Microporosity and Catalytic Activity for Hydrodesulfurization of Pharmacosiderite Mo4P3O16 Synthesized at a Moderate Temperature.

Pharmacosiderite Mo4P3O16 (Pharma-MoPO) consists of [Mo4O4] cubane unit and [PO4] tetrahedral to form an open framework with a microporous structure similar to that of LTA-type zeolite. Although attractive applications are expected due to its microporous structure and redox-active components, its physicochemical properties have been poorly investigated due to the specificity of its synthesis, which requires a high hydrothermal synthesis temperature of 360 °C. In this study, we succeeded in synthesizing Pharma-MoPO by hydrothermal synthesis at 230 °C, which can be applied using a commercially available autoclave by changing the metal source. Through the study of the solids and liquids obtained after hydrothermal syntheses, the formation process of Pharma-MoPO under our studied synthesis conditions was proposed. Advanced characterizations provided detailed structural information on Pharma-MoPO, including the location site of a countercation NH4+. Pharma-MoPO could adsorb CO2 with the amount close to the number of cages without removing NH4+. Pharma-MoPO exhibited stable catalytic activity for the hydrodesulfurization of thiophene while maintaining its crystal structure, except for the introduction of sulfide by replacing lattice oxygens. Pharmacosiderite Mo4P3O16 was successfully obtained by hydrothermal synthesis at a moderate temperature, and its microporosity for CO2 adsorption and catalytic properties for hydrodesulfurization were discovered.

In Situ Spectroscopic Study of CO2 Capture and Methanation over Ni-Ca Based Dual Functional Materials.

Carbon dioxide capture and reduction (CCR) to CH4 using dual-functional materials (DFMs) have recently attracted significant attention as a promising strategy for carbon capture and utilization. In this study, we investigate the mechanism of CCR to CH4 over Al2 O3 -supported Ni-Ca DFMs (Ni-Ca/Al2 O3 ) under cyclic feeds of model combustion exhaust (2.5 % CO2 +0 or 10 % O2 /N2 ) and H2 at 500 °C. Various spectroscopic analyses, including time-resolved in situ X-ray diffraction and X-ray absorption spectroscopy, were conducted during CO2 capture and the subsequent H2 -reduction steps. Based on these analyses, we propose a mechanism of CCR to CH4 over Ni-Ca based DFMs. During the CO2 capture step, the Ni0 species underwent complete oxidation in the presence of O2 to yield NiO. Subsequently, CO2 was captured through the interaction between the CaO surface and CO2 , resulting in the formation of CaCO3 layers on the CaO particles. When the gas flow was switched to H2 , NiO was partially to provide Ni0 sites, which acted as active sites for H2 -reduction of the adjacent CaCO3 layers to yield CaO and gas-phase products, CH4 and H2 O.

Difference in cadmium chemisorption on calcite and vaterite porous particles.

Cadmium is adsorbed on calcium carbonate via chemisorption. All calcium carbonate polymorphs generate otavite (cadmium carbonate), indicating that the crystallographic differences in calcium carbonate should affect the chemisorption equilibrium and kinetics. This study investigates the influences of the polymorph and specific surface area on cadmium adsorption. Here, we synthesise two polymorphs of porous calcium carbonate: calcite and vaterite with a wide range of specific surface areas. Then the equilibrium of cadmium adsorption is evaluated using adsorption isotherm models. Based on the Langmuir model with linear regression analysis, the maximum adsorptions of porous calcite and vaterite particles are 287.8 mg/g and 883.5 mg/g, respectively. The kinetics of cadmium chemisorption show clear differences between polymorphs. The calculated rate constant of the porous calcite particles using a pseudo-second-order reaction and Elovich models are two orders larger than that of porous vaterite particles. Although the adsorbed amount is superior for porous vaterite particles, porous calcite particles exhibit a faster reaction and relatively high adsorbed capacity for cadmium ions.

Key particle properties of shells for cadmium chemisorption.

Previous studies on cadmium adsorption of calcium carbonate have found that polymorph, and, crystallinity are influential factors for adsorbing cadmium ions. The predominant factor for cadmium adsorption has yet to be elucidated because these factors are linked. To overcome this, here each factor is investigated separately. First, atmospheric grinding prepared surf clam (aragonite phase) and scallop (calcite phase) shells with similar crystallite sizes and specific surface areas. Using adsorption isotherm models, kinetics, X-ray diffraction analysis, and TEM observations, both calcite and aragonite react with cadmium to form cadmium carbonate. The chemisorption follows the adsorption mechanism reported in the literature. Based on the Langmuir isotherm model fitting, the maximum adsorbed amount for the ground surf clam shells is 633.3 mg/g, while that for scallop shells is 195.8 mg/g. Then fine surf clam shell particles with a similar specific surface area, and with a relatively wide range of the aragonite ratio, and crystallite size are prepared via a combination of grinding and a subsequent calcination process. Our experiments where one explanatory variable is changed at a time demonstrate that the polymorph ratio and crystallite size of the ground shells play key roles in the chemisorption.

Pure hydroxyapatite synthesis originating from amorphous calcium carbonate.

We report a synthesis strategy for pure hydroxyapatite (HAp) using an amorphous calcium carbonate (ACC) colloid as the starting source. Room-temperature phosphorylation and subsequent calcination produce pure HAp via intermediate amorphous calcium phosphate (ACP). The pre-calcined sample undergoes a competitive transformation from ACC to ACP and crystalline calcium carbonate. The water content, ACC concentration, Ca/P molar ratio, and pH during the phosphorylation reaction play crucial roles in the final phase of the crystalline phosphate compound. Pure HAp is formed after ACP is transformed from ACC at a low concentration (1 wt%) of ACC colloid (1.71 < Ca/P < 1.88), whereas Ca/P = 1.51 leads to pure ß-tricalcium phosphate. The ACP phases are precursors for calcium phosphate compounds and may determine the final crystalline phase.