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.

Measuring energy spectra of TeV gamma-ray emission from the Cygnus region of our galaxy with Milagro

High energy gamma rays can provide fundamental clues to the origins of cosmic rays. In this thesis, TeV gamma-ray emission from the Cygnus region is studied. Previously the Milagro experiment detected five TeV gamma-ray sources in this region and a significant excess of TeV gamma rays whose origin is still unclear. To better understand the diffuse excess the separation of sources and diffuse emission is studied using the latest and most sensitive data set of the Milagro experiment. In addition, a newly developed technique is applied that allows the energy spectrum of the TeV gamma rays to be reconstructed using Milagro data. No conclusive statement can be made about the spectrum of the diffuse emission from the Cygnus region because of its low significance of 2.2 σ above the background in the studied data sample. The entire Cygnus region emission is best fit with a power law with a spectral index of α=2.40 (68% confidence interval: 1.35-2.92) and a exponential cutoff energy of 31.6 TeV (10.0-251.2 TeV). In the case of a simple power law assumption without a cutoff energy the best fit yields a spectral index of α=2.97 (68% confidence interval: 2.83-3.10). Neither of these best fits are in good agreement with the data. The best spectral fit to the TeV emission from MGRO J2019+37, the brightest source in the Cygnus region, yields a spectral index of α=2.30 (68% confidence interval: 1.40-2.70) with a cutoff energy of 50.1 TeV (68% confidence interval: 17.8-251.2 TeV) and a spectral index of α=2.75 (68% confidence interval: 2.65-2.85) when no exponential cutoff energy is assumed. According to the present analysis, MGRO J2019+37 contributes 25% to the differential flux from the entire Cygnus at 15 TeV.