Littérature scientifique sur le sujet « Gold/Gallium/Calcium catalysts »

In order to reconstruct the crystallization conditions of the gallium epidote analogue Ca2Al2Ga(Si3O12)(OH) from the Tykotlova gold-sulphide ore occurrence in the Polar Urals, for the first time, a series of epidote-gallium epidote solid solutions were synthesized. The parameters of the unit cell were calculated for these phases, and IR and Raman spectra were obtained. It was concluded that gallium is predominantly in position M3, which allows us to consider the gallium epidote as an independent mineral specie. Stable Ga-containing aluminosilicate and silicate phases in the Ca-Ga-Al-Fe-Si-O system were obtained as by-products of the synthesis (analogs of the grossular-andradite garnet and calcium feldspar).

Gold supported hydroxyapatite (HA) and calcium deficient hydroxyapatite (CDHA) was studied for the room temperature CO oxidation. Nanostructured gold catalyst has been prepared by deposition precipitation method, whereas HA was synthesized by microwave synthesis. Inorder to understand the influence of surface properties of HA, support HA was synthesized with different Ca/P ratios (1.67, 1.62, 1.57, 1.534 and 1.5). The gold supported catalysts were characterized by XRD, BET, ICP-OES and TEM. Typical results indicate that gold supported 1.57 HA shows higher activity compared to other HA catalysts (1.67, 1.62, 1.534 and 1.5) which may be due to the presence of optimum number of acidic and basic sites.

Gold catalysts based on SBA-15, NbSBA-15 (Nb introduced in one pot synthesis) and Nb₂O₅/SBA-15 (prepared by impregnation of SBA-15) were doped with calcium species introduced before Au loading and were tested in gas-phase methanol oxidation.

Non-coking stable alkaline earth metal (M = Mg, Sr, and Ba) modified Ga-NaY catalysts were prepared by ionic-exchange and tested in oxidative dehydrogenation (ODH) of n-octane using air as the source of oxygen. The role of the alkaline earth metals in NaY was to poison the acid sites while enhancing the basic sites responsible for ODH. The exception was the calcium modified NaY, which was more acidic than the parent NaY, coking and unstable under the ODH conditions used in this study. The role of gallium was to enhance the dehydrogenation pathway and improve the stability of NaY. The sequence of increasing selectivity to octenes followed the order: CaGa-NaY < Ga-NaY< MgGa-NaY < SrGa-NaY < BaGa-NaY. The highest octene selectivity obtained was 37% at iso-conversion of 6 ± 1% when BaGa-NaY was used at a temperature of 450 °C. The activity of the catalysts was directly proportional to the reducibility of the catalysts, which is in agreement with expectations.

AbstractThe bio-relevant metals (and derived compounds) of the Periodic Table of the Elements (PTE) are in the focus. The bulk elements sodium (Na), potassium (K), magnesium (Mg), and calcium (Ca) from the s-block, which are essential for all kingdoms of life, and some of their bio-activities are discussed. The trace elements of the d-block of the PTE as far as they are essential for humans (Mn, Fe, Co, Cu, Zn, Mo) are emphasized, but V, Ni, Cd, and W, which are essential only for some forms of life, are also considered. Chromium is no longer classified as being essential. From the p-block metals only the metalloid (half-metal) selenium (Se) is essential for all forms of life. Two other metalloids, silicon and arsenic, are briefly mentioned, but they have not been proven as being essential for humans. All metals of the PTE and a plethora of their compounds are used in industry and many of them are highly toxic, like lead (Pb), which is discussed as a prime example. Several metals of the PTE, that is, their ions and complexes, are employed in medicine and we discuss the role of lithium, gallium, strontium, technetium, silver, gadolinium (the only f-block element), platinum, and gold.

Fine chemistry historically relies on the fossil fuel industry, implying oil extraction and refining [1]. The rarefaction of this resource and adverse environmental consequences of its extraction motivate research for alternative sources of chemicals. Low carbon footprint chemicals can be synthesized from nonedible biomass waste [2]; cellulose extracted from biomass can therefore play an important role, being a clean and widely accessible carbon source. One can extract D-Glucose (units that constitute cellulose) from cellulose and obtain numerous chemicals of interest, such as sorbitol [3][4] or gluconic acid [5][6] (gluconate in alkaline media), respectively by selective reduction or oxidation. Searching for high-performance non-enzymatic catalysts to perform such reactions brought us to study the activity and selectivity of gold and nickel in alkaline media. At the anode, results from differential electrochemical mass spectrometry (DEMS) seem to indicate that the glucose oxidation on a gold surface initiates by its dissociative adsorption (dehydrogenation): the dihydrogen (H2) produced likely originates from the formation of metastable H adsorbates (Had) [7] that diffuse onto the surface [8] and recombine into H2. In parallel, the adsorbed glucose oxidizes into value-added products such as gluconic acid, through a mechanism proposed from in situ (Fourier Transform InfraRed spectroscopy, FTIR) and ex situ (products analysis by High Performance Liquid Chromatography, HPLC) observations, and on the evaluation of the number of exchanged electrons using the rotating ring disk electrode (RRDE). Confronting the experimental data to a microkinetics model enables to validate the proposed mechanism and to estimate the kinetics rate constants. At the cathode, the glucose reduction reaction (GRR) into sorbitol competes with the hydrogen evolution reaction (HER). The HER activity of nickel strongly depends on its surface oxidation state [9], which can be tuned to search the best selectivity towards sorbitol. Combining high value-added compounds production with H2 as by-product allows to improve the overall energy efficiency of this electrolysis. [1] P. G. Levi and J. M. Cullen, “Mapping global flows of chemicals: from fossil fuel feedstocks to chemical products,” Environ. Sci. Technol., vol. 52, no. 4, pp. 1725–1734, 2018, doi: 10.1021/acs.est.7b04573. [2] D. Saygin, D. J. Gielen, M. Draeck, E. Worrell, and M. K. Patel, “Assessment of the technical and economic potentials of biomass use for the production of steam, chemicals and polymers,” Renew. Sustain. Energy Rev., vol. 40, pp. 1153–1167, 2014, doi: 10.1016/j.rser.2014.07.114. [3] B. García, J. Moreno, G. Morales, J. A. Melero, and J. Iglesias, “Production of sorbitol via catalytic transfer hydrogenation of glucose,” Appl. Sci., vol. 10, no. 5, 2020, doi: 10.3390/app10051843. [4] X. Guo et al., “Selective hydrogenation of D-glucose to D-sorbitol over Ru/ZSM-5 catalysts,” Chinese J. Catal., vol. 35, no. 5, pp. 733–740, May 2014, doi: 10.1016/S1872-2067(14)60077-2. [5] H. S. Isbell, H. L. Frush, and F. J. Bates, “Manufacture of calcium gluconate by electrolytic oxidation of dextrose,” Ind. Eng. Chem., vol. 24, no. 4, pp. 375–378, 1932, doi: 10.1021/ie50268a003. [6] S. Anastassiadis and I. Morgunov, “Gluconic acid production,” Recent Pat. Biotechnol., vol. 1, no. 2, pp. 167–180, May 2007, doi: 10.2174/187220807780809472. [7] M. M. Jaksic, B. Johansen, and R. Tunold, “Electrochemical behaviour of gold in acidic and alkaline solutions of heavy and regular water,” Int. J. Hydrogen Energy, vol. 18, no. 2, pp. 91–110, Feb. 1993, doi: 10.1016/0360-3199(93)90196-H. [8] J. Cornejo-Romero, A. Solis-Garcia, S. M. Vega-Diaz, and J. C. Fierro-Gonzalez, “Reverse hydrogen spillover during ethanol dehydrogenation on TiO2-supported gold catalysts,” Mol. Catal., vol. 433, pp. 391–402, 2017, doi: 10.1016/j.mcat.2017.02.041. [9] A. G. Oshchepkov et al., “Nanostructured nickel nanoparticles supported on vulcan carbon as a highly active catalyst for the hydrogen oxidation reaction in alkaline media,” J. Power Sources, vol. 402, no. June, pp. 447–452, 2018, doi: 10.1016/j.jpowsour.2018.09.051. Figure 1

There are thirty-five (35) metals with public health implications due to occupational or residential exposure; twenty-three (23) of these are called heavy elements or metals. They are Antimony, Arsenic, Bismuth, Cadmium, Cerium, Chromium, Cobalt, Copper, Gallium, Gold, Iron, Lead, Manganese, Mercury, Nickel, Platinum, Silver, Tellurium, Thallium, Tin, Uranium, Vanadium, and Zinc. Interestingly, minute amount of these elements are common in our environment and diet and are actually necessary for a balanced health, but increased consumption may cause acute or chronic toxicity (poisoning). Allergies are not uncommon and repeated long-term exposure to these metals such as Zinc, Lead, Chromium, Selenium, Nickel, Cobalt and Cadmium may cause cancer. The alarming perceived increase of these pollutants around the south-western regions of Nigeria have necessitated the need to evaluate water and sediment samples of Osun river, popularly known for its cultural practices and activities. The physicochemical properties of samples such as pH, TDS EC, Total Dissolved Solid (TDS), Conductivity, Total Hardness, Sodium, Potassium, Phosphate, Nitrate, Chloride were analyzed and result showed compliance with recommended WHO standards. Trace and heavy metal composition in water using standard methods indicates the presence of Calcium (5.11±0.04ppm), Magnesium (0.54±0.004ppm), Potassium (1.28±0.01ppm) and Iron (0.05±0.00ppm) while sediment sample contained high composition of Zinc (21.99±2.67ppm), Iron (261.6±2.00ppm) and Manganese (105.6+0.50ppm). Results obtained from proximate analysis of both water and sediment samples, shows that there are no heavy metals presence in Osun River that could pose a threat to public health. Rather, there are more minerals and nutrients in availability which implies that water sample lacks considerable pollutants and can be certified healthy for moderate consumption and domestic uses which is within permissible value limits of WHO standards. Ashaolu V. O. | Research Scholar, Department of Chemistry, LIFE, Loyola College, Chennai-600034

Nous avons mené des recherches approfondies sur plusieurs réactions innovantes dans le domaine de la synthèse organique. Dans un premier temps, nous avons développé une réaction de cyclisation déshydratante ainsi que deux réactions en tandem, initiées par une cyclisation intramoléculaire. Ces réactions se caractérisent par leur haute diastéréosélectivité et l'utilisation d'un catalyseur à base d'un métal du groupe principal, agissant en tant qu'acide de Lewis. Cette approche nous a permis de synthétiser 27 nouveaux composés cycliques, avec des rendements pouvant atteindre 97 %. Dans un deuxième temps, nous avons mis au point une réaction tandem combinant une réaction de métathèse carbonyl-ène et un couplage déshydratant, réalisée à l'aide d'un catalyseur cationique à base de gallium sur des dérivés du benzhydrol. Cette méthode a conduit à la synthèse de 15 nouveaux composés, avec des rendements pouvant aller jusqu'à 67 %. Enfin, nous nous sommes intéressés à la réactivité des dérivés du bicyclobutane dans des cycloadditions en présence d'espèces insaturées et d'un catalyseur à base d'or. Cette approche a permis la synthèse de 5 nouveaux bioisostères du benzène, avec des rendements pouvant atteindre 90 %
We conducted extensive research on several innovative reactions in the field of organic synthesis. Initially, we developed a dehydrating cyclization reaction, as well as two tandem reactions initiated by this cyclization. These reactions are characterized by high diastereoselectivity and the use of a main-group metal-based catalyst acting as a Lewis acid. This approach allowed us to synthesize 27 new cyclic compounds with yields reaching up to 97%. Furthermore, we also developed a tandem reaction combining carbonyl-ene metathesis and a dehydrating coupling, carried out using a gallium-based cationic catalyst on benzhydrol derivatives. This method led to the synthesis of 15 new compounds, with yields of up to 67%. Finally, we investigated the reactivity of bicyclobutane derivatives in cycloadditions with unsaturated species in the presence of a gold-based catalyst. This approach enabled the synthesis of 5 new benzene bioisosteres with yields reaching up to 90%