Bifunctional Au-nanorod@Fe3O4 nanocomposites: synthesis, characterization, and their use as bioprobes

Membrane gas separation technology has been rapidly growing for industrial applications such as air separation, carbon dioxide (CO₂) separation from natural gas production, hydrogen separation, etc. Needs for CO₂ separation are increasing as carbon capture technology has been recognized as an essential part when combating the global warming issue. Membrane gas separation technology deals with mass transport phenomena through the membrane engineered on a sub-nanoscale controlling transport properties of small gas molecules such as CO₂, N₂, O₂, H₂, etc. In this review, we will report on the recent developments in capture technologies utilizing various membranes including nano-engineered thermally rearranged (TR) polymers. TR polymer membranes show high gas permeability as well as good separation properties, especially in CO₂ separation processes such as from post-combustion flue gas and natural gas sweetening.     

整体煤气化联合循环合成气水合物法分离CO2的分子动力学模拟

利用分子动力学（MD）模拟方法研究整体煤气化联合循环（IGCC）合成气（CO₂/H₂）水合物法分离CO₂的分离机理,系统研究了CO₂水合物、H₂水合物以及合成气水合物法一级分离所得CO₂/H₂混合气体水合物的微观结构及性质.模拟分析n个CO₂或H₂与水合物笼状结构的整体结合能ΔE关键词： 水合物法分离 分子动力学模拟 整体煤气化联合循环合成气 2分离')" href="#">CO₂分离     

Melting and subsolidus phase relations in the system K2CO3–MgCO3 at 3 GPa

ABSTRACT

As part of an investigation of carbonate systems under mantle pressures and temperatures, phase relations in the K₂CO₃–MgCO₃ system have been studied at 3?GPa and 800–1300°C. Subsolidus assemblages comprise the stability fields of K₂CO₃?+?K₂Mg(CO₃)₂ and K₂Mg(CO₃)₂?+?MgCO₃ with the transition boundary near 50?mol% K₂CO₃ in the system. The K₂CO₃–K₂Mg(CO₃)₂ eutectic is located at 840°C and 52?mol% K₂CO₃. The K₂CO₃ content in the melt coexisting with potassium carbonate increases to 85?mol% as temperature increases to 1050°C. K₂CO₃ remains solid up to 1250 and melts at 1300°C. K₂Mg(CO₃)₂ melts incongruently at 890°C to produce magnesite and a liquid containing 51?mol% K₂CO₃. As temperature increases to 1300°C, the K₂CO₃ content in the liquid coexisting with magnesite decreases to 27?mol%.     

Formation,growth and ageing of clathrate hydrate crystals in a porous medium

An experimental study was performed to visually observe the driving force dependence of hydrate growth in a porous medium filled with either liquid water and dissolved CO₂ or liquid water and gaseous CO₂. The given system subcooling, ΔT _sub, i.e. the deficiency of the system temperature from the triple CO₂?hydrate?water equilibrium temperature under a given pressure, ranged from 1.7?K to 7.3?K. The fine dendrites initially formed at ΔT _sub?=?7.3?K changed quickly into particulate crystals. For ΔT _sub?=?1.7?K, faceted hydrate crystals grew and the subsequent morphological change was hardly identified for an eight-day observation period. These results indicate that the physical bonding between hydrate crystals and skeletal materials becomes stronger with decreasing driving force, suggesting that the fluid dynamic and mechanical properties of hydrate-bearing sediments vary depending on the hydrate crystal growth process.     

The Ca-looping process for CO<Subscript>2</Subscript> capture and energy storage: role of nanoparticle technology

The calcium looping (CaL) process, based on the cyclic carbonation/calcination of CaO, has come into scene in the last years with a high potential to be used in large-scale technologies aimed at mitigating global warming. In the CaL process for CO₂ capture, the CO₂-loaded flue gas is used to fluidize a bed of CaO particles at temperatures around ~?650 °C. The carbonated particles are then circulated into a calciner reactor wherein the CaO solids are regenerated at temperatures near ~?950 °C under high CO₂ concentration. Calcination at such harsh conditions causes a marked sintering and loss of reactivity of the regenerated CaO. This main drawback could be however compensated from the very low cost of natural CaO precursors such as limestone or dolomite. Another emerging application of the CaL process is thermochemical energy storage (TCES) in concentrated solar power (CSP) plants. Importantly, carbonation/calcination conditions to maximize the global CaL-CSP plant efficiency could differ radically from those used for CO₂ capture. Thus, carbonation could be carried out at high temperatures under high CO₂ partial pressure for maximum efficiency, whereas the solids could be calcined at relatively low temperatures in the absence of CO₂ to promote calcination. Our work highlights the critical role of carbonation/calcination conditions on the performance of CaO derived from natural precursors. While conditions in the CaL process for CO₂ capture lead to a severe CaO deactivation with the number of cycles, the same material may exhibit a high and stable conversion at optimum CaL-CSP conditions. Moreover, the type of CaL conditions influences critically the reaction kinetics, which plays a main role on the optimization of relevant operation parameters such as the residence time in the reactors. This paper is devoted to a brief review on the latest research activity in our group concerning these issues as well as the possible role of nanoparticle technology to enhance the activity of Ca-based materials at CaL conditions for CO₂ capture and energy storage.     

B40 fullerene: An efficient material for CO2 capture,storage and separation

Novel nanomaterials are promising for capture, storage and separation of CO₂. By density functional calculations, we find that the newly discovered B₄₀ fullerene is a suitable candidate. CO₂ forms stable chemisorptions with B₄₀ on specific sites, which is validated by the high adsorption energy, large charge transfer, and kinetic feasibility for B₄₀(CO₂) complexes. Due to the strong chemisorption, B₄₀ shows high adsorption capacity for CO₂ (up to 13.87 mmol/g). In addition, B₄₀ shows good selectivity for CO₂ and is efficient in separating it from gas mixtures like CO₂/N₂, CO₂/H₂, and CO₂/CH₄.     

The system Na2CO3–MgCO3 at 3 GPa

It was suggested that Na–Mg carbonates might play a substantial role in mantle metasomatic processes through lowering melting temperatures of mantle peridotites. Taking into account that natrite, Na₂CO₃, eitelite, Na₂Mg(CO₃)₂, and magnesite, MgCO₃, have been recently reported from xenoliths of shallow mantle (110–115?km) origin, we performed experiments on phase relations in the system Na₂CO₃–MgCO₃ at 3?GPa and 800–1250°C. We found that the subsolidus assemblages comprise the stability fields of Na-carbonate?+?eitelite and eitelite?+?magnesite with the transition boundary at 50?mol% Na₂CO₃. The Na-carbonate–eitelite eutectic was established at 900°C and 69?mol% Na₂CO₃. Eitelite melts incongruently to magnesite and a liquid containing about 55?mol% Na₂CO₃ at 925?±?25 °C. At 1050 °C, the liquid, coexisting with Na-carbonate, contains 86–88?mol% Na₂CO₃. Melting point of Na₂CO₃ was established at 1175?±?25 °C. The Na₂CO₃ content in the liquid coexisting with magnesite decreases to 31?mol% as temperature increases to 1250°C. According to our data, the Na- and Mg-rich carbonate melt, which is more alkaline than eitelite, can be stable at the P–T conditions of the shallow lithospheric mantle with thermal gradient of 45?mW/m² corresponding to temperature of 900 °C at 3?GPa.     

Investigation of Gas Degradation in CO2 ? N2 Pulse Discharges I. Long Term Behaviour of Pulsed Laser Discharges in CO2 — N2 Gas Mixtures

The correlation between the plasma resistance and the laser output parameters has been investigated in pulsed CO₂ — N₂ discharges. The strong increase of the discharge resistance during gas degradation can be explained on the basis of strong attaching gas components. In degraded mixtures a supression of discharge instabilities together with the restoration of the laser pulse energy is possible by increasing the reduced electric field E/N temporarily.     

The gas-phase pyrolysis of methyl azidoformate in the absence and presence of water: a theoretical study

The potential energy surface profiles for the gas-phase pyrolysis of methyl azidoformate (MA, CH₃OC(O)N₃) in the absence and presence of one water molecule have been investigated by ab initio methods at CCSD(T)/6-311++G(2df,2pd)//MP2(full)/6-311++G(d,p)+0.95×ZPE levels of theory. Three types of mechanisms are discussed for the gas-phase decomposition of CH₃OC(O)N₃. Ab initio calculations show that a four-membered-ring intermediate can be formed by the stepwise routes. The resulting intermediate can undergo two competitive decomposition channels to generate the major products CO₂?+?CH₂?=?NH and HNCO?+?HC(O)H. The calculated results are in qualitative agreement with the observed experimental data. However, CH₃ONCO can be produced from the Curtius-type rearrangement route. This is an intriguing finding in this study. Moreover, the effect of one water molecule on the gas-phase pyrolysis of MA has been also explored. We find that the relative energy of the hydrated transition states is effectively lowered when water is added to the reaction. However, the estimated rate constant at 625?K for the naked reaction is about 30 times faster than the reaction with water. Thus, a single water molecule cannot play an important role in the thermal decomposition of MA.     

Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

Selectivity enhancement in tritium isotope separation by multiple frequency multiple photon dissociation of the CTF3/CHF3 System

Isotope separation of tritium by multiple photon dissociation process in multiple frequency fields of a TEA-CO₂ laser is reported for the first time. A ten-fold improvement in the bulk selectivity was obtained in 8.5 Torr CTF₃/CHF₃ in the presence of buffer gas at room temperature using 9R(8) to 9R(14) CO₂ laser lines compared to single frequency excitation. Investigations of various process parameters such as exciting laser frequencies, pulse energy, sample and buffer gas pressure indicate that this is a promising technique for the separation of tritium.     

Comparison of chemical solvents for mitigating CO2 emissions from coal-fired power plants

There is a growing concern about the effect of greenhouse gases on global warming. Among the many greenhouse gases, CO₂ produced from burning fossil fuels is a major contributor due to the huge volumes emitted into the atmosphere. According to the estimates of the Intergovernmental Panel on Climate Change (IPCC), a worldwide reduction in the emission of greenhouse gases by more than 60% is necessary to avert significant global climate changes.This paper examines the key issues involved in greenhouse gas emissions from coal-fired power plants. At the present time, absorption by chemical solvents appears to be best option for the separation of CO₂ from low pressure flue gas streams. The costs of separation and disposal of CO₂ from existing coal fired, air blown boilers are estimated to increase the cost of electricity by about 75%. Therefore, there is a need to optimize the selection of processing solvents and operating parameters to minimize the cost of separation. Increasing the inlet flue gas pressure did not improve mass transfer rates sufficiently to compensate for the higher compression costs. The effects of other process variables were also examined.In this work, we have examined the cost effectiveness of six ethanolamine-based solvents. Overall, monoethanolamine (MEA) was found to be the best solvent.     

X-ray preionized CO2 laser

A short pulse (100 ns) high-energy x-ray source has been used to preionize a transversely excited carbon dioxide gas discharge laser of 600 cm³ active volume. The maximum output power of 60 MW in a 50 ns FWHM pulse was achieved from a CO₂–N₂–He–CO–Xe static gas mixture at 600 Torr pressure. The energy conversion efficiency was 6%.     

Elucidation of the crystallization kinetics for sodium-alumino-silicate glasses containing different amounts of manganese oxide

The glass samples [40SiO₂?+?5Al₂O₃?+?{55???x}Na₂O?+?xMnO₂] where x?=?0.05, 0.2, 0.4, 0.6, 0.8, and 1?mol% MnO₂ before and after being heat treated were subjected to X-ray diffraction. The diffraction lines provided clear evidence of the nucleation and growth, which are characteristic of sodium silicate phase. Crystallization studies were conducted using differential thermal analysis. Crystallization peak temperatures were identified and the transformed fractions were determined. Both the rate of growth, K ₀, and the activation energy, E, depend on the influence of manganese ions in the glass network as a modifier or as a former and the manganese content. The values of the Avrami parameter, n, were calculated using two methods and were in excellent agreement. The process of nucleation and growth rate depends on the manganese content.     

Holey Graphitic Carbon Derived from Covalent Organic Polymers Impregnated with Nonprecious Metals for CO2 Capture from Natural Gas

Natural gas (NG), as a renewable and clean energy gas, is considered to be one of the most attractive energy carriers owing to its high calorific value, low price, and less pollution. Efficiently capturing CO₂ from NG is a very important issue since CO₂ reduces energy density of natural gas and corrodes equipment in the presence of water. In this study, the authors use holey graphene‐like carbon derived from covalent organic polymers (COP) impregnated with nonprecious metals, i.e., COP graphene, as highly efficient separation materials. The dual‐site Langmuir–Freundlich adsorption model based ideal absorbed solution theory is applied to explore the adsorption selectivity. The experimental results along with first principles calculations show Mn‐impregnated COP graphene exhibits greater CO₂/CH₄ selectivity than Fe and Co impregnated materials. Particularly, the selectivity of C–COP–P–Mn reaches 11.4 at 298 K and 12 bars, which are much higher than those in many reported conventional porous materials and can be compared to the highest separation performance under similar condition. Importantly, all the three COP graphene show remarkably high regenerability (R > 77%), which are much better than many reported promising zeolites, active carbon, and metal organic frameworks. Accordingly, COP graphene are promising cyclic adsorbents with high selectivity for separation and purification of CO₂ from natural gas.     

Food technological potentials of CO2 gas hydrate technology for the concentration of selected juices*

ABSTRACT

CO₂ gas hydrate technology seems to be a gentle way to concentrate juices, especially comparing to evaporation processes which achieve high levels of concentration and is furthermore energetically favorable in contrast to freeze concentration processes. CO₂ can form gas hydrates at around 30–80 bar and 274–283 K. For evaluating this new technology, it is not only important to know the phase equilibrium lines of commercial juices like apple and orange juices but also how the application of e.g. a bubble column affects the gas hydrate formation and separation from the concentrated product. In order to support the experimental outcome, numerical modeling seems suitable to understand the physical background of this novel concentration technology. This includes the simulation of temperature, velocity, pressure and concentration fields using finite volume technique. All three work packages combined will lead to a better understanding of the behavior of gas hydrate technology used to concentrate liquid food.     

The combined effect of H2O and SO2 on CO2 uptake and sorbent attrition during fluidised bed calcium looping

The effect of steam and sulphur dioxide on CO₂ capture by limestone during calcium looping was studied in a novel lab-scale twin fluidised bed device (Twin Beds – TB). The apparatus consists of two interconnected batch fluidised bed reactors which are connected to each other by a duct permitting a rapid and complete pneumatic transport of the sorbent (limestone) between the reactors. Tests were carried out under typical calcium looping operating conditions with or without the presence of H₂O and/or SO₂ during the carbonation stage. Carbonation was carried out at 650°C in presence of 15% CO₂, 10% steam (when present) and by investigating two SO₂ levels, representative of either raw (1500?ppm) or pre-desulphurised (75?ppm) typical flue gas derived from coal combustion. The sorbent used was a reactive German limestone. Its performance was evaluated in terms of CO₂ capture capacity, sulphur uptake, attrition and fragmentation. Results demonstrated the beneficial effect of H₂O and the detrimental effect of SO₂ on the CO₂ capture capacity. When both species were simultaneously present in the gas, steam was still able to enhance the CO₂ capture capacity even outweighing the negative effect of SO₂ at low SO₂ concentrations. A clear relationship between degrees of Ca carbonation and sulphation was observed. As regards the mechanical properties of the sorbent, both H₂O and SO₂ hardened the particle surface inducing a decrease of the measured attrition rate, that was indeed always very low. Conversely, the fragmentation tendency increased in presence of H₂O and SO₂ most likely due to the augmented internal stresses within the particles. Clear bimodal particle size distributions for in-bed sorbent fragments were observed. Microstructural scanning electron microscope and porosimetric characterisations aided in explaining the observed trends.     

Adsorption of small molecules on transition metal doped rhodium clusters Rh3X (X = 3d, 4d atom): a first-principles investigation

The adsorption behaviours of seven molecules (CO, CO₂, N₂, NO, O₂, N₂O and NO₂) on Rh₃X (X?=Sc-Zn, Y-Cd) clusters are systematically investigated by density-functional calculations. Rh₃X clusters exhibit physical adsorption when interacting with CO₂, CO, N₂ and NO. The adsorption energies (E_ads) can be ranked as follows: NO?>?CO?>?CO_2?≥?N₂. Compared with pure Rh₄ cluster, the adsorption capacity changes with the doping element. Chemical adsorption can be obtained for Rh₃X when adsorbing O₂, N₂O and NO₂. E_ads shows an order of E_ads(O₂)?>?E_ads(NO₂)?>?E_ads(N₂O). When O₂ is adsorbed, energy barrier with doping Tc or Cr atom is substantially reduced, which indicates that chemical reactivity of O₂ on Rh₄ can be significantly enhanced. The doped rhodium clusters can be viewed as good candidates in the discrimination between different gas molecules.     

Lithium-functionalized germanene: A promising media for CO2 capture

Density functional theory (DFT) is employed to investigate the interactions of CO₂ gas molecules with pristine and lithium-functionalized germanene. It is discovered that although a single CO₂ molecule is weakly physisorbed on pristine germanene, a significant improvement on its adsorption energy is found by utilizing Li-functionalized germanene as the adsorbent. Excitingly, the moderate adsorption energy at high CO₂ coverage secures an easy release step. Moreover, the structure of Li-functionalized germanene can be fully recovered after removal of CO₂ gas molecules. Our results suggest that Li-functionalized germanene show promise for CO₂ sensing and capture with a storage capacity of 12.57 mol/kg.     

Particle imaging of ignition and devolatilization of pulverized coal during oxy-fuel combustion

Oxy-fuel combustion of coal is a promising technology for cost-effective power production with carbon capture and sequestration that has ancillary benefits of emission reductions and lower flue gas cleanup costs. To fully understand the results of pilot-scale tests of oxy-fuel combustion and to accurately predict scale-up performance through CFD modeling, fundamental data are needed concerning coal and coal char combustion properties under these unconventional conditions. In the work reported here, the ignition and devolatilization characteristics of both a high-volatile bituminous coal and a Powder River Basin subbituminous coal were analyzed in detail through single-particle imaging at a gas temperature of 1700 K over a range of 12–36 vol % O₂ in both N₂ and CO₂ diluent gases. The bituminous coal images show large, hot soot cloud radiation whose size and shape vary with oxygen concentration and, to a lesser extent, with the use of N₂ versus CO₂ diluent gas. Subbituminous coal images show cooler, smaller emission signals during devolatilization that have the same characteristic size as the coal particles introduced into the flow (nominally 100 μm). The measurements also demonstrate that the use of CO₂ diluent retards the onset of ignition and increases the duration of devolatilization, once initiated. For a given diluent gas, a higher oxygen concentration yields shorter ignition delay and devolatilization times. The effect of CO₂ on coal particle ignition is explained by its higher molar specific heat and its tendency to reduce the local radical pool. The effect of O₂ on coal particle ignition results from its effect on the local mixture reactivity. CO₂ decreases the rate of devolatilization because of the lower mass diffusivity of volatiles in CO₂ mixtures, whereas higher O₂ concentrations increase the mass flux of oxygen to the volatiles flame and thereby increase the rate of devolatilization.