From modification to mechanism: Supercritical hydrothermal synthesis of nano-zirconia

Nano-zirconia has been widely applied due to its excellent physical and chemical properties (e.g., high strength, corrosion resistance, oxygen ion conductivity). Existing preparation methods of nano-zirconia tend to require long reaction time, and the sizes of final particles are large with uneven distributions. Sub-/supercritical hydrothermal synthesis of nanoparticles is favored by researchers owing to controllable reaction process, uniform particle size distribution, good reproducibility, short reaction time, high conversion rate and harmlessness to environment. In this paper, the characteristics and mechanisms of dissolution, crystallization and growth of nano-zirconia during sub-/supercritical hydrothermal synthesis are systematically reviewed. The influences of process and material parameters on the size and purity of particles are analyzed. Then, the reaction mechanism and product phase transition mechanism during hydrothermal synthesis of zirconia are summarized to provide a theoretical reference for the oriented preparation. Finally, the improvement and commercialization of sub-/supercritical hydrothermal synthesis technology are evaluated, and the future research topics are proposed.     

In Silico Investigation of Potential Applications of Gamma Carbonic Anhydrases as Catalysts of CO2 Biomineralization Processes: A Visit to the Thermophilic Bacteria Persephonella hydrogeniphila,Persephonella marina,Thermosulfidibacter takaii,and Thermus thermophilus

Carbonic anhydrases (CAs) have been identified as ideal catalysts for CO₂ sequestration. Here, we report the sequence and structural analyses as well as the molecular dynamics (MD) simulations of four γ-CAs from thermophilic bacteria. Three of these, Persephonella marina, Persephonella hydrogeniphila, and Thermosulfidibacter takaii originate from hydrothermal vents and one, Thermus thermophilus HB8, from hot springs. Protein sequences were retrieved and aligned with previously characterized γ-CAs, revealing differences in the catalytic pocket residues. Further analysis of the structures following homology modeling revealed a hydrophobic patch in the catalytic pocket, presumed important for CO₂ binding. Monitoring of proton shuttling residue His69 (P. marina γ-CA numbering) during MD simulations of P. hydrogeniphila and P. marina’s γ-CAs (γ-PhCA and γ-PmCA), showed a different behavior to that observed in the γ-CA of Escherichia coli, which periodically coordinates Zn²⁺. This work also involved the search for hotspot residues that contribute to interface stability. Some of these residues were further identified as key in protein communication via betweenness centrality metric of dynamic residue network analysis. T. takaii’s γ-CA showed marginally lower thermostability compared to the other three γ-CA proteins with an increase in conformations visited at high temperatures being observed. Hydrogen bond analysis revealed important interactions, some unique and others common in all γ-CAs, which contribute to interface formation and thermostability. The seemingly thermostable γ-CA from T. thermophilus strangely showed increased unsynchronized residue motions at 423 K. γ-PhCA and γ-PmCA were, however, preliminarily considered suitable as prospective thermostable CO₂ sequestration agents.     

渣油催化临氢热转化钼铁双金属催化剂的研究

Replacement of precious single metal catalysts with cost-effective, highly-dispersed composite catalysts for catalytic hydrothermal conversion of residue holds tremendous promise for the residue upgrading technologies. Organic metals were added to the feed as the oil-soluble precursors, and transformed into the catalytic active phases in this work. Physical properties and structures of the composite catalysts had been investigated by X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope and transmission electron microscopy. The composite catalysts were found to be highly efficient in the catalytic hydrothermal conversion of both model compound and residue. Increased metal dispersion and synergistic effects of two metals played indispensable roles in such catalytic system. Results showed that under the test conditions in the article, the catalyst had the best catalytic performance when the mass ratio of molybdenum to iron was 1.5.     

Super-oleophilicity Co-doping Co2+/F-/TiO2 one-dimensional nanotubes for photocatalytic denitrification of light oil

In this study, a simple hydrothermal synthesis method was adapted for the preparation of Co-doping Co²⁺/F^-/TiO₂ nanotubes photocatalyst, and the micro-nano structure of catalysts prepared by biomimetic technology which makes the catalyst have super-oleophilicity property. Co²⁺/F^-/TiO₂ revealed improved photocatalytic performance for denitrification of light oil compared to single TiO₂ photocatalysts. The enhance of photocatalytic activity can be attributed to narrowing the band gap, increasing the light response wavelength and exposing more highly active crystal surfaces due to synergistic effects of Co²⁺ and F^? in the photocatalyst.     

减压渣油与FCC油浆共炭化的化学组成变化

考察了齐鲁石化胜利炼油厂催化油浆（FCC）和胜利减压渣油（VR）在490℃，0.8MPa下不同混合比的原料和不同反应时间的中间产物的HS、TS、PS、P及其1h中间产物的HS和TS的^1H-NMR。数据结果反映了体系的反应速度。掺入FCC油浆抑制了VR的反应活性，降低了体系的反应速度，增加了基质的溶解度；1h中间产物的组成结构更接近于原料及反应体系的反应性和基质的溶解度；1h中间产物的芳香度越高，取代基越少，侧链越短，基质对VR中的活性反应组分在炭化早期生成的高度缩合物质的溶解度越大。     

Hydrothermal Reaction Mechanism and Pathway for the Formation of K2Ti6O13 Nanowires

Calculations and detailed first principle and thermodynamic analyses have been performed to understand the formation mechanism of K₂Ti₆O₁₃ nanowires (NWs) by a hydrothermal reaction between bulk Na₂Ti₃O₇ crystals and a KOH solution. It is found that direct ion exchange between K⁺ and Na⁺ plus H⁺ interactions with [TiO₆] octahedra in Na₂Ti₃O₇ promote the formation of an intermediate H₂K₂Ti₆O₁₄ phase. The large lattice mismatch between this intermediate phase and the bulk Na₂Ti₃O₇ structure, and the large energy reduction associated with the formation of this intermediate phase, drive the splitting of the bulk crystal into H₂K₂Ti₆O₁₄ NWs. However, these NWs are not stable because of large [TiO₆] octahedra distortion and are subject to a dehydration process, which results in uniform K₂Ti₆O₁₃ NWs with narrowly distributed diameters of around 10 nm.     

Influence of the oxygen content of low-rank coals on the development of porosity during carbonization

The development of porosity in the course of carbonization of a flame coal, original and pre-oxidized, was studied by means of the adsorption of benzene and carbon dioxide. The results were compared with corresponding data for cokes from a xylitic brown coal. The influence of coal oxygen content on the formation of coke porosity and its thermal dependence is discussed.     

Geochemical characteristics of the Yufuin outflow plume, Beppu hydrothermal system, Japan

Thermal water at Yufuin (Kyushu Island, Japan) is tapped through about 820 shallow wells and used mainly for hot-spring bathing purposes. Chemical and isotopic data for fluids from wells and fumaroles in Yufuin and Beppu indicate that the thermal activity at Yufuin represents a dilute, westward-flowing hydrothermal outflow plume from the Beppu hydrothermal system. Two other (eastward-flowing) outflow plumes have long been recognized at Beppu, but the Yufuin outflow plume is first recognized here. The Yufuin outflow plume is apparently a mixture of two end-member fluids: (1) deep high-temperature (250–300°C) fluid from the Beppu system having high chloride concentration (1400–1600 mg/L) and a δ¹⁸O value near −6.0%, and (2) meteoric water having low chloride concentration (≤7 mg/L) and a δ¹⁸O value near −9.2%.A permeable conduit for the vertical and lateral transport of deep fluid from the Beppu system is provided by the Yufuin Fault zone, which extends westward from the southern flank of Mt. Tsurumi volcano to the town of Yufuin. Stable isotope ratios and chloride concentrations for shallow groundwaters near the eastern end of the fault, at an elevation near 700 m, are consistent with those required for the low-chloride meteoric end-member of the Yufuin thermal waters. Recharge of this meteoric water, as well as mixing with the Beppu deep fluid, may occur along the Yufuin Fault. Enthalpy-chloride relations indicate additional conductive heating of the Yufuin waters, in the amount of 350–500 kJ/kg beyond that which can be accounted for by mixing between Beppu deep fluid and meteoric water. This could be a result of conductive heating with convection to a depth of 1–2 km. Estimates of the magnitude of the heat source for the Beppu hydrothermal system should take into account the heat being discharged at Yufuin.     

纳米钛酸盐催化合成碳酸二正丁酯

以廉价的偏钛酸为原料,采用水热法和乙醇热法制备了纳米钛酸盐(简称钛酸盐),并对其进行了X射线粉末衍射和X射线光电子能谱表征。考察了钛酸盐的种类、制备方法、晶型对催化碳酸二甲酯(DMC)与正丁醇酯交换反应的影响。实验结果表明,乙醇热法比水热法制备的钛酸盐粒径小;对于不同的钛酸盐,随钛酸盐碱性的增强,催化活性提高,但由于三价钛的存在,钛酸锂对产物碳酸二正丁酯(DBC)的选择性低于钛酸钡;钛酸钾的催化活性最高,DMC转化率达到65%,DBC选择性达到100%,DBC收率达到65%,并在5次循环使用过程中,催化性能稳定;对于同种钛酸盐,催化活性随粒径的增加而减小;对于钛酸钡,立方相结构的催化活性优于四方相结构。