Lv et al. Int J Opt Photonic Eng 2017, 2:005 International Journal of Optics and Photonic VIBGYOR Engineering ISSN: 2631-5092 Composition and Fluorescence of Gadolinium (III) Acetyl- Research Article: Open Access Research acetonate Derivatives by Solvothermal Method Fengzhu Lv*, Yihe Zhang*, Xue Chen and Yong Ma Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing, China Abstract Gadolinium (III) acetylacetonate was treated by solvothermal method to produce gadolinium complexes with acetylacetonate and -OH groups. The composition, fluorescence, and magnetic properties of the products were studied in detail. The fluorescence showed the products possessed higher energy emission and excitation fluorescence compared to Gadolinium (III) acetylacetonate. Also the product produced at 160 °C possessed higher fluorescent intensity and responding ability toward external magnetic field. So the products were hydrophobic materials with magnetic and fluorescent properties. Keywords Gadolinium (III) acetylacetonate derivatives, Solvothermal method, Luminescence Introduction fluorescence and magnetic properties, by simple method is the project of researchers [8,9]. Generally, rare earth complexes have many potential applications in novel lighting devices, optical fibers and Thermal decomposition of metal acetylacetonates has luminescent sensors benefiting from their long emission recently attracted much attention to fabricate thin films and lifetime, narrow bandwidth and large Stokes shift in vis- nanoparticles of metals, metal alloys and metal oxides for ible and near-infrared regions under Ultraviolet (UV) microelectronic, catalytic and biomedical applications [10- excitation [1-3]. The luminescence intensity of rare earth 13]. Colloidal cubic Gd2O3 nanorings and nanoplates were complexes related to the absorption efficiency of ligands, selectively prepared from low-temperature (90 °C) hydroly- which is dependent on the ligand molecule with large sis of Gd-(AcAc)3 and subsequent in situ thermal dehydra- π-conjugated system. Good solubility of substituted rare tion of the hydrolyzed precursor-surfactant aggregates at earth β-diketonate complexes in common organic sol- 320 oC [14]. But seldom reports focus on the partial decom- vents highly enhances their applications in the solution posed samples as which is preferred possessing solubility in processable organic semiconductors and also provides organic solvent and changed fluorescence compared to rare more efficient approach to fabricate OLED devices by earth acetylacetonate. solution techniques [4,5]. So the fluorescence of some In the present work Gadolinium (III) acetylacetonate rare earth β-diketonate complexes were studied and hydrate was treated by solvothermal method in absolute modified to widen their application [6,7]. But prepara- diphenyl ether which is a water lack system where the tion of multifunctional materials, such as materials with hydrolysis of acetylacetonate is limited. The products *Corresponding author: Fengzhu Lv and Yihe Zhang, Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, No. 29 Xueyuan Road, Haidian District, Beijing 100083, China, Tel: +86-10- 82322759, Fax: +86-10-82322345, E-mail: [email protected]; [email protected] Received: March 09, 2017: Accepted: July 22, 2017: Published: July 24, 2017 Copyright: © 2017 Lv F, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. Citation: Lv F, Zhang Y, Chen X, Ma Y (2017) Composition and Fluorescence of Gadolinium (III) Acetylacetonate Derivatives by Solvothermal Method. Int J Opt Photonic Eng 2:005 Lv et al. Int J Opt Photonic Eng 2017, 2:005 ISSN: 2631-5092 | • Page 2 of 8 • were preferred possessing solubility in organic solvent different temperature for 2.0 h. After that the autoclave and changed fluorescence compared to rare each acety- was cooled to room temperature, the as-obtained yellow lacetonate as well as magnetic properties. So different suspension was mixed with an equal volume of acetone, kinds of Gadolinium (III) acetylacetonate derivatives and the formed precipitate was separated by centrifuga- were produced. The composition, fluorescence and mag- tion and washed with acetone. The final samples were netic properties were studied in detail. Under appropri- assigned as Gd-S-T, where T indicated the formed tem- ate preparation conditions, Gadolinium (III) acetylace- perature by solvothermal. Gd-S-160 was grounded and tonate derivatives with higher fluorescent intensity and calcinated at 450 °C for 10 h in air to give Gd-C-160. magnetic properties were produced. Afterwards, Gd-C-160 was furnace-cooled to room tem- perature, and grounded again into powder for measure- Experimental ment. Materials Characterization The raw material for synthesis of Gadolinium (III) Thermal Gravimetric Analysis (TGA) was measured acetylacetonate derivatives was gadolinium acetylace- on Perkin-Elmer TGA 7 with a heating rate of 20 °C/min tonate trihydrate (Gd(AcAc) ·3H O, MW = 508.62 g/ 3 2 ranging from 45 °C to 800 °C in air, on the same time mol), which was purchased from Beijing HWRK Chem- a NETZSCH STA 449F3 Thermo Gravimetric Analy- ical Co., Ltd.. Diphenyl ether was applied by Sinopharm ser was coupled, using a heated capillary at 190 °C, to a Chemical Reagent Beijing Co., Ltd. Other solvents were QMS 403 Mass Spectrometer (TGA-Ms) to identify the from Beijing Chemical factory. released gases during the thermal degradation of a ma- Preparation of Gadolinium (III) acetylacetonate terial. The Fourier Transform Infrared Spectra (FTIR) derivatives of the solid samples was obtained with a Perkin Elmer Spectrum 100 FT-IR spectrometer. KBr pellet was used In a typical synthesis for the derivatives of Gd(A- as background. The structure of the products was stud- cAc)3·3H2O, 1.5787 g (0.003 mol) of Gd(AcAc)3·3H2O ied by powder X-ray diffraction (Rigaku D/max-rA) was dispersed into 10.5 mL of absolute diphenyl ether equipped with Cu Kα (λ = 0.1542 nm) radiation at 40 kV to form a solution under magnetic stirring, which was and 30 mA. The surface morphology and the elemental poured into 25 ml teflon-lined autoclave and heated at distribution of the samples were probed with Scanning 1.0 Gd(AcAc) .3H O 0.55 3 2 (b) Gd(AcAc)3.3H2O (a) Gd-S-160 ) 0.50 Gd-S-220 Gd-S-160 C o 0.8 Gd-S-220 / 0.45 o / o ) ( 0.40 o / t o ( h 0.35 0.6 g t i h e 0.30 g i W e 0.25 0.4 . W v i 0.20 r e 0.15 D 0.2 0.10 0.05 0.0 0.00 100 200 300 400 500 600 700 800 200 300 400 500 600 700 800 Temperature (oC) o Temperature ( C) 1.0 (c) CO 0.8 2 ) o / o ( CO 0.6 t h g i e 0.4 W H2O 0.2 O2 0.0 100 200 300 400 500 600 700 800 o Temperature ( C) Figure 1: TGA (a) and DTA (b) curves of Gd(AcAc)3·3H2O, Gd-S-160, and Gd-S-220, TGA-Ms of Gd-S-160 (c). Citation: Lv F, Zhang Y, Chen X, Ma Y (2017) Composition and Fluorescence of Gadolinium (III) Acetylacetonate Derivatives by Solvothermal Method. Int J Opt Photonic Eng 2:005 Lv et al. Int J Opt Photonic Eng 2017, 2:005 ISSN: 2631-5092 | • Page 3 of 8 • Electron Microscope (SEM, HITACHI S-4300) operated at an acceleration voltage of 5 kV. The zeta potential and (h) size distribution of the hybrid particles were measured 3415 1548 499 ) o on Malvern Instruments Zetasizer Nano-ZS90. The Ul- / (g) o 1441 ( traviolet-Visible (UV-vis) spectra were measured with e (f) UV6100 double beam spectrophotometer. Room tem- c n a (e) perature excitation and emission spectra were charac- t t terized by F97 spectrofluorometer (Shanghai Lengguang i m (d) s Technology Co., China) with a 150 W Xe lamp as the n a excitation source. The temperature-dependent lumi- r (c) T nescence properties were measured on the fluorescence (b) 3300 536 spectrophotometer (F-4600, HITACHI, Japan), which 1523 1391 (a) 1602 was equipped with a self-made heating attachment and a 1016 918 computer controlled electric furnace. The luminescence 4000 3500 3000 2500 2000 1500 1000 500 decay curve was obtained from a spectrofluorometer Wavenumber (cm-1) (HORIBA, JOBIN YVON FL3-21) with a 335 nm pulse Figure 2: FI-IR spectra of a) Gd(AcAc)3·3H2O; b) Gd-S-140; laser radiation (nano-LED) as the excitation source, and c) Gd-S-160; d) Gd-S-180; e) Gd-S-200; f) Gd-S-220; g) Gd- the pulse width of the laser was 12 ns. S-240 and h) Ga-S-260 prepared in 2 h. Results and Discussion To prepare derivatives of Gd(AcAc)3·3H2O by solvo- thermal method, TGA together with Differential Ther- 1065 ) (d) o mal Analysis (DTA) were performed to determine the / o 863 ( 3409 decomposition temperature of Gd(AcAc) ·3H O. As 1531 537 3 2 e (c) 1411 c shown in Figure 1a, the weight losses for all the samples n a 3407 t below 150 °C are assigned to the departure of adsorbed t water and comlexed water with gadolinium [15]. Gd(A- i 1550 1441 m (b) s cAc)3·3H2O exhibits complicated decomposition behav- n a ior due to more ligands in it. It shows one little and two r broad DTA peaks with shoulders between 190-350 °C T (a) and 350-500 °C (Figure 1b). So it is preferred, Gd(A- 495 cAc)3·3H2O derivatives may form around 200 °C where Gd(AcAc)3·3H2O decomposes partially.