Search results for: Csaba Barnabas Horvath

Authors: Jing-Yang Chung, Chi-Wei Liao, Jing Li, Bor Kae Chang, Cheng-Yu Wang

Abstract:

Chemical hydride ammonia borane (AB, NH3BH3) draws attentions to hydrogen energy researches for its high theoretical gravimetrical capacity (19.6 wt%). Nevertheless, the elevated AB decomposition temperatures (Td) and unwanted byproducts are main hurdles in practical application. It was reported that the byproducts and Td can be reduced with nanoconfinement technique, in which AB molecules are confined in porous materials, such as porous carbon, zeolite, metal-organic frameworks (MOFs), etc. Although nanoconfinement empirically shows effectiveness on hydrogen generation temperature reduction in AB, the theoretical mechanism is debatable. Low Td was reported in AB@IRMOF-1 (Zn4O(BDC)3, BDC = benzenedicarboxylate), where Zn atoms form closed metal clusters secondary building unit (SBU) with no exposed active sites. Other than nanosized hydride, it was also observed that catalyst addition facilitates AB decomposition in the composite of Li-catalyzed carbon CMK-3, MOF JUC-32-Y with exposed Y3+, etc. It is believed that nanosized AB is critical for lowering Td, while active sites eliminate byproducts. Nonetheless, some researchers claimed that it is the catalytic sites that are the critical factor to reduce Td, instead of the hydride size. The group physically ground AB with ZIF-8 (zeolitic imidazolate frameworks, (Zn(2-methylimidazolate)2)), and found similar reduced Td phenomenon, even though AB molecules were not ‘confined’ or forming nanoparticles by physical hand grinding. It shows the catalytic reaction, not nanoconfinement, leads to AB dehydrogenation promotion. In this research, we explored the possible criteria of hydrogen production temperature from nanoconfined AB in MOFs with different pore sizes and active sites. MOFs with metal SBU such as Zn (IRMOF), Zr (UiO), and Al (MIL-53), accompanying with various organic ligands (BDC and BPDC; BPDC = biphenyldicarboxylate) were modified with AB. Excess MOFs were used for AB size constrained in micropores estimated by revisiting Horvath-Kawazoe model. AB dissolved in methanol was added to MOFs crystalline with MOF pore volume to AB ratio 4:1, and the slurry was dried under vacuum to collect AB@MOF powders. With TPD-MS (temperature programmed desorption with mass spectroscopy), we observed Td was reduced with smaller MOF pores. For example, it was reduced from 100°C to 64°C when MOF micropore ~1 nm, while ~90°C with pore size up to 5 nm. The behavior of Td as a function of AB crystalline radius obeys thermodynamics when the Gibbs free energy of AB decomposition is zero, and no obvious correlation with metal type was observed. In conclusion, we discovered Td of AB is proportional to the reciprocal of MOF pore size, possibly stronger than the effect of active sites.

Keywords: ammonia borane, chemical hydride, metal-organic framework, nanoconfinement

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Authors: Gabriela T. Nakashima, Elias R. D. Padilla, Joao L. Barros, Gabriela B. Belini, Hiroyuki Yamamoto, Fabio M. Yamaji

Abstract:

Biochar can be an alternative to use sugarcane trash. Biochar is a solid material obtained from pyrolysis, that is a biomass thermal degradation with low or no O₂ concentration. Pyrolysis transforms the carbon that is commonly found in other organic structures into a carbon with more stability that can resist microbial decomposition. Biochar has a versatility of uses such as soil fertility, carbon sequestration, energy generation, ecological restoration, and soil remediation. Biochar has a great ability to retain water and nutrients in the soil so that this material can improve the efficiency of irrigation and fertilization. The aim of this study was to characterize biochar produced from sugarcane trash in three different pyrolysis temperatures and determine the lowest temperature with the high yield and carbon content. Physical characterization of this biochar was performed to help the evaluation for the best production conditions. Sugarcane (Saccharum officinarum) trash was collected at Corredeira Farm, located in Ibaté, São Paulo State, Brazil. The farm has 800 hectares of planted area with an average yield of 87 t·ha⁻¹. The sugarcane varieties planted on the farm are: RB 855453, RB 867515, RB 855536, SP 803280, SP 813250. Sugarcane trash was dried and crushed into 50 mm pieces. Crucibles and lids were used to settle the sugarcane trash samples. The higher amount of sugarcane trash was added to the crucible to avoid the O₂ concentration. Biochar production was performed in three different pyrolysis temperatures (200°C, 325°C, 450°C) in 2 hours residence time in the muffle furnace. Gravimetric yield of biochar was obtained. Proximate analysis of biochar was done using ASTM E-872 and ABNT NBR 8112. Volatile matter and ash content were calculated by direct weight loss and fixed carbon content calculated by difference. Porosity measurement was evaluated using an automatic gas adsorption device, Autosorb-1, with CO₂ described by Nakatani. Approximately 0.5 g of biochar in 2 mm particle sizes were used for each measurement. Vacuum outgassing was performed as a pre-treatment in different conditions for each biochar temperature. The pore size distribution of micropores was determined using Horváth-Kawazoe method. Biochar presented different colors for each treatment. Biochar - 200°C presented a higher number of pieces with 10mm or more and did not present the dark black color like other treatments after 2 h residence time in muffle furnace. Also, this treatment had the higher content of volatiles and the lower amount of fixed carbon. In porosity analysis, while the temperature treatments increase, the amount of pores also increase. The increase in temperature resulted in a biochar with a better quality. The pores in biochar can help in the soil aeration, adsorption, water retention. Acknowledgment: This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brazil – PROAP-CAPES, PDSE and CAPES - Finance Code 001.

Keywords: proximate analysis, pyrolysis, soil amendment, sugarcane straw

Procedia PDF Downloads 168

Authors: Tibor Ajtai, Máté Pintér, Noémi Utry, Gergely Kiss-Albert, Andrea Palágyi, László Manczinger, Csaba Vágvölgyi, Gábor Szabó, Zoltán Bozóki

Abstract:

According to the best knowledge of the authors, here we experimentally demonstrate first, a quantified correlation between the real-time measured optical feature of the ambient and the off-line measured toxicity data. Finally, using these correlations we are presenting a novel methodology for real time characterisation of ambient toxicity based on the multi wavelength aerosol phase photoacoustic measurement. Ambient carbonaceous particulate matter is one of the most intensively studied atmospheric constituent in climate science nowadays. Beyond their climatic impact, atmospheric soot also plays an important role as an air pollutant that harms human health. Moreover, according to the latest scientific assessments ambient soot is the second most important anthropogenic emission source, while in health aspect its being one of the most harmful atmospheric constituents as well. Despite of its importance, generally accepted standard methodology for the quantitative determination of ambient toxicology is not available yet. Dominantly, ambient toxicology measurement is based on the posterior analysis of filter accumulated aerosol with limited time resolution. Most of the toxicological studies are based on operational definitions using different measurement protocols therefore the comprehensive analysis of the existing data set is really limited in many cases. The situation is further complicated by the fact that even during its relatively short residence time the physicochemical features of the aerosol can be masked significantly by the actual ambient factors. Therefore, decreasing the time resolution of the existing methodology and developing real-time methodology for air quality monitoring are really actual issues in the air pollution research. During the last decades many experimental studies have verified that there is a relation between the chemical composition and the absorption feature quantified by Absorption Angström Exponent (AAE) of the carbonaceous particulate matter. Although the scientific community are in the common platform that the PhotoAcoustic Spectroscopy (PAS) is the only methodology that can measure the light absorption by aerosol with accurate and reliable way so far, the multi-wavelength PAS which are able to selectively characterise the wavelength dependency of absorption has become only available in the last decade. In this study, the first results of the intensive measurement campaign focusing the physicochemical and toxicological characterisation of ambient particulate matter are presented. Here we demonstrate the complete microphysical characterisation of winter time urban ambient including optical absorption and scattering as well as size distribution using our recently developed state of the art multi-wavelength photoacoustic instrument (4λ-PAS), integrating nephelometer (Aurora 3000) as well as single mobility particle sizer and optical particle counter (SMPS+C). Beyond this on-line characterisation of the ambient, we also demonstrate the results of the eco-, cyto- and genotoxicity measurements of ambient aerosol based on the posterior analysis of filter accumulated aerosol with 6h time resolution. We demonstrate a diurnal variation of toxicities and AAE data deduced directly from the multi-wavelength absorption measurement results.

Keywords: photoacoustic spectroscopy, absorption Angström exponent, toxicity, Ames-test

Procedia PDF Downloads 276