Na Promotion of Pt/m-ZrO2 Catalysts for the Steam Reforming of Formaldehyde
Michela MartinelliElijah S. GarciaZahra RajabiCaleb D. WatsonA. Jeremy KropfDonald C. CronauerGary Jacobs
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The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H2O revealed that formaldehyde is adsorbed at reduced defect sites on zirconia, where it is converted to formate species through the addition of labile bridging OH species. Formate species achieve a maximum intensity in the range of 125–175 °C, where only slight changes in intensity are observed. Above this temperature, the formate decomposition reactivity strongly depends on the Na loading, with the optimum loadings being 1.8%Na and 2.5%Na. CO2 temperature programmed desorption results, as well as a greater splitting observed between the formate νasym(OCO) and νsym(OCO) bands in infrared spectroscopy, indicate greater basicity is induced by the presence of Na. This strengthens the interaction between the formate -CO2 functional group and the catalyst surface, weakening the formate C-H bond. A shift in the ν(CH) band of formate to lower wavenumbers was observed by addition of Na, especially at 1.8%Na and higher loadings. This results in enhanced decarboxylation and dehydrogenation of formate, as observed in in situ DRIFTS, temperature-programmed reaction/mass spectrometry experiments of the steam reforming of formaldehyde, and fixed bed reaction tests. For example, 2.5%Na addition of 2.5% increased the CO2 selectivity from 83.5% to 99.5% and the catalysts achieved higher stable conversion at lower temperature than NiO catalysts reported in the open literature. At 5%Na loading, Pt sites were severely blocked, hindering H-transfer.Keywords:
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Three new heterometallic formate coordination polymers formulated as [Na2Co(HCOO)4]∞ (1), [NaCo(HCOO)3]∞ (2), and [Na2Co7(HCOO)16]∞ (3) were obtained by adjusting the solvent and ratio of the reactants. In 1, a (4,4) cobalt formate layer is formed and the sodium ions connect the layers to form a three-dimensional (3D) framework. In 2, each formate ligand binds two Co(2+) and two Na(+) ions with a syn,syn,anti,anti coordination mode to form a chrial network with 4,6-connected topology. 3 is a Na(+)-ion-linked 3D framework based on the cobalt formate layer, which has a 10-membered metal ring. Magnetic studies indicate the existence of ferromagnetic interactions between adjacent Co(2+) ions in 1, while dominating antiferromagnetic couplings in 2 and 3.
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Abstract Alcaligenes eutrophus JMP 134 was chemostatically grown on 2,4‐dichlorophenoxyacetic acid (2,4‐D) at a dilution rate of 0.06 h −1 ; formate was fed as an auxiliary energy source. The simultaneous utilization of both components resulted in an increase in growth yield. As an example, this figure increased from 0.18 g dry mass/g 2,4‐D to 0.25 g dry mass/g 2,4‐D during growth on 1 g/l 2,4‐D plus 3 g/l sodium formate. The increase was correlated to energy generated from formate oxidation. Accordingly, a P/O‐quotient of 1 was derived for the energy transduction of NADH obtained from formate oxidation as it was for the overall efficiency during growth on 2,4‐D itself. This low energy yield was attributed to uncoupling exerted by 2,4‐D. The theoretical maximum yield coefficient of 0.69 g/g could not be reached due to the limiting activity of formate dehydrogenase in the conversion of the required quantities of formate.
Sodium formate
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This paper summarized the main research on sodium formate single crystal,and its complex salts lithium-sodium formate monohydrate and sodium-cadmium formate were also included.It is of practical interest for their nonlinear optical characteristics.We also give some suggests on the work.
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In order to control potassium formic quality, detecting method of formic functional content was studied to optimize the ratio of sodium formate to potassium formate, and to make formate drilling fluid exhibits its characteristic fully. Formic functional group content in solid formate and in the filtrate of drilling fluid was introduced respectively, and influences of KMnO 4 concentration and addition on the determination were studied. In addition, formic functional group content of lab fluid and field fluid filtrates were determined. At the same time, effect of drilling fluid additives on the results was also analyzed. Lab data showed that this method is suitble for determining formic group content of formate additives and formate drilling fluid with the result is liable in high accuracy. Finally, the technical index of potassium formate was determined, that is: w(H 2O)≥8.0%, w(KCOOH)(purity)90%, w(K +)≥40.0%, density of saturated salt solution≥1.55 g/cm 3.
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