2019), 102984. DOI URL
[48]	X. Song, X. Li, X. Zhang, Y. Wu, C. Ma, P. Huo, Y. Yan, Appl. Catal. B 268 (2020), 118736. DOI URL
[49]	F.M. Wu, N. Wang, S.F. Pang, Y.H. Zhang, Spectrochim. Acta Part A 208 (2019) 255-261. DOI URL
[50]	S. Guo, Z. Deng, M. Li, B. Jiang, C. Tian, Q. Pan, H. Fu, Angew. Chem. Int. Ed. 55(2016) 1830-1834. DOI URL
[51]	L. Jiang, X. Yuan, G. Zeng, X. Chen, Z. Wu, J. Liang, J. Zhang, H. Wang, H. Wang, ACS Sustainable Chem. Eng. 5(2017) 5831-5841. DOI URL
[52]	Y. Li, S. Wang, W. Chang, L. Zhang, Z. Wu, S. Song, Y. Xing, J. Mater. Chem 7(2019) 20640-20648.
[53]	S. Zhao, Y.W. Zhang, Y.M. Zhou, Y.Y. Wang, K.B. Qiu, C. Zhang, J.S. Fang, X.L. Sheng, Carbon 126 (2018) 247-256. DOI URL
[54]	Z. Tong, D. Yang, X. Zhao, J. Shi, F. Ding, X. Zou, Z. Jiang, Chem. Eng. J. 337(2018) 312-321. DOI URL
[55]	W. Wang, Z. Zeng, G. Zeng, C. Zhang, R. Xiao, C. Zhou, W. Xiong, Y. Yang, L. Lei, Y. Liu, D. Huang, M. Cheng, Y. Yang, Y. Fu, H. Luo, Y. Zhou, Chem. Eng. J. 378(2019), 122132. DOI URL
[56]	F. Dong, Z. Zhao, T. Xiong, Z. Ni, W. Zhang, Y. Sun, W.K. Ho, ACS Appl. Mater. Interfaces 5 (2013) 11392-11401. DOI URL
[57]	X. Chen, R. Shi, Q. Chen, Z. Zhang, W. Jiang, Y. Zhu, T. Zhang, Nano Energy 59 (2019) 644-650. DOI URL
[58]	B. Li, Y. Si, B.X. Zhou, Q. Fang, Y.Y. Li, W.Q. Huang, W. Hu, A. Pan, X. Fan, G.F. Huang, ACS Appl. Mater. Interfaces 11 (2019) 17341-17349. DOI URL
[59]	E.X. Han, Y.Y. Li, Q.H. Wang, W.Q. Huang, L. Luo, W. Hu, G.F. Huang, J. Mater. Sci 35(2019) 2288-2296.
[60]	H.W. Zhang, Y.Y. Li, W.Q. Huang, B.X. Zhou, S.F. Ma, Y.X. Lu, A.L. Pan, G.F. Huang, Carbon 148 (2019) 231-240. DOI
[61]	Y. Cui, M. Li, H. Wang, C. Yang, S. Meng, F. Chen, Sep. Purif. Technol. 199(2018) 251-259. DOI URL
[62]	L. Luo, H.W. Zhang, E.X. Han, B.X. Zhou, W.Q. Huang, W. Hu, G.F. Huang, J. Chem. Technol 95(2019) 758-769.
[63]	T. Ma, J. Bai, Q. Wang, C. Li, Dalton Trans. 47(2018) 10240-10248. DOI URL
[64]	W.D. Oh, L.W. Lok, A. Veksha, A. Giannis, T.T. Lim, Chem. Eng. J. 333(2018) 739-749. DOI URL
[65]	Y.Y. Li, B.X. Zhou, H.W. Zhang, S.F. Ma, W.Q. Huang, W. Peng, W. Hu, G.F. Huang, Nanoscale 11 (2019) 6876-6885. DOI URL
[66]	Y. Tang, H. Zhou, K. Zhang, J. Ding, T. Fan, D. Zhang, Chem. Eng. J. 262(2015) 260-267. DOI URL