SYNTHESIS OF SUPER SYNTHESIS OF SUPER NANOPOROUS SYNTHESIS OF SUPER SYNTHESIS OF SUPER-NANOPOROUS NANOPOROUS NANOPOROUS CARBON ALLOY BY CARBON ALLOY BY ELECTROOXIDATION OF A ZEOLITE ELECTROOXIDATION OF A ZEOLITE ELECTROOXIDATION OF A ZEOLITE ELECTROOXIDATION OF A ZEOLITE TEMPLATED CARBON TEMPLATED CARBON E. Morallón, D. Cazorla- E. Morallón, D. Cazorla -Amorós, Amorós, Universidad de Alicante R. Berenguer R. Berenguer R. Berenguer R. Berenguer Universidad de Málaga H. Nishihara, H. H. Nishihara, H. Itoi Itoi, T. Kyotani , T. Kyotani Tohoku University Tohoku University
Strategic Japanese Strategic Japanese- -Spanish Spanish Cooperative Program (FY2011) Cooperative Program (FY2011) Cooperative Program (FY2011) Cooperative Program (FY2011) “ UNIQUE SUPER UNIQUE SUPER- -POROUS CARBON POROUS CARBON ALLOYS FOR ASYMMETRIC HYBRID ALLOYS FOR ASYMMETRIC HYBRID SUPERCAPACITORS” SUPERCAPACITORS” Diego Cazorla Diego Cazorla- -Amorós, Emilia Morallón Amorós, Emilia Morallón Universidad de Alicante Tomás Cordero, Tomás Cordero, José Rodríguez Tomás Cordero, José Rodríguez Tomás Cordero, José Rodríguez José Rodríguez Universidad de Málaga Takashi Takashi Kyotani Kyotani Tohoku University Tohoku University PRI-PIBJP-2011-0766
Workshop (2013) Sendai SJ-NANO 2013 Alicante Málaga Málaga Alicante University University Alicante 2
Japan Japan- -Spain Spain Cooperation Cooperation Project (2012 Project (2012- -2014) 2014) Project Title: “ Unique super-porous carbon alloys for Unique super porous carbon alloys for asymmetric hybrid supercapacitors ” Objective: The aim of this project is to synthesize unique The aim of this project is to synthesize unique porous carbon alloy and to develop a carbon- based asymmetric hybrid supercapacitor using based asymmetric hybrid supercapacitor using the carbon alloy as a positive electrode. SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
-High surface area area DLC DLC -High pseudo- capacitance capacitance (redox rxn.) SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Concept of Carbon Alloy: Carbon materials can be developed with a wide range p g of structures, textures and properties. This led to the Japanese Carbon Group to propose in 1992: “Carbon alloys are materials mainly composed of carbon atoms in multi-component systems, in f b t i lti t t i which each component has physical and/or chemical interactions with each other. Here h i l i t ti ith h th H carbons with different hybrid orbitals account as different components” diff t t ” (Carbon alloys, E Yasuda et al Editors, Elsevier, 2003, p.9). SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Concept of Carbon Alloy: Carbon materials can be developed with a wide range p g of structures, textures and properties. This lead to the Japanese Carbon Group to propose in 1992: TO SYNTHESIZE A SUPER- “Carbon alloys are materials mainly composed NANOPOROUS CARBON NANOPOROUS CARBON of carbon atoms in multi-component systems, in f b t i lti t t i ALLOY BASED ON ZEOLITE which each component has physical and/or TEMPLATED CARBON (ZTC) TEMPLATED CARBON (ZTC) chemical interactions with each other. Here h i l i t ti ith h th H carbons with different hybrid orbitals account as diff different components” t t ” (Carbon alloys, E Yasuda et al Editors, Elsevier, 2003, p.9). SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
What is ZTC? Nano-sized carbon material with taylored and ordered pore network prepared taylored and ordered pore network prepared using zeolite as template nanopore: 1.2 nm carbon/zeolite composite carbon filling filling zeolite removal zeolite Y (template) Kyotani et al. Chem. Mater. 9 (1997), 609. Kyotani et al. Chem. Commun. (2000) 2365. K t i t l Ch C (2000) 2365 Nishihara et al. Carbon , 47 (2009) 1220. ( ) SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
What is ZTC? Nano-sized carbon material with taylored and ordered pore network prepared taylored and ordered pore network prepared using zeolite as template nanopore: 1.2 nm carbon/zeolite composite carbon filling filling zeolite removal zeolite Y (template) Kyotani et al. Chem. Mater. 9 (1997), 609. Kyotani et al. Chem. Commun. (2000) 2365. K t i t l Ch C (2000) 2365 Nishihara et al. Carbon , 47 (2009) 1220. ( ) SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
nanopore: 1.2 nm 1 2 U i Unique features ZTC f t ZTC - 3D-nanographene network g p - uniform nanopore size (1.2 nm) - high surface area (up to 4000 m 2 /g) high surface area (up to 4000 m 2 /g) - large amount of carbon edge sites! - all edge sites and graphene surface are fully exposed! These features are beneficial to use ZTC as an electrode for electrochemical capacitors SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
U i Unique features ZTC f t ZTC These features are beneficial to the use ZTC as an electrode for electrochemical capacitors - Adequate electrolyte accessibility Adequate electrolyte accessibility - High mass transfer rate - High surface area (high double layer capacitance) High surface area (high double layer capacitance) - Formation of large amount of functional groups (redox properties, pseudocapacitance) p p p p ) SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
U i Unique features ZTC f t ZTC These features are beneficial to the use ZTC as an electrode for electrochemical capacitors - Adequate electrolyte accessibility Adequate electrolyte accessibility - High mass transfer rate - High surface area (high double layer capacitance) High surface area (high double layer capacitance) - Formation of large amount of functional groups (redox properties, pseudocapacitance) p p p p ) SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
U i Unique features ZTC f t ZTC Hypothetical oxidation process of ZTC and the modelled molecular structure of fully-oxidized ZTC. SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
U i Unique features ZTC f t ZTC SUPER SUPER- NANOPOROUS CARBON CARBON ALLOY! Hypothetical oxidation process of ZTC and the modelled molecular structure of fully-oxidized ZTC. SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Main problems to achieve the objective -ZTC has a quite fragile structure q g -ZTC is very reactive -Easy structure degradation y g SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Main problems to achieve the objective -ZTC has a quite fragile structure q g -ZTC is very reactive -Easy structure degradation y g SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Main problems to achieve the objective -ZTC has a quite fragile structure q g -ZTC is very reactive -Easy structure degradation y g SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Objective of this work: To make a detailed study of the ZTC To make a detailed study of the ZTC electrooxidation to get large concentration of surface oxygen groups and high surface area surface oxygen groups and high surface area SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Experimental section ti SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Electrochemical oxidation: -Galvanostatic oxidation: I= 2-50 mA, t= 1-15h, , , T= 25ºC; Electrolytes: 1.0M NaOH, 1.0M H 2 SO 4 , 2wt% NaCl - Cyclic voltammetry: ∆ E= -0.1-1.2 V, v= 1 mV/s, 1 0M H SO 1.0M H 2 SO 4 SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Electrochemical oxidation: -Galvanostatic oxidation: I= 2-50 mA, t= 1-15h, , , T= 25ºC; Electrolytes: 1.0M NaOH, 1.0M H 2 SO 4 , 2wt% NaCl 3-electrode cell filter filter Ti/RuO 2 anode CE: Pt paste filter mass = 100 mg area = 2.25 cm 2 WE: (Ti/RuO 2 + ZTC paste) thickness = 2 mm thickness = 2 mm SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
3-electrode cell T = 25 ºC T = 25 C Ti or Pt REF: Electrochemical Ag/AgCl/Cl- sat. oxidation: oxidation: -Cyclic voltammetry: ∆ E= -0.1-1.2 V, v= 1 , Electrolyte: mV/s, 1.0M H 2 SO 4 1M H 2 SO 4 aq. WE: 90 wt% active material CE: Pt wire 5 wt% acetilene black 5 wt% PFTE 5 wt% PFTE mass = 5-10 mg area = 1 cm 2 thickness = 0 18 mm thickness = 0.18 mm SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Chemical oxidation: - Oxidation by HNO 3 at different temperatures (45ºC, 80 ºC) and times (from 15 min to 15h). (45 C, 80 C) and times (from 15 min to 15h). Oxidation by H 2 O 2 was also done. SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Characterization Structural-Textural Structural-Textural - N 2 adsorption (-196 ºC) - CO 2 adsorption (0 C) CO adsorption (0 ºC) - X-ray diffraction (XRD) Surface Chemistry - Temperature-programmed desorption (TPD) - X-ray photoelectron spectroscopy (XPS) SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
Results and di discussion. i SJ-NANO 2013 Alicante Alicante University University 2 Workshop (2013)
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