teresa j. bandosz - beyond adsorption: new...

BEYOND ADSORPTION: NEW PERSPECTIVES AND CHALLENGES FOR NANOPOROUS CARBONS

Teresa J. Bandosz1*

Department of Chemistry, The City college of New York, New York, NY, USA*corresponding author email: [email protected]

Our inspiration in the science of graphene combined with the comprehensive knowledge of activated carbons surface features directed us to look at carbons from another perspective, from the perspective of nanotechnology. Therefore, the objective of this to talk is to present history and new perspectives for nanoporous carbons. Their ancient applications starting from the discovered by our ancestors amazing ability of char to filtrate, preserve and disinfect and ending on energy harvesting, advanced catalysis and sensing are briefly discussed.Some results obtained by us recently on ORR, photoactivity and toxic gas sensing are also briefly addressed here.1 They are very new and many questions have arisen. Obviously many of them need answers, and many approaches need improvements. Nevertheless, for many of these applications adsorption can be a first step and a developed surface area is essential. The latter feature is unique of nanoporous carbons and is a significant asset of these materials. One has to take into account that explaining the complex phenomena on nanoporous carbons is not easy owing to the combination of the porosity and surface chemistry effects. One thing is certainly true: “adventurous” graphene features can be found in nanoporous carbons and they deserve to be explored and used to their full extent. Moreover, this talk intends to show that nanoporous carbons, though a “ poor person graphene” are still an exciting research topic.

Figure1.”Beyond adsorption” applications of nanoporous carbons.

References [1] T.J. Bandosz. The Chemical Record. 2016, 16, 205-2018.

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mailto:[email protected]

NANOPOROUS CARBONS IN ELECTROCHEMICAL CAPACITORS:BEYOND THE EDL STORAGE

François Béguin*, Qamar Abbas, Patryk Przygocki, Krzysztof Fic, Elżbieta FrąckowiakPoznan University of Technology, ICTE, Berdychowo 4, 60965 Poznan, Poland

*corresponding author email: [email protected] AbstractThe most common electrochemical capacitor stores charges in the electrical double-layer which is formed at the electrode/electrolyte interface. The energy stored is given by the formula E = ½ CU2, where C and U are capacitance and voltage, respectively. Organic electrolytes are the most widely used in commercial systems, allowing voltage values of 2.7-2.8 V to be reached [1]. The capacitance is generally enhanced by using high surface area activated carbon (AC) electrodes. In the last years, it has been clearly established that carbons with most of their pores ranging around 1 nm are preferable to materials with highly developed BET surface area [2]. Simultaneously, ex-situ and in-situ investigations on electrodes during charging enabled to better understand the ion fluxes and also to demonstrate that ions are at least partially desolvated in the pores of carbon [3]. Notwithstanding, most organic electrolytes are based on unsafe and environmentally unfriendly acetonitrile as solvent. Therefore, aqueous electrolytes are a better option provided that energy values comparable to organic systems could be reached. In this context, we have demonstrated high voltages up to ca. 1.9 V with aqueous alkali sulfates, owing to the high local pH in the pores of the negative AC electrode where OH - ions are trapped [4]. Besides in aqueous alkali iodides, the positive electrode of AC/AC capacitors has a battery like behavior owing to the iodine/iodide redox system, leading to a hybrid-type of cell with doubled capacitance as compared to a typical EDL one [5]. The use of TPD and Raman spectroscopy allowed us to attribute the redox performance of the positive electrode to iodine encapsulation in the pores of AC. By using mixed alkali iodide + alkali sulfate in an AC/AC cell, we could finally combine the advantages of the two electrolytes, e.g., high capacitance and high voltage, and in total reach an energy density which approaches that of systems based on organic electrolyte [6].

Acknowledgements The project DS 03/31/DSPB/0310/2016 and the NCN OPUS project UMO 2014/15/B/ST4/04957 are acknowledged for supporting this research.

References

[1] R. Kötz, M. Carlen, Electrochim. Acta 2000, 45, 2483-2498[2] F. Béguin, V. Presser, A. Balducci, E. Frackowiak, Adv. Mater. 2014, 26, 2219-2251[3] M. Deschamps, E. Gilbert, P. Azais, E. Raymundo, F. Béguin et al., Nature Mater. 2013, 12, 351-358[4] Q. Gao, L. Demarconnay, E. Raymundo, F. Béguin, Energy Environ. Sci. 2012, 5, 9611-9617[5] G. Lota, E. Frackowiak, Electrochem. Comm. 2009, 11, 87-90[6] Q. Abbas, P. Babuchowska, E. Frąckowiak, F. Béguin, J. Power Sources 2016, http://dx.doi.org/10.1016/j.jpowsour.2016.03.094

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HIGHLY POLAR CARBON MATERIALS FOR ELECTROCHEMICAL APPLICATIONS, FUEL CELLS AND WATER ADSORPTION

Stefan Kaskel1,2*

1TU Dresden, Germany2Fraunhofer IWS, Dresden, Germany

*corresponding author email: [email protected]

Coordination polymers are ideal precursors for the design of highly polar carbons by pyrolysis. The particle morphology of the original coordination polymer crystals is retained leading to “rectangular” carbons. Interestingly despite a low metal content, these carbons are highly hydrophilic as evidenced by water adsorption isotherms due to a high amount of hetero atoms in the framework (N,O) [1]. The high polarity is beneficial for further oxide functionalization. In our recent work we found these materials to be highly efficient supports for fuel cell catalysts [2]. A correlation of hydrophilicity and catalytic performance is possible indicating the importance of water adsorption at the interface. However, these polar carbons also exhibit excellent performance in other electrocatalytic applications. In lithium sulfur batteries, they show a high retention of polysulfides, and thus are potentially interesting materials to suppress the polysulfide shuttle mechanism responsible for capacity fading in lithium sulfur batteries.

Figure1.Typical SEM of a “rectangular” carbon (left) and water adsorption isotherms (right) at 298 K.

References [1] G.P. Hao, G. Mondin, S. Kaskel, et al. Angew Chem., Int. Ed. 2015, 54(6), 1941.[2] G.P. Hao, Q. Zhang, M. Oschatz, P. Strasser, S. Kaskel et al. Chem. Commun. 2015, 51, 17285.[3] K. Kaneko, Nat. Chem. 2015, 7, 194-196.

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A VARIETY OF GAS-CARBON INTERACTIONS-ADSORPTION, CHEMISORPTION, ABSORPTION, OCCLUSION -

Katsumi KanekoCenter for Energy and Environmental Science

Shinshu UniversityNagano, Japan

[email protected]

Molecules can interact with solids in a different way. The well-known representative interactions are physical adsorption (adsorption), chemisorption, absorption, and occlusion, although we have no clear classification of these interactions. Carbon can offer different kinds of structure and property and then there are many gas-carbon interactions. In this presentation, a clear classification of the gas-solid interactions will be shown to give a bright indication to find out new science beyond physical adsorption on carbon.

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CARBON SURFACE MODIFICATION DURING CAPACITOR OPERATION

Elzbieta Frackowiak1*, Krzysztof Fic1, Minglong He2, Erik J. Berg2, Petr Novak2

1Poznan University of Technology, Institute of Chemistry and Technical Electrochemistry, Berdychowo 4, 60-965 Poznan, Poland

2Electrochemistry Laboratory, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland

*email: [email protected]

Carbon-based supercapacitors operating in aqueous electrolytes at voltage higher than 1.23 V attract significant attention for next-generation high power, low cost and environmentally friendly energy storage applications. Cell ageing is however markedly pronounced at elevated voltages and results in accelerated overall performance fade and increased safety concerns. On-line electrochemical mass spectrometry, combined with cell pressure analysis, provide a powerful means for in situ investigation of degradation mechanisms in aqueous electrolyte/carbon based supercapacitors. The activated carbon electrodes possess high specific surface area and oxygen-based surface functionalities (mainly phenol, lactone and anhydride groups), which are oxidized already at cell voltage of 0.6 V to provoke the evolution of minor amounts of CO and CO2. Noticeable water decomposition starts at high voltage of 1.6 V with the evolution of H 2 on the negative electrode and carbon corrosion on the positive electrode with the generation of CO and CO2. A short-term cycling leads to partly reversible gas evolution/consumption side-reactions giving negligible capacitance. On the other hand, long-term cycling causes irreversible side-reactions, deteriorates the electrochemical performance, and increases the internal pressure of the cell. Repeated galvanostatic cycling (U < 2 V) is confirmed as a more harmful technique for the electrode integrity compared to the voltage holding in a floating test. In situ gas analysis provides valuable insights into electrochemical cell ageing aspects, such as the nature and potential onsets of side reactions.

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GLOBULAR PROTEINS CONFINED IN POROUS CARBONS

Balázs Nagy,1 Ajna Tóth,1 Irina Savina,2 Sergey Mikhalovsky,2,3 Lyuba Mikhalovska,2 Erik Geissler,4 Krisztina László1

1Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, H-1521 Budapest, Hungary

2School of Pharmacy and Biomolecular Sciences, University of Brighton, Brighton, BN2 4GJ, United Kingdom

3School of Engineering, Nazarbayev University, Astana, 010000, Republic of Kazakhstan4Université Grenoble Alpes and CNRS, LIPhy, F-38000 Grenoble, France

corresponding author email: [email protected]

The way in which biomolecules adsorb and migrate on solid surfaces, notably on porous substrates, is the focus of converging interests from investigations into protein conformation, physical adsorption processes, and medical applications. This contribution reports of the concentration distribution of two model proteins adsorbed from aqueous solution by high surface area carbon aerogel, using macroscopic adsorption measurements, small angle neutron and X-ray scattering (SANS and SAXS). The proteins investigated were bovine serum albumin (67 kDa), and bovine pancreatic trypsin inhibitor (BPTI), also known under the name aprotinin (6.5 kDa). The carbon substrate, an open structured carbon aerogel was derived from a resorcinol–formaldehyde polymer aerogel. Although it possesses a high proportion of pores that are either closed or inaccessible to low temperature nitrogen vapour, the size distribution of the accessible pores is broad enough to accommodate BSA molecules. In the hydrophobic carbon the BSA molecules migrate individually into pores that are compatible with their size, whereas BPTI forms clusters having the same size as BSA. The distribution of BSA within the carbon was deduced from SANS experiment and was confirmed by nitrogen adsorption measurements on protein loaded samples [1,2]. These observations have relevance in biomedical applications, such as haemoperfusion or as a medium for protein storage.

Acknowlegements We are grateful to Isabelle Grillo and the Institut Laue-Langevin, Grenoble, France for access to the D11 and D16 instruments and also to the European Synchrotron Radiation Facility for access to the French CRG beam line BM02.

References [1] B.Nagy, A. Tóth, I. Savina, S. Mikhalovsky, L. Mikhalovska, I. Grillo, E. Geissler, K. László. dx.doi.org/10.1016/j.carbon.2016.04.081[2] B. Nagy, A. Tóth, I. Savina, S. Mikhalovsky, L. Mikhalovska, E. Geissler, K. László Adsorption of Globular Proteins by High Surface Area Porous Carbons (in preparation)

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http://dx.doi.org/10.1016/j.carbon.2016.04.081


GRAPHITIC FOAMS: TOPOLOGY, POROUS ACTIVATION, AND CHARACTERIZATION

Juan Matos1*, Antonio G. Souza-Filho2, Eduardo Barros2, José A. Rodriguez3 and Mark M. Turnbull4

1Biomaterials Department, Technological Development Unit, University of Concepción, Chile. 2Department of Physics, Federal University of Ceará, Fortaleza-CE, 60455-900, Brazil. 3Chemistry

Department, Brookhaven National Laboratory, Upton, NY 11973, USA. 4Carlson School of Chemistry and Biochemistry, Clark University, Worcester, MA 01610, U.S.A.


The synthesis of glassy-shape 2D and 3D polygonal random networks of carbon (RNC) have been performed from the controlled pyrolysis of saccharose in absence or presence of KOH. The topological properties of the bi-dimensional (2D) RNC are significantly different from other 2D cell structures. The pentagon was found to be the most abundant polygon in the film RNW. In addition, three-dimensional (3D) irregular sponge balls were obtained with a similar randomly structure to that in the films. The sponges were composed by an assembly of carbonaceous grains with different sizes where the carbon grains developed into a continuous of 3D RNC in the form of tubes with coiled shapes. The formation of coils was attributed to the diffusion of potassium particles within the carbonaceous matrix. XRD showed that graphite is the main crystalline phase; nevertheless, XANES, NEXAFS and XPS showed important differences with respect to graphite while RAMAN spectroscopy suggested some similitudes with graphene. EPR and SQUID results clearly indicate that the present RNC have para/diamagnetic behaviour that strongly depend of synthesis and activation conditions. Finally, the activation of the present RNC by physical activation under CO2 flow or by pyrolysis under N2 flow have shown that it is possible to obtain RNC with BET surface areas up to 850 and 981 m2.g-1

under flow of N2 and CO2, respectively.

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S-DOPPED CARBON SPHERES BY HYDROTHERMAL SYNTHESIS FOR CATALYTIC APPLICATION

Tiago A.G. Duarte1,2,*, Luísa M.D.R.S. Martins1,3, Ana P. Carvalho2, Armando J.L. Pombeiro1

1 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal

2 Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal

3 Chemical Engineering Department, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, R. Conselheiro Emídio Navarro, 1959-007 Lisboa, Portugal


Carbon spheres have drawing the attention of the scientific community due to their high electrical conductivity and excellent chemical stability, which can also be allied to a developed porosity. As a consequence, the potentialities of these materials as supercapacitors, catalyst supports and adsorbents have being explored. One possible strategy to synthetize these type of materials is through hydrothermal treatments. The most commonly used carbon precursors to prepare hydrochars are renewable biomasses, e.g. glucose, xylose, maltose, sucrose, amylopectin or starch.[1]The carbon spheres tested in this study were obtained by hydrothermal treatment using sucrose aqueous solutions in the presence of different S containing compounds, e.g. sulfuric acid, p-toluenesulfonic acid, and a vinyl sulfonic acid. The S undopped carbons have acidic surfaces (pHpzc values of ca. 2.0) with a large fraction of carboxylic acids and alcohols. It is expected that the introduction of sulfonic groups will increase of surface acidity allowing us to consider the use of these carbons as catalysts for esterification reactions. These reactions are important for biodiesel production and also in the food industry, and are usually catalysed by strong acids as H2SO4.[2] The results obtained so far point out the potentialities of these materials as alternatives to strong inorganic acids, being a step forward to turn esterification a more green process.

Acknowlegements This work has been partially supported by the Foundation for Science and Technology (FCT), Portugal (UID/QUI/00100/2013, PTDC/QEQ-ERQ/1648/2014, PTDC/QEQ-QIN/3967/2014 and UID/MULTI/00612/2013). Tiago A.G. Duarte is thankful to FCT for his CATSUS Ph.D. fellowship (PD/BD/105993/2014).References [1] R. Demir-Cakan, N. Baccile, M. Antonietti, M.M. Titirici, Chem. Mater., 2009, 21, 484-490.[2] M. Wu, Y. Wang, D. Wang, M. Tan, P. Li, W. Wu, N. Tsubaki, J. Porous Mater., 2016, 23, 263-271.

Figure 1. Scheme of esterification reaction catalyzed by hydrochar.

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MOVING TOWARDS REAL MODELS OF GRAPHENE NANOWINDOWS

Fernando Vallejos-Burgos* and Katsumi KanekoCenter for Energy and Environmental Science, Shinshu University, Nagano, Japan


Without any doubt graphene science has experienced a boom in popularity in the recent years. Synthesis processes continuously improve and will soon achieve exceptional defect-free qualities in large amounts. An important (potential) application of graphene will be its use as an atomically thin membrane exhibiting ultra-fast molecule permeation and high selectivity.1 Computer calculations describing this behaviour are just as good as a correct model of the nanowindow is employed. Disappointingly, the oversimplified models employed at the beginning of the graphene membrane era are still being applied in the recent literature2–6 in molecular dynamics calculations of permeation, despite having much better experimental evidence to improve nanowindow description.This presentation will discuss and show the importance of employing reliable and more mature nanowindow models7–9 instead of simplistic ones which should be considered obsolete except for quick exploratory studies.

References(1) Surwade, S. P.; Smirnov, S. N.; Vlassiouk, I. V.; Unocic, R. R.; Veith, G. M.; Dai, S.; Mahurin, S. M. Water Desalination Using Nanoporous Single-Layer Graphene. Nat Nano 2015, 10 (5), 459–464.(2) Du, H.; Li, J.; Zhang, J.; Su, G.; Li, X.; Zhao, Y. Separation of Hydrogen and Nitrogen Gases with Porous Graphene Membrane. J. Phys. Chem. C 2011, 115 (47), 23261–23266.(3) Sun, C.; Boutilier, M. S. H.; Au, H.; Poesio, P.; Bai, B.; Karnik, R.; Hadjiconstantinou, N. G. Mechanisms of Molecular Permeation through Nanoporous Graphene Membranes. Langmuir 2014, 30 (2), 675–682.(4) Azamat, J.; Khataee, A.; Joo, S. W. Molecular Dynamics Simulation of Trihalomethanes Separation from Water by Functionalized Nanoporous Graphene under Induced Pressure. Chem. Eng. Sci. 2015, 127, 285–292.(5) Ohba, T. Consecutive Water Transport through Zero-Dimensional Graphene Gates of Single-Walled Carbon Nanohorns. J. Phys. Chem. C 2016, 120 (16), 8855–8862.(6) Tao, Y.; Xue, Q.; Liu, Z.; Shan, M.; Ling, C.; Wu, T.; Li, X. Tunable Hydrogen Separation in Porous Graphene Membrane: First-Principle and Molecular Dynamic Simulation. ACS Appl. Mater. Interfaces 2014, 6 (11), 8048–8058.(7) Chen, Q.; Yang, X. Pyridinic Nitrogen Doped Nanoporous Graphene as Desalination Membrane: Molecular Simulation Study. J. Membr. Sci. 2015, 496, 108–117.(8) Wen, B.; Sun, C.; Bai, B. Inhibition Effect of a Non-Permeating Component on Gas Permeability of Nanoporous Graphene Membranes. Phys. Chem. Chem. Phys. 2015, 17 (36), 23619–23626.(9) Sun, C.; Wen, B.; Bai, B. Application of Nanoporous Graphene Membranes in Natural Gas Processing: Molecular Simulations of CH4/CO2, CH4/H2S and CH4/N2 Separation. Chem. Eng. Sci. 2015, 138, 616–621.

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POROUS CARBONS AS PROMISSING ENRICHMENT MATERIALS FOR TRACE LEVEL ANALYSIS OF PHARMACEUTICAL COMPOUNDS

Ana S. Mestre1,2*, Samir M. Ahmad1, Nuno R. Neng1, Conchi O. Ania3, J.M.F. Nogueira1, Ana P. Carvalho1

1 Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016, Lisboa, Portugal

2 REQUIMTE/LAQV, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto Portugal

3 ADPOR Group, Instituto Nacional del Carbón (INCAR-CSIC) 33080 Oviedo, Spain


The quantification of pharmaceutical compounds (PhCs) in real water matrices continues to be a challenge for analytical chemistry mainly due to their occurrence at trace levels (ppb to ppt). To overcome this problem scientists usually start by using enrichment techniques that allow to isolate and pre-concentrate the PhCs from the complex matrices prior to the quantification by, for example, chromatographic analysis. However the performance of the enrichment techniques is highly dependent on the structure and chemical properties of the target molecules. There are several static microextraction techniques to monitor priority pollutants, but most of them have low effectiveness when the quantification of polar compound at trace level is envisage. Among the available options, bar adsorptive microextraction (BAμE) [1] is a very promising methodology due to the large set of extractive solid materials (e.g. porous carbons or polymers) that can be selected to assure high performance even for polar analytes. In this work we present the potentialities of porous carbon materials obtained by conventional and innovative methodologies as enrichment materials for the BAμE technique. The enrichment step was followed by liquid desorption and the quantification of the pharmaceuticals in synthetic and environmental water matrices was made by high performance liquid chromatography with diode array detection (HPLC-DAD). The model compounds selected for this study included three pharmaceutical compounds (carbamazepine, mefenamic acid and diclofenac), two steroid hormones (17α-ethinylestradiol and 17β-estradiol), a lipid regulator (gemfibrozil), a lipid regulator metabolite (clofibric acid), and an antibacterial/antifungal agent (triclosan). The influence of the experimental conditions during enrichment step (e.g. matrice pH or extraction solvent) in the recovery yields will be discussed and correlated with the textural and surface properties of the carbons. The porous carbons obtained by hydrothermal carbonization of carbohydrates with a eutectic salt mixture proved to be promising materials for PhCs quantification in real aqueous matrices, outperforming the results of an activated carbon with a more developed micro- and mesoporous network.Reference[1] Nogueira, J.M.F. Analytica Chimica Acta. 2012, 757, 1-10.

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ON THE POSSIBILITIES OF PHOTOCHEMISTRY OF NANOPOROUS CARBONS

Alicia Gomis-Berenguer1*, Jesus Iniesta2, Conchi O. Ania1 1Instituto nacional del carbón (INCAR-CSIC), 33011 Oviedo, Spain

2Dept. Química Física e Instituto de Electroquímica, Universidad de Alicante, E-03080 Alicante, Spain


Recently, the self-photochemical activity of semiconductor-free nanoporous carbons under different irradiation conditions was demonstrated, showing their ability to photogenerate radical oxygen species in aqueous environments that are capable of converting high and low energy photons in chemical reactions. This has opened new perspectives in the field of applied photochemistry based on carbon materials covering environmental remediation, water splitting, enhanced adsorption/oxidation, or photoluminescence [1-3]. Although, different techniques have been used to study this behavior, such as photocatalytic performance, spectroscopic techniques and electrochemical tools, the exact mechanism governing the photochemical behavior of amorphous carbons is not yet fully understood.Aiming to through some light on the field, in this work we have combined flash photolysis and electrochemical tools to study the carbon/light interactions. Flash photolysis is a powerful technique that allowed, for the first time, register the transient species when an aqueous suspension of nanoporous carbon is irradiated by a laser flash, pointing out the formation of excited species when light interacts with carbon materials. On the other hand, the preparation of thin film carbon electrodes permitted to measure the phogenerated current when these electrodes are illuminated with polychromatic light, demonstrating the ability of nanoporous carbons to promote the photooxidation of water.

References [1] Velasco, Fonseca, Parra, Lima, Ania. Carbon. 2012, 50, 249-258.[2] Velasco, Lima, Ania. Angew. Chem.Int. Ed. 5 2014, 5, 4146-48.[3] Velo-Gala, López-Peñalver, Sánchez Polo, Rivera Utrilla. Applied Catalysis B: Environmental. 2013, 142-143, 694.

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ADSORPTION AND PHASE BEHAVIOR OF WATER IN NANOPOROUS CARBONS

Matthias Thommes *and Katie A. Cychosz Quantachrome Instruments, Boynton Beach, FL 33426

E-mail: [email protected]

We present a systematic study of the adsorption and phase behavior of water in a series of nanoporous carbons. Ordered mesoporous CMK carbons, as well as various active carbon samples have been characterized by combining nitrogen (77 K) and argon (87 K) adsorption with recently developed quenched solid density functional theory (QSDFT). Systematic, high resolution water adsorption experiments have been performed in the temperature range from 298-318 K in order to determine the effect of pore size and pore geometry on the adsorption, pore filling, condensation and hysteresis behavior. Water adsorption hysteresis was observed for both purely microporous and micro-mesoporous carbons. In order to better understand the origin of hysteresis, we also performed hysteresis scanning experiments and the obtained results will be discussed in this lecture. Furthermore, our results indicate that the water adsorption mechanism in mesopores is controlled by a clustering mechanism (similar to the water adsorption mechanism into micropores), while the desorption/evaporation process in carbon mesopores is in line with Kelvin type behavior. Summarizing, our studies reveal how the interplay between confined geometry effects, the strength of the adsorption forces and temperature influence the adsorption, wetting, and phase behavior of pore fluids. The obtained results demonstrate that water adsorption is quite sensitive to both small changes in pore structure and surface chemistry showing the potential of water adsorption as a powerful complimentary tool for the characterization of nanoporous carbons.

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HOW NY WOULD LOOK LIKE ON THE NANOSCALE: HIERARCHICAL POROUS CARBONS BY DESIGN

Nina Fechler1*, Thomas Jordan1, Thomas Berthold1, Christian Mbaya Mani1

1Max Planck Institute of Colloids and Interfaces, Department of Colloid Chemistry, Am Mühlenberg 1, 14476 Potsdam, Germany

*corresponding author email: [email protected] only high tech industry but also everyday life has implemented carbon materials in many ways.[1] However, besides the quest for convenient precursors, hard templating or activation processes still have to be applied for the introduction of an adequate porosity. Additionally, opposed to inorganic systems the rational synthesis of functional carbons remains one of the big challenges.[2] This is mainly related to the common necessity of high temperature treatments which essentially hinders external control during main parts of the synthesis. Therefore, approaches to circumvent this limitation are strongly needed and one possibility could be the “encoding of functionality” in the precursors, i.e. as much information as possible is already inherently present in the starting material. More

specifically, the pre-setting/introduction of periodic binding motifs in the binding pool of carbon will overcome plane homogeneous and thus restricted systems leading to mosaic-like functional patterns.[3, 4] Here, we recently introduced the one-pot synthesis of porous, cube-shaped carbon composites and carbon microparticles from a self-assembly process of zinc ions and squaric acid.[5] By thermal annealing of preformed cubic crystals, they can then be transformed into the corresponding

hierarchically porous zinc oxide carbon composites or carbon microparticles in high yields and retention of the macroscopic mesostructured (Fig. 1). Due to the homogeneous structure, the carbons possess controlled hierarchical pore architectures ranging from micro- to macro-pores with high surface areas of 1400 m2g-1. This makes these materials attractive for applications where high surface areas and mass-transport are important, which is representatively demonstrated with the applications as supercapacitor electrode material.References[1] H.-P. Cong; J.-F. Chena; S.-H. Yu, Chem. Soc. Rev. 2014, 43, 7295.[2] W. Li , Q. Yue , Y. Deng, D. Zhao, Adv. Mater. 2013, 25, 5129.[3] Y. Zheng, Y. Jiao, Y. Zhu, L. H. Li, Y. Han, Y. Chen, A. Du, M. Jaroniec, S. Z. Qiao, Nat. Commun. 2014, 5, 3783.[4] G.-P. Hao, G. Mondin, Z. Zheng, T. Biemelt, S. Klosz, R. Schubel, A. Eychmüller, S. Kaskel, Angew. Chem. Int. Ed. 2015, 54, 1941[5] C. M. Mani, T Berthold, N. Fechler, “Cubism” on the Nanoscale: from Squaric Acid to Porous Carbon Cubes, Small 2016, accepted.

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NANOPOROUS CARBONS DOPED WITH NANOPARTICULATED MATERIALS TOWARDS APPLICATIONS IN ELECTROSENSING AND

ELECTROCATALYSIS

Jesus Iniesta1*, Alicia Gomis-Berenguer2, Leticia García-Cruz1, Naiara Hernández-Ibáñez1, Vicente Montiel1

1 Departamento de Química Físisca e Instituto de Electroquímica, Universidad de Alicante, 03080 Alicante, Spain

2 ADPOR Group, Instituto Nacional del Carbón (INCAR, CSIC), 33011 Oviedo, Spain


Novel methodologies for the synthesis of a wide variety of nanoporous carbons with controlled textural properties and surface chemistry are prompting many emerging applications in the field of electrochemistry. Paradigmatic cases include the use of doped micro- and mesoporous carbons with nanoparticulated materials, resonating in applications such as electrosensing of analytes and biomarkers in complex biological systems, electrocatalytic oxidation of alcohols for fuel cells and electrosynthesis purposes, and bioelectrocatalysis for oxygen or carbon dioxide reduction or hydrogen oxidation among many others. The confinement of nanoparticulated systems on nanostructured porous carbons gains vital advantages regarding the highly distributed metallic nanoparticle and thereby lowering the aggregation, the high electroactive surface area and the enhancement of mechanical and electrochemical stability. This communication pays a more particular attention on the preparation, characterization and applications of nickel and cooper incorporation to a wide variety of nanoporous carbons highlighting on the electrooxidation of alcohols for sensing and electrocatalysis applications. Moreover, cooper doped nanoporous carbons have also been explored for the electrode preparation towards carbon dioxide electroreduction. Finally different free and cooper doped nanoporous carbons materials have been studied for the enzyme formate dehydrogenase immobilization to tackle the fabrication of a biocathode and to improve the enzyme stability in long term reactions. The feasibility of the nanoporous carbon-based electrode preparation at laboratory or pilot plant scale will shortly be described and opened for discussion.

Acknowlegements The authors acknowledge the Spanish MINECO through projects CTQ2013- 48280-C3-3-R and CTM2014/56770-R.

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CARBON MATERIALS WITH TUNABLE POROSITY AS SUPPORTS FOR BIOMOLECULES (AND BEYOND)

Miguel A. Montes-Morán*MCAT, Instituto Nacional del Carbón, INCAR-CSIC, Apartado 73 33080 Oviedo, Spain


The use of carbon materials as catalysts supports is well known and reported. However, their role in supporting biocatalysts is much more restricted. The key features that make carbons attractive in most adsorption applications are possibly related with the development of high-surface areas and micropore volumes. These two characteristics are, in principle, not very relevant when dealing with biomolecules which are in the nm size-range. The rise of the so-called ordered mesoporous carbons during the last decade prompted a growing interest of carbon materials for hosting enzymes and other proteins. The possibility of giving a further impulse to carbon materials in the field of biocatalysis comprises several aspects. Some of them are certainly familiar to carbon researchers in the field of adsorption, namely the tuning of the surface chemistry to improve the loading and activity of the biomolecules. Others are more related to some end-use properties, including their morphologies, particle size and cost.In this work, we present an easy route to prepare carbons with a pore size that can be adapted to the size of a given macromolecule. Carbons will also exhibit high enough mesopore volumes to host important quantities of such molecules. The key step to these novel carbons is to synthesize resorcinol/formaldehyde xerogels using microwave energy, which has been developed in our group and allows a precise control of the porosity. Carbonization of the resulting xerogels is carried out under controlled conditions to maintain the original porous texture. We will show results of the immobilization of a standard biomolecule (cytochrome c) on carbons with different mesopore average size to show the critical effects on protein loading and activity. The versatility of carbon surface chemistry and its impact on the immobilization of biomolecules is also highlighted.

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PHOTODESIGNING THE POROSITY AND SURFACE FUNCTIONALIZATION OF NANOPOROUS AND METAL-DECORATED

CARBONS

María C. Fernández de Córdoba1*, Mohamed Zaier2, Conchi O. Ania2 and Lavinia Balan2

1ADPOR Group, Instituto Nacional del Carbón (INCAR, CSIC), 33011 Oviedo, Spain2Institut de Sciences des Matériaux de Mulhouse (IS2M, CNRS), rue Jean Starcky, 68057 Mulhouse

Cedex, France

* [email protected]

Recent advances in synthetic chemistry has allowed to obtain nanoporous carbon materials with well-defined and controlled architectures (in terms of particle size and shape, uniformity of porosity, connectivity) that offer unexpected opportunities many different fields (covering for instance catalysis, sensing, adsorption, environmental chemistry, biomedical applications, energy conversion and so forth). This fact lies in both, the flexibility of the coordination chemistry of carbon atoms and in their ability to bind other heteroatoms either on the surface or inserted within the structural framework. Among different strategies, the use of sol-gel polycondensation methods has become an interesting route to obtain nanoporous carbons with varied features. However these procedures are strongly dependent on many operational parameters (such as nature of precursors, temperature and pH of the sol-gel reaction, post-synthetic treatments) and usually involve long reaction time (that limit the large-scale implementation of theses processes). The objective of this work was to explore the potentialities of the use of light activation to promote the cross-linking of polymeric precursors in the synthesis of nanoporous carbons and Ag/Au-functionalized carbons. By using various polymers and additives (electrolytes, chromophores), we have studied the effect of the carbon precursor on the chemical composition and textural properties of the resulting nanoporous carbons. Additionally we investigated the incorporation of either silver or gold salts to produce metal-polymer nanoassemblies and Ag/Au-functionalized nanoporous, evaluating the dispersion of the metallic nanoparticles within the carbon matrix, as well as the effect on the textural, structural and chemical features of the resulting carbons.

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HOMOGENEOUS DIAMETER DESIGN OF Ni-Mg/MWCNT AND Ni-Ca/MWCNT

Juan Matos1*, Jose J. Rangel-Méndez2, and Javier A. Arcivar-Orozco3

1Biomaterials Department, Technological Development Unit, University of Concepción, Chile. 2Division of Environmental Sciences, Instituto Potosino de Investigación Científica y Tecnológica, C.P. 78216, San Luís Potosí, S.L.P., México. 3Centro de Innovación

Aplicada en Tecnologías Competitivas (CIATEC), Omega 201, Fracc. Ind. Delta, 37545 León, Guanajuato, México.


Ultramicroporous activated carbon (AC) can be efficiently used as catalytic support for the homogeneous design of Ni-Mg/MWCNT and Ni-Ca/MWCNT from the dry methane reforming (DMR) under mild experimental conditions (650ºC, 1atm) on AC-supported Ni-based catalysts. It was found that Ni-Mg catalyst showed the highest initial catalytic activity followed by Ni-Ca/AC catalyst. As expected, catalysts promoted with the most basic oxides such as MgO or CaO showed moderate deactivation after 24h reaction ascribed to the basic Lewis behavior which stabilizes Ni-based catalysts. It was found that AC plays a template role for the production of highly homogeneous diameter of the multi-walled carbon nanotubes (MW-CNT) with a mean diameter of about 15nm. The evolution of the MW-CNT from the inside of the activated carbon framework to the external surface was also verified and the stability of Ni-Mg/AC catalyst was attributed to an efficient distribution of Ni nanoparticles. By contrast, Ni-Ca/MWCNT showed preferentially a nanoribbon shape. In both composites, an increase in the BET surface area was verified after several hours of reaction indicating both a clean-up of the pores of the AC-support and an additional contribution to the surface area by means of the CNT formed during reaction.

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APPLICATION OF NANOPOROUS CARBONS IN SELF-CLEANING SEMICONDUCTOR-BASED PAINTS

Raquel García-González*, María C. Fernández de Córdoba, Conchi O. Ania2

ADPOR Group, Instituto Nacional del Carbón (INCAR-CSIC) Oviedo (33011) Spain

* [email protected]

One of the most crucial aspects worldwide is air quality that needs a strict control to avoid health issues. Photocatalytic self-cleaning paints have become, since their appearance, an interesting alternative to remove pollutants in both indoor and outdoor applications. The oxidation process of self-cleaning paints may be applied to biological pollution (i.e., moulds) as well as to inorganic and organic contaminants. In the latter cases, the self-cleaning action aims to achieve the complete mineralization of the pollutants to obtain harmless products. In this context, the aim of this work is to study the incorporation of nanorpous carbons in the formulation of semiconductor-based self-cleaning paints, and to explore their role on the photocatalytic activity of the resulting paints, under several illumination conditions for indoor and outdoor applications. As additives in the formulation of the paints, we have selected nanoporous carbons showing photocatalytic activity in aqueous phase. The activity of these paints was compared to that of commercial ones (mainly based on TiO2) tested under different experimental conditions (as humidity, organic pollutant probes, nature of the semiconductor) and illumination systems, including simulated solar light.

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QUALITY OF INFORMATION ON MATERIALS POROUS STRUCTURE FROM VARIOUS MODELS FOR ADSORPTION PHENOMENA –

DISCUSSION

Magda Ziółkowska1*, Janina Milewska-Duda1, Jan T. Duda2

1AGH University of Science and Technology, Faculty of Energy and Fuels Al. Mickiewicza 30, 30-059 Kraków, Poland

2AGH University of Science and Technology, Faculty of Management ul. Gramatyka 8, 30-251 Kraków, Poland

*[email protected]

An identification of materials porous structure from experimental adsorption measurements requires an assumption of mathematical model that enables to identify certain surface properties and adsorption mechanism features. The aim of the mathematical modelling is to get the most reliable picture of the materials porous structure and in particular to obtain predictable quantities to provide the comparison between different types of materials. The results of such analyses and, in themselves, surface structure parameters may be essentially different, employing different interpretations of adsorption mechanisms and corresponding mathematical models.In particular, strongly recommended Density Functional Theory1 provides information on a pore volume distribution (with arbitrary presumed pore shape), whereas elaborated in our team, LBET class adsorption models2 enable to deduce the pore structure on the basis of adsorbate clusters distribution. An exemplary complementary study, applying both approaches i.e. DFT and LBET was already provided2, yielding quite satisfactory results for the both theories. Nevertheless, the question is what information drawn from such analyses is more valuable, from the viewpoint of practical identification of material porous structure, especially when fast evaluations are required e.g. in industrial applications.The flash talk is intended to discuss the challenge of the validity of material porous structure characterizations, as a simple tool for scientist and in industrial applications for characterization of materials porous structure.AcknowlegementsThe research led Author’s team is supported by the AGH University of Science and Technology in Krakow grant No. 11.11.210.213.References[1] Dąbrowski, A. Adv. Colloid Interface Sci. 2001, 93, 135–224.[2] Duda, J. T.; Jagiełło, L.; Jagiełło, J.; Milewska-Duda, J. Appl. Surf. Sci. 2007, 253,

5616–5621.

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ROLE OF NANOPOROUS CARBONS AS ADDITIVES TO WO3

PHOTOANODES

Alicia Gomis-Berenguer 1 , Jesús Iniesta2, Conchi O. Ania1

1 ADPOR Group, Instituto Nacional del Carbón (INCAR-CSIC) Oviedo (33011) Spain2 Dept. Química Física e Instituto de Electroquímica, Universidad de Alicante, E-03080 Alicante,

Spain

*[email protected]

Photoelectrochemical water splitting using semiconductor photoelectrodes is one of the most promising and environmentally friendly methods of capturing the energy of light and producing hydrogen from water. Numerous studies have examined the photoelectrocatalytic properties of tungsten trioxide (WO3) that is one of the most attractive semiconductor materials for the photoelectrochemical oxidation of water due to its energetically favorable valence band position for water oxidation, strong absorption within the solar spectrum (band gap between 2.4 and 2.8 eV) and appreciable photostability in water. However, it presents a rapid electron/hole recombination rate provoking a diminution on its activity under illumination conditions; for this reason extensive work has been carried out to improve the activity of this semiconductor, including different synthetic routes to control the particle size, crystallinity and morphology. Among different approaches, the use of nanoporous carbon materials as additives has been reported as an effective strategy to increase the photoactivity of semiconductors, due to their role as supports favoring the mass transfer and interfacial electronic effects, as well as their ability to generate oxygen radical species upon light exposure. Aiming at throwing some light on this topic, we have explored the role of nanoporous carbon additives with an amorphous structure and varied physicochemical properties in the photoelectrochemical performance of WO3/carbon mixtures. With this purpose, we have optimized the amount of carbon additive incorporated to the hybrid composites, as well as the interactions at the carbon/semiconductor interface upon illumination. Our results pointing out the outstanding role of the carbon material as additive through an increase in the exploitation of light energy thin film WO3/carbon electrodes, particularly under visible light.

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mailto:*[email protected]

TRYING TO SOLVE THE PUZZLE: THE BALANCE BETWEEN CHEMICAL AND STRUCTURAL PROPERTIES FOR THE

ENHANCEMENT OF SENSOR SENSITIVITY

N. A. Travlou1,2, M. Seredych1, E. Rodriguez Castellon3, T. J. Bandosz1,2*

1The City College of New York, CUNY, 160 Convent Ave, New York, NY, USA2Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, New York,

NY 100163Departamento de Química Inorgánica, Universidad de Málaga, 29071 Málaga, Spain


The application of carbon based materials as gas sensors has been extensively addressed in the literature. The requirement for high-cost doping processes targeting the improvement of the selectivity directed our attention to the application of nanoporous carbons as gas sensors. So far carbons of various structural and chemical features have been tested [1-3]. The sensitivity of their response is monitored based on the extent of the signal change upon their exposure to a target gas. Our results show that the sensors’ sensitivities are comparable to those reported for modified graphene. They also respond linearly to changes in ammonia concentrations. The mechanisms involved in their electrical performance include various processes, such as specific interactions of the gas molecules with surface groups, pore-filling with NH3, and electron-hole conductivity. The extent of these processes strongly depends on the surface chemical features and structural properties of nanoporous carbons. A different chemical arrangement of a specific heteroatom, may cause a different effect on the conduction type of the materials, depending on the type of the charge carries that predominates. Changes in the surface chemistry occur simultaneously with changes in porosity. The relationship between the volume of ultramicropores and the sensitivity of the chips may be either direct or indirect, suggesting that the structural and chemical features of the carbons can act either synergistically or competitively. Many concerns arise in attempt to improve the carbon chips sensitivity. Do surface chemical features which determine the conduction type of the materials play a predominant role in the electrical performance of a sensor? Is it possible that by altering the surface chemistry, we may control the type of charge carries and nature of specific interactions but simultaneously diminish the effect of porosity and physical adsorption on sensing? A great challenge to address is to find a subtle balance between the chemical and structural features of nanoporous carbons, aiming to enhance the carbon chip sensitivity.

References[1] N.A. Travlou; M. Seredych; E. Rodríguez-Castellon; T.J. Bandosz. J. Mater Chem. A, 2015, 3, 3821-3831[2] N.A. Travlou; M. Seredych; E. Rodríguez-Castellon; T.J. Bandosz. Carbon, 2016, 96, 1014-1021[3] N.A. Travlou; C. Ushay; E. Rodríguez-Castellon; T.J. Bandosz. ACS Sens., 2016, DOI: 10.1021/acssensors.6b0009

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POROSITY VS. CHEMISTRY: HOW TO INCREASE THE EFFICIENCY OF CH4 FORMATION IN CO2 ELECTROREDUCTION ON NANOPOROUS

CARONS?

Wanlu Li,1 Mykola Seredych,2 Enrique Rodríguez-Castellón3 and Teresa J. Bandosz 1, 2*

1Department of Chemistry and Biochemistry, The City College of New York, New York, NY, 10031, USA

2Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, New York, NY, 10016, USA

3Departamento de Química Inorgánica, Universidad de Málaga, Málaga, Spain

* corresponding author email: [email protected]

Heterogeneous nanoporous carbons have been studied as catalysts for CO2

electrochemical reduction in aqueous media. CO and CH4 were detected as the main reduction products with the predominance of the former species. CH4 the latter is exclusively formed on the heteroatom doped nanoporous carbons. The initial stage of the CO2 reduction to CH4 involves the reaction of CO2 to form adsorbed CO [1]. This process requires eight electrons at the same time with protons transfer. It is proposed that on nanoporous carbon, the strongly adsorbed CO intermediate in the ultra-micropores with a polarity provided by the heteroatoms likely accepts both electrons and protons simultaneously and thus CH4 is formed [2]. Both porous structure and surface chemistry are important for this process. Specific pores enhance the retention of adsorbed CO and surface chemistry provides the proper binding energy for electron transfer. Also surface acidity could influence the protonation of adsorbed CO for methane formation. However, there are still questions about how to balance the porous structure and surface chemistry to achieve high efficiency of CH4 formation. What is the best acidity for methane formation? What is the best porosity for CH4 formation and for further release it from the pores? The flash talk is intended to discuss about the challenges and problems in improving faradaic efficiency of CO2 reduction to CH4.

References[1] M. Gattrell, N. Gupta, A. Co, Journal of Electroanalytical Chemistry. 2006, 594,1–19

[2] W. Li, Seredych,M., Rodríguez-Castellón, E., Bandosz, T.J. ChemSusChem. 2016, 9, 606.

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GENERATION OF NANOPOROUS CARBONS BY MOLECULAR DYNAMICS

Carla de Tomas1*, Irene Suarez-Martinez, Nigel A. Marks 1Department of Physics and Astronomy, School of Science, Curtin University, Bentley Campus,

Perth, WA 6102, Australia


Short AbstractAtomistic models of nanoporous carbon have high value from both a conceptual and a practical point of view. Despite their utility, nanoporous carbon models are highly non-trivial to construct. Historically, a range of different approaches have been employed, the simplest being two infinite graphene sheets. More complex methods involve the manual construction of fullerenic fragments, with the most sophisticated approaches using simulation techniques such as Monte Carlo or Molecular Dynamics. Some simulations use experimental data as the starting point for atomistic reconstruction, while others attempt to mimic the laboratory formation process itself.

Here we present Molecular Dynamics (MD) simulations in which high-temperature annealing of an amorphous carbon precursor is employed to generate nanoporous carbon networks. The key to this approach lies in the choice of an appropriate and transferable interatomic potential. We consider five common potentials for carbon and find that the final structure is strongly dependent on the choice of potential (see Figure 1). To explain these differences we compute a range of microstructural properties such as ring statistics, coordination fractions and 002 ordering, and relate these to the description of bonding implicit in the potential. Using this insight we propose how best to use MD simulation to construct nanoporous carbon networks.

Figure 1: Nanoporous carbon structures generated by high-temperature annealing of a 1.5 g/cc amorphous

carbon precursor. The choice of carbon interatomic potential results in large differences in microstructure.

The images shown are a 1 nm slice from a simulation cell containing 32,768 atoms.

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HOW TO BUILD POROUS AND PHOTOACTIVE CARBON COMPOSITES PROVIDING MAXIMUM LIGHT ACTIVITY?

Mykola Seredych, Teresa J. Bandosz* Department of Chemistry, The City College of New York,160 Convent Ave, New York, NY, 10031,

USA


Graphitic carbon nitride, g-C3N4, is a new organic semiconductor, which has recently attracted an increased attention owing to its photoactive properties [1]. g-C3N4 is a nonporous materials of low electrical conductivity (~ 0.9x10-9 S m-1) with a band gap in the range of visible light (2.70 eV – 2.90 eV) [2]. Since the first two features limit g-C3N4

applications as an efficient photocatalyst or photoelectrocatalyst, various methods have been explored to enhance its surface properties [2]. To advance the functional features of g-C3N4 we built its composite with a visible light photoactive S-doped carbon derived from a commodity polymer, poly(sodium 4-styrene sulfonate) [3]. A recently developed dispersive force-based method [4] was used for the synthesis of the composite. Building the composite not only resulted in a synergistic effect in porosity, surface chemistry, and electrical conductivity but it also decreased the band gap energy from 2.91 eV for g-C3N4

to 2.79 eV for the composite. Both carbon and the composite show marked photosensitivity and only the composite reveals a visible light driven reduction activity under the cathodic current. Important assets of these materials for catalysis and solar energy harvesting are their porosity and electrical conductivity.

The flash talk is intended to discuss synthesis routes of porous and photoactive carbon-based composites of optimal visible light activity.

References [1] Wang, X.C.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, J.M.; Domen, K.; Antonietti, M. Nat. Mater. 2009, 8, 76-80.[2] Wang, X.; Blechert, S.; Antonietti, M. ACS Catal. 2012, 2, 1596-1606.[3] Singh, K.; Seredych, M.; Rodriguez Castellon, E.; Bandosz, T.J. ChemElectroChem 2014, 1, 565-572.[4] Seredych, M.; Bandosz, T.J. Carbon 2015, 95, 580-588.

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IN-SITU TECHNIQUES FOR CAPACITOR INVESTIGATION

Krzysztof Fic, Elżbieta Frąckowiak1*

1Poznan University of Technology, Institute of Chemistry and Technical Electrochemistry, Berdychowo 4, 60-965 Poznan, Poland


This study is focused on the employment of in-situ techniques such as Raman spectroscopy or Quartz Crystal Microbalance (EQCM) for determination of charge storage phenomena and recognition of ageing factors in activated carbon-based supercapacitors. In-situ Raman investigation for activated carbon electrodes operating in neutral aqueous media like Li2SO4 or LiNO3 solutions indicated that there is a mild oxidation of positive electrode during cycling (vibration modes from oxygen-based functionalities found) whereas the surface chemistry of negative electrode is rather stable. EQCM study confirmed significant frequency/mass variation on the positive side, whereas negative electrode remained stable. Interesting results were obtained for carbon electrodes operating in KI or KBr solutions. It has been confirmed that iodide anion undergoes several redox processes and strongly interacts with activated carbon surface. An oxidation of carbon surface has been identified near to iodide/iodine redox activity potentials. EQCM study confirmed the presence of various iodine species in the electrolyte. Carbon ‘corrosion’ has been observed especially for more concentrated iodide solution. However, we proved that IO3

- anion does not contribute significantly to this process. It has also been observed that bromide has similar affinity to carbon surface as iodide, but typical <C>-Br bonds have not been found to date.

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WORKSHOP PARTICIPANTS

NAME (last, first) Affiliation1 Ania, Conchi O CSIC, Spain2 Bandosz, Teresa J. City College of New York, USA3 Barrett, Philip Praxair, USA4 Beguin, Francois Poznan University of Technology, Poland5 Carvalho, Ana Paula Universidade de Lisboa, Portugal6 Celzard, Alain Université de Lorraine, France7 Kimberly Chung US Army ARDEC, USA8 De Tomas, Carla Curtin University, Australia9 Fechler, Nina Max Planck Institute of Colloids and Interfaces,

Germany10 Fernandez de Cordoba, Maria C

CSIC, Spain11 Fic, Krzysztof Poznan University of Technology, Poland12 Fierro, Vanessa

Institut Jean Lamour, CNRS- Université de Lorraine13 Frackowiak, Elzbieta Poznan University of Technology, Poland14 Garcia-Cruz, Leticia Unviersidad Alicante, Spain15 Garcia-Gonzalez, Raquel CSIC, Spain16 Gomis- Berenguer, Alicia CSIC, Spain17 Giannkoudakis, Dimitrios City College of New York, USA18 Kaneko, Katsumi Shinshu University, Japan19 Kaskel, Stefan TU Dresden, Germany20 Karwacki, Christopher U.S. Army ECBC, USA21 Laszlo, Krisztina Budapest University of Technology and Economics,

Hungary22 Li, Wanlu City College of New York, USA23 Matos, Juan University of Concepción, Chile24 Mestre, Ana Sofia Universidade de Lisboa, Portugal25 Montes, Miguel CSIC, Spain26 Ossler Fredrik Lund University, Sweden27 Seredych, Mykola City College of New York, USA28 Taylor, Bruce KX Technologies, USA29 Thommes, Matthias Quantachrome Instruments, USA30 Travlou, Nikolina City College of New York, USA31 Vallejos- Burjos, Fernando Shinshu University, Japan32 Venkataraman, Swaminathan US Army ARDEC, USA33 Wang, Jinwen KX Technologies, USA34 Ziolkowska, Magda AGH University of Science and Technology,

Poland

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teresa j. bandosz - beyond adsorption: new...

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