La prise de conscience de l'importance de la gestion des déchets et de la préservation des ressources a conduit de plus en plus d'acteurs du monde agricole à s'intéresser au compostage comme mode de traitement d'effluents d'élevage ou de boues de stations d'épuration. Les filières d'utilisation de ces substrats, épandage, compostage ou autre, doivent donc être comparées. On sait en effet que l'agriculture est responsable d'une part importante des émissions d'ammoniac (NH3) et de protoxyde d'azote (N2O) et ainsi, indirectement ou directement, de l'augmentation de la concentration de N2O dans l'atmosphère. Trois séries d'expérimentations ont été menées respectivement sur des mélanges d'écorces de peuplier et de fientes de poules pondeuses, sur du fumier de poulet sans ou avec additifs et sur un mélange de paille et de boues de station d'épuration rurale, en parallèle avec un nouveau mélange d'écorces et de fientes. La première a permis de mesurer les émissions de gaz azotés d'un andain (25 m3) en cours de compostage. Elles étaient de 50% environ de l'azote initial sous forme N- NH3 et de moins de 1% sous forme N-N2O. La production de N2O était associée à des activités de nitrification/dénitrification et avait principalement lieu en phase de maturation. La seconde a révélé, pour du compostage de courte durée (1,5 mois) et en taille expérimentale (2 m3), les conditions dans lesquelles les émissions de NH3 et de N2O étaient les plus fortes ou les plus faibles et lesquelles favorisaient l'activité de dénitrification des micro-organismes. L'augmentation du rapport carbone/azote et l'addition de composés ou microorganismes adéquats font passer les pertes en NNH3 de 55 à 7% de l'azote initial. Leur effet sur la libération de N2O (0,2-0,9%) dépend de nombreux facteurs. La troisième a montré que les andains de compostage (10 et 25 m3) devaient être considérés comme des écosystèmes à part entière composés de différents compartiments (grossièrement entrée, fond, sortie et croûte) où les populations microbiennes s'organisent différemment, l'entrée étant productrice de N2O, le fond et la sortie, producteurs, en équilibre ou consommateurs suivant les moments. La taille de l'andain en expérimentation est donc une donnée capitale pour considérer les résultats comme représentatifs de la réalité.

Recently, memory-cells employing discrete traps as the charge storage media have been attracting a lot of attention as a promising candidate to replace conventional DRAM or Flash memories. Conventional floating gate (FG) non-volatile memories (NVMs) present critical issues on device scalability beyond the sub-50nm node. In achieving non-volatility in conventional FG memories, thicker control and tunnel oxide (~8nm) are required to guarantee longer retention time. Relatively, nano-dots memories causes more resistant leakage charges by localized storage sites, thus improving the device retention characteristics. Hence, nano-dots memories allow more aggressive scaling of the tunnel oxide and exhibit superior characteristics compared to Flash memories in term of operation voltage, write / erase speed, retention time and endurance. The advantages of metal nano-dots compared with other material counterparts include higher density of states , stronger coupling with the channel, better size scalability, and the design freedom of engineering the work function to optimize device characteristics. However, tungsten nano-dots are the most interested in all of metal dots is that tungsten metal has more extra attractive advantages, such as ultra high melting point make high process temperature caused superior thermal stability of device and wide application in VLSI technology nowadays caused real possibility of tungsten nano-dots NVMs fabricated in industry in practice. This dissertation is divided into four sections: (1) discussion of basic properties for tungsten nano-dots memory devices; (2) Tunneling Oxide Engineering,; (3) Improvement by novel processes; and (4) The influence with supercritical CO2 (SCCO2) and vapor treatment. Initially, formative mechanism of tungsten nano-dots and electrical characteristics of devices was investigated in the first section. Tungsten nano-dots were formed by oxidizing tungsten silicide / amorphous silicon double stack film at high temperature condition. From electrical measurement, the better characteristics have been achieved for oxidation condition at 1050¢XC / 120 sec. Secondly, the rapid thermal anneal (RTA) oxidation is used to grow tunnel oxide by two different forming gas (O2/N2O). Comparison of electrical characteristics, program characteristics of the device using tunnel oxide with N2O process is inferior than the common device. However, endurance is a important electrical characteristics in the semiconductor device especially apply on the non-volatile memory. Thirdly, novel processes were employed into fabrication of tungsten nano-dots memory devices, include the N2O oxidation and NH3 plasma treatment. The purpose of novel processes is production additional trapping states in nonvolatile memories, which is considerably as combination nano-dots with SONOS structure. In the final section, the application of supercritical CO2 with vapor on tungsten nano-dots memoery devices have been studying. It is found that the device treated by SCCO2 which electrical characteristics is improved obviously. Furthermore, this technology also can fabricate the nano-dots memory which is like the device used high temperature oxidation process. It suggests that the SCCO2 with vapor treatment could oxidize silicide film under a low temperature environment. This novel oxidation process has some advantages and could be noticed in the semiconductor industry.

No description available.

L'objectif de ma thèse est de conduire et d'utiliser les observations de haute précision de gaz à effet de serre pour estimer les émissions de ces gaz à différentes échelles en France, du locale au régionale. Le réseau français de mesure de gaz à effet de serre, géré par l'équipe RAMCES, est constitué de trois observatoires équipés de systèmes de mesure par chromatographie en phase gazeuse. Ces chromatographes en phase gazeuse sont situés à Gif-sur-Yvette, Trainou (forêt d'Orléans) et au sommet du Puy-de-Dôme. Ils ont été optimisés pour la mesure continue et de haute précision des principaux gaz à effet de serre : CO2, CH4, N2O et SF6. Ayant installé le GC au Puy-de-Dôme au cours de l'année 2010, je présenterai et analyserai en détail la série temporelle obtenue depuis son installation. Les mesures de gaz à effet de serre et des traceurs associés m'ont permis d'utiliser une approche multigaz pour contraindre leurs émissions à différentes échelles. A une échelle départementale et régionale, j'ai utilisé le 222Rn comme traceur de masses d'air pour quantifier les flux surfaciques mensuels de N2O à Gif-sur-Yvette et Trainou. Les émissions annuelles de N2O estimées à Gif-sur-Yvette et Trainou sont respectivement de 0.34/0.51 et 0.52 g(N2O) m-2 a-1. Le cycle saisonnier des émissions de N2O a permis de mettre en évidence l'impact de l'agriculture sur les émissions lors de l'apport d'engrais azoté dans les sols. J'ai mis en évidence une corrélation entre les flux de N2O annuels et les précipitations annuelles à Gif-sur-Yvette. A une échelle locale, j'ai utilisé le CO2 et ses isotopes mesurés lors d'une campagne réalisée pendant l'hiver 2010 à Paris, pour estimer les flux de CO2 parisien. Les mesures de 14CO2 atmosphérique m'ont permis de montrer que les flux de CO2 parisien en hiver sont essentiellement anthropiques (77 %) avec une contribution significative des émissions biogéniques (23 %). L'analyse du 13CO2 à quant à lui mis en évidence que les 77 % d'émission de CO2 d'origine fossile sont dues à 70 % à l'utilisation de gaz naturel et 30 % à l'utilisation de pétrole.

Nitrous oxide (N₂O) is a powerful greenhouse gas, and its atmospheric concentration is increasing dramatically. N₂O is produced through the microbially-mediated processes of nitrification and denitrification. Since these processes have different substrates and isotopic enrichment factors, stable isotope analysis (δ¹⁵N and δ¹⁸O) of N₂O can be used to study the production of this important greenhouse gas. Although production in rivers accounts for a significant portion of the global N₂O budget, the isotopic composition of N₂O from this source is poorly characterized. Most of the previous work using stable isotopes of N₂O has been conducted in terrestrial or oceanic environments, and only one published study has measured δ¹⁵N and δ¹⁸O of N₂O produced in a riverine environment. The purpose of this research project was to use stable isotope analysis to characterize the processes responsible for N₂O production in the Grand River, Ontario, Canada, and to determine the spatial and temporal variability of the isotopic composition of the N₂O flux. To meet the study objectives, an offline “purge and trap” method was developed to collect and purify dissolved N₂O for stable isotope analysis. Using this method, δ¹⁵N and δ¹⁸O analysis of dissolved N₂O is possible for samples with concentrations as low as 6 nmol N₂O/L. Due to the isotopic effects of gas exchange and the back flux of tropospheric N₂O, there is a complex relationship between the δ¹⁵N and the δ¹⁸O of source, dissolved, and emitted N₂O in aquatic environments. A simple box model (SIDNO – Stable Isotopes of Dissolved Nitrous Oxide) was developed to properly interpret isotopic data for dissolved N₂O. Using this model, it was determined that the isotopic composition of emitted N₂O is much more representative of N₂O production in aquatic environments than the isotopic composition of dissolved N₂O. If the concentration, δ¹⁵N and δ¹⁸O of dissolved N₂O are measured, the magnitude and isotopic composition of the N₂O flux can be calculated. Sampling downstream of the major wastewater treatment plants (WWTPs) on the Grand River indicates that nitrification and denitrification in the river are strongly tied to diel changes in dissolved oxygen (DO) concentration. During the day, when DO concentrations are high, nitrification or nitrifier-denitrification is the dominant N₂O production pathway, with sediment denitrification also contributing to N₂O production. At night, when DO concentrations are low, denitrification in the sediments and at the sediment / water interface is the dominant production pathway. Using the SIDNO model, N₂O produced during the day was found to have a δ¹⁵N of -22‰ and a δ¹⁸O of 43‰. N₂O produced at night had a δ¹⁵N of -30‰ and a δ¹⁸O of 30‰. The isotopic composition of N₂O emitted from the Grand River is dominated by night-time production downstream of the Waterloo and Kitchener WWTPs during the summer. The flux and time weighted annual average isotopic composition of N₂O emitted from the Grand River is -18.5‰ and 32.7‰ for δ¹⁵N and δ¹⁸O respectively. These values are significantly more depleted than the only other published data for riverine N₂O production. If the Grand River is representative of global riverine N₂O production, these results will have significant implications for the global isotopic budget for atmospheric N₂O.

Nitrous oxide (N₂O) is a powerful greenhouse gas, and its atmospheric concentration is increasing dramatically. N₂O is produced through the microbially-mediated processes of nitrification and denitrification. Since these processes have different substrates and isotopic enrichment factors, stable isotope analysis (δ¹⁵N and δ¹⁸O) of N₂O can be used to study the production of this important greenhouse gas. Although production in rivers accounts for a significant portion of the global N₂O budget, the isotopic composition of N₂O from this source is poorly characterized. Most of the previous work using stable isotopes of N₂O has been conducted in terrestrial or oceanic environments, and only one published study has measured δ¹⁵N and δ¹⁸O of N₂O produced in a riverine environment. The purpose of this research project was to use stable isotope analysis to characterize the processes responsible for N₂O production in the Grand River, Ontario, Canada, and to determine the spatial and temporal variability of the isotopic composition of the N₂O flux. To meet the study objectives, an offline “purge and trap” method was developed to collect and purify dissolved N₂O for stable isotope analysis. Using this method, δ¹⁵N and δ¹⁸O analysis of dissolved N₂O is possible for samples with concentrations as low as 6 nmol N₂O/L. Due to the isotopic effects of gas exchange and the back flux of tropospheric N₂O, there is a complex relationship between the δ¹⁵N and the δ¹⁸O of source, dissolved, and emitted N₂O in aquatic environments. A simple box model (SIDNO – Stable Isotopes of Dissolved Nitrous Oxide) was developed to properly interpret isotopic data for dissolved N₂O. Using this model, it was determined that the isotopic composition of emitted N₂O is much more representative of N₂O production in aquatic environments than the isotopic composition of dissolved N₂O. If the concentration, δ¹⁵N and δ¹⁸O of dissolved N₂O are measured, the magnitude and isotopic composition of the N₂O flux can be calculated. Sampling downstream of the major wastewater treatment plants (WWTPs) on the Grand River indicates that nitrification and denitrification in the river are strongly tied to diel changes in dissolved oxygen (DO) concentration. During the day, when DO concentrations are high, nitrification or nitrifier-denitrification is the dominant N₂O production pathway, with sediment denitrification also contributing to N₂O production. At night, when DO concentrations are low, denitrification in the sediments and at the sediment / water interface is the dominant production pathway. Using the SIDNO model, N₂O produced during the day was found to have a δ¹⁵N of -22‰ and a δ¹⁸O of 43‰. N₂O produced at night had a δ¹⁵N of -30‰ and a δ¹⁸O of 30‰. The isotopic composition of N₂O emitted from the Grand River is dominated by night-time production downstream of the Waterloo and Kitchener WWTPs during the summer. The flux and time weighted annual average isotopic composition of N₂O emitted from the Grand River is -18.5‰ and 32.7‰ for δ¹⁵N and δ¹⁸O respectively. These values are significantly more depleted than the only other published data for riverine N₂O production. If the Grand River is representative of global riverine N₂O production, these results will have significant implications for the global isotopic budget for atmospheric N₂O.

Aquatic plants or macrophytes are known as conduits of Methane (CH4), Carbon dioxide (CO2) and Nitrous oxide (N2O) which contribute to the total fluxes of the Greenhouse gases emissions from lakes. Recent studies emphasized that the knowledge on plant mediated emissions calls for more systematic and comparative data especially in the areas of spatial and temporal variability. In this study I measured diel (24 hour) and diurnal(  daily hours only) plant mediated fluxes during four sampling sessions using chamber method from a  Swedish lake in summer 2012. The measurements were conducted on two macrophyte population patterns of mixed plant communities and Equisetum fluviatile (specie-specific) community. CH4 emissions were higher in darker hours and there were no diel correlation between CH4 fluxes and average diel temperature. CH4 fluxes varied between 0.42 mmol m-2d-1 and 2.3 mmol m-2d-1. The CO2 fluxes had negative fluxes in day and positive during the day which was logical due to macrophyte respiration and photosynthesis mechanisms. Occasional daily positive fluxes were seen (only) during the rainy hours and there were no correlation between temperature and diel CO2 fluxes. The total net CO2 exchange was 2.8mmol m-2d-1 indicating that there was more CO2 release in the littoral zone of that lake. N2O fluxes did not show any clear diel or monthly pattern and the fluxes ranged between positive and negative numbers. The N2O fluxes did not exceed 2µmol m-2 d-1 with the total average flux of 0.8µmol m-2 d-1.

In this thesis we have utilized few-cycle pulses in the range 10-15s, to initiate CE to allow us to image the structure, dynamics, and kinetics of ionization and dissociation of triatomic molecules. We have made a series of measurements of this process for CO2 and N2O, by varying the laser pulse duration from 7 to 500 fs with intensity ranging from 2.5×1014 to 4×1015 (W/cm2), in order to identify the charge states and time scales involved. This is a new approach in CEI introducing a multi-dimensional aspect to the science of non-perturbative laser-molecule interaction. We refer to this approach as FEmtosecond Multi-PUlse Length Spectroscopy (FEMPULS). The use of a time and position sensitive detector allow us to observe all fragment ions in coincidence. By representing the final fragmentation with Dalitz and Newton plots, we have identified the underlying break up dynamics. Momentum conservation has been used to extract the correlated fragment ions which come from a single parent ion. This is achieved by considering that the total momentum of all correlated fragments must add up to zero. One of the main outcomes of our study is observation of charge resonance enhanced ionization (CREI) for triatomic molecules. In the case of CO2, we found that for the 4+ and higher charge states, 100 fs is the time scale required to reach the critical geometry RCO= 2.1Å and ӨOCO =163º (equilibrium CO2 geometry is RCO= 1:16Å and ӨOCO =172º. The CO23+ molecule, however, appears always to begin dissociation from closer than 1.7 Å indicating that dynamics on charge states lower than 3+ is not sufficient to initiate CREI. Finally, we make quantum ab initio calculations of ionization rates for CO2 and identify the electronic states responsible for CREI. Total kinetic energy (KER) has been measured for channels (1, 1, 1) to (2, 2, 2) and it was found that the (1, 1, 1) channel is not Coulombic, while (2, 2, 2) channel is very close to Coulombic (KER close to 90% of the coulombic potential). As another outcome of our study, for the case of N2O, we observed for the first time that there are two stepwise dissociation pathways for N2O3+: (1) N2O3+ → N++ NO2+ → N+ + N++ O+ and (2) N2O3+ → N22++O+ → N+ + N++ O+ as well as one for N2O4+ → N2++ NO2+ → N2+ + N++ O+. The N22+ stepwise channel is suppressed for longer pulse length, a phenomenon which we attribute to the influence which the structure of the 3+ potential has on the dissociating wave packet propagation. Finally, by observing the KER for each channel as a function of pulse duration, we show the increasing importance of CREI for channels higher than 3+.

Das Spurengas Lachgas (N₂O) trägt zur Klimaerwärmung und Zerstörung der Ozonschicht in der Atmosphäre bei. Mit einem Anteil von ca. 70% sind landwirtschaftliche Böden weltweit Hauptverursacher der hohen anthropogenenN₂O Emissionen. N₂O entsteht in Böden durch verschiedene mikrobiologische Prozesse, bei denen N₂O unter anderem aus düngerbürtigem N gebildet wird. Die Entwicklung effektiver Minderungsmaßnahmen wird erst möglich, wenn ein Verständnis der N₂O Quellprozesse und ihrer Dynamik in Böden vorhanden ist. In dieser Studie wurde die Denitrifikation als ein Quellprozess untersucht, der zusammen mit Nitrifikation und Nitrifizierer-Denitrifikation hauptsächlich für die N₂O Emissionen aus Böden verantwortlich ist. Die Denitrifikation beschreibt die Reduktion von Nitrat (NO₃^-) zu N2, wobei Nitrit (NO₂^-), Stickstoffmonoxid (NO) und N₂O Zwischenprodukte dieses Reaktionsweges sind. Lange Zeit galten heterotrophe Bakterien als alleinige Verursacher von N₂O Emissionen aus der Denitrifikation. Im Jahr 1972 wurde allerdings in Versuchen mit Pilzreinkulturen nachgewiesen, dass auch Pilze in der Lage sind, N₂O über die Denitrifikation zu bilden. Zwei Jahrzehnte später wurde gezeigt, dass den meisten Pilzen das Enzym N₂O-Reduktase fehlt. Somit ist nicht N₂, sondern N₂O das hauptsächliche Endprodukt der pilzlichen Denitrifikation. Dies lässt vermuten, dass die Bildung von N₂O durch pilzliche Denitrifikation noch unterschätzt wird, vorausgesetzt Pilze und Bakterien haben ähnliche Prozessraten. Bisher wurde jedoch nicht ausgiebig erforscht, welchen Anteil die einzelnen mikrobiellen Gemeinschaften an der N₂O Bildung tatsächlich haben. Zur Unterscheidung der N₂O Bildungsprozesse in Bezug auf die beteiligten Mikroorganismen stellt die Isotopenanalyse von N₂O eine vielversprechende Anwendung dar. Vor allem die ¹⁵N-Positionspräferenz im N₂O (SP = site preference, d.h. die Differenz zwischen den δ¹⁵N-Werten der außenständigen und zentralen N-Atome im linearen N₂O-Molekül) aus der Denitrifikation zeigte starke Unterschiede zwischen Reinkulturen einiger Bakterien (SP = -11 bis 0 ‰) und zwei untersuchten Pilzen (SP ~ 37 ‰). Jedoch wurden Bakterienreinkulturen bisher ausgiebiger untersucht als Pilzreinkulturen, auch wenn bekannt ist, dass sich die beteiligten Enzyme bei der Denitrifikation, bis auf die NO-Reduktase, zwischen Bakterien und Pilzen nicht unterscheiden. Die verschiedenen NO-Reduktasen sind vermutlich die Ursache für die unterschiedlichen SP-Werte des von Pilzen und Bakterien produzierten N₂O. Des Weiteren wurde bei Bakterien ein Austausch der Sauerstoffatome von Zwischenprodukten der Denitrifikation und dem umgebenden Wasser gefunden, der zwischen 4 und 100% beträgt. Ob es einen solchen Sauerstoffaustausch auch bei Pilzen gibt, ist bisher jedoch unerforscht. Würde der Sauerstoffaustausch bei pilzlicher Denitrifikation nicht erfolgen, ermöglichte dies neben der unterschiedlichen SP eine weitere Unterscheidung der Herkunft des N₂O. Der Sauerstoffaustausch würde signifikante Unterschiede in der O Isotopensignatur im N₂O pilzlicher bzw. bakterieller Herkunft verursachen. In der vorliegenden Studie, die Aufschluss über die pilzliche N₂O Produktion aus der Denitrifikation geben soll, wurden drei Hauptthemen behandelt. In einem Isotopen-Tracerexperiment mit <up>18</sup>O-angereichertem Wasser wurde untersucht, ob bei sechs Pilzreinkulturen ein Sauerstoffaustausch zwischen Wasser und Zwischenprodukten der Denitrifikation stattfindet. Die Pilzreinkulturen zeigten tatsächlich durch Inkorporation von ¹⁸O aus Wasser in N₂O einen Sauerstoffaustausch. Auch Pilze können bis zu 100% des O während der Denitrifikation austauschen. Eine Unterscheidung zwischen der Denitrifikation durch Bakterien und Pilze anhand der Sauerstoffsignatur ist somit nicht möglich. Das zweite Thema sollte Auskunft darüber geben, ob hohe SP-Werte des N₂O aus der Denitrifikation bei Pilzreinkulturen allgemeingültig sind. Neben den zwei bisher untersuchten wurden vier weitere Pilzreinkulturen inkubiert. Diese Studie zeigte für die getesteten Pilzarten ebenfalls höhere SP-Werte (SP = 19.7 bis 32.6 ‰) im Vergleich zum Wertebereich von Bakterienreinkulturen. Basierend auf den Ergebnissen zum Sauerstoffaustausch aus dem Isotopen-Tracerexperiment wurde für die jeweiligen sechs Pilze, anhand der im Rahmen dieses Versuchs ermittelten natürlichen Sauerstoffisotopensignaturen, Mechanismen zur O Isotopenfraktionierung untersucht. Dafür wurden, neben den Werten des Sauerstoffaustausches und der natürlichen O Isotopensignatur der Pilzreinkulturen, Werte für Fraktionierungseffekte aus der Literatur in einem Isotopenfraktionierungsmodell angewendet, um die Beteiligung der verschiedenen Enzyme, die während der Denitrifikation an dem Sauerstoffaustausch beteiligt sind, abzuschätzen. Im Vergleich zu den NO₃^-- und NO-Reduktasen wies die N₂O^--Reduktase einen maßgeblich höheren Sauerstoffaustausch auf. Die Erkenntnisse aus den Experimenten mit den Pilzereinkulturen sollten im Rahmen des dritten Themas auf Ihre Übertragbarkeit auf die mikrobiellen Gemeinschaften in Böden untersucht werden, indem Bodeninkubationsversuche mit selektiver Hemmung der Organismengruppen (Pilze und Bakterien) durchgeführt wurden. Bei dieser Modifizierung der Methode zur Substrat-induzierten Respiration mit selektiver Hemmung (SIRIN) sollte untersucht werden, ob sich die spezifischen SP-Werte für Bakterien und Pilze nach selektiver Wachstumshemmung von Bodengemeinschaften durch spezifische Antibiotika nachweisen lassen. Die Ausprägung des Hemmungseffekts auf SP-Werte in den drei getesteten Böden entsprach nicht den Erwartungswerten, die sich aus den SP-Werten der Pilz- und Bakterienreinkulturen ergaben. Die ermittelten SP-Werte lagen in den meisten Fällen im Bereich jener bakterieller Reinkulturen und eine Hemmung der Bakterien führte in keinem Fall zu der erwarteten Veränderungen der SP-Werte. Folglich konnten die SP-Werte dieser Versuche nicht dazu dienen, die N₂O Bildung in den gehemmten Varianten den verschiedenen Organismengruppen zu zuordnen. Ungeklärt blieb, ob dies durch fehlende Eignung der modifizierten SIRIN-Methode zu erklären ist, oder ob die an Reinkulturen beobachteten SP-Unterschiede zwischen Pilzen und Bakterien nicht auf mikrobielle Gemeinschaften der Versuchsböden übertragbar sind. Im Hinblick auf nach wie vor bestehende methodische Defizite bei der Untersuchung der Pilzdenitrifikation im Boden sollte dies in weitergehenden Studien geklärt werden.

While hundreds of papers have been published on frustrated Lewis pairs (FLPs) – the combination of bulky Lewis acids and bases which cannot form adducts – few of these use aluminum-based Lewis acids. The research outlined in this thesis expands the small molecule activation chemistry of FLPs to include Al.Combinations of bulky phosphines and AlX3 (X = halide or C6F5) with CO2 leads to the rapid activation to form the complexes R3P(CO2)(AlX3)2 (R = otol, Mes). Subsequent treatment with ammonia borane (AB) results in the rapid reduction of the CO2 fragment to methanol after water quench. Subsequent reactivity studies have established that AB adducts of AlX3, which react with CO2, are key intermediates in this chemistry. Further studies with Mes3P(CO2)(AlX3)2 revealed that these can reduce exogenous CO2 to CO, along with the generation of Mes3P(C(OAlX2)2O)(AlX3) and [Mes3PX][AlX4]. Detailed experimental and theoretical mechanistic investigations outline a possible mechanism involving direct CO2 insertion into free AlX3, followed by nucleophilic attack by PMes3 resulting in the expulsion of CO. Reactions with olefins were also investigated. While addition products of the type R3P(CH2CH2)AlX3 could be obtained with ethylene, C–H bond activation occurred with bulkier olefins. The resulting allyl species underwent subsequent C–C bond forming reactions with other olefins or CO2. Hydrogen was also activated using PR3/AlX3 FLPs to form species of the general formula, [R3PH][(H)(AlX3)2] (X = I, C6F5). These were found to reduce unactivated olefins, generating the redistributed products [R3PH][AlX4] and RAlX2 (R = alkyl). Attempts to circumvent this redistribution and favour alkyl protonation, thus generating a catalytic hydrogenation catalyst, are also discussed. Finally, the activation of N2O was also examined. While addition products could be formed, unexpected aromatic or benzylic C–H bond activation chemistry occurred in the presence of excess Al. A radical reaction pathway is proposed