| 1. |
- Ma, Chunyan, et al.
(författare)
-
Thermodynamic study of imidazolium halide ionic liquid–water binary systems using excess Gibbs free energy models
- 2023
-
Ingår i: Journal of Molecular Liquids. - : Elsevier. - 0167-7322 .- 1873-3166. ; 391, Part B
-
Tidskriftsartikel (refereegranskat)abstract
- In this work, the excess Gibbs free energy models, i.e., non-random two-liquid (NRTL) model and electrolyte NRTL model, including the original one and those with new strategies (association or hydration), were used to describe the macroscopic properties and interpret the microstructure of ionic liquid (IL) - H2O binary systems, clarifying the role of IL association and ion hydration in model development. To provide systematic data for model development, the enthalpy of mixing of three imidazolium-based IL-H2O systems containing the same cation but different sizes of anions, i.e., Cl−, Br−, and I−, were measured. The models were developed and evaluated based on the newly measured data and the osmotic coefficient from the literature. The results reveal that the model reflecting the intrinsic mechanism of dissociation and hydration gives the best modeling results; and the ionic strength and the degree of IL dissociation as a function of water content can be predicted using the newly established model. The study clarifies the significance of IL association and anion hydration in model development and quantitatively demonstrates how water content influences the microstructure and real species in IL-H2O systems.
|
|
| 2. |
- Dong, Yihui, et al.
(författare)
-
Excellent Trace Detection of Proteins on TiO2Nanotube Substrates through Novel Topography Optimization
- 2020
-
Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 124:50, s. 27790-27800
-
Tidskriftsartikel (refereegranskat)abstract
- For improving the surface-enhanced Raman scattering (SERS) performance of nanomaterials to achieve trace detection of proteins and complex biological systems, structural and topographical control is one of the important strategies. In this work, a facial and effective method to optimize the topography of TiO2 nanotube arrays (TNAs) is demonstrated, together with a significant enhancement of the SERS performance of cytochrome C (Cyt C) on TNAs. An enhancement factor (EF) up to 104, which is obtained with the newly developed method on the basis of the quantification of atomic force microscopy (AFM)-measured interaction force, is achieved, corresponding to a superior detection limit of Cyt C down to 10-7 M. The main reason is that adjusting the fluoride contents in an electrolyte (from 0.4 to 0.1 wt %) can reduce the content and sizes of cracks, as well as the tube ruptures of TNAs, where the fluoride content at 0.2 wt % can successfully provide the excellent and optimized topography of TNAs. The TNAs with the optimized topography, especially those with larger tube diameters, demonstrated the importance of structural integrity on a remarkably excellent SERS performance in the trace detection of proteins. The proposed method will stimulate the development and optimization of the active substrate on the SERS applications in biology, bioanalysis, and nanoscience. © 2020 American Chemical Society.
|
|
| 3. |
- Sun, Yunhao, et al.
(författare)
-
How to detect possible pitfalls in ePC-SAFT modelling : Extension to ionic liquids
- 2020
-
Ingår i: Fluid Phase Equilibria. - : Elsevier. - 0378-3812 .- 1879-0224. ; 519
-
Tidskriftsartikel (refereegranskat)abstract
- An ion-specific electrolyte perturbed-chain statistical associating fluid theory (ePC-SAFT) has been developed to describe the thermodynamic and transport properties of ionic liquids (ILs) for developing IL-based technologies to separate CO2 from gas mixtures. However, as it has been pointed out previously, SAFT-based models can lead to a pitfall, manifesting as an additional fictitious liquid-liquid critical line connected to an additional mechanically stable critical point when modeling pure substances. In this work, a method for detecting a pitfall in ILs was developed, where an expression with ionic term for calculating the critical point with ePC-SAFT was derived and an algorithm for detecting the additional fictitious phase equilibrium for ILs was proposed. The pitfall occurrence for an extended set ILs taken from our previous work was investigated. It shows that a pitfall occurs only for one single IL among all 96 ILs in the temperature and pressure range of interest. For [C8mpy][BF4], at 290.27–291.78 K, a pitfall may occur at the pressures of interest; at 273.15–290.20 K, it may occur at any given pressure. The ion-specific ePC-SAFT parameters for [C8mpy]+ may therefore need to be modified in the future when more reliable experimental results are available for parameter fitting.
|
|
| 4. |
- Wang, Hui, et al.
(författare)
-
Experimental and theoretical study on ion association in [Hmim][halide] + water/isopropanol mixtures
- 2023
-
Ingår i: Fluid Phase Equilibria. - : Elsevier. - 0378-3812 .- 1879-0224. ; 566
-
Tidskriftsartikel (refereegranskat)abstract
- The electrical conductivities of the dilute solutions containing ionic liquids (1-hexyl-3-methylimidazolium chloride [Hmim]Cl, 1-hexyl-3-methylimidazolium bromide [Hmim]Br, and 1-hexyl-3-methylimidazolium iodide [Hmim]I) with water and isopropanol were determined in the temperature ranging from 293.15 to 313.15 K. The liquid densities of all binary mixtures were further determined for model parameterization. In theoretical modeling, the limiting molar conductivities Λ0(T) were first obtained using the Debye-Hückel-Onsager (DHO) equation, and thereafter the ion association constants KA(T) were determined using the Shedlovsky equation. The effects of temperature, dielectric constant, and anion size on the values of Λ0(T) and KA(T) were systematically discussed. The Eyring activation enthalpy of charge transport ∆H* and the Walden values Λ0η for all studied binary mixtures were obtained from the temperature-dependent Λ0(T).
|
|
| 5. |
- Ma, Chunyan, et al.
(författare)
-
CO2 Separation by a Series of Aqueous Morpholinium-Based Ionic Liquids with Acetate Anions
- 2020
-
Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 8:1, s. 415-426
-
Tidskriftsartikel (refereegranskat)abstract
- In this work, CO2 absorption capacities in a series of aqueous N-alkyl-N-methylmorpholinium-based ILs with acetate as the counterpart anion were investigated. Among these ILs, N-butyl-N-methylmorpholinium acetate ([Bmmorp][OAc]) with the highest CO2 absorption capacity was screened for thermodynamic modeling. The non-random two-liquid model and the Redlich–Kwong equation of state (NRTL-RK model) were used to describe the phase equilibria. The CH4 absorption capacity in the aqueous [Bmmorp][OAc] was also measured in order to verify the results predicted from the thermodynamic modeling, and the comparison shows the reliability of the model prediction. The parameters were embedded into the commercial software Aspen Plus. After that, the aqueous [Bmmorp][OAc] solutions with 30–40 wt % of water were selected to carry out process simulation for CO2 separation from biogas, and it was found that using these aqueous [Bmmorp][OAc] gave rise to lower energy usage and smaller size of equipment than other physical solvents. The results suggest that aqueous [Bmmorp][OAc] solution can be used as an alternative to organic solvents and has the potential to decrease the cost of CO2 separation.
|
|
| 6. |
- Li, Hailong, 1976-, et al.
(författare)
-
A new modification on RK EOS for gaseous CO2 and gaseous mixtures of CO2 and H2O
- 2006
-
Ingår i: International Journal of Energy Research. - : Hindawi Limited. - 0363-907X .- 1099-114X. ; 30:3, s. 135-148
-
Tidskriftsartikel (refereegranskat)abstract
- To develop an equation of state with simple structure and reasonable accuracy for engineering application, Redlich-Kwong equation of state was modified for gaseous CO2 and CO2-H2O mixtures. In the new modification, parameter 'a' of gaseous CO2 was regressed as a function of temperature and pressure from recent reliable experimental data in the range: 220-750 K and 0.1-400 MPa. Moreover, a new mixing rule was proposed for gaseous CO2-H2O mixtures. To verify the accuracy of the new modification, densities were calculated and compared with experimental data. The average error is 1.68% for gaseous CO2 and 0.93% for gaseous mixtures of CO2 and H2O, Other thermodynamic properties, such as enthalpy and heat capacities of CO2 and excess enthalpy of gaseous CO2-H2O mixtures, were also calculated; results fit experimental data well, except for the critical region.
|
|
| 7. |
- Bao, Ningzhong, et al.
(författare)
-
Thermodynamic modeling and experimental verification for ion-exchange synthesis of K2O·6TiO2 and TiO2 fibers from K2O·4TiO2
- 2002
-
Ingår i: Fluid Phase Equilibria. - 0378-3812 .- 1879-0224. ; 193, s. 229-243
-
Tidskriftsartikel (refereegranskat)abstract
- A thermodynamic model was established to determine ion-exchange conditions for the synthesis of potassium hexatitanate (K2O·6TiO2) and titanium dioxide (TiO2) from potassium tetratitanate (K2O·4TiO2) fiber. In the proposed model equilibrium species in the solid phase and corresponding ion-exchange equilibrium constants at 298.15 K were determined from the experimental data of Sasaki et al. [Inorg. Chem. 24 (1985) 2265]. In order to verify the proposed model, prediction results were compared with experimental data determined in literature and those measured in this work. The comparison shows a good agreement. Based on this, the proposed model was also used to predict more extensive suitable conditions for the synthesis of K2O·6TiO2 and TiO2.
|
|
| 8. |
- Bülow, M., et al.
(författare)
-
Incorporating a concentration-dependent dielectric constant into ePC-SAFT. An application to binary mixtures containing ionic liquids
- 2019
-
Ingår i: Fluid Phase Equilibria. - : Elsevier. - 0378-3812 .- 1879-0224. ; 492, s. 26-33
-
Tidskriftsartikel (refereegranskat)abstract
- Primitive thermodynamic models for electrolyte solutions require the dielectric constant ε. This property strongly depends on the concentration of the electrolytes in the mixture. Neglecting this dependency might be reasonable for modeling solutions at low electrolyte concentrations. However, in solutions containing ionic liquids (ILs) and especially for the calculation of liquid-liquid equilibria (LLE) of systems with ILs, liquid phases often contain high IL concentrations. At such conditions, neglecting the influence of concentration on ε is an oversimplification. In this work, an approach to account for the concentration-dependent dielectric constant within the Debye-Hückel theory was implemented into electrolyte Perturbed-Chain Statistical Associating Fluid Theory (original ePC-SAFT). This new approach was then applied to model LLE of binary mixtures containing water and commonly used hydrophobic ILs. These common ILs are comprised of the IL-cations [C n mim] + , [C n py] + , [C n mpy] + , [C n mpyr] + , [C 4 m 4 py] + and the IL-anions [BF 4 ] - , [NTf 2 ] - , [PF 6 ] - , [TFO] - . The LLE of binary mixtures water + IL were modeled at ambient pressure and different temperatures with the new ePC-SAFT and with the original ePC-SAFT [Ji et al. DOI: 10.1016/j.fluid.2012.05.029] without the concentration-dependent ε. Overall, the new approach within ePC-SAFT shows superior modeling as well as correlation capability compared to original ePC-SAFT, which was concluded by comparing both models with LLE data from literature.
|
|
| 9. |
- Cao, Jian, et al.
(författare)
-
Heterogeneous consecutive reaction kinetics of direct oxidation of H2 to H2O2: Effect and regulation of confined mass transfer
- 2023
-
Ingår i: Chemical Engineering Journal. - : Elsevier. - 1385-8947 .- 1873-3212. ; 455
-
Tidskriftsartikel (refereegranskat)abstract
- Porous catalysts in heterogeneous reactions have played an important role in the modern chemical industry, but it is still challenging to quantitatively describe mass transfer and surface reaction behaviors of reactants in nano-confined space. Direct synthesis of hydrogen peroxide (H2O2) is considered as an attractive alternative to anthraquinone oxidation process, while the confined mass transfer of H2O2 in porous catalysts limits the reactivity. In this work, taking the consecutive reaction of H2O2 synthesis as an example, a quantitative method in modeling the effects of confined mass transfer on the reactivity was studied. More specifically, calorimetry was developed to characterize the confined structures of porous carbon experimentally, the linear nonequilibrium thermodynamics and the statistical mechanics method were further combined. Then, the heterogeneous consecutive reaction kinetics and the Thiele modulus influenced by confined mass transfer were modeled. Consequently, regulation strategies were proposed with the help of theoretical models. The optimized catalyst with biological skeleton carbon support and 0.5 wt% palladium loading shows an excellent catalytic performance. Lastly, for the mesoscience in heterogeneous reaction, the resistance was explored as a quantitative descriptor to compromise in the competition between mass transfer and surface reaction. The mesoscale structures were considered as the dynamic spatiotemporal distribution of substance concentrations, and the resistance minimization multi-scale (RMMS) model was proposed.
|
|
| 10. |
- Carvalho, Lara, et al.
(författare)
-
Alkali enhanced biomass gasification with in situ S capture and a novel syngas cleaning : Part 2: Techno-economic analysis
- 2018
-
Ingår i: Energy. - : Elsevier. - 0360-5442 .- 1873-6785. ; 165:Part B, s. 471-482
-
Tidskriftsartikel (refereegranskat)abstract
- Previous research has shown that alkali addition has operational advantages in entrained flow biomass gasification and allows for capture of up to 90% of the biomass sulfur in the slag phase. The resultant low-sulfur content syngas can create new possibilities for syngas cleaning processes. The aim was to assess the techno-economic performance of biofuel production via gasification of alkali impregnated biomass using a novel gas cleaning systemcomprised of (i) entrained flow catalytic gasification with in situ sulfur removal, (ii) further sulfur removal using a zinc bed, (iii) tar removal using a carbon filter, and (iv) CO2 reductionwith zeolite membranes, in comparison to the expensive acid gas removal system (Rectisol technology). The results show that alkali impregnation increases methanol productionallowing for selling prices similar to biofuel production from non-impregnated biomass. It was concluded that the methanol production using the novel cleaning system is comparable to the Rectisol technology in terms of energy efficiency, while showing an economic advantagederived from a methanol selling price reduction of 2–6 €/MWh. The results showed a high level of robustness to changes related to prices and operation. Methanol selling prices could be further reduced by choosing low sulfur content feedstocks.
|
|
