(Table 1, Page 1046-1047) Chemical composition of iron-manganese concretions from the Indian Ocean recovered by the R/V Vityaz and the R/V Ob

The data given in this and previous communications is insufficient to assess the quantitative role of these supplementary sources in the Indian Ocean, but they do not rule out their local significance. Elucidation of this problem requires further data on the characteristics of the composition and structure of nodules in various different metallogenic regions of the ocean floor. A study of the distribution of ore elements in nodules both depthwise and over the area of the floor together with compilation of the first schematic maps based on the results of analyses of samples from 54 stations) enables us to give a more precise empirical relation between the Mn, Fe, Ni, Cu, and Co contents in Indian Ocean nodules, the manganese ratio and the values of the oxidation potential, which vary regularly with depth. This in turn also enables us to confirm that formation of nodules completes the prolonged process of deposition of ore components from ocean waters, and the complex physico-chemical transformations of sediments in the bottom layer. Microprobe investigation of ore rinds revealed the nonuniform distribution of a num¬ber of elements within them, owing to the capacity of particles of hydrated oxides of manganese and iron to adsorb various elements. High concentration of individual elements is correlated with local sectors of the ore rinds, in which the presence of todorokite, in particular, has been noted. The appearance of this mineral apparently requires elevated Ca, Mg, Na, and K concentrations, because the stable crystalline phase of this specific mineral form of the psilomelane group may be formed when these cations are incorporated into a lattice of the delta-MnO2 type.

Annotated record and chemical composition of Mn deposits from R/V Mahi Cruise Abyssal Hills 69 stations

A University of Hawaii oceanographic cruise, Abyssal Hills 69, with the R/V Mahi, was carried out to study the association of manganese nodules with an abyssal hill. Manganese nodules from three dredge hauls on an abyssal hill located at 36°W and 157°W exhibited differences in morphology and composition between stations only three miles apart. The morphology of the nodules suggests that nodules from a single site have similar morphologies because they began growth at the same time, probably because of a volcanic event. Differences in morphology between stations indicate a local supply of elements. Atomic absorption analysis for manganese, iron, cobalt, nickel, and copper revealed that nodules nearest to a probable fault line and source of volcanism have a, lower manganese to iron ratio than nodules farther removed. This finding supports the theory that volcanism contributes to the formation of some nodules. Additional evidence showing association with volcanism consists of volcanic nuclei in nodules, crusts formed on layers of volcanic ash, and basalt encrusted to various degrees. The variation in cobalt, nickel, and copper contents Gt the nodules from a single dredge is two-to threefold, but iron content is more uniiorm. Four of the six cores from the area increased in manganese concentration with depth, suggesting that diffusion is concentrating manganese in the upper zone of the sediments or in nodules. The author concludes that volcanism is contributing to the formation of nodules by supplying nuclei and transition elements, but is not necessary for the formation of manganese nodules.

(Table 3, page 280) Chemical composition of micronodules from a series of stations and sediment depths from Areas C, F, G and K in the Pacific Ocean from R/V Sonne Cruise SO06

Compositional data for coexisting manganese nodules, micronodules, sediments and pore waters from five areas in the equatorial and S.W. Pacific have been obtained. This represents the largest study of its type ever undertaken to establish the distribution of elements between the various phases within the sediment column. The composition of manganese nodules, micronodules and sediments (on a carbonate-free basis) shows marked differences between the equatorial high productivity zone and the low productivity region of the S.W. Pacific. In the case of the nodules, th is reflects an increased supply of transition elements (notably Ni, Cu and Zn) to the nodules as a result of the in situ dissolution of siliceous tests within the sediment column in the equatorial Pacific high productivity zone. Micronodules display similar, but somewhat different, compositions to those of the associated nodules in each area. Micronodule composition is therefore influenced by the same basic factors that control nodule composition, but is modified by dissolution of the micronodules in situ within the sediment column. Locally, as in the area immediately south of the Marquesas Fracture Zone, the micronodule population is contaminated by small, angular volcanic rock fragments; this leads to apparently anomalous micronodule compositions. Micronodules appear to be a transient feature in the sediment column, especially in the equatorial Pacific. Dissolution of micronodules in the sediment column therefore represents an important source of elements for the growth of manganese nodules in the equatorial Pacific. Sediment composition is markedly influenced by the carbonate content. On a carbonate-free basis, the sediments from the equatorial high productivity zone are quite distinct in composition from those in the S.W. Pacific. This reflects differences in the lithology of the sediments. In the Aitutaki Passage, the local influence of volcanoclastic material in sediment composition has been established. The major cations and anions in pore waters measured here show no major differences between equatorial and S.W. Pacific sediments. Silica is, however, higher in equatorial Pacific pore waters reflecting the dissolution of siliceous tests in these sediments.

Annotated record of the detailed examination of Mn deposits from R/V Xiang Yang Hong 16 stations (1983) in the Pacific Ocean

Electron microprobe and X-ray diffraction data for north Pacific manganese nodules reveal that the transition metal distributions are controlled by the mineralogy. Microlayers rich in 10Å-manganates generally have high Mn/Fe ratios and positive correlations between Ni, Cu and Mn, and between Co and Fe. Microlayers rich in vernadite, on the other hand, show low Mn/Fe ratios, and Co, Ni and Cu all show positive correlations with Mn. The 10Å-manganates form mainly in porewaters with high Mn/Fe ratios. The Ni2+ and Cu2+ ions are post-depositionally incorporated into the interlayers of the manganates, whereas Co3+ is substituted for Fe3+ in ferric oxyhydroxides. In seawater with a low Mn/Fe ratio, on the other hand, the adsorption of positively charged ferric oxyhydroxides on negatively charged [MnO6] octahedral layers suppresses the growth of 10Å-manganates, enhancing the formation of vernadite. Positively charged hydroxides of Co3+, Ni2+ and Cu2+ are also adsorbed on the [MnO6] layers. These mechanisms of mineral formation and metal uptake are corroborated by data for other oceanic non-hydrothermal manganese nodules and crusts.

Annotated record and chemical analysis of manganese nodules from R/V Moana Wave Cruise Mn-74-01 and Mn-74-02 stations

Cruise Mn-74-02 of the R/V MOANA WAVE was the second part of the field work of the NSF/IDOE Inter-University Ferromanganese Research Program in 1974, and we gratefully acknowledge the support of the office for the International Decade of Ocean Exploration and the Office of Oceanographic Facilities and Support. This program was designed to investigate the origin, growth, and distribution of copper/nickel-rich manganese nodules in the Pacific Ocean. The field effort was designed to satisfy sample requirements of the fifteen principal investigators, while increasing general knowledge of the copper/nickel-rich nodule deposits of the equatorial Pacific. This report is the second of a series of cruise reports designed to assist sample requests for documented nodules, sediment, and water samples so that laboratory results can be realistically compared and related to the environment of nodule growth. Nodule samples and bathymetric and navigational data are archived at the Hawaii Institute of Geophysics, University of Hawaii. Bulk chemical analyses of nodules and reduction of survey data were carried out at Hawaii. Sediment cores were stored at the University of Hawaii and at Scripps Institution of Oceanography. The SIO analytical facility provided stratigraphic data on sediment chemistry.

Self‐cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Mechanochemical synthesis of TiO2/NiFe2O4 magnetic catalysts for operation under RF field

Composite NiFe2O4–TiO2 magnetic catalysts were prepared by mechanochemical synthesis from a mixture of titania supported nickel ferrite nanoparticles and P25 titania (Evonic). The former provides fast and efficient heating under radiofrequency field, while the latter serves as an active catalyst or catalyst support. The highest heating rate was observed over a catalyst prepared for a milling time of 30 min. The catalytic activity was measured over the sulfated composite catalysts in the condensation of aniline and 3-phenylbutyric acid in a stirred tank reactor and in a continuous RF heated flow reactor in the 140–170 °C range. The product yield of 47% was obtained over the sulfated P25 titania catalyst in the flow reactor.

New biomass derived carbon catalysts for biomass valorization

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the utilization of renewables for production of energy and chemicals (biorefining) has gained considerable attention. Biomass is the only sustainable source of organic compounds that has been proposed as petroleum equivalent for the production of fuels, chemicals and materials. In fact, it would not be wrong to say that the only viable answer to sustainably convene our future energy and material requirements remain with a bio-based economy with biomass based industries and products. This has prompted biomass valorization (biorefining) to become an important area of industrial research. While many disciplines of science are involved in the realization of this effort, catalysis and knowledge of chemical technology are considered to be particularly important to eventually render this dream to come true. Traditionally, the catalyst research for biomass conversion has been focused primarily on commercially available catalysts like zeolites, silica and various metals (Pt, Pd, Au, Ni) supported on zeolites, silica etc. Nevertheless, the main drawbacks of these catalysts are coupled with high material cost, low activity, limited reusability etc. – all facts that render them less attractive in industrial scale applications (poor activity for the price). Thus, there is a particular need to develop active, robust and cost efficient catalytic systems capable of converting complex biomass molecules. Saccharification, esterification, transesterification and acetylation are important chemical processes in the valorization chain of biomasses (and several biomass components) for production of platform chemicals, transportation fuels, food additives and materials. In the current work, various novel acidic carbons were synthesized from wastes generated from biodiesel and allied industries, and employed as catalysts in the aforementioned reactions. The structure and surface properties of the novel materials were investigated by XRD, XPS, elemental analysis, SEM, TEM, TPD and N2-physisorption techniques. The agro-industrial waste derived sulfonic acid functionalized novel carbons exhibit excellent catalytic activity in the aforementioned reactions and easily outperformed liquid H2SO4 and conventional solid acids (zeolites, ion-exchange resins etc). The experimental results indicated strong influence of catalyst pore-structure (pore size, pore-volume), concentration of –SO3H groups and surface properties in terms of the activity and selectivity of these catalysts. Here, a large pore catalyst with high –SO3H density exhibited the highest esterification and transesterification activity, and was successfully employed in biodiesel production from fatty acids and low grade acidic oils. Also, a catalyst decay model was proposed upon biodiesel production and could explain that the catalyst loses its activity mainly due to active site blocking by adsorption of impurities and by-products. The large pore sulfonated catalyst also exhibited good catalytic performance in the selective synthesis of triacetin via acetylation of glycerol with acetic anhydride and out-performed the best zeolite H-Y with respect to reusability. It also demonstrated equally good activity in acetylation of cellulose to soluble cellulose acetates, with the possibility to control cellulose acetate yield and quality (degree of substitution, DS) by a simple adjustment of reaction time and acetic anhydride concentration. In contrast, the small pore and highly functionalized catalysts obtained by hydrothermal method and from protein rich waste (Jatropha de-oiled waste cake, DOWC), were active and selective in the esterification of glycerol with fatty acids to monoglycerides and saccharification of cellulosic materials, respectively. The operational stability and reusability of the catalyst was found to depend on the stability of –SO3H function (leaching) as well as active site blocking due to adsorption of impurities during the reaction. Thus, our results corroborate the potential of DOWC derived sulfated mesoporous active carbons as efficient integrated solid acid catalysts for valorization of biomass to platform chemicals, biofuel, bio-additive, surfactants and celluloseesters.

Nanostructured catalysts for the development of the hydrogen economy

La catalyse joue un rôle essentiel dans de nombreuses applications industrielles telles que les industries pétrochimique et biochimique, ainsi que dans la production de polymères et pour la protection de l’environnement. La conception et la fabrication de catalyseurs efficaces et rentables est une étape importante pour résoudre un certain nombre de problèmes des nouvelles technologies de conversion chimique et de stockage de l’énergie. L’objectif de cette thèse est le développement de voies de synthèse efficaces et simples pour fabriquer des catalyseurs performants à base de métaux non nobles et d’examiner les aspects fondamentaux concernant la relation entre structure/composition et performance catalytique, notamment dans des processus liés à la production et au stockage de l’hydrogène. Dans un premier temps, une série d’oxydes métalliques mixtes (Cu/CeO2, CuFe/CeO2, CuCo/CeO2, CuFe2O4, NiFe2O4) nanostructurés et poreux ont été synthétisés grâce à une méthode améliorée de nanocasting. Les matériaux Cu/CeO2 obtenus, dont la composition et la structure poreuse peuvent être contrôlées, ont ensuite été testés pour l’oxydation préférentielle du CO dans un flux d’hydrogène dans le but d’obtenir un combustible hydrogène de haute pureté. Les catalyseurs synthétisés présentent une activité et une sélectivité élevées lors de l’oxydation sélective du CO en CO2. Concernant la question du stockage d’hydrogène, une voie de synthèse a été trouvée pour le composét mixte CuO-NiO, démontrant une excellente performance catalytique comparable aux catalyseurs à base de métaux nobles pour la production d’hydrogène à partir de l’ammoniaborane (aussi appelé borazane). L’activité catalytique du catalyseur étudié dans cette réaction est fortement influencée par la nature des précurseurs métalliques, la composition et la température de traitement thermique utilisées pour la préparation du catalyseur. Enfin, des catalyseurs de Cu-Ni supportés sur silice colloïdale ou sur des particules de carbone, ayant une composition et une taille variable, ont été synthétisés par un simple procédé d’imprégnation. Les catalyseurs supportés sur carbone sont stables et très actifs à la fois dans l’hydrolyse du borazane et la décomposition de l’hydrazine aqueuse pour la production d’hydrogène. Il a été démontré qu’un catalyseur optimal peut être obtenu par le contrôle de l’effet bi-métallique, l’interaction métal-support, et la taille des particules de métal.