Improved photocatalytic activity of surface charge functionalized ZnO nanoparticles using aniline

doi:10.1016/j.jmst.2020.09.041

Abstract

Abstract:

Functionalization of aniline molecules on zinc oxide (ZnO) nanoparticles is reported using a simple impregnation technique. Functionalized ZnO samples were systematically characterized based on morphology, surface and optical properties, and photocatalytic performance towards methyl orange (MO). Aniline functionalization increased the surface charge of the modified ZnO. Compared to pristine ZnO, the aniline-functionalized ZnO yielded faster photodegradation of MO, degrading 98.29 % of MO in 60 min and superoxide radicals were the major species during the MO photodegradation reaction. These results indicate that the improvement of photocatalytic degradation could be attributed to opposite charge-induced surface adsorption. Hence, protonated amine as a positively charged molecule was expected to increase the surface adsorption of MO (as an anionic dye) on ZnO nanoparticles surfaces, thereby increasing their photocatalytic degradation performance.

Key words: Photocatalysts, Surface charge, ZnO, Aniline, Methyl orange

Chatchai Rodwihok, Korakot Charoensri, Duangmanee Wongratanaphisan, Won Mook Choi, Seung Hyun Hur, Hyun Jin Park, Jin Suk Chung. Improved photocatalytic activity of surface charge functionalized ZnO nanoparticles using aniline[J]. J. Mater. Sci. Technol., 2021, 76: 1-10.

Figures/Tables 13

Fig. 1. FE-SEM images of (a) ZnO, (b) ZnO/An1, (c) ZnO/An2 and (d) ZnO/An3.

Fig. 2. EDS-mapping images of pristine ZnO and aniline functionalized ZnO.

Table 1 Summaries of crystal information and surface charge.

Samples	XRD			Zetasizer Nano ZS
	Lattice constant (Å)		Crystal size (nm)	Average size (nm)	Zeta potential (mV)
	a	c
ZnO	3.253	5.213	95.08 ± 5.52	198.23 ± 7.22	17.50 ± 0.46
ZnO/An1	3.253	5.213	84.00 ± 6.90	236.95 ± 6.86	22.63 ± 0.31
ZnO/An2	3.253	5.213	92.96 ± 5.76	262.69 ± 5.54	24.77 ± 0.31
ZnO/An3	3.253	5.213	89.85 ± 8.06	246.20 ± 5.69	25.87 ± 0.55

Fig. 3. HR-TEM images of (a) ZnO, (b) ZnO/An1, (c) ZnO/An2 and (d) ZnO/An3.

Fig. 4. XRD patterns of ZnO and functionalized ZnO samples.

Fig. 5. FT-IR of ZnO and functionalized ZnO samples; (a) 400-4000?cm-1, (b) C-N stretching region: 1350-1400?cm-1, and (c) N-H bend vibrational region: 1500-2000?cm-1.

Fig. 6. XPS of ZnO and ZnO/An3 samples; (a) XPS Survey spectrum, (b) deconvoluted XPS N 1s and (c) XPS Zn 2p.

Fig. 7. UV-vis spectra of ZnO and functionalized ZnO samples; (inset) optical energy bandgap.

Table 2 Optical energy band gap and photocatalytic performance.

Sample	UV-vis	Photocatalytic performance
	Eg (eV)	MO degradation in 60 min	kc (min^-1)	R2	MO mineralization in 60 min
ZnO	3.222	39.96 %	0.008	0.9516	22.19%
ZnO/An1	3.214	74.09%	0.021	0.9635	27.12%
ZnO/An2	3.219	96.63%	0.054	0.9948	38.21%
ZnO/An3	3.215	98.29 %	0.066	0.9975	44.07%

Fig. 8. (a) VB-XPS spectra and (b) energy band edge position of pristine ZnO and aniline functionalized ZnO.

Fig. 9. The MO photodegradation process of (a) ZnO, (b) ZnO/An1, (c) ZnO/An2, and (d) ZnO/An3.

Fig. 10. (a) Photodegradation percentage, and (b) kinetic adsorption curves during MO photodegradation of ZnO and functionalized ZnO samples.

Fig. 11. (a) Degradation and mineralization percentage of MO, (b) PL spectra of pristine ZnO and aniline functionalized ZnO catalyst, (c) photodegradation percentage of MO in the absence and presence of various scavenges (EDTA, p-Benzoquinone, and iso-propanol) under fluorescent illumination (Catalyst: ZnO/An3 sample) and (d) the adsorption process of MO (anionic dye) on aniline functionalized ZnO.

References 43

[1]	C. Rodwihok, D. Wongratanaphisan, T.V. Tam, W.M. Choi, S.H. Hur, J.S. Chung, Applied Sciences-Basel, 10 (2020), pp. 1697-1711
[2]	M. Kumar, R. Tamilarasan, Polish J. Chem. Technol., 15 (2013), pp. 29-39 DOI URL
[3]	J.S. Chang, J. Strunk, M.N. Chong, P.E. Poh, J.D. Ocon, J. Hazard. Mater., 381 (2020), p. 120958 DOI URL
[4]	J. Kaur, S. Bansal, S. Singhal, Physica B-Condensed Matter, 416 (2013), pp. 33-38 DOI URL
[5]	A. Paliwal, A. Sharma, M. Tomar, V. Gupta, Sensors and Actuators B-Chemical, 250 (2017), pp. 679-685 DOI URL
[6]	Y. Hou, A.H. Jayatissa, Prog. Natl. Sci.-Mater.Int., 27 (2017), pp. 435-442
[7]	V.M. Latyshev, T.O. Berestok, A.S. Opanasyuk, A.S. Kornyushchenko, V.I. Perekrestov, Solid State Sci., 67 (2017), pp. 109-113 DOI URL
[8]	W. Ponhan, S. Phadungdhitidhada, S. Choopun, Mater. Today Proc., 4 (2017), pp. 6342-6348
[9]	A. Hezam, K. Namratha, Q.A. Drmosh, B.N. Chandrashekar, G.K. Jayaprakash, C. Cheng, S.S. Swamy, K. Byrappa, Ceram. Int., 44 (2018), pp. 7202-7208 DOI URL
[10]	T. Marimuthu, A. Narayanasamy, T. Rangasamy, J. Alloys. Compd., 693 (2016), pp. 1011-1019 DOI URL
[11]	A.F.V. da Fonseca, R.L. Siqueira, R. Landers, J.L. Ferrari, N.L. Marana, J.R. Sambrano, F.D. La Porta, M.A. Schiavon, J. Alloys. Compd., 739 (2018), pp. 939-947 DOI URL
[12]	T. Voss, S.R. Waldvogel, Mater. Sci. Semicond. Process., 69 (2017), pp. 52-56 DOI URL
[13]	M. Liu, K. Li, F.M. Kong, J. Zhao, Q.Y. Yue, X.J. Yu, Photon. Nanostruct.-Fund. Appl., 16 (2015), pp. 9-15 DOI URL
[14]	T. Iqbal, A. Aziz, M.A. Khan, S. Andleeb, H. Mahmood, A.A. Khan, R. Khan, M. Shafique, Mater. Sci. Eng. B-Adv.Funct. Solid-State Mater., 228 (2018), pp. 153-159
[15]	G. Singh, E. Joyce, J. Beddow, T. Mason, World J. Microbiol. Biotechnol., 2 (2012), pp. 106-120
[16]	P. Panchal, D.R. Paul, A. Sharma, P. Choudhary, P. Meena, S.P. Nehra, J. Colloid Interface Sci., 563 (2020), pp. 370-380 DOI URL
[17]	T. Lv, L.K. Pan, X.J. Liu, T. Lu, G. Zhu, Z. Sun, J. Alloys. Compd., 509 (2011), pp. 10086-10091 DOI URL
[18]	H. Jung, T.T. Pham, E.W. Shin, Appl. Surf. Sci., 458 (2018), pp. 369-381 DOI URL
[19]	J.J. He, C.G. Niu, C. Yang, J.D. Wang, X.T. Su, RSC Adv., 4 (2014), pp. 60253-60259 DOI URL
[20]	C. Rodwihok, S. Choopun, P. Ruankham, A. Gardchareon, S. Phadungdhitidhada, D. Wongratanaphisan, Appl. Surf. Sci., 477 (2019), pp. 159-165 DOI URL
[21]	S. Sucharitakul, R. Panyathip, S. Choopun, Materials, 11 (2018), pp. 1360-1374 DOI URL
[22]	C. Khaywimut, C. Bhoomanee, S. Choopun, P. Ruankham, Mater. Today Proc., 17 (2019), pp. 1231-1239
[23]	M. Samadi, M. Zirak, A. Naseri, E. Khorashadizade, A.Z. Moshfegh, Thin Solid Films, 605 (2016), pp. 2-19 DOI URL
[24]	C.B. Ong, L.Y. Ng, A.W. Mohammad, Renew. Sustain.Energy Rev., 81 (2018), pp. 536-551
[25]	H. Park, Y. Park, W. Kim, W. Choi, J. Photochem. Photobiol. C-Photochem. Rev., 15 (2013), pp. 1-20 DOI URL
[26]	A. Mondal, N. Giri, S. Sarkar, S. Majumdar, R. Ray, Mater. Sci. Semicond. Process., 91 (2019), pp. 333-340 DOI URL
[27]	N.R. Khalid, A. Hammad, M.B. Tahir, M. Rafique, T. Iqbal, G. Nabi, M.K. Hussain, Ceram. Int., 45 (2019), pp. 21430-21435 DOI
[28]	A. Riaz, A. Ashraf, H. Taimoor, S. Javed, M.A. Akram, M. Islam, M. Mujahid, I. Ahmad, K. Saeed, Coatings, 9 (2019), pp. 202-217 DOI URL
[29]	M. Fu, Y.L. Li, S.W. Wu, P. Lu, J. Liu, F. Dong, Appl. Surf. Sci., 258 (2011), pp. 1587-1591 DOI URL
[30]	H. Park, W. Choi, J. Phys. Chem. B, 109 (2005), pp. 11667-11674 DOI URL
[31]	H. Park, W. Choi, Langmuir, 22 (2006), pp. 2906-2911 DOI URL
[32]	R.Q. Guan, J.X. Li, J.K. Zhang, Z. Zhao, D.D. Wang, H.J. Zhai, D.W. Sun, ACS Omega, 4 (2019), pp. 20742-20747 DOI URL
[33]	D. Dash, N.R. Panda, D. Sahu, Appl. Surf. Sci., 494 (2019), pp. 666-674 DOI URL
[34]	R. Klaysri, T. Tubchareon, P. Praserthdam, J. Ind. Eng. Chem., 45 (2017), pp. 229-236 DOI URL
[35]	F. Cheng, S.M. Sajedin, S.M. Kelly, A.F. Lee, A. Kornherr, Carbohydr. Polym., 114 (2014), pp. 246-252 DOI PMID
[36]	T. Santhaveesuk, K. Shimanoe, K. Suematsu, S. Choopun, Phys. Status Solidi, 215 (2018), p. 1700784
[37]	C. Rodwihok, D. Wongratanaphisan, Y.L. Thi Ngo, M. Khandelwal, S.H. Hur, J.S. Chung, Nanomaterials, 9 (2019), p. 1441 DOI URL
[38]	H.G. Yu, P. Xiao, J. Tian, F.Z. Wang, J.G. Yu, ACS Appl. Mater. Interf., 8 (2016), pp. 29470-29477 DOI URL
[39]	R. Koferstein, L. Jager, S.G. Ebbinghaus, Solid State Ion., 249 (2013), pp. 1-5
[40]	H.P. Wu, S.L. Lin, C.X. Chen, W. Liang, X.Y. Liu, H.X. Yang, Mater. Res. Bull., 83 (2016), pp. 434-441 DOI URL
[41]	T.-D. Nguyen-Phan, E.J. Kim, S.H. Hahn, W.-J. Kim, E.W. Shin, J. Colloid Interface Sci., 356 (2011), pp. 138-144 DOI PMID
[42]	T.T. Pham, N.H. Chinh, H.J. Lee, T.D. Nguyen-Phan, T.H. Son, C.K. Kim, E.W. Shin, Ceram. Int., 41 (2015), pp. 11184-11193 DOI URL
[43]	S. Luo, C. Liu, S. Zhou, W. Li, C. Ma, S. Liu, W. Yin, H.J. Heeres, W. Zheng, K. Seshan, S. He, Chemosphere, 261 (2020), p. 127731 DOI URL