伽马射线辐照制备还原氧化石墨烯
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摘要
在氮气气氛中,以乙二胺(EDA)作为自由基捕获剂,利用γ射线辐照技术在水体系中将氧化石墨烯(GO)辐照还原功能化,制备高分散性的氨基功能化还原氧化石墨烯(rGO)。考察吸收剂量(5.3、15、20、35.3 kGy)对rGO还原程度和功能化程度的影响,并通过傅里叶变换红外光谱(FT-IR)、紫外-可见光吸收光谱(UV-vis)、X射线光电子能谱(XPS)、X射线衍射(XRD)和热重分析(TGA)等方法分析GO的化学结构及还原程度。直观上看,辐照后,GO溶液逐渐呈现棕黑色,随着吸收剂量的增加,溶液颜色加深,且具有良好分散性。FT-IR谱显示,经过γ射线辐照后,初始GO上的羰基被还原去除,EDA小分子被连接到了rGO片层上。UV-vis、XPS、TGA及XRD谱图表明,随着吸收剂量的增大可以使氧化石墨烯还原程度提高,当吸收剂量35.3 kGy时,C/O可达7.21。EDA有机小分子与氧化性的·OH反应,在无氧条件下转化为还原性的自由基,参与到与GO之间的氧化还原反应中,并被接枝到GO层的表面。
We report here a rapid and cost-effective approach for reduction and functionalization of graphene oxide(GO) using ethylenediamine(EDA) in water medium by gamma-ray irradiation in a nitrogen atmosphere. The reduction degree, which can be controlled by varying the absorbed doses(5.3, 15, 20, and 35.3 kGy), was investigated in detail by ultra-violet visible(UV-vis) spectroscopy, Fourier transform infrared spectroscopy(FT-IR), X-ray diffract meter(XRD), X-ray photoelectron spectroscopy(XPS), and thermogravimetric analysis(TGA). It was found that the GO dispersion changed from yellow to black with increasing absorbed doses. The results of FT-IR, UV-vis, TGA, and XPS demonstrated that the reduction degree increased with absorbed dose and modification of GO with N-H from EDA molecules occurred. The rGO dispersion in water was stable without precipitate. The ratio of C/O reached 7.21 in rGO-at 35.3 kGy. In addition, a reduction mechanism for determining interactions among the EDA molecules, active radicals from the radiolysis of water, oxygen-containing groups on GO sheets, and some EDA molecules attached onto the rGO sheet because of the recombination of radicals is proposed.
We report here a rapid and cost-effective approach for reduction and functionalization of graphene oxide(GO) using ethylenediamine(EDA) in water medium by gamma-ray irradiation in a nitrogen atmosphere. The reduction degree, which can be controlled by varying the absorbed doses(5.3, 15, 20, and 35.3 kGy), was investigated in detail by ultra-violet visible(UV-vis) spectroscopy, Fourier transform infrared spectroscopy(FT-IR), X-ray diffract meter(XRD), X-ray photoelectron spectroscopy(XPS), and thermogravimetric analysis(TGA). It was found that the GO dispersion changed from yellow to black with increasing absorbed doses. The results of FT-IR, UV-vis, TGA, and XPS demonstrated that the reduction degree increased with absorbed dose and modification of GO with N-H from EDA molecules occurred. The rGO dispersion in water was stable without precipitate. The ratio of C/O reached 7.21 in rGO-at 35.3 kGy. In addition, a reduction mechanism for determining interactions among the EDA molecules, active radicals from the radiolysis of water, oxygen-containing groups on GO sheets, and some EDA molecules attached onto the rGO sheet because of the recombination of radicals is proposed.
引文
1 Rao C N R,Sood A K,Subrahmanyam K S,et al,Graphene:the new two-dimensional nanomaterial[J].Angewandte Chemie International Edition,2009,48(42):7752-7777.DOI:10.1002/anie.200901678.
2 Shen J,Hu Y,Shi M,et al,Fast and facile preparation of graphene oxide and reduced graphene oxide nanoplatelets[J].Chemistry of Materials,2009,21(15):3514-3520.DOI:10.1021/cm901247t.
3 Hummers W S,Offeman R E.Preparation of graphitic oxide[J].Journal of the American Chemical Society,1958,80:1339.DOI:10.1021/ja01539a017.
4 Park S,Ruoff R S.Chemical methods for the production of graphenes[J].Nature Nanotech,2009,4:217-224.DOI:10.1038/nnano.2009.58.
5 Shin H J,Kim K K,Benayad A,et al.Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance[J].Advanced Functional Materials,2009,19(12):1987-1992.DOI:10.1002/adfm.200900167.
6 Wang H,Robinson J T,Li X,et al.Solvothermal reduction of chemically exfoliated graphene sheets[J].Journal of the American Chemical Society,2009,131(29):9910-9911.DOI:10.1021/ja904251p.
7 Zhang B,Li L,Wang Z,et al.Radiation induced reduction:an effective and clean route to synthesize functionalized graphene[J].Journal of Materials Chemistry,2012,22(16):7775-7781.DOI:10.1039/C2JM16722K.
8 Kumar P,Das B,Chitara B,et al.Novel radiation-induced properties of graphene and related materials[J].Macromolecular Chemistry and Physics,2012,213(10-11):1146-1163.DOI:10.1002/macp.201100451.
9 Liu H,Miao W,Yang S,et al.Controlled synthesis of different shapes of Cu2O via?-irradiation[J].Crystal Growth&Design,2009,9(4):1733-1740.DOI:10.1021/cg800703n.
10 Zhang Y,Ma H L,Zhang Q,et al.Facile synthesis of well-dispersed graphene by?-ray induced reduction of graphene oxide[J].Journal of Materials Chemistry,2012,22(26):13064-13069.DOI:10.1039/C2JM32231E.
11 Li J,Zhang B,Li L,et al.?-ray irradiation effects on graphene oxide in an ethylenediamine aqueous solution[J].Radiation Physics and Chemistry,2014,94:80-83.DOI:10.1016/j.radphyschem.2013.06.029.
12 He Y,Li J,Luo K,et al.Engineering reduced graphene oxide aerogel produced by effectiveγ-ray radiation-induced self-assembly and its application for continuous oil-water separation[J].Industrial&Engineering Chemistry Research,2016,55(13):3775-3781.DOI:10.1021/acs.iecr.6b00073
13 He Y L,Li J H,Li L F,et al.The synergy reduction and self-assembly of graphene oxide via gamma-ray irradiation in an ethanediamine aqueous solution[J].Nuclear Science and Techniques,2016,27(3):61.DOIhttps://doi.org/10.1007/s41365-016-0068-8
14张伯武,俞初红,沈蓉芳,等.伽马射线辐照技术制备石墨烯基功能材料的研究进展[J].辐射研究与辐射工艺学报,2017,35(2):020101.DOI:10.11889/j.1000-3436.2017.rrj.35.020101.ZHANG Bowu,YU Chuhong,SHEN Rongfang,et al.Progress in research on preparation of graphene-based functional materials using gamma-ray irradiation technology[J].Journal of Radiation Research and Radiation Processing,2017,35(2):020101.DOI:10.11889/j.1000-3436.2017.rrj.35.020101.
2 Shen J,Hu Y,Shi M,et al,Fast and facile preparation of graphene oxide and reduced graphene oxide nanoplatelets[J].Chemistry of Materials,2009,21(15):3514-3520.DOI:10.1021/cm901247t.
3 Hummers W S,Offeman R E.Preparation of graphitic oxide[J].Journal of the American Chemical Society,1958,80:1339.DOI:10.1021/ja01539a017.
4 Park S,Ruoff R S.Chemical methods for the production of graphenes[J].Nature Nanotech,2009,4:217-224.DOI:10.1038/nnano.2009.58.
5 Shin H J,Kim K K,Benayad A,et al.Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance[J].Advanced Functional Materials,2009,19(12):1987-1992.DOI:10.1002/adfm.200900167.
6 Wang H,Robinson J T,Li X,et al.Solvothermal reduction of chemically exfoliated graphene sheets[J].Journal of the American Chemical Society,2009,131(29):9910-9911.DOI:10.1021/ja904251p.
7 Zhang B,Li L,Wang Z,et al.Radiation induced reduction:an effective and clean route to synthesize functionalized graphene[J].Journal of Materials Chemistry,2012,22(16):7775-7781.DOI:10.1039/C2JM16722K.
8 Kumar P,Das B,Chitara B,et al.Novel radiation-induced properties of graphene and related materials[J].Macromolecular Chemistry and Physics,2012,213(10-11):1146-1163.DOI:10.1002/macp.201100451.
9 Liu H,Miao W,Yang S,et al.Controlled synthesis of different shapes of Cu2O via?-irradiation[J].Crystal Growth&Design,2009,9(4):1733-1740.DOI:10.1021/cg800703n.
10 Zhang Y,Ma H L,Zhang Q,et al.Facile synthesis of well-dispersed graphene by?-ray induced reduction of graphene oxide[J].Journal of Materials Chemistry,2012,22(26):13064-13069.DOI:10.1039/C2JM32231E.
11 Li J,Zhang B,Li L,et al.?-ray irradiation effects on graphene oxide in an ethylenediamine aqueous solution[J].Radiation Physics and Chemistry,2014,94:80-83.DOI:10.1016/j.radphyschem.2013.06.029.
12 He Y,Li J,Luo K,et al.Engineering reduced graphene oxide aerogel produced by effectiveγ-ray radiation-induced self-assembly and its application for continuous oil-water separation[J].Industrial&Engineering Chemistry Research,2016,55(13):3775-3781.DOI:10.1021/acs.iecr.6b00073
13 He Y L,Li J H,Li L F,et al.The synergy reduction and self-assembly of graphene oxide via gamma-ray irradiation in an ethanediamine aqueous solution[J].Nuclear Science and Techniques,2016,27(3):61.DOIhttps://doi.org/10.1007/s41365-016-0068-8
14张伯武,俞初红,沈蓉芳,等.伽马射线辐照技术制备石墨烯基功能材料的研究进展[J].辐射研究与辐射工艺学报,2017,35(2):020101.DOI:10.11889/j.1000-3436.2017.rrj.35.020101.ZHANG Bowu,YU Chuhong,SHEN Rongfang,et al.Progress in research on preparation of graphene-based functional materials using gamma-ray irradiation technology[J].Journal of Radiation Research and Radiation Processing,2017,35(2):020101.DOI:10.11889/j.1000-3436.2017.rrj.35.020101.