Fabrication and Photocatalytic Activity of Cu2O Nanobelts on Nanoporous Cu Substrate

doi:10.1007/s40195-018-0813-6

Acta Metallurgica Sinica (English Letters) ›› 2019, Vol. 32 ›› Issue (1): 63-73.DOI: 10.1007/s40195-018-0813-6

• Orginal Article • Previous Articles Next Articles

Fabrication and Photocatalytic Activity of Cu₂O Nanobelts on Nanoporous Cu Substrate

Yun Li¹, Chuan Ji¹, Yu-Chen Chi¹, Zhen-Hua Dan², Hai-Feng Zhang³, Feng-Xiang Qin¹

1.School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
2.College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China
3.Shengyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Science, Shengyang 110016, China

Received:2018-07-19 Revised:2018-08-04 Online:2019-01-10 Published:2019-01-18
Contact: Dan Zhen-Hua,Qin Feng-Xiang
About author:
Author brief introduction:Dao-Kui Xu Professor of IMR, CAS, and “Young Merit Scholar” of Corrosion Center in the Institute of Metal Research (IMR), Chinese Academy of Sciences (CAS). He achieved Ph.D. degree from IMR, CAS, in 2008, during which he obtained “Chinese Academy of Sciences-BHP Billiton” Scholarship award, “Shi Changxu” Scholarship award and “Zhu-LiYueHua” Excellent Doctorate Student Scholarship of Chinese Academy of Sciences. He worked as a Research Fellow in ARC Center of Excellence, Design of Light Metals, Department of Materials Engineering, Monash University, Australia (2008.10-2011.10). He published more than 60 peer-reviewed scientific papers, attended 20 invited lectures and holds seven patents. His papers were cited more than 1200 times. His research interests mainly include: (1) fatigue behavior and fracture toughness of light metals, such as Mg, Al and Ti alloys; (2) effects of alloying, heat treatment and thermomechanical processes on the microstructural evolution and mechanical improvement of light metals; (3) corrosion, stress corrosion cracking and corrosion fatigue behavior of lightweight alloys; and (4) design of new lightweight alloys with a good balance of properties in terms of mechanical property and corrosion resistance.

Abstract

Abstract:

In this paper, we report the fabrication of the photocatalysts composed of Cu₂O nanobelts and nanoporous Cu (NP Cu) substrate, which is obtained by soaking the NP Cu in dehydrated ethanol. The NP Cu substrate is achieved by dealloying of Ti_40.6Zr_9.4Cu_40.6Ni_6.3Sn_3.1 amorphous ribbons in HF solutions. The dealloying process is considered to be a thermally activated process, obeying the Arrhenius law. The surface diffusivity increases with increasing dealloying temperature and concentration of HF solutions. The activation energy of the diffusion of Cu adatoms is estimated to be 76.4 kJ/mol. The Cu₂O nanobelts with the width of 10-15 nm and the length of about 1 μm are formed on the surface of NP Cu after immersion in dehydrated ethanol. The photocatalysts of Cu₂O on nanoporous Cu exhibit superior photocatalytic activity toward the degradation of methyl orange and methylene blue under the irradiation of the sunlight due to the coexistence of Cu₂O semiconductor nanobelts and large amount of heterojunctions as flowing path for photoelectrons.

Key words: Nanoporous Cu, Dealloying, Cu₂O, Photocatalytic activity

Yun Li, Chuan Ji, Yu-Chen Chi, Zhen-Hua Dan, Hai-Feng Zhang, Feng-Xiang Qin. Fabrication and Photocatalytic Activity of Cu₂O Nanobelts on Nanoporous Cu Substrate[J]. Acta Metallurgica Sinica (English Letters), 2019, 32(1): 63-73.

Figures/Tables 12

Fig. 1 XRD patterns of the as-spun Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1 amorphous ribbons a and dealloyed ribbons after dealloying in 0.1 M HF at 313 K b, 333 K c, as well as in 0.2 M HF at 333 K d for 4 h

Fig. 2 SEM images of Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1 ribbons dealloyed in 0.1 M HF solution at 313 K a, 0.1 M HF solution at 333 K b, in 0.2 M HF solution at 333 K c after 2 h (1), 4 h (2), 6 h (3), 8 h (4)

Fig. 3 The mean pore size, d, and the mean ligament size, l, of dealloyed Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1 ribbons as a function of time, in 0.1 M and 0.2 M HF solutions at different temperatures

Fig. 4 The atomic percentages of the elements of dealloyed Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1 ribbons as a function of time, in 0.1 M and 0.2 M HF solutions at different temperatures

Table 1 Mean pore size, lattice constant and the surface diffusivity of NP Cu dealloyed by Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1 ribbons

HF concentration (M)	Temperature (K)	d(t) (nm)	α (nm)	D_s (10^-19 m² s^-1)
0.1 M HF	313	42.3	0.361616	9.87
	333	58.2	0.361643	37.00
	348	87.8	0.361551	201.00
0.2 M HF	333	99.2	0.362073	314.00

Fig. 5 Arrhenius plot of natural logarithm of surface diffusivity, ln (Ds), of dealloyed Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1 ribbons versus the reciprocal of dealloying temperatures, 1000/T, after dealloying in 0.1 M HF solution for 4 h

Fig. 6 SEM images of Cu2O obtained after soaking in dehydrated ethanol for 1 days a, b, 2 days c, d, 3 days e, f

Fig. 7 Relationship between width, coverage fraction of Cu2O nanobelts and NP Cu after immersion in dehydrated ethanol for different times

Fig. 8 XPS spectra of the Cu 2pa, Sn 3db,Ni 2pc, O 1sd in the dealloyed samples after soaking in dehydrated ethanol for 3 days

Fig. 9 UV-Vis spectra of MO a, b, MB solutions c, d degraded by Cu2O@NP Cu

Table 2 Degradation efficiency and reaction rate constant of MO and MB solutions degraded by Cu2O@NP Cu soaking in ethanol for different days

Forming time for Cu₂O nanobelts (days)	Degradation efficiency (%)		K_obs (min^-1)
Forming time for Cu₂O nanobelts (days)	MO	MB	MO	MB
0	7.1	7.4	-	-
1	88.0	69.1	-	-
2	92.0	80.1	-	-
3	93.6	95.9	0.0624	0.0544

Fig. 10 UV-Vis spectra of: MO a; MB b versus time during the degradation process by Cu2O@NP Cu catalysts. The inset is the normalized concentration (Ct/C0) versus time of: MO and MB solutions

References

[1]	J. Erlebacher, M.J. Aziz, A. Karma, N. Dimitrov, K. Sieradzki, Nature 410, 450 (2001)
[2]	Y. Ding, Y.J. Kim, J. Erlebacher, Adv. Mater. 16, 1897(2004)
[3]	Z.H. Zhang, Y. Wang, Z. Qi, W.H. Zhang, J.Y. Qin, J. Frenzel, J. Phys. Chem.C 113, 12629 (2009)
[4]	S.H. Joo, S.J. Choi, I. Oh, J. Kwak, Z. Liu, O. Terasaki, R. Ryoo, Nature 412, 169 (2001)
[5]	L.H. Qian, W. Shen, B. Das, B. Shen, G.W. Qin, Chem. Phys. Lett. 479, 259(2009)
[6]	D.V. Pugh, A. Dursun, S.G. Corcoran, J. Mater. Res. 18, 216(2002)
[7]	W.B. Liu, S.C. Zhang, N. Li, J.W. Zheng, Y.L. Xing, J. Electrochem. Soc. 157, D666(2010)
[8]	X.L. Tan, Y.Y. Tang, Y. Liu, J.S. Luo, K. Li, X.B. Liu, Mater. Rev. 23, 68(2009)
[9]	W.Y. Zhang, Z.P. Xi, M. Fang, Y.N. Li, G.Z. Li, L. Zhang, Rare Metal Mater.Eng. 37, 1129(2008)
[10]	A. Dursun, D.V. Pugh, S.G. Corcoran, J. Electrochem. Soc. 150, B355(2003)
[11]	Z.C. Liu, S. Koh, C.F. Yu, P. Strasser, J. Electrochem. Soc. 154, B1192(2007)
[12]	A. Dursun, D.V. Pugh, S.G. Corcoran, J. Electrochem. Soc. 152, B65(2005)
[13]	W.B. Liu, S.C. Zhang, N. Li, J.W. Zheng, Y.L. Xing, Corros. Sci. 53, 809(2011)
[14]	J.R. Hayes, A.M. Hodge, J. Biener, A.V. Hamza, K. Sieradzki, J. Mater. Res. 21, 2611(2006)
[15]	F.U. Renner, Y. Gründer, P.F. Lyman, J. Zegenhagen, Thin Solid Films 515, 5574 (2007)
[16]	S.L. Zhu, J.L. He, X.J. Yang, Z.D. Cui, L.L. Pi, Electrochem. Commun. 13, 250(2011)
[17]	Z.H. Dan, F.X. Qin, Y. Sugawara, I. Muto, A. Makino, N. Hara, Mater. Lett. 94, 128(2013)
[18]	J.S. Yu, Y. Ding, C.X. Xu, A. Inoue, T. Sakurai, M.W. Chen, Chem. Mater. 20, 4548(2008)
[19]	N. Weng, F. Wang, F.X. Qin, W.Y. Tang, Z.H. Dan, Materials 10, 1001 (2017)
[20]	I. Grozdanov, Mater. Lett. 19, 281(1994)
[21]	Y.W. Tang, Z.G. Chen, Z.J. Jia, L.S. Zhang, J.L. Li, Mater. Lett. 59, 434(2005)
[22]	B. Zhou, Z.G. Liu, H.X. Wang, W.H. Su, Catal. Lett. 132, 75(2009)
[23]	T.Y. Kou, C.H. Jin, C. Zhang, Z.H. Zhang, RSC Adv. 2, 12636(2012)
[24]	L.F. Li, W.X. Zhang, C. Feng, X.W. Luan, J. Jiang, M.L. Zhang, Mater. Lett. 107, 123(2013)
[25]	X.Q. Li, T. Fang, Y.S. Luo, J.L. Li, Chemistry 69, 290 (2006)
[26]	Z.H. Dan, J.F. Lu, F. Li, F.X. Qin, H. Chang, Nanomaterials 8, 18 (2018)
[27]	Z.H. Dan, Y.L. Yang, F.X. Qin, H. Wang, H. Chang, Materials 11, 446 (2018)
[28]	J.M. Dona, J. González-Velasco, J. Phys. Chem. 97, 4714(1993)
[29]	F. Montalenti, R. Ferrando, Phys. Rev. B Condens. Matter 59, 5881 (1999)
[30]	E.G. Seebauer, C.E. Allen, Prog. Surf. Sci. 49, 265(1995)
[31]	Z.H. Dan, F.X. Qin, S. Yamaura, Y. Sugawara, I. Muto, N. Hara, J. Alloys Compd. 581, 567(2013)
[32]	F.X. Qin, Y. Li, Y.C. Chi, Z.H. Dan, H.F. Zhang, J. Mater. Sci., under review
[33]	F. Wang, H. Wang, H.F. Zhang, Z.H. Dan, N. Weng, W.Y. Tang, F.X. Qin, J. Non-Cryst.Solids 491, 34 (2018)
[34]	M.J. Mandry, G. Rosenblatt, J. Electrochem. Soc. 119, 29(1972)
[35]	I. Medved, A. Trnik, R. Cerny, Jaids-J. Acq. Imm. Def. 7, 86(2013)
[36]	Y.W. Tan, X.Y. Xue, Q. Peng, Y.D. Li, Nano Lett. 7, 3723(2007)
[37]	C.H. Kuo, C.H. Chen, M.H. Huang, Adv. Funct. Mater. 17, 3773(2007)
[38]	H. Xu, W.Z. Wang, W. Zhu, J. Phys. Chem.B 110, 13829 (2006)
[39]	E. Ko, J. Choi, K. Okamoto, Y. Taket, J. Lee, ChemPhysChem 7, 1505 (2006)
[40]	S. Kenane, L. Piraux, J. Mater. Res. 17, 401(2002)
[41]	B.L. Tang, G.H. Jiang, Z. Wei, X. Li, X.H. Wang, T.T. Jiang, Acta Metall. Sin. (Engl. Lett.). 27, 124(2014)
[42]	W.B. Liu, L. Chen, X. Dong, J.Z. Yan, N. Li, S.Q. Shi, S.C. Zhang, Sci. Rep. 6, 36084(2016)

Fabrication and Photocatalytic Activity of Cu₂O Nanobelts on Nanoporous Cu Substrate

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References

Related Articles 7

Recommended Articles

Metrics

Comments

[1]	K. P. Ganesan, N. Anandhan, T. Marimuthu, R. Panneerselvam, A. Amali Roselin. Effect of Deposition Potential on Synthesis, Structural, Morphological and Photoconductivity Response of Cu₂O Thin Films by Electrodeposition Technique [J]. Acta Metallurgica Sinica (English Letters), 2019, 32(9): 1065-1074.
[2]	Yibin RenEmail author, Jun Li, Ke Yang. Preliminary Study on Porous High-Manganese 316L Stainless Steel Through Physical Vacuum Dealloying [J]. Acta Metallurgica Sinica (English Letters), 2017, 30(8): 731-734.
[3]	Harshad R. Patil, Z. V. P. Murthy. Vanadium-Doped Magnesium Oxide Nanoparticles Formation in Presence of Ionic Liquids and Their Use in Photocatalytic Degradation of Methylene Blue [J]. Acta Metallurgica Sinica (English Letters), 2016, 29(3): 253-264.
[4]	Yi-Bin Ren,Yu-Xia Sun,Ke Yang. Study on Micron Porous Copper Prepared by Physical Vacuum Dealloying [J]. Acta Metallurgica Sinica (English Letters), 2016, 29(12): 1144-1147.
[5]	Ramakrishna Dadigala, Bhagavanth Reddy Gangapuram, Rajkumar Bandi, Ayodhya Dasari, Veerabhadram Guttena. Synthesis and Characterization of C-TiO₂/FeTiO₃ and CQD/C-TiO₂/FeTiO₃ Photocatalysts with Enhanced Photocatalytic Activities Under Sunlight Irradiation [J]. Acta Metallurgica Sinica (English Letters), 2016, 29(1): 17-27.
[6]	K. Lingaraju, H. Raja Naika, K. Manjunath, G. Nagaraju, D. Suresh, H. Nagabhushana. Rauvolfia serpentina-Mediated Green Synthesis of CuO Nanoparticles and Its Multidisciplinary Studies [J]. Acta Metallurgica Sinica (English Letters), 2015, 28(9): 1134-1140.
[7]	Y.Zeng, J.T.Liu, W.J.Qian, J.H.Gao. PHOTOCATALYTIC PERFORMANCE OF PLASMA SPRAYED TiO2-ZnFe2O4 COATINGS [J]. Acta Metallurgica Sinica (English Letters), 2005, 18(3): 363-368 .