Věra Mansfeldová: Time-resolved potentiometry on liquid-liquid interface (Dissertation thesis) Abstract The aim of this work is to explore the method of temporal resolution in potentiometry as a new prospective electrochemical analytical technique. In connection with interface of two immiscible electrolyte solutions (ITIES) it may find utilization in analytical chemistry. This technique up to my knowledge has not been published yet. Potential response of analyte on liquid/liquid interface includes both distribution processes, their temporal resolution and redox processes, which specificity can modified by changing the composition of individual phases. Unlike "classic" potentiometric techniques, limited just to potential determination, this method, which I have given the working name "time resolved potentiometry at liquid-liquid interface" utilizes time development of potential response, which was found to be an analyte-specific function. The time resolved potentiometry presented in this work includes time course of potential response to analytical parameters specific for particular analyte. It brings series of data characterizing the analyte in given environment in a similar manner as spectra and may allow creating analyte-specific data package - fingerprint. Combination with ITIES allows, unlike...

Diese Dissertation unter dem Titel Experimentelle Bestimmung der elektronischen Eigenschaften anwendungsrelevanter Grenzflächen organischer Halbleiter mittels Photoelektronenspektroskopie wurde am Leibniz Institut für Festkürper- und Werkstoffforschung (IFW) Dresden am Institut für Festkörperforschung (IFF) unter der Betreuung von Prof. Dr. B. Büchner angefertigt. Zur wissenschaftlichen Untersuchung kamen hierbei zwei Typen anwendungsrelevanter Grenzflächen. Zum einem wurde der Einfluss einer Elektrodenpräparation unter Normalbedingungen mittels ex-situ Reinigungsverfahren im Vergleich zu insitu präparierten Kontakten auf das elektronische Verhalten des organischen Halbleiters Sexithiophen an Grenzflächen zu metallischen Substraten studiert. Als Substratmaterialien kamen hierbei die Metalle Silber, Palladium, Gold und Platin zum Einsatz. In einer zweiten Studie wurden die Grenzflächen der organischen Halbleiter Sexithiophen und Kupfer(II)- Phthalocyanin in Kontakt zu dünnen Filmen des Übergangsmetalloxides La0.7Sr0.3MnO3 untersucht. Auch hier wurde eine vergleichende Untersuchung für ex-situ und in-situ gereinigte La0.7Sr0.3MnO3-Kontakte durchgeführt. Die hierzu verwendeten Filme wurden im IFW Dresden am Institut für Metallische Werkstoffe (IMW) hergestellt. Auch im Rahmen dieser Untersuchungen stand der Einfluss von Sauerstoff auf das elektronische und chemische Verhalten an den Grenzflächen im Vordergrund.

Title Interaction of Organic Molecules with Metal Passivated Silicon Surfaces Studied via STM Author Petr Zimmermann Department Department of Plasma and Surface Science Supervisor Doc. RNDr. Pavel Sobotík, CSc. Department of Plasma and Surface Science Abstract Organic molecules offer a wide range of optical, electronic or chemical properties. Coupling them to silicon could pave way to novel applications and devices, however, a controlled molecular functionalization of silicon remains challenging due to the presence of highly reactive dangling bonds on its surfaces. We attempt to decrease the reactivity of low index silicon surfaces with an ultra-thin layer of a metal adsorbates and study their interaction with organic molecules via scanning tunnelling microscopy. In the first part we investigate the interaction of ethylene, a small unsaturated molecule, with tin and indium 1D chains grown on Si(001) - 2 × 1. The chains consist of dimers structurally analogous to the dimers of the underlying Si(001) - 2 × 1 surface. Aided by photoelectron spectroscopy we find that the Sn chains are less reactive than the Si(001) surface and that the absence of a π dimer bond renders indium chains inert. In the second part we study the interaction of copper phthalocyanine, a small macrocyclic heteroaromatic compound, with the...

For inorganic semiconductors such as silicon, crystalline order leads to bands in the electronic structure which give rise to drastic differences with respect to disordered materials. Distinct band features lead to photo-effect, and the band structure can be tuned to optimize the performance of the photovoltaic (PV) device. An example is the presence of an indirect band gap. For organic semiconductors, such effects are typically precluded, since most organic materials employed are disordered, which hampers their characterization and theoretical analysis. The inspiration for this thesis came from the very first evidence of an indirect band gap exhibited by highly ordered and crystalline porphyrin-based surface-mounted metal-organic framework (PP-based SURMOF) material [J. Liu et al. Angew. Chem. Int. Ed. 2015, 54, 7441]. The presence of an indirect band gap should in principle result in suppressed charge recombination and efficient charge separations which would significantly enhance the PV device performance. However, the energy gain from the electronic band dispersion in the reported Pd-PP-Zn-SURMOF is far too low (≈5 meV) and results in a very low photocurrent generation (efficiency 0.2%), which is certainly not sufficient for the application. Another noticeable shortcoming is the weakly absorbing Q-bands of the employed PP chromophore (Pd-metal containing porphyrinoid, Pd-PP) in the visible region of the solar spectrum. Nevertheless, this novel research has highlighted the potential to improve the photophysical properties of PP-based SURMOFs by (i) introducing various functional groups or metal ions to the PP-core and (ii) controlling the PP-stacking behavior in layered materials. To overcome the posed shortcomings of the PP-MOF prototype PV material and to exploit the potential of PP-based SURMOFs, we have employed the following approach to increase the light absorption and the electronic band dispersion. Firstly, we proposed a computationally feasible simplified time-dependent approach to investigate the light absorption properties of PP derivatives or related PP-containing materials. Secondly, we predicted the light absorption properties of multi-functionalized PPs (i.e. tuning the weakly absorbing Q-bands), thus allowing us to identify different PP linkers with different light absorption properties, allowing to bridge the so-called green gap. Finally, we incorporated the most promising PP linkers for the construction of SURMOFs and applied state-of-the-art DFT methods in various approximations to optimize the PP-stacking behavior to achieve the desired photophysical properties. Besides PPs, we have extended our investigations to phthalocyanines (PCs) as alternative individual SURMOF building blocks, because they do not only exhibit structural robustness and stability but also possess enhanced absorption in the visible and the near IR spectral regions in comparison to PPs. Hence, the exploitation of PCs could enrich the library of SURMOFs with the desired optical quality.

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Phthalocyanine (Pc) sind aufgrund ihrer einfachen Herstellung, bekannten Eigenschaften und großen chemischen Stabilität viel versprechende organische Substanzen für verschiedene Anwendungen in der Wissenschaft und Industrie. Im Rahmen dieser Arbeit wurden die elektronischen Eigenschaften von annellierten dinuklearen (ZnPc-ZnPc, H2Pc-H2Pc) und trinuklearen Pc im Vergleich zu mononuklearen Pc (H2Pc, ZnPc) und einfach kovalent über eine Ethandiol-Brücke verknüpfte dimere Pc (DH2, DZn) untersucht. Die stationären Absorptions- und Fluoreszenzspektren von DZn sind vergleichbar mit denen eines unsymmetrisch substituierten mononuklearen ZnPc. Die elektronischen Eigenschaften von DH2 sind von drei verschiedenen Phänomenen beeinflusst: Aggregation, exzitonische Wechselwirkung und der Existenz unterschiedlicher NH-Tautomere. Die große bathochrome Verschiebung der Q-Bande von annellierten dinuklearen und trinuklearen Pc im Vergleich zu den mononuklearen Analogon zeigt die Expansion des pi-Elektronensystems in solchen annellierten Systemen. Zeitabhängige Dichtefunktionalrechnungen (TD-DFT) ergaben für das dinukleare H2Pc-H2Pc erstmals drei verschiedene NH-Tautomere mit unterschiedlichen Molekülorbitalen und Absorptionsspektren. Ein Vergleich der berechneten Resultate mit den experimentellen Ergebnissen aus stationärer und zeitaufgelöster Spektroskopie ermöglichte erstmals die Bestimmung der elektronischen Parameter der einzelnen NH-Tautomere des annellierten dinuklearen H2Pc-H2Pc in Lösung. In Übereinstimmung mit den TD-DFT-Rechnungen wurde nur eine mögliche Spezies für das dinukleare ZnPc-ZnPc im Experiment gefunden. Erste spektroskopische Untersuchungen an den neuen trinuklearen annellierten Pc ergaben einen Hinweis darauf, dass die NH-Tautomerie einen großen Einfluss auf deren elektronischen Eigenschaften selbst bei Raumtemperatur hat. / Phthalocyanines (Pcs) are auspicious molecules for a broad variety of scientific and industrial applications, because of their simple production, well-defined properties and high chemical stability. The photophysical properties of annulated dinuclear (ZnPc-ZnPc, H2Pc-H2Pc) and trinuclear Pcs in comparison to mononuclear Pcs (H2Pc, ZnPc) and dimeric Pcs, covalently linked by an ethandiol-bond (DH2 and DZn), were investigated in this study. Absorption and fluorescence spectra of dimeric DZn resemble those of an asymmetric substituted mononuclear ZnPc. The photophysical properties of DH2 are influenced by three different phenomena, namely aggregation, excitonic interaction and the existence of different NH-tautomers. Strong bathochromic Q-band-shifts of annulated dinuclear and trinuclear Pcs in comparison to the mononuclear analogues show expansion of the pi-electron system in such annulated molecules. For the first time, the existence of three NH-tautomers with different molecular orbitals and absorption spectra were shown by time-dependent density functional theory (TD-DFT) calculations of dinuclear H2Pc-H2Pc. Theoretical calculations and experimental data obtained by steady state and time resolved spectroscopy were matched. This approach enabled the determination of photophysical properties of individual NH-tautomers of dinuclear H2Pc-H2Pc in solution. In accordance to the TD-DFT calculations only one dinuclear ZnPc-ZnPc species was experimentally established. First spectroscopic investigations of novel trinuclear Pc gave an evidence that NH-tautomerism might have a strong influence on their photophysical properties, even at room temperature.

Made available in DSpace on 2017-07-24T19:38:07Z (GMT). No. of bitstreams: 1 Cleverson S Santos.pdf: 2872449 bytes, checksum: 6d5838a843155793c2eb115ea3d233c4 (MD5) Previous issue date: 2012-03-13 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The research focused on the development of electrochemical sensors based on LBL films have grown exponentially in recent years. In this context, this paper reports the development of an electrochemical sensor using the Layer-by-layer (LbL) technique, which enables the construction of ultrathin films from electrostatic interactions between oppositely charged polyelectrolytes. For this purpose, the tetrasulfonated nickel phthalocyanine (NiTsPc) was used as polyanion molecule and the 3-n-propilpyridinium silsesquioxane chloride (SiPy+Cl-) as the polycation. This silsesquioxane polyelectrolyte is an excellent ion exchange and has high ability to form stable films on the surface of solid substrates. The LbL films were built using two different architectures: one with an outer layer of phthalocyanine designated as (SiPy+Cl-/NiTsPc)n and another with the phthalocyanine as the inner layer, (NiTsPc/SiPy+Cl-)n with different bilayers, (where n = number of bilayers). The deposition of the bilayers was monitored using the UV-VIS spectroscopy in the region from 500 to 800 nm, where the phthalocyanines exhibit two absorption bands, one related to the dimeric species at 630 nm and another at 669 nm related to monomeric form. It was observed that the parameters:immersion time, pH and concentration directly influenced the construction of these films and therefore they were optimized. The optimized parameters were: immersion time of 280 s, pH = 8 and concentrations of polyeletrolytes solutions of 2 mg mL-1, which provided stable and homogeneous films, with higher concentrations of monomeric species. Monitoring the bilayers deposition in the UV-VIS region, a linear relationship was obtained between the absorbance and the number of bilayers deposited. FTIR and Raman spectra showed that the interactions between the polyelectrolytes occurs by the SO3 groups in the structure of tetrasulfonated phthalocyanines with the pyridinium groups present in the structure of the SiPy+Cl-. Using the AFM technique, it was observed that the average roughness of the films decreased with the increase of bilayers. On the other hand, the thickness of the films increased with the number of bilayers, and the average thickness of each bilayer was 22 nm for the architecture (SiPy+Cl-/NiTsPc)n, and 19.2 nm for the opposite configuration. The electrodes were applied for simultaneous determination of dopamine (DA) in the presence of the interfering species, such as ascorbic acid (AA) and uric (UA). It was observed that the architecture as well as the thickness of the films has influenced significantly the electrochemical response in the presence of analytes. The film with the highest current density and less positive potential values for these analytes was (SiPy+Cl-/NiTsPc)2. For this electrode, f om the cyclic voltammetry technique, anodic peaks were observed at 0.30 V,0.68 V and 0.74 V in the presence of DA, AA and UA, respectively. Studies in different scan rates in presence of dopamine showed that the kinetics of electron transfer is controlled by diffusion of species to the electrode surface. Using the square wave voltammetry, DA was detected in presence of AA with a peak separation potential of 350 mV. However, for a fixed concentration of DA, it was observed an increase of the intensity of peak current with increasing of AA concentration, which is an indication that the AA electrocatalyzes the oxidation reaction of DA to dopaminequinone, causing an increase in the current, which prevents the accurate determination of these analytes simultaneously. On the other hand, in the presence of UA in a fixed concentration of 4.7 x 10-4 mol L-1, it was possible to quantify DA in the range of 1.0 x 10-5 to 9.9 x 10-5 mol L-1 with a detection limit of 2.37 x 10-6 mol L-1 and quantification limit of 7.9 x 10-6 mol L-1 with peak separation Ep= 500 mV. By varying both the concentration of DA and UA, in the range of 1.0 x 10-4 to 9.0 x 10-4 mol L-1 for DA and 1.0 x 10-5 to 9.9 x 10-5 mol L-1 for UA, it was obtained a correlation coefficient of R = 0.997 and R = 0.988 for AU and DA respectively. The results showed that the electrode (SiPy+Cl-/NiTsPc)2 is selective and sensitive for DA determination in presence of interfering species AA and UA. / As pesquisas voltadas para o desenvolvimento de sensores eletroquímicos a base de filmes LbL têm crescido exponencialmente nos últimos anos. Neste âmbito, este trabalho relata o desenvolvimento de um sensor eletroquímico, utilizando a técnica Layer-by-Layer (LbL), a qual possibilita a construção de filmes ultrafinos a partir de interações eletrostáticas entre polieletrólitos de cargas opostas. Para tanto foi utilizado como poliânion a molécula ftalocianina tetrassulfonada de níquel (NiTsPc), e como policátion o cloreto de 3-npropilpiridínio silsesquioxano (SiPy+Cl-). Tal composto constitui um excelente trocador iônico, além de apresentar alta capacidade de formação de filmes estáveis sobre a superfície de substratos sólidos. Foram construídos filmes em duas arquiteturas: uma com a ftalocianina na camada mais externa designada como (SiPy+Cl-/NiTsPc)n e outra com esta na camada mais interna, (NiTsPc/SiPy+Cl-)n com diferentes bicamadas, (onde n= número de bicamadas). A deposição das bicamadas foi monitorada utilizando-se a técnica de espectroscopia de absorção na região do UV-VIS, mais precisamente na região de 500 a 800 nm, onde as ftalocianinas apresentam duas bandas de absorção, uma referente a forma agregada em 630 nm e outra referente a forma monomérica em 669 nm. Foi observado que as variáveis: tempo de imersão, pH e concentração dos polieletrólito influenciam diretamente na construção dos filmes e portanto estas foram otimizadas. Os parâmetros otimizados foram: tempo de imersão de 280 s, pH = 8 e concentrações de 2 mg mL-1 obtendo-se filmes estáveis e homogêneos, com maiores concentrações de espécies monoméricas em relação a espécies agregadas. O monitoramento da deposição das bicamadas na região do UV-VIS mostrou uma relação linear entre absorbância e o número de bicamadas depositadas. Os espectros de FTIR e Raman, evidenciaram as interações entre os grupos SO3 presentes na estrutura das ftalocianinas tetrassulfonadas com os grupos piridínios presentes na estrutura do SiPy+Cl-. Utilizando a técnica de microscopia de força atômica foi possível verificar que a rugosidade média dos filmes diminuiu em função do aumento do número de bicamadas. Por outro lado, a espessura dos filmes aumentou com o número de bicamadas, sendo que a espessura média de cada bicamada foi de 22 nm para a configuração (SiPy+Cl-/NiTsPc)n, e de 19,2 nm para a configuração oposta. Os eletrodos foram aplicados na determinação simultânea de dopamina (DA) em meio aos interferentes ácido ascórbico (AA) e úrico (AU). Observou-se que a arquitetura assim como a espessura dos filmes influenciaram de maneira significativa na resposta eletroquímica na presença dos analitos. O filme que apresentou maior intensidade de corrente e valores de potencial de pico menos positivos foi (SiPy+Cl-/NiTsPc)2. Para este eletrodo, a partir da técnica de voltametria cíclica, foram observados picos anódicos em 0,30 V, 0,68 V e 0,74 V, na presença de DA, AA e AU, respectivamente. Estudos da variação da velocidade de varredura para dopamina mostraram que a cinética de transferência eletrônica é controlada pela difusão de espécies a superfície do eletrodo. Utilizando a técnica de voltametria de onda quadrada, detectou-se DA na presença de AA, com separação de potenciais de pico de 350 mV. No entanto, para uma concentração fixa de DA, foi observado um aumento da intensidade de corrente de pico com o aumento da concentração de AA, o que é um indicativo de que o AA eletrocatalisa a reação de oxidação de dopaminaquinona a DA novamente, o que impossibilita a determinação precisa destes analitos simultaneamente. Por outro lado, na presença de AU com concentração fixa de 4,7 x 10-4 mol L-1, foi possível quantificar DA na faixa de 1,0 x 10-5 a 9,9 x 10-5 mol L-1 com limite de detecção de 2,4 x 10-6 mol L-1 e quantificação de 7,9 x 10-6 mol L-1 com separação de potencial de pico de 500 mV. Variando-se simultaneamente a concentração das duas espécies, DA e AU, na faixa de 1,0 x 10-4 a 9,0 x 10-4 mol L-1 para DA e 1,0 x 10-5 a 9,9 x 10-5 mol L-1 para AU, obteve-se coeficiente de correlação iguais a R = 0,997 e R = 0,988, para AU e DA respectivamente. Os resultados mostram que o eletrodo é seletivo e sensível a determinação de DA em meio aos interferentes AA e AU.

L’approche « bottum-up » via l’auto-assemblage moléculaire est considéré comme une voie prometteuse pour contrôler la fabrication de nouveaux matériaux et leur intégration dans des dispositifs hybrides présentant de propriétés nouvelles. Dans ce travail, nous avons synthétisé plusieurs hybrides à base de molécules organiques (fullerène, porphyrines, phtalocyanine), d’oligonucléotides ou de nanotubes de carbone.Dans un premier temps, nous nous sommes intéressés à la synthèse d’une nouvelle famille de produits constituée d’une unité C60 lié à deux chromophores positionnés face à face et permettant la formation de complexes hôte-invités. Nous avons montré que ces composés s’assemblent pour donner des structures supramoléculaires en solution et sur surface. Les interactions électroniques et la compléxation entre le fullerène et les deux chromophores (porphyrines et phtalocyanines) ont été étudiées par spectroscopie optique et RMN ainsi que par voltammétrie cyclique.Parmi les outils de l’approche « bottom-up », l’ADN a montré son extraordinaire potentiel pour la fabrication d’assemblages bio-dirigés. En effet, la synthèse de matériaux hybrides à base d’ADN permet un contrôle précis (théoriquement à l’échelle d’une base, ~3,4Å) du positionnement des groupements fonctionnels dans un matériau. Dans le but de former des réseaux bi- et tridimensionnels à base d’ADN permettant le positionnement de nano-objets, nous avons synthétisé des hybrides à base d’oligonucléotides et de porphyrines (molécule 2D) ou d’adamantane (molécule 3D). Des édifices supramoléculaires simples ont été réalisés et le travail se poursuit en vue de la réalisation de réseaux fonctionnels.Enfin, dans une dernière partie, nous nous sommes intéressés à la fonctionnalisation des nanotubes de carbone monoparoi (SWNT) avec des chromophores de type porphyrines et phtalocyanines. Alors que les porphyrines présentent une absorption intense presque exclusivement dans le bleu, les phtalocyanines absorbent principalement dans le rouge. Combiner ces deux chromophores à la surface des nanotubes de carbone présente donc un intérêt particulier pour la collecte de lumière car les deux composés absorbent des régions complémentaires du spectre visible. Ce travail ouvre la voie vers l'étude des propriétés optoélectroniques des hybrides à base de nanotubes et en particulier leur utilisation pour la conversion d’énergie lumineuse en énergie électrique (application photovoltaïque). / An Approach "bottum-up" via molecular self-assembly is considered as a promising way to control the manufacture of new materials and their integration into hybrid devices with novel properties. In this work, we have synthesized several hybrids based on organic molecules (fullerene, porphyrin, phthalocyanine), oligonucleotides or carbon nanotubes.At first, we were interested in the synthesis of a new family of products consisting of a unit C60 linked to two chromophores positioned face to face and allowing the formation of host-guest complexes. We have shown that these compounds are combined to give supramolecular structures in solution and on the surface. Electronic interactions and complexation between fullerene and the two chromophores (porphyrins and phthalocyanines) were studied by NMR and optical spectroscopy as well as cyclic voltammetry.Among the tools of the "bottom-up", DNA showed its tremendous potential for the production of bio-directed assembly. Indeed, the synthesis of hybrid materials based DNA allows precise control (theoretically on the scale of a base, ~ 3.4 Å) of the positioning of the functional groups in a material. In order to form networks and bi-dimensional DNA-based for positioning nano-objects, we have synthesized hybrid oligonucleotide-based and porphyrin molecule (2D) or adamantane molecule (3D). Supramolecular structures have been made and this work is ongoing to achieve functional networks.Finally, in a last part, we are interested in the functionalization of single-walled carbon nanotubes (SWNTs) with chromophores like porphyrins and phthalocyanines. While porphyrins exhibit almost exclusively an intense absorption in the blue (around 420-440 nm), phtalocyanines absorb mainly in the red spectral region. Taken together these two chromophores have interesting light harvesting, photophysical and redox properties; the two components will participate independently to increase the overall absorption in the visible range of the solar spectrum. This work opens the route to study the optoelectronic properties of hybrid nanotube and in particular their use for the conversion of light energy into electrical energy (photovoltaic application).

Neste trabalho, foram desenvolvidos sensores eletroquímicos para a detecção amperométrica do óxido nítrico (NO) fundamentada na aplicação da ftalocianina tetrasulfonada de níquel (NiTsPc) e do poli(5-amino 1-naftol) (poli(5-NH2 1-NAP)). NiTsPc foi eletrodepositada por voltametria cíclica sobre o eletrodo de platina e caracterizada eletroquimicamente em diferentes pHs. A detecção amperométrica de NO foi bastante sensível, mas o eletrodo não apresenta seletividade suficiente, motivo pelo qual este material foi substituído pelo poli(5-NH2 1-NAP) modificado com citocromo c. A imobilização foi caracterizada por voltametria cíclica e microbalança a cristal de quartzo. As detecções amperométricas do NO foram efetuadas aplicando o potencial em -0,6 V e foi observado que a variação da corrente devido à adição do NO ocorreu somente no segundo dia após a imobilização da proteína, o que pode estar relacionado a mudanças de estrutura do citcocromo c covalentemente ligado. O poli(5-NH2 1-NAP) foi também eletropolimerizado sobre nanotubos de carbono, obtendo assim um eletrodo nanoestruturado e o citocromo c foi imobilizado nessa estrutura. Assim como para os eletrodos maciços, ele não respondeu ao NO logo após a imobilização do citocromo c, respondendo somente no segundo dia e apresentou um melhor desempenho devido a sua maior área superficial. / In this work, electrochemical sensors for nitric oxide (NO) amperometric detection were prepared. For this purpose nickel tetrasulfonated phthalocyanine (NiTsPc) and poly(5-amino 1-naphthol) (poly(5-NH2 1-NAP)) modified with cytochrome c were applied. NiTsPc was electropolymerized by cyclic voltammery at platinum electrode and were electrochemically characterized in differents pHs. NO amperometric detections were very sensitive, but the electrode does not present satisfactory selectivity, and because of this, the material was replaced by poly(5-NH2 1-NAP) modified with cytochrome c. The immobilization was characterized by cyclic voltammetry and electrochemical crystal microbalance. NO amperometric detection has been carried out by applying -0.6 V and it was observed that the current due the NO sensing was only observed at the second day after protein immobilization. This can be related with cytochrome c structural change. For nanostructuring the surface of Poly(5-NH2 1-NAP) it was electropolymerized on carbon nanotubes felt electrodes and cytochrome c was immobilized. As well as the bulk electrode, the nanostructured one did not sense NO immediately after the cytochrome c immobilization, being possible to observe current only after the second day displaying a much better performance due to its high superficial area.