Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

The effect of the relationship between particle size (d), inter-particle distance (x(i)), and metal loading (y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5-3 nm) and x(i)/d (>5) values, was evaluated. It was found that for y < 30 wt%, the optimum values of both d and x(i)/d can be always obtained. For y >= 30 wt%, instead, the positive effect of a thinner catalyst layer of the fuel cell electrode than that using catalysts with y < 30 wt% is concomitant to a decrease of the effective catalyst surface area due to an increase of d and/or a decrease of x(i)/d compared to their optimum values, with in turns gives rise to a decrease in the catalytic activity. The effect of the x(i)/d ratio has been successfully verified by experimental results on ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x(i)/d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.

CARBON MARKET AND INSTITUTIONS: OPPORTUNITIES IN THE SEARCH OF A NEW MODEL FOR DEVELOPMENT

Seeking alternatives for the economic system to face the several crises it has gone through lately (electrical power, cultural, financing and technological) brought about a new market involving the Kyoto Protocol signatory countries: the carbon market. The present article aims at assessing the carbon market institutional issue in Brazil by identifying the risks and opportunities inherent to the institutional agent characteristics and to that market rules. The research methodology was bibliographic and based on the analysis of the Securities and Exchange Commission of Brazil (Comissao de Valores Mobiliarios and Bolsa Mercantil de Valores) contents. Its theoretical basis rests on concepts of the institution and the new institutional economy. The results show that in spite of the risks and institutional problems it involves, the carbon market is promising due to the opportunities create by new technologies and energies developed to achieve and sustain the capitalist system new cycle, addressed to produce a clean development.

Deep ocean ventilation, carbon isotopes, marine sedimentation and the deglacial CO2 rise

The link between the atmospheric CO2 level and the ventilation state of the deep ocean is an important building block of the key hypotheses put forth to explain glacial-interglacial CO2 fluctuations. In this study, we systematically examine the sensitivity of atmospheric CO2 and its carbon isotope composition to changes in deep ocean ventilation, the ocean carbon pumps, and sediment formation in a global three-dimensional ocean-sediment carbon cycle model. Our results provide support for the hypothesis that a break up of Southern Ocean stratification and invigorated deep ocean ventilation were the dominant drivers for the early deglacial CO2 rise of ~35 ppm between the Last Glacial Maximum and 14.6 ka BP. Another rise of 10 ppm until the end of the Holocene is attributed to carbonate compensation responding to the early deglacial change in ocean circulation. Our reasoning is based on a multi-proxy analysis which indicates that an acceleration of deep ocean ventilation during the early deglaciation is not only consistent with recorded atmospheric CO2 but also with the reconstructed opal sedimentation peak in the Southern Ocean at around 16 ka BP, the record of atmospheric δ13CCO2, and the reconstructed changes in the Pacific CaCO3 saturation horizon.

Deep ocean ventilation, carbon isotopes, marine sedimentation and the deglacial CO2 rise

The link between the atmospheric CO2 level and the ventilation state of the deep ocean is an important building block of the key hypotheses put forth to explain glacial-interglacial CO2 fluctuations. In this study, we systematically examine the sensitivity of atmospheric CO2 and its carbon isotope composition to changes in deep ocean ventilation, the ocean carbon pumps, and sediment formation in a global 3-D ocean-sediment carbon cycle model. Our results provide support for the hypothesis that a break up of Southern Ocean stratification and invigorated deep ocean ventilation were the dominant drivers for the early deglacial CO2 rise of ~35 ppm between the Last Glacial Maximum and 14.6 ka BP. Another rise of 10 ppm until the end of the Holocene is attributed to carbonate compensation responding to the early deglacial change in ocean circulation. Our reasoning is based on a multi-proxy analysis which indicates that an acceleration of deep ocean ventilation during early deglaciation is not only consistent with recorded atmospheric CO2 but also with the reconstructed opal sedimentation peak in the Southern Ocean at around 16 ka BP, the record of atmospheric δ13CCO2, and the reconstructed changes in the Pacific CaCO3 saturation horizon.

A gas ion source for radiocarbon measurements at 200 kV

The novel tabletop miniaturized radiocarbon dating system (MICADAS) at ETH Zurich features a hybrid Cs sputter negative ion source for the measurement of solid graphite and gaseous CO2 samples. The source produces stable currents of up to 6 mu A C- out of gaseous samples with an efficiency of 3-6%. A gas feeding system has been set up that enables constant dosing of CO2 into the Cs sputter ion source and ensures stable measuring conditions. The system is based on a syringe in which CO2 gas is mixed with He and then pressed continuously into the ion source at a constant flow rate. Minimized volumes allow feeding samples of 3-30 mu g carbon quantitatively into the ion source. In order to test the performance of the system, several standards and blanks have successfully been measured. The ratios of C-14/C-12 could be repeated within statistical errors to better than 1.0% and the C-13/C-12 ratios to better than 0.2%. The blank was < 1 pMC.

Exposure dating of Late Glacial and pre-LGM moraines in the Cordon de Doña Rosa, Northern/Central Chile (~ 31°S)

Despite the important role of the Central Andes (15–30° S) for climate reconstruction, knowledge about the Quaternary glaciation is very limited due to the scarcity of organic material for radiocarbon dating. We applied 10Be surface exposure dating (SED) on 22 boulders from moraines in the Cordon de Doña Rosa, Northern/Central Chile (~31° S). The results show that several glacial advances in the southern Central Andes occurred during the Late Glacial between ~14.7±1.5 and 11.6±1.2 ka. A much more extensive glaciation is dated to ~32±3 ka, predating the temperature minimum of the global LGM (Last Glacial Maximum: ~20 ka). Reviewing these results in the paleoclimatic context, we conclude that the Late Glacial advances were most likely caused by an intensification of the tropical circulation and a corresponding increase in summer precipitation. High-latitude temperatures minima, e.g. the Younger Dryas (YD) and the Antarctic Cold Reversal (ACR) may have triggered individual advances, but current systematic exposure age uncertainties limit precise correlations. The absence of LGM moraines indicates that moisture advection was too limited to allow significant glacial advances at ~20 ka. The tropical circulation was less intensive despite the maximum in austral summer insolation. Winter precipitation was apparently also insufficient, although pollen and marine studies indicate a northward shift of the westerlies at that time. The dominant pre-LGM glacial advances in Northern/Central Chile at ~32 ka required lower temperatures and increased precipitation than today. We conclude that the westerlies were more intense and/or shifted equatorward, possibly due to increased snow and ice cover at higher southern latitudes coinciding with a minimum of insolation.

Performance evaluation and characterization of symmetric capacitors with carbon black, and asymmetric capacitors using a carbon foam supported nickel electrode

This thesis evaluates a novel asymmetric capacitor incorporating a carbon foam supported nickel hydroxide positive electrode and a carbon black negative electrode. A series of symmetric capacitors were prepared to characterize the carbon black (CB) negative electrode. The influence of the binder, PTFE, content on the cell properties was evaluated. X-ray diffraction characterization of the nickel electrode during cycling is also presented. The 3 wt% and 5 wt% PTFE/CB symmetric cells were examined using cyclic voltammetry (CV) and constant current charge/discharge measurements. As compared with symmetric cells containing more PTFE, the 3 wt% cell has the highest average specific capacitance, energy density and power density over 300 cycles, 121.8 F/g, 6.44 Wh/kg, and 604.1 W/kg, respectively. Over the 3 to 10 wt% PTFE/CB range, the 3 wt% sample exhibited the lowest effective resistance and the highest BET surface area. Three asymmetric cells (3 wt% PTFE/CB negative electrode and a nickel positive) were fabricated; cycle life was examined at 3 current densities. The highest average energy and power densities over 1000 cycles were 20 Wh/kg (21 mA/cm2) and 715 W/kg (31 mA/cm2), respectively. The longest cycle life was 11,505 cycles (at 8 mA/cm2), with an average efficiency of 79% and an average energy density of 14 Wh/kg. The XRD results demonstrate that the cathodically deposited nickel electrode is a typical α-Ni(OH)2 with the R3m structure (ABBCCA stacking); the charged electrodes are 3γ-NiOOH with the same stacking as the α-type; the discharged electrodes (including as-formed electrode) are aged to β’-Ni(OH)2 (a disordered β) with the P3m structure (ABAB stacking). A 3γ remnant was observed.

Performance evaluation of a novel asymmetric capacitor using a light-weight, carbon foam supported nickel electrode

Electrochemical capacitors have been an important development in recent years in the field of energy storage. Capacitors can be developed by utilizing either double layer capacitance at the electrode/solution interfaces alone or in combination with a battery electrode associated with a faradic redox process in one electrode. An asymmetric capacitor consisting of electrochemically deposited nickel hydroxide, supported on carbon foam as a positive electrode and carbon sheet as a negative electrode has been successfully assembled and cycled. One objective of this study has been to demonstrate the viability of the nickel carbon foam positive electrode, especially in terms of cycle life. Electrochemical characterization shows stable, high cycle performance in 26 wt. % KOH electrolyte with a maximum energy density of 4.1 Wh/Kg and a relaxation time constant of 6.24 s. This cell has demonstrated high cycle life, 14,500 cycles, with efficiency better than 98%. In addition, the cell failure mechanism and self-discharge behavior of the aforesaid capacitor are analyzed.

Synthesis of novel solid materials from carbon dioxide and carbon monoxide

The increase of atmospheric CO2 has been identified as the primary cause for the observed global warming over the past century. The geological and oceanic sequestration of CO2 has issues, such as cost and leakage as well as effects on sea biota. The ideal solution should be the conversion of CO2 into useful materials. However, most processes require high energy input. Therefore, it is necessary to explore novel processes with low energy demands to convert CO2 to useful solid materials. Amorphous carbon nitride and graphone received much attention due to their unusual structures and properties as well as their potential applications. However, to date there has been no attempt to synthesize those solid materials from CO2. Lithium nitride (Li3N) and lithium imide (Li2NH) are important hydrogen storage materials. However, their optical properties and reactivity has not yet studied. This dissertation research is aimed at the synthesis of carbon nitrides and graphone from CO2 and CO via their reaction with Li3N and Li2NH. The research was focused on (1) the evaluation of Li3N and Li2NH properties, (2) thermodynamic analysis of conversion of carbon dioxide and carbon monoxide into carbon nitride and other solid materials, (3) synthesis of carbon nitride from carbon dioxide, and (4) synthesis of graphone from carbon monoxide. First, the properties of Li3N, Li2NH, and LiNH2 were investigated. The X-ray diffraction measurements revealed that heat-treatment at 500°C introduce a phase transformation of β-Li3N to α-Li3N. Furthermore, the UV-visible absorption evaluation showed that the energy gaps of α-Li3N and β-Li3N are 1.81 and 2.14 eV, respectively. The UV-visible absorption measurements also revealed that energy gaps are 3.92 eV for Li2NH and 3.93 eV for LiNH2. This thermodynamic analysis was performed to predict the reactions. It was demonstrated that the reaction between carbon dioxide and lithium nitride is thermodynamically favorable and exothermic, which can generate carbon nitride and lithium cyanamide. Furthermore, the thermodynamic calculation indicated that the reaction between carbon monoxide and lithium imide can produce graphone and lithium cyanamide along with releasing heat. Based on the above thermodynamic analysis, the experiment of CO2 and Li3N reaction and CO and Li2NH were carried out. It was found that the reaction between CO2 and Li3N is very fast and exothermic. The XRD and element analysis revealed that the products are crystal lithium cyanamide and amorphous carbon nitrides with Li2O and Li2CO3. Furthermore, TEM images showed that carbon nitrides possess layer-structure, namely, it is graphene-structured carbon nitride. It was found that the reaction between Li2NH and CO was also exothermic, which produced graphone instead of carbon nitride. The composition and structures of graphone were evaluated by XRD, element analysis, TEM observation, and Raman spectra.

A Novel Approach to Carbon Dioxide Capture and Storage

The novel approach to carbon capture and storage (CCS) described in this dissertation is a significant departure from the conventional approach to CCS. The novel approach uses a sodium carbonate solution to first capture CO2 from post combustion flue gas streams. The captured CO2 is then reacted with an alkaline industrial waste material, at ambient conditions, to regenerate the carbonate solution and permanently store the CO2 in the form of an added value carbonate mineral. Conventional CCS makes use of a hazardous amine solution for CO2 capture, a costly thermal regeneration stage, and the underground storage of supercritical CO2. The objective of the present dissertation was to examine each individual stage (capture and storage) of the proposed approach to CCS. Study of the capture stage found that a 2% w/w sodium carbonate solution was optimal for CO2 absorption in the present system. The 2% solution yielded the best tradeoff between the CO2 absorption rate and the CO2 absorption capacity of the solutions tested. Examination of CO2 absorption in the presence of flue gas impurities (NOx and SOx) found that carbonate solutions possess a significant advantage over amine solutions, that they could be used for multi-pollutant capture. All the NOx and SOx fed to the carbonate solution was able to be captured. Optimization studies found that it was possible to increase the absorption rate of CO2 into the carbonate solution by adding a surfactant to the solution to chemically alter the gas bubble size. The absorption rate of CO2 was increased by as much as 14%. Three coal combustion fly ash materials were chosen as the alkaline industrial waste materials to study the storage CO2 and regeneration the absorbent. X-ray diffraction analysis on reacted fly ash samples confirmed that the captured CO2 reacts with the fly ash materials to form a carbonate mineral, specifically calcite. Studies found that after a five day reaction time, 75% utilization of the waste material for CO2 storage could be achieved, while regenerating the absorbent. The regenerated absorbent exhibited a nearly identical CO2 absorption capacity and CO2 absorption rate as a fresh Na2CO3 solution.

Correlating the Ancient Maya and Modern European Calendars with High-Precision AMS 14C Dating

The reasons for the development and collapse of Maya civilization remain controversial and historical events carved on stone monuments throughout this region provide a remarkable source of data about the rise and fall of these complex polities. Use of these records depends on correlating the Maya and European calendars so that they can be compared with climate and environmental datasets. Correlation constants can vary up to 1000 years and remain controversial. We report a series of high-resolution AMS C-14 dates on a wooden lintel collected from the Classic Period city of Tikal bearing Maya calendar dates. The radiocarbon dates were calibrated using a Bayesian statistical model and indicate that the dates were carved on the lintel between AD 658-696. This strongly supports the Goodman-Martinez-Thompson (GMT) correlation and the hypothesis that climate change played an important role in the development and demise of this complex civilization.

Intercomparison of C-14 Analysis of Carbonaceous Aerosols: Exercise 2009

Radiocarbon analysis of the carbonaceous aerosol allows an apportionment of fossil and non-fossil sources of airborne particulate matter (PM). A chemical separation of total carbon (TC) into its subfractions organic carbon (OC) and elemental carbon (EC) refines this powerful technique, as OC and EC originate from different sources and undergo different processes in the atmosphere. Although C-14 analysis of TC, EC, and OC has recently gained increasing attention, interlaboratory quality assurance measures have largely been missing, especially for the isolation of EC and OC. In this work, we present results from an intercomparison of 9 laboratories for C-14 analysis of carbonaceous aerosol samples on quartz fiber filters. Two ambient PM samples and 1 reference material (RM 8785) were provided with representative filter blanks. All laboratories performed C-14 determinations of TC and a subset of isolated EC and OC for isotopic measurement. In general, C-14 measurements of TC and OC agreed acceptably well between the laboratories, i.e. for TC within 0.015-0.025 (FC)-C-14 for the ambient filters and within 0.041 (FC)-C-14 for RM 8785. Due to inhomogeneous filter loading, RM 8785 demonstrated only limited applicability as a reference material for C-14 analysis of carbonaceous aerosols. C-14 analysis of EC revealed a large deviation between the laboratories of 28-79 as a consequence of different separation techniques. This result indicates a need for further discussion on optimal methods of EC isolation for C-14 analysis and a second stage of this intercomparison.