Hong Kong University of Science and Technology-1 (HKUST-1) is metal organic framework (MOF) that composed from ligand BTC (1,3,5-benzene tricarboxylic) and copper ions. The method used in this study is solvotermal with variations nickel ion doping and additions acetic acid as modulator. The purpose of this study is to increase the hydrogen storage capacity. The results obtained were characterized by XRD showed that the HKUST-1 and Ni-HKUST-1 has formed, showed by peaks at 2 theta = 6.7, 9.5, 11.6, 13.4, and 19.0

Ediati, Ratna

Safii, Farhan Fikri

English

IPTEK Journal of Proceedings Series

  The 1st International Seminar on Science and Technology  H616-163 August 5th 2015, Postgraduate Program Institut Teknologi Sepuluh Nopember, Surabaya, Indonesia  Synthesis Of Nickel (Ni) Doped HKUST-1 using Solvotermal Method with Addition of Acetic Acid as Modulator  Farhan Fikri Safii1, Ratna Ediati1  Abstract – Hong Kong University of Science and Technology-1 (HKUST-1) is metal organic framework (MOF) that composed from ligand BTC (1,3,5-benzene tricarboxylic) and copper ions. The method used in this study is solvotermal with variations nickel ion doping and additions acetic acid as modulator. The purpose of this study is to increase the hydrogen storage capacity. The results obtained were characterized by XRD showed that the HKUST-1 and Ni-HKUST-1 has formed, showed by peaks at 2 theta = 6.7, 9.5, 11.6, 13.4, and 19.0.   Index Terms – Doping nickel, HKUST-1, MOF. INTRODUCTION1 Metal Organic Framework (MOF) is porous crystalline material composed by coordination bonds between metal ion and multi dentate organic ligand forming a three-dimensional extended network with cavities [1]. MOF have large surface area (500-6500 m2/ g), low density (0.17 to 1.7 g/cm3) and controllable pores, and have been applied as gas storage, in particular hydrogen gas [2]. Hydrogen storage in MOF is performed by physisorption which influenced by the interaction of molecular hydrogen with MOF surface, surface area and pore volume [3].  Among other MOFs, HKUST-1 is capable of storage H2 effectively. HKUST-1 (Hong Kong University of Science and Technology-1) is composed of a ligand BTC (1, 3, 5-benzene tricarboxylic) and copper ions in the lattice cube (Fm-3m). Cu2+ ions form a dimer in which each copper atom coordinated with four oxygen sources from the linker 1, 3, 5-benzene tricarboxylic and water molecules. The existence of water molecules in the first coordination copper ions directs the possibility of the presence of a coordinative vacancy on the species Cu2+, so HKUST-1 has the potential for interaction with hydrogen and can be applied as a hydrogen storage material [4]. HKUST-1 has been reported [4-5] as a hydrogen storage material and has a hydrogen storage capacity 0.47 and 0.02% at temperature of 30 °C. Hydrogen storage capacity in the HKUST-1 has been reported to be lower than that of MIL-101 which has hydrogen storage capacity 1.14 wt.% [6], therefore  it is necessary to increase the hydrogen storage capacity in the HKUST-1. Increasing the surface area and pore volume with doping metal ions and the addition of a modulator during the synthesis is one of method to increase the hydrogen storage capacity as reported [7-8]. This study reports the synthesis of nickel doping in                                                  1Farhan Fikri Safii, Ratna Ediati are with Department of Chemistry, Faculty of Mathematics and Science, Institut Teknologi Sepuluh Nopember, Surabaya. Email: saya.alka@gmail.com; ratna.ediati@gmail.com HKUST-1 (Cu3(BTC)2) with solvotermal method and the addition of acetic acid as a modulator.  MATERIAL AND METHOD A. Material Cupric nitrate trihydrate (Cu(NO3)2.3H2O) (Merck 99,0%), nickel nitrate hexahydrate (Ni(NO3)2.6H2O) (Merck 99,0%), acetic acid (Merck 99,0%), Benzene-1,3,5-tricarboxylic acid (H3BTC) (Sigma-Aldrich, 99,0%), N'N-dimethylformamide (DMF) (Merck, 99.8%), ethanol, methanol and aquades. B. Procedure Synthesis of HKUST-1. Cupric nitrate trihydrate (4,19 g) was dissolved in 33 mL of aquades. Benzene-1,3,5-tricarboxylic acid (2,10 g) was dissolved in 67 mL of solvent consisted by DMF : etanol (1:1 v/v).  Cupric nitrat and benzene-1, 3, 5-tricarboxylic acid solutions are mixed and stirred. The mixture was transferred into teflon-lined stainless steel autoclave. It was kept in oven at temperature of 120 ℃ for 12 hours. After 12 hours, the autoclave was cooled down naturally into room temperature. Products were separated by filtration and washed by DMF and methanol. Then it was dried at room temperature. The procedure above was repeated with the addition of acetic acid as a modulator. Synthesis of Ni-HKUST-1. synthesis of Ni-HKUST-1 was performed by similar procedure of HKUST-1 as described above with some modification of nickel nitrate hexahydrate (Ni(NO3)2·6H2O) addition. The weight ratio of (Cu(NO3)2·2.5H2O) and Ni(NO3)2·6H2O) are 95:5; 90:10; 80:20 and 70:30%. The result will be characterized by XRD, FTIR, SEM, Nitrogen Adsorption-Desorption, TGA. RESULT AND DISCUSSION Blue colored was obtained from the synthesis. Solids synthetic results adding with acetic acid as the modulator has a smaller mass than the solids synthesized without added acetic acid. XRD characterization of all samples  show in Figure 1.    H616-164   The 1st International Seminar on Science and Technology  August 5th 2015, Postgraduate Program Institut Teknologi Sepuluh Nopember, Surabaya, Indonesia  Figure 1. XRD pattern of HKUST-1 and Ni-HKUST-1 a) simulated, b)100% Cu, c)5% Ni, d) 10% Ni, e) 20% Ni, f)30% Ni, g)100% Cu + Mod, h)5% Ni + Mod, i)10% Ni + Mod, j)20% Ni + Mod, k)30% Ni + Mod According to Figure 1, synthesized materials show peaks at 2 theta = 6.7, 9.5, 11.6, 13.4, and 19.0. Those characteristic peaks correspond to peaks of simulation and material HKUST-1, which has been reported [9]. This indicates that HKUST-1 has been formed. Ni ion doping in HKUST-1 does not change the pattern of diffractogram of Ni-HKUST-1 for all concentration studied. This shows that the doping metal ions Ni does not affect the structure of HKUST-1. To observe the morphology of the HKUST-1 and Ni-HKUST-1 materials the SEM analysis was performed and shown in Figure 2. As seen in Figure 2, that the HKUST-1 and Ni-HKUST-1 have the shape of octahedral morphology. The doped HKUST-1 looks octahedral more regular than that of without doping, which is not doped and added with a modulator.  Figure 2. Photo sem of HKUST-1 and Ni-HKUST-1 CONCLUSION In this study HKUST-1 and Ni-HKUST-1 has been successfully synthesized. Ni doping does not affect to the morphology of HKUST-1.  ACKNOWLEDGEMENTS The author are grateful to fellow research team, and the Laboratory of Materials Chemistry and Energy, Department of Chemistry, Institut Teknologi  Sepuluh Nopember (ITS) Surabaya. REFERENCES [1] Wee, Lik H, et al., “Heteropolyacid encapsulated in Cu3(BTC)2 nanocrystals: An effective esterification catalyst” Catalysis Today, Vol. 171, hal. 275– 280, 2011.  [2] Xiang, Zhonghua, et al., “Lithium Doping On Metal-Organik Framework for Enhancing H2 Storage” International Journal of Hydrogen Energy, Vol. 30, hal. 1-5, 2011.  [3] Sculley, Julian, et al., “The current status of hydrogen storage in metal–organic frameworks—updated” Energy Environ. Sci., Vol. 4, hal. 2721-2735, 2011.  [4] Lin, Kuen Song, et al.,“Synthesis and characterization of porous HKUST-1 metal organic frameworks for hydrogen storage”, International Journal of Hydrogen Energy, Vol. 37, hal. 13865-13871, 2012.  [5] Ya Liu, Ying, et al., “Improved hydrogen storage in the modified metal-organic frameworks by hydrogen spillover effect”, International Journal of Hydrogen Energy, Vol. 32, hal. 4005 – 4010, 2007.  [6] Li, Yingwei and Ralph T. Yang “Hydrogen Storage in Metal-Organic and Covalent-Organic Frameworks by Spillover”, AIChE Journal, Vol. 54, hal. 269-279, 2007.  [7] Na Li-yan, et al., “Nano/Micro HKUST-1 Fabricated by coordination Modulation Method at Room Temperatur”, Chem. Res.Chinese Universities. Vol 24, hal. 555-558, 2012.    [8] Wang, Fangli, et al., “The controlled regulation of morphology and size of HKUST-1 by “coordination modulation method””, Microporous and Mesoporous Materials, Vol. 173, hal. 181–188, 2013. 

Synthesis Of Nickel (Ni) Doped HKUST-1 using Solvotermal Method with Addition of Acetic Acid as Modulator

Center for Scientific Publication

http://iptek.its.ac.id/index.php/jps/article/download/1163/984

Synthesis Of Nickel (Ni) Doped HKUST-1 using Solvotermal Method with Addition of Acetic Acid as Modulator

Abstract

Similar works

Full text

Available Versions

IPTEK Journal of Proceedings Series

Center for Scientific Publication