TAP CHI HOA HOC
DOL 10.15625/0866-7144.2015-0083
T. 53(1)32-34 THANG 2 NAM 2015
NGHIEN CLPU T 6 N G HOP D 6 N G KIM LOAI CO KICH IHUOC NANO B A N G PHU'ONG PHAP KHIJ GLYXERAT TRONG VI SONG
Dinh Xu5n Lgc'"^, Nguyen Hoang Dny^, Pham Duy K h a n h \ Lirong Thi Bich^ Ngo Trung Kien^va Nguyin FhwoTig Tiing
' Vi^n Khoa hgc Vgt lieu, Vi^n Hdn lam Khoa hgc vd Cdng nghi Viet Nam
^Viin Khoa hgc Vgt lieu ifng dung, Vien Hdn Idm Khoa hgc vd Cong nghe Viet Nam Din Tda sogn 1-7-2014; Chip nhan dang 13-2-2015
Abstract
Copper metal materials with nano size were successfiilly synthesized by copper glycerate reduction method in microwave. The technical analysis of morphology, structure and infrared spectroscopy of the materials were carried out The morphology and the structure of the prepared materials were characterized by field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD). FESEM images and XRD pattems showed that the materials have phase single and the size of 60-100 nm. UV-VIS spectrum shows absorption peak at 595 nm.
Keywords. Copper metal, oxalate, glycine, UV-VIS spectmm, microwave.
I.GI61 THIEU
Vat li?u ddng kim logi d kich thude nano da dugc quan tim nghien ciiu vi ddng la mgt trong nhung kim loai quan frgng dugc iing dyng nhilu frong eac nganh ky thugt. Ngay nay ddng kim logi cd kich thuoc nano da dugc dua vao nhieu iing dung nhu: sii dung lam chit xuc tie, frong cac thiit bj quang hge, hay sii dyng trong cac linh kien dien tii...[l]. Nano ddng dugc tdng hgp bing nhilu phuong phap khac nhau nhu: phan hiiy nhi?t [2], biic xa [3], phdng di^n hd quang [4], ky thuat vi nhd [5], ky thuat sieu tdi hgn [6], dung ky thugt lade [7].... Vi?c tdng hgp ddng kim loai cd kich thuoc nano kha de vi phin iing xay ra rit nhanh va em diu nhung cho hieu suit phin iing eao, vi vay hat nano dong cd gia thanh kha re. Do dd day la mgt trong nhihig uu diem Idn ciia kim loai ddng cd kich thude nano frong viec iing dung diing dl thay thi cho cac kim loai quy hiem nhu vang va bgc.
Da tdng hgp thanh cdng vat lifu kim logi ddng cd kich thude nano bing phuong phap khir ddng glyxerat frong vi sdng d nhiet dp ldn hon 200 "C frong khoang thdi gian 5 phut. Day la phuong phap hda udt diing glyxerin vdi sy hd frg ciia polyme:
polyvinyl pyrroiido (PVP) lam mdi trudng on dinh va tao kich thude hgt.
2. THU'C NGHIEM 2.1. Hda chat
Ddng sunfat (CUSO4.5H2O), glyxerin, axeton, axit oxalic (C2H2O4.2H2O), polyvinyl pyrroHdo (PVP), tit c i cac hda chit fren cd do sach PA.
2.2. Tong hop vat lieu
Can lugng mudi CUSO4.5H2O (ddng sunfat) va C2H2O4.2H2O (axit oxalic) vdi ty le moi da tinh sin, sau dd hda tan hai mudi nay vao trong nude cit. Vira khuay viia trgn hai dung dich mudi nay vao nhau de tgo thanh ket tiia oxalat ddng mau xanh cdban. Tach va nia sgch ket tua oxalat ddng nhilu lin bing nude cit, siy khd tua d nhiet do 70-80 °C trong chan khdng rdi nghiin mjn. Bgt ddng oxalat da dugc nghiin min sau do lai dugc cin theo ty le moi 1:1 vdi polyme PVP va glyxerin. Giir mdi lugng 30 ml glyxerin, cho vao 50 mg ddng oxalat, va tuong ty la lugng PVP, vira khuay vira dun ndng din 90 °C cho tan hit dong oxalat frong glyxerin, tgo thanh dich co mau xanh luc nhat. Dung djch PVP trong glyxerin tao thanh dich trong suot. Them din timg lugng nhd dung djch ddng oxalat trong glyxerin vao dung dich PVP, khuay ky rdi dua vao chay vi sdng trong thdi gian 5 phut d nhiet do hon 200 T . Do nang lugng vi sdng la rit ldn, vi vgy cac moi lien kit trong phan tir glyxerat ddng cd thi bi be gay va sip xip lai nhanh chdng nen djch san phim fri mau xanh lyc frd thanh cd mau dd ddng. Cudi cung san phim dugc dem ket tiia va rira sgch nhilu lin bing each them axeton va nude cat. Ly tim kit tiia va cudi cimg dem siy san
TCHH,T 53(1), 2015
pham trong moi truong khi N; a nhiet do 70-80 "C thu dugc hot min mau do dac tnmg cua dong kim loai. Phan ihig khir d6ng (II) glyxerat dugc bieu dien nhu sau:
1) C u C j O j . a H j O f 2 C , H 5 ( 0 H ) j J S ^ C H j - 0 O - C H j
I '^Cu I
CH - o ' ' ^ O - C H f CjO,'- + 2HjO + 2H*
I 'H ii I
C H i - O " H O - C H ;
C H , - O O - C H j I ' " C u ' ' I
' ^ p - C H + CS>,' + 2HjO + 2H*
H I HO-CH2
Dinh Xuan hoc vd cdng su
2) CH
I
HCH2- OH 240°C^
Cu + 2C,H705 + 2H2O + 2H*
3. KET QUA VA T H A O LUAN
Hinh 1 la dudng nhieu xa tia X ciia vat li?u ddng kim loai cd kich thude nano dugc do fren he do nhilu xg tia X (SIEMEN-D5000) cua Vien Khoa hgc Vat lieu (vdi ngudn phat tia X la CUKQ, va >. = 0,1541 nm). Tren gian do nhilu xg tia X, quan sat thiy chi cd mgt dudng nhieu xa tia X duy nhat va phii hgp vdi the chuin sd 4-0836 eiia vit lieu ddng kim logi, chiing td vit lieu da che dugc la tinh khiet.
Tuy nhien, dudng nhilu xg kha sic net vdi do ban rdng ciia vgch phd hep, cho thay hgt vit lieu cd kich thude edn kha Idn. Tren hinh 2, inh FESEM (Hitachi-S4800) cho thiy hgt vit lieu dgng tinh the vdi kich thude khoang 50-60 nm. Cac tinh the cd dang lap phuong gidng tinh the ciia hgt NaCI va khdng ddng diu, tuy nhien cac hat tinh the da khdng bi kit dam. Nhu vay anh FESEM cho kit qui phii hgp vdi dudng nhieu xg tia X cua vit lieu.
3.1. Anh huong ciia nhiet do
Khio sit anh hudng nhiet do ciia phuong phap khli ddng glyxerat frong vi sdng len tinh chat cua ddng kim loai cho thiy: khi nhi?t dg < 200 °C djch san phim vin cdn lin nhieu ddng oxalat nen cd mau dd lin mau xanh lyc, tuong irng vdi dinh hip thu UV-VIS khoang 570 nm.
Nhi?t do tang din len 210, 220, 230 "C, mau dd ciia dich phan ling cung dam dan len, cac dinh hap thy ciing dich chuyln din vl viing budc sdng dai.
Nhiet dg phan iing dat din 240 °C, mau dd cua ddng kim loai da ro rang, khi dd dinh hap thu UV-VIS cua dong kim logi dvi tri 584 nm.
Hinh 2: Anh FESEM cua vat lieu ddng kim loai kich thude nano
Hinh 1: XRD ciia vit lieu ddng kim logi kich thude nano 3.2. Anh hudng cua nong do (PVP)
Anh hudng cua ndng do polyme: polyvinyl pyrroiido (PVP) lam mdi trudng dn djnh va tgo kich thude hgt len hat ddng kim logi cung da dugc chiing tdi khao sat (bang 1).
Bdng I: Ty le ndng do polyme PVP/ddng oxalat Mau
Ml M2 M3 M4
Tyle PVP/CuQO,
l/IO 1/8 1/6 1/4
Mau M5 M6 M7 M8
Tyle PVP/CuCiO,
1/2 1/1 1,25/1 1,50/1 Ket qua bang 1 cho thay, ndng do polyme tang Ien, dudng kinh ciia hat ddng kim loai cung nhd hon.
Khi ty le polyme: polyvinyl pyrroiido so vdi ddng oxalat tang len den I:I(M6), thi kich thuoc hat dong kim loai dgt khoang 50 nm. Ket qua cho thay kich thude cua hat ddng kim loai phii hgp vdi trong anh chyp FESEM.
TCHH, T. 53(1), 2015
Hinh 3: (1) Anh ciia dung dich mudi ddng oxalat, (2) Anh dung djch mudi ddng (II) glyxerat, (3) Anh dung dich vgt li^u ddng kim logi cd kich thude nano
Ket qua phin tich miu vit lieu bang phd hdng ngogi (IR) (hinh 4) ciing cho thay vat lieu chiing-tdi tao dugc bang phuong phap khii ddng (II) glyxerat frong vi sdng la ddng kim logi cd do tinh khiet cao.
Quan sat phd hdng ngoai (IR) cho thay ro viing dinh hap thu 3383,44 em"' la bien dang keo eiia lien ket O-H trong dung mdi hiiu co vi nude. Viing dinh hip thy tir 2883,90 din 2937,00 cm"' la biin dgng keo Clia lien kit C-H. Viing dinh hip thy tir 1231,42 din 1457,89 cm"' la biin dgng udn eiia lien ket C-H.
Vung dinh hip thu tir 993,19 den 1109,99 cm' la bien dang keo cua lien ket C-0. Cudi cimg viing dinh hap thy 1653,51 cm"' dugc cho la die trung ciia hat nano dong kim logi [8].
Hinh 4: Phd hdng ngogi (IR) ciia ddng kim loai cd kich thude nano
4. KET LUAN
Bang phuong phap khii dong (II) glyxerat cd su hd frg cua vi sdng, trong mdi trudng dn djnh va tgo
Nghiin ciru tdng hap ddng kim logi...
kich thuoc hgt la polyme; polyvinyl pyrroiido (PVP), chiing tdi da budc diu chi tao dugc vat Ii6u ddng kim loai cd kich thude nano. Cac ky thuat phan tich danh gia ciu friic, chyp inh vi hinh thai va do phd hip thu UV-VIS.... da budc diu cho thay ro vgt lieu cd ciu tnic dgc frung ciia kim loai ddng vdi kich thude cac hgt la 50-60 nm.
T A I L I E U THAM K H A O
1 C. Yong, B. C. Zhang, et al. Cool copper template for formation of oriented nanocrystalline a-tanlalium, J.
Phys. Chem. B, 106, 12366-12368 (2002).
2. Masoud Salavati Niasari, Fatemeh Davar, Noshin Mir. Synthesis and characterization of metallic copper nano-particles via thermal decomposition.
Polyhedron, 27, 3514-3518 (2008).
3. S. S. JoShi, et al. Synthesis of high-cocenlration cu nanoparticles in aqueous CTAB solutions, Nanosfruct. Mater., 10, 1135(1998).
4. X. F. Zhang, et al. High permittivity from defective carbon coated Cu nanocapsules, Nanotech, 18, 275701 (2007).
5. M. P. Pileni, et al. Direct relationship between shape and size of template and synthesis of copper metal particles, Adv. Mater., 11, 1358 (1999).
6. K. J. Ziegler, et al. Synthesis of organically stabilized copper nanoparticles in supercritical water, J. Am.
Chem. Soc, 123, 7797 (2001).
7 R. G. Song, et al. Investigation of metal nanoparticles produced by laser ablation and their catalytic activity, Appl. Surf. Sci. 253, 3093 (2007).
8. Thi My Dung Dang, Thi Tuyet Thu Le, Eric Fribourg-Blanc and Mau Chien Dang. Synthesis and optical properties of copper nanoparticles prepared by a chemical reduction method, Adv. Nat. Sci.:
Nanosci. Nanotechnoi. 2 (2011) 015009 (6pp).
9. Bong Kyun Park, Sunho Jeong, Dongjo Kim, Jooho Moon, Soonkwon Lim, Jang Sub Kim. Synthesis and size control of monodisperse copper nanoparticles by polyol method. J. Coll. Int. Sci., 311, 417-424 (2007).
10. Razium Ali Soomro, Syed Tufail Hussain Sherazi, et al, Synthesis of air stable copper nanoparticles and their use in catalysis. Advanced Materials Letters, Accepted Manuscript, Accepted Date 18 October (2013).
11. Azam Nasirian. Synthesis and characterization ofCu nanoparticles and studying of their catalytic properlies. Int. J. Nano. Dim., 2(3). 159-164 (2012) ISSN: 2008-8868.
12. Shaowei Chen and Jennifer M. Sommers.
Alkanethiolate Protected Copper Nanoparticles- Spectroscopy, Electrochemistry, and Solid Slate Morphological Evolution, I. Phys. Chem. BIOS, 8816-8820(2001).
Liin h?: Dinh Xuan Lgc
Vi?n Khoa hgc Vgt lieu, Vien Han lam Khoa hgc va Cdng ngh? Viet Nam
Sd 18, Hoang Qudc Viet, Qugn Ciu Giiy, Ha Ngi. E-mail: [email protected].
