Currently,the process of extracting rubidium from ores has attracted a great deal of attention due to the increasing application of rubidium in high-technology field.A novel process for the comprehensive utilization o...Currently,the process of extracting rubidium from ores has attracted a great deal of attention due to the increasing application of rubidium in high-technology field.A novel process for the comprehensive utilization of rubidium ore resources is proposed in this paper.The process consists mainly of mineral dissociation,selective leaching,and desilication.The results showed that the stable silicon–oxygen tetrahedral structure of the rubidium ore was completely disrupted by thermal activation and the mineral was completely dissociated,which was conducive to subsequent selective leaching.Under the optimal conditions,extractions of 98.67% Rb and 96.23%K were obtained by leaching the rubidium ore.Moreover,the addition of a certain amount of activated Al(OH)_(3) during leaching can effectively inhibit the leaching of silicon.In the meantime,the leach residue was sodalite,which was successfully synthesized to zeolite A by hydrothermal conversion.The proposed process provided a feasible strategy for the green extraction of rubidium and the sustainable utilization of various resources.展开更多
The activation and dissociation of hydrogen molecules(H_(2))on the Cu(001)surface are studied theoretically.Using first-principles calculations,the activation barrier for the dissociation of H_(2) on Cu(001)is determi...The activation and dissociation of hydrogen molecules(H_(2))on the Cu(001)surface are studied theoretically.Using first-principles calculations,the activation barrier for the dissociation of H_(2) on Cu(001)is determined to be~0.59 eV in height.It is found that the electron transfer from the copper substrate to H_(2) plays a key role in the activation and breaking of the H–H bond,and the formation of the Cu–H bonds.Two stationary states are identified at around the critical height of bond breaking,corresponding to the molecular and the dissociative states,respectively.Using the transfer matrix method,we also investigate the role of quantum tunneling in the dissociation process along the minimum energy pathway(MEP),which is found to be significant at or below room temperature.At a given temperature,the tunneling contributions due to the translational and the vibrational motions of H_(2) are quantified for the dissociation process.Within a wide range of temperature,the effects of quantum tunneling on the effective barriers of dissociation and the rate constants are observed.The deduced energetic parameters associated with the thermal equilibrium and non-equilibrium(molecular beam)conditions are comparable to experimental data.In the low-temperature region,the crossover from classical to quantum regime is identified.展开更多
Food safety is a major issue to public health and have attracted global attention.Fast,sensitive,and reliable detection methods for food hazardous substances is highly desirable.Aptamers which can bind to the target m...Food safety is a major issue to public health and have attracted global attention.Fast,sensitive,and reliable detection methods for food hazardous substances is highly desirable.Aptamers which can bind to the target molecules with high affinity and specificity represent an attractive tool for the recognition of food hazardous substances,which play an important role in the development and application of new food safety detection technology.But current assays for characterizing small molecule-aptamer binding are limited by either the mass sensitivity or the size differentiation ability.Herein,we proposed a comprehensive method for assessing the dissociation equilibria of small molecule-aptamer,which is immobilized-free under ambient conditions.The design employs the Le Chatelier’s principle and could be used to effectively measure small molecule-aptamer interactions.ATP binding aptamer and anti-aflatoxin B1 aptamer were used as the model system to determine their affinity,in which their dissociation equilibria measurements are in excellent close to their previous work.Due to the simplicity and sensitivity of this new method,we believe that it could be recommended as an effective tool for characterizing small molecule-aptamer interactions and promote the further application of small molecular aptamer in food safety.展开更多
Ammonia (NH<sub>3</sub>) dissociation and oxidation in a cylindrical quartz reactor has been experimentally studied for various inlet NH<sub>3</sub> concentrations (5%, 10%, and 15%) and reacto...Ammonia (NH<sub>3</sub>) dissociation and oxidation in a cylindrical quartz reactor has been experimentally studied for various inlet NH<sub>3</sub> concentrations (5%, 10%, and 15%) and reactor temperatures between 700 K and 1000 K. The thermal effects during both NH<sub>3</sub> dissociation (endothermic) and oxidation (exothermic) were observed using a bundle of thermocouples positioned along the central axis of the quartz reactor, while the corresponding NH<sub>3</sub> conversions and nitrogen oxides emissions were determined by analysing the gas composition of the reactor exit stream. A stronger endothermic effect, as indicated by a greater temperature drop during NH<sub>3</sub> dissociation, was observed as the NH<sub>3</sub> feed concentration and reactor temperature increased. During NH<sub>3</sub> oxidation, a predominantly greater exothermic effect with increasing NH<sub>3</sub> feed concentration and reactor temperature was also evident;however, it was apparent that NH<sub>3</sub> dissociation occurred near the reactor inlet, preceding the downstream NH<sub>3</sub> and H<sub>2</sub> oxidation. For both NH<sub>3</sub> dissociation and oxidation, NH<sub>3</sub> conversion increased with increasing temperature and decreasing initial NH<sub>3</sub> concentration. Significant levels of NO<sub>X</sub> emissions were observed during NH<sub>3</sub> oxidation, which increased with increasing temperature. From the experimental results, it is speculated that the stainless-steel in the thermocouple bundle may have catalysed NH<sub>3</sub> dissociation and thus changed the reaction chemistry during NH<sub>3</sub> oxidation.展开更多
It is well known that methane hydrate has been identified as an alternative resource due to its massive reserves and clean property. However, hydrate dissociation during oil and gas development(OGD) process in deep wa...It is well known that methane hydrate has been identified as an alternative resource due to its massive reserves and clean property. However, hydrate dissociation during oil and gas development(OGD) process in deep water can affect the stability of subsea equipment and formation. Currently, there is a serious lack of studies over quantitative assessment on the effects of hydrate dissociation on wellhead stability. In order to solve this problem, ABAQUS finite element software was used to develop a model and to evaluate the behavior of wellhead caused by hydrate dissociation. The factors that affect the wellhead stability include dissociation range, depth of hydrate formation and mechanical properties of dissociated hydrate region. Based on these, series of simulations were carried out to determine the wellhead displacement. The results revealed that, continuous dissociation of hydrate in homogeneous and isotropic formations can causes the non-linear increment in vertical displacement of wellhead. The displacement of wellhead showed good agreement with the settlement of overlying formations under the same conditions. In addition, the shallower and thicker hydrate formation can aggravate the influence of hydrate dissociation on the wellhead stability. Further, it was observed that with the declining elastic modulus and Poisson's ratio, the wellhead displacement increases. Hence, these findings not only confirm the effect of hydrate dissociation on the wellhead stability, but also lend support to the actions, such as cooling the drilling fluid, which can reduce the hydrate dissociation range and further make deepwater operations safer and more efficient.展开更多
The changes in the mechanical properties of gas hydrate-bearing sediments(GHBS) induced by gas hydrate(GH) dissociation are essential to the evaluation of GH exploration and stratum instabilities. Previous studies pre...The changes in the mechanical properties of gas hydrate-bearing sediments(GHBS) induced by gas hydrate(GH) dissociation are essential to the evaluation of GH exploration and stratum instabilities. Previous studies present substantial mechanical data and constitutive models for GHBS at a given GH saturation under the non-dissociated condition. In this paper, GHBS was formed by the gas saturated method, GH was dissociated by depressurization until the GH saturation reached different dissociation degrees. The stress–strain curves were measured using triaxial tests at a same pore gas pressure and different confining pressures. The results show that the shear strength decreases progressively by 30%–90% of the initial value with GH dissociation, and the modulus decreases by 50% –75%. Simplified relationships for the modulus, cohesion, and internal friction angle with GH dissociated saturation were presented.展开更多
Dislocation structures in polycrystalline Ni 3Al alloy doped with palladium deformed at room temperature have been investigated by transmission electron microscopy. The structure consists mainly of dislocations dissoc...Dislocation structures in polycrystalline Ni 3Al alloy doped with palladium deformed at room temperature have been investigated by transmission electron microscopy. The structure consists mainly of dislocations dissociated into a /2〈011〉 super partials bounding an anti phase boundary (APB). Dislocations dissociated into a /3〈112〉 super Shockley partials bounding a superlattice intrinsic stacking fault (SISF) are also common debris. The majority of the SISFs are truncated loops, i.e. the partials bounding the SISF are of similar Burgers vector. These faulted loops are generated from APB coupled dislocations, according to a mechanism for formation of SISFs proposed by Suzuki et al , and recently modified by Chiba et al . The APB energies for {111} and {010} slip planes are measured to be 144±20 mJ/m 2 and 102±11 mJ/m 2 respectively, and the SISF energy has been estimated to be 12 mJ/m 2 in this alloy. It is concluded that the dislocation structure in Ni 74.5 Pd 2Al 23.5 alloy deformed at room temperature is similar to that in binary Ni 3Al, and the difference in fault energies between these two alloys is small. Thus, it seems unlikely that the enhancement of ductility of Ni 74.5 Pd 2Al 23.5 results from only such a small decrease of the ordering energy of the alloy. SISF bounding dislocations also have no apparent influence on the ductilization of Ni 74.5 Pd 2Al 23.5 alloy.展开更多
Methane hydrate is considered as a potential energy source in the future due to its abundant reserves and high energy density.To investigate the influence of initial hydrate saturation,production pressure,and the temp...Methane hydrate is considered as a potential energy source in the future due to its abundant reserves and high energy density.To investigate the influence of initial hydrate saturation,production pressure,and the temperature of thermal stimulation on gas production rate and cumulative gas production percentage,we conducted the methane hydrate dissociation experiments using depressurization,thermal stimulation and a combination of two methods in this study.It is found that when the gas production pressures are the same,the higher the hydrate initial saturation,the greater change in hydrate reservoir temperature.Therefore,it is easier to appear the phenomenon of icing and hydrate reformation when the hydrate saturation is higher.For example,the reservoir temperature dropped to below zero in depressurization process when the hydrate saturation was about 37%.However,the same phenomenon didn’t appear as the saturation was about 12%.This may be due to more free gas in the reservoir with hydrate saturated of 37%.We also find that the temperature variation of reservoir can be reduced effectively by combination of depressurization and thermal stimulation method.And the average gas production rate is highest with combined method in the experiments.When the pressure of gas production is 2 MPa,compared with depressurization,the average of gas production can increase 54%when the combined method is used.The efficiency of gas production is very low when thermal stimulation was used alone.When the temperature of thermal stimulation is 11℃,the average rate of gas production in the experiment of thermal stimulation is less than 1/3 of that in the experiment of the combined method.展开更多
The methane hydrate formation and the methane hydrate dissociation behaviors in montmorillonite are experimentally studied. Through the analyses of the microstructure characteristic, the study obtains the porous chara...The methane hydrate formation and the methane hydrate dissociation behaviors in montmorillonite are experimentally studied. Through the analyses of the microstructure characteristic, the study obtains the porous characteristic of montmorillonite. It is indicated that methane hydrate in montmorillonite forms the structure I (si) crystal. Meanwhile, molecular dynamics simulation is carried out to study the processes of the methane hydrate formation and the methane hydrate dissociation in montmorillonite. The microstructure and microscopic properties are analyzed. The methane hydrate formation and methane hydrate dissociation mechanisms in the montmorillonite nanopore and on the montmorillonite surface are expounded. Combining the experimental and simulating analyses, the results indicate the methane hydrate formation and methane hydrate dissociation processes have little influence upon the crystal structure of porous media from either micro- or macro-analysis. It is beneficial to the fundamental researches on the exploitation and security control technologies of natural gas hydrate in deep-sea sediments.展开更多
The effects of air dissociation on ?at-plate hypersonic boundary-layer ?ow instability and transition prediction are studied. The air dissociation reactions are assumed to be in the chemical equilibrium. Based on the ...The effects of air dissociation on ?at-plate hypersonic boundary-layer ?ow instability and transition prediction are studied. The air dissociation reactions are assumed to be in the chemical equilibrium. Based on the ?at-plate boundary layer, the ?ow stability is analyzed for the Mach numbers from 8 to 15. The results reveal that the consideration of air dissociation leads to a decrease in the unstable region of the ?rst-mode wave and an increase in the maximum growth rate of the second mode. High frequencies appear earlier in the third mode than in the perfect gas model, and the unstable region moves to a lower frequency region. When the Mach number increases, the second-mode wave dominates the transition process, and the third-mode wave has little effect on the transition. Moreover, when the Mach number increases from 8 to 12, the N-factor envelope becomes higher, and the transition is promoted. However, when the Mach number exceeds 12, the N-factor envelope becomes lower, and the transition is delayed. The N-factor envelope decreases gradually with the increase in the altitude or Mach number.展开更多
Disulfur dichloride is a hazardous substance, which is irritating to the eyes. It is significant to study the physical and dissociation properties under external electric fields. The bond length, energy, dipole moment...Disulfur dichloride is a hazardous substance, which is irritating to the eyes. It is significant to study the physical and dissociation properties under external electric fields. The bond length, energy, dipole moment, orbital energy level distribution, infrared spectra and dissociation properties of disulfur dichloride molecule under different external fields are obtained by using the density functional theory at the B3LYP/6-311++G(d, p) basis set level. In addition, ultraviolet-visible absorption spectra of the molecule in different electric fields are studied with configuration interaction-single excitation(CIS)/6-311++G(d, p) method. According to the results, it has been found that as the electric field exerted along the positive direction of the z-axis increases, the two sulfur-chlorine(S-Cl) bond lengths become longer and tend to break, while the sulfur-sulfur(S-S) bond length becomes shorter and the energy gap decreases. The infrared spectrum and ultraviolet-visible absorption spectra both exhibit red shift under electric field. Moreover, by scanning the potential energy surface of disulfur dichloride about S-Cl bond, the dissociation barrier decreases with the increase of positive electric field. When the external electric field arrives at 0.040 atomic units, the barrier disappears, meaning the dissociation of disulfur dichloride. The present results offer an important reference to further study of disulfur dichloride.展开更多
Density functional theory is used to investigate the adsorption,diffusion,and dissociation of H_(2)O on kaolinite(001)surface.It is found that the preferred adsorption sites on the kaolinite(001)surface for H_(2)O are...Density functional theory is used to investigate the adsorption,diffusion,and dissociation of H_(2)O on kaolinite(001)surface.It is found that the preferred adsorption sites on the kaolinite(001)surface for H_(2)O are the threefold hollow sites with the adsorption energies ranging from 1.06 to 1.15 eV.H_(2)O does not adsorb on the six-fold hollow site of the aluminium(001)face of the third layer of kaolinite,implying that it is difficult for water molecules to penetrate the ideal kaolinite(001)surface.In addition,we calculate the energetic barriers for the diffusion of H_(2)O between the most stable and next most stable adsorption sites,which range from 0.073 to 0.129eV.The results also show that H_(2)O molecules are easy to diffuse on kaolinite(001)surface.Finally,our study indicates that no dissociation state exists for the H_(2)O on kaolinite(001)surface.展开更多
BACKGROUND Most Mahaim fibers are right free-wall atriofascicular accessory pathways with only antegrade conduction.Concealed Mahaim fiber is not very rare;however,concealed nodoventricular fiber is a very rare kind o...BACKGROUND Most Mahaim fibers are right free-wall atriofascicular accessory pathways with only antegrade conduction.Concealed Mahaim fiber is not very rare;however,concealed nodoventricular fiber is a very rare kind of retrograde accessory pathway in supraventricular tachycardia with atrioventricular(AV)dissociation.Only a few cases about successful ablation of the nodoventricular accessory pathway have been reported.We describe the case of a 32-year-old woman who underwent an electrophysiology study and radiofrequency(RF)ablation of a rare narrow QRS tachycardia with AV dissociation.CASE SUMMARY A 32-year-old woman with a history of paroxysmal palpitation was admitted to our hospital for RF ablation.Electrocardiography revealed a narrow QRS complex tachycardia with the same morphology in sinus rhythm.Echocardiography showed no structural heart disease.A right-sided concealed AV accessory pathway and a right-sided concealed nodoventricular accessory pathway were involved in the orthodromic atrioventricular reciprocating tachycardia.His bundle-ventricular interval during tachycardia was the same as that in sinus rhythm.The tachycardia could be initiated and entrained by ventricular pacing.Premature right ventricular stimulus introduced during the His-bundle refractory period when tachycardia occurred was able to advance the next atrial potential.The earliest atrial activation was mapped near the proximal slow AV nodal pathway.RF ablation of both accessary pathways was successfully performed under the guidance of a three-dimensional mapping system by recording the earliest retrograde atrial potential,and tachycardia could no longer be induced.CONCLUSION Narrow QRS tachycardia with AV dissociation is inducible by concealed nodoventricular fiber and ablated by recording the earliest retrograde atrial potential.展开更多
The water dissociation mechanism on a bipolar membrane under the electrical field was investigated and characterized in terms of ionic transport and limiting current density. It is considered that the depletion layer ...The water dissociation mechanism on a bipolar membrane under the electrical field was investigated and characterized in terms of ionic transport and limiting current density. It is considered that the depletion layer exists at the junction of a bipolar membrane, which is coincided with the viewpoint of the most literatures, but we also consider that the thickness and conductivity of this layer is not only related with the increase of the applied voltage but also with the limiting current density. Below the limiting current density, the thickness of the depletion layer keeps a constant and the conductivity decreases with the increase of the applied voltage; while above the limiting current density, the depletion thickness will increase with the increase of the applied voltage and the conductivity keeps a very low constant. Based on the data reported in the literatures and independent determinations, the limiting current density was calculated and the experimental curves Ⅰ-Ⅴ in the two directions were展开更多
In this work,several experiments were conducted at isobaric and isothermal condition in a CSTR reactor to study the kinetics of methane hydrate formation and dissociation.Experiments were performed at five temperature...In this work,several experiments were conducted at isobaric and isothermal condition in a CSTR reactor to study the kinetics of methane hydrate formation and dissociation.Experiments were performed at five temperatures and three pressure levels(corresponding to equilibrium pressure).Methane hydrate formation and dissociation rates were modeled using mass transfer limited kinetic models and mass transfer coefficients for both formation and dissociation were calculated.Comparison of results,shows that mass transfer coefficients for methane hydrate dissociation are one order greater than formation conditions.Mass transfer coefficients were correlated by polynomials as relations of pressure and temperature.The results and the method can be applied for prediction of methane production from naturally occurring methane hydrate deposits.展开更多
Understanding the kinetics and viscosity of hydrate slurry in gas-water-sand system is of great significance for the high-efficiency and high-safety development of natural gas hydrates.The effect of micronsized sands ...Understanding the kinetics and viscosity of hydrate slurry in gas-water-sand system is of great significance for the high-efficiency and high-safety development of natural gas hydrates.The effect of micronsized sands with various concentrations and particle sizes on the hydrate formation,dissociation,and viscosity in gas-water-sand system are investigated in this work.The experimental results show that the hydrate induction time in the sandy system is slightly prolonged compared to the pure gas-water system,and the inhibition effect first strengthens and then weakens as the sand concentration increases from0 wt%to 5 wt%.Besides,the difference of hydrate formation amount in various cases is not obvious.The concentration and particle size of sand have little effect on the kinetics of hydrate formation.Both promoting and inhibiting effects on hydrate formation have been found in the sandy multiphase fluid.For the viscosity characteristics,there are three variations of hydrate slurry viscosity during the formation process:Steep drop type,S-type and Fluctuation type.Moreover,appropriate sand size is helpful to reduce the randomness of slurry viscosity change.Meanwhile,even at the same hydrate volume fraction,the slurry viscosity in the formation process is significantly higher than that in dissociation process,which needs further research.This work provides further insights of hydrate formation,dissociation,and viscosity in gas-water-sand system,which is of great significance for safe and economic development of natural gas hydrates.展开更多
Density functional theory(DFT)calculations have been performed to investigate the hydrogen dissociation and diffusion on Mg(0001)surface with Ni incorporating at various locations.The results show that Ni atom is pref...Density functional theory(DFT)calculations have been performed to investigate the hydrogen dissociation and diffusion on Mg(0001)surface with Ni incorporating at various locations.The results show that Ni atom is preferentially located inside Mg matrix rather than in/over the topmost surface.Further calculations reveal that Ni atom locating in/over the topmost Mg(0001)surface exhibits excellent catalytic effect on hydrogen dissociation with an energy barrier of less than 0.05 eV.In these cases,the rate-limiting step has been converted from hydrogen dissociation to surface diffusion.In contrast,Ni doping inside Mg bulk not only does little help to hydrogen dissociation but also exhibits detrimental effect on hydrogen diffusion.Therefore,it is crucial to stabilize the Ni atom on the surface or in the topmost layer of Mg(0001)surface to maintain its catalytic effect.For all the case of Ni-incorporated Mg(0001)surfaces,the hydrogen atom prefers firstly immigrate along the surface and then penetrate into the bulk.It is expected that the theoretical findings in the present study could offer fundamental guidance to future designing on efficient Mg-based hydrogen storage materials.展开更多
The dissociation of a [1-01] superdislocation in Ni 3Al was studied by computer simulation techniques using the embedded atom method (EAM). Three types of dissociation were obtained, depending on the initial position ...The dissociation of a [1-01] superdislocation in Ni 3Al was studied by computer simulation techniques using the embedded atom method (EAM). Three types of dissociation were obtained, depending on the initial position of elastic centers of the superdislocation. One is the stable planar dissociation that the superdislocation dissociates on only one {111} plane into a pair of 1/2[1-01] superpartials separated by antiphase boundary (APB). Another stable dissociation is that it occurs on two adjacent {111} planes joined by an intersecting {111} or (010) plane. The metastable one is that the dissociation occurs in T shape: the superdislocation dissociates on two intersecting {111} planes into three partials: one 1/2[1-01] partial and two widely separated 1/6〈112〉 Shockley partials with a complex stacking fault (CSF) in between.展开更多
A DFT study of H2 dissociation on a series of Mo x S y clusters was performed, including homolytic and heterolytic dissociation. The preference for the two pathways on these models show much difference, as the Mo coor...A DFT study of H2 dissociation on a series of Mo x S y clusters was performed, including homolytic and heterolytic dissociation. The preference for the two pathways on these models show much difference, as the Mo coordination number increases, the homolytic dissociation becomes easier, whereas the heterolytic dissociation becomes more difficult. Furthermore, frontier orbital theory was used to analyze the dissociation mechanisms of these two pathways. It was found that the symmetry and energy gap of Mo x S y's HOMO and H2's LUMO are the decisive factors in H2 activation.展开更多
Nickel molybdate(NiMoO_(4))attracts superior hydrogen desorption behavior but noticeably poor for efficiently driving the hydrogen evolution reaction(HER)in alkaline media due to the sluggish water dissociation step.H...Nickel molybdate(NiMoO_(4))attracts superior hydrogen desorption behavior but noticeably poor for efficiently driving the hydrogen evolution reaction(HER)in alkaline media due to the sluggish water dissociation step.Herein,we successfully accelerate the water dissociation kinetics of NiMoO_(4)for prominent HER catalytic properties via simultaneous in situ interfacial engineering with molybdenum dioxide(MoO_(2))and doping with phosphorus(P).The as-synthesized P-doped NiMoO_(4)/MoO_(2)heterostructure nanorods exhibit outstanding HER performance with an extraordinary low overpotential of-23 m V at a current density of 10 m A cm^(-2),which is highly comparable to the performance of the state-of-art Pt/C coated on nickel foam(NF)catalyst.The density functional theory(DFT)analysis reveals the enhanced performance is attributed to the formation of MoO_(2)during the in situ epitaxial growth that substantially reduces the energy barrier of the Volmer pathway,and the introduction of P that provides efficient hydrogen desorption of Ni MoO_(2).This present work creates valuable insight into the utilization of interfacial and doping systems for hydrogen evolution catalysis and beyond.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.U1802253 and 52034002)the Fundamental Research Funds for the Central Universities,China(No.FRF-TT-19-001)。
文摘Currently,the process of extracting rubidium from ores has attracted a great deal of attention due to the increasing application of rubidium in high-technology field.A novel process for the comprehensive utilization of rubidium ore resources is proposed in this paper.The process consists mainly of mineral dissociation,selective leaching,and desilication.The results showed that the stable silicon–oxygen tetrahedral structure of the rubidium ore was completely disrupted by thermal activation and the mineral was completely dissociated,which was conducive to subsequent selective leaching.Under the optimal conditions,extractions of 98.67% Rb and 96.23%K were obtained by leaching the rubidium ore.Moreover,the addition of a certain amount of activated Al(OH)_(3) during leaching can effectively inhibit the leaching of silicon.In the meantime,the leach residue was sodalite,which was successfully synthesized to zeolite A by hydrothermal conversion.The proposed process provided a feasible strategy for the green extraction of rubidium and the sustainable utilization of various resources.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11474285 and 12074382)。
文摘The activation and dissociation of hydrogen molecules(H_(2))on the Cu(001)surface are studied theoretically.Using first-principles calculations,the activation barrier for the dissociation of H_(2) on Cu(001)is determined to be~0.59 eV in height.It is found that the electron transfer from the copper substrate to H_(2) plays a key role in the activation and breaking of the H–H bond,and the formation of the Cu–H bonds.Two stationary states are identified at around the critical height of bond breaking,corresponding to the molecular and the dissociative states,respectively.Using the transfer matrix method,we also investigate the role of quantum tunneling in the dissociation process along the minimum energy pathway(MEP),which is found to be significant at or below room temperature.At a given temperature,the tunneling contributions due to the translational and the vibrational motions of H_(2) are quantified for the dissociation process.Within a wide range of temperature,the effects of quantum tunneling on the effective barriers of dissociation and the rate constants are observed.The deduced energetic parameters associated with the thermal equilibrium and non-equilibrium(molecular beam)conditions are comparable to experimental data.In the low-temperature region,the crossover from classical to quantum regime is identified.
基金supported by the National Key R&D Program of China(2017YFC1600603)the Funds for Huangshan Professorship of Hefei University of Technology(407-037019).
文摘Food safety is a major issue to public health and have attracted global attention.Fast,sensitive,and reliable detection methods for food hazardous substances is highly desirable.Aptamers which can bind to the target molecules with high affinity and specificity represent an attractive tool for the recognition of food hazardous substances,which play an important role in the development and application of new food safety detection technology.But current assays for characterizing small molecule-aptamer binding are limited by either the mass sensitivity or the size differentiation ability.Herein,we proposed a comprehensive method for assessing the dissociation equilibria of small molecule-aptamer,which is immobilized-free under ambient conditions.The design employs the Le Chatelier’s principle and could be used to effectively measure small molecule-aptamer interactions.ATP binding aptamer and anti-aflatoxin B1 aptamer were used as the model system to determine their affinity,in which their dissociation equilibria measurements are in excellent close to their previous work.Due to the simplicity and sensitivity of this new method,we believe that it could be recommended as an effective tool for characterizing small molecule-aptamer interactions and promote the further application of small molecular aptamer in food safety.
文摘Ammonia (NH<sub>3</sub>) dissociation and oxidation in a cylindrical quartz reactor has been experimentally studied for various inlet NH<sub>3</sub> concentrations (5%, 10%, and 15%) and reactor temperatures between 700 K and 1000 K. The thermal effects during both NH<sub>3</sub> dissociation (endothermic) and oxidation (exothermic) were observed using a bundle of thermocouples positioned along the central axis of the quartz reactor, while the corresponding NH<sub>3</sub> conversions and nitrogen oxides emissions were determined by analysing the gas composition of the reactor exit stream. A stronger endothermic effect, as indicated by a greater temperature drop during NH<sub>3</sub> dissociation, was observed as the NH<sub>3</sub> feed concentration and reactor temperature increased. During NH<sub>3</sub> oxidation, a predominantly greater exothermic effect with increasing NH<sub>3</sub> feed concentration and reactor temperature was also evident;however, it was apparent that NH<sub>3</sub> dissociation occurred near the reactor inlet, preceding the downstream NH<sub>3</sub> and H<sub>2</sub> oxidation. For both NH<sub>3</sub> dissociation and oxidation, NH<sub>3</sub> conversion increased with increasing temperature and decreasing initial NH<sub>3</sub> concentration. Significant levels of NO<sub>X</sub> emissions were observed during NH<sub>3</sub> oxidation, which increased with increasing temperature. From the experimental results, it is speculated that the stainless-steel in the thermocouple bundle may have catalysed NH<sub>3</sub> dissociation and thus changed the reaction chemistry during NH<sub>3</sub> oxidation.
基金supported by the Program for the Changjiang Scholars and Innovative Research Team in University (No. IRT_14R58)the National Natural Science Foundation of China (No. 51704311)+3 种基金the Fundamental Research Funds for the Central Universities (No. 16CX06 033A)the National Key Research and Development Program (No. 2016YFC0304005)the National Basic Research Program of China (973 Program) (No. 2015CB251 201)the Qingdao Science and Technology Project (No. 15-9-1-55-jch)
文摘It is well known that methane hydrate has been identified as an alternative resource due to its massive reserves and clean property. However, hydrate dissociation during oil and gas development(OGD) process in deep water can affect the stability of subsea equipment and formation. Currently, there is a serious lack of studies over quantitative assessment on the effects of hydrate dissociation on wellhead stability. In order to solve this problem, ABAQUS finite element software was used to develop a model and to evaluate the behavior of wellhead caused by hydrate dissociation. The factors that affect the wellhead stability include dissociation range, depth of hydrate formation and mechanical properties of dissociated hydrate region. Based on these, series of simulations were carried out to determine the wellhead displacement. The results revealed that, continuous dissociation of hydrate in homogeneous and isotropic formations can causes the non-linear increment in vertical displacement of wellhead. The displacement of wellhead showed good agreement with the settlement of overlying formations under the same conditions. In addition, the shallower and thicker hydrate formation can aggravate the influence of hydrate dissociation on the wellhead stability. Further, it was observed that with the declining elastic modulus and Poisson's ratio, the wellhead displacement increases. Hence, these findings not only confirm the effect of hydrate dissociation on the wellhead stability, but also lend support to the actions, such as cooling the drilling fluid, which can reduce the hydrate dissociation range and further make deepwater operations safer and more efficient.
基金supported by the National Natural Science Foundation of China(Grants 41376078,51639008,and 51239010)the China Geological Survey(Grant DD20160216)the Youth Innovation Promotion Association of Chinese Academy of Sciences(Grant 2017027)
文摘The changes in the mechanical properties of gas hydrate-bearing sediments(GHBS) induced by gas hydrate(GH) dissociation are essential to the evaluation of GH exploration and stratum instabilities. Previous studies present substantial mechanical data and constitutive models for GHBS at a given GH saturation under the non-dissociated condition. In this paper, GHBS was formed by the gas saturated method, GH was dissociated by depressurization until the GH saturation reached different dissociation degrees. The stress–strain curves were measured using triaxial tests at a same pore gas pressure and different confining pressures. The results show that the shear strength decreases progressively by 30%–90% of the initial value with GH dissociation, and the modulus decreases by 50% –75%. Simplified relationships for the modulus, cohesion, and internal friction angle with GH dissociated saturation were presented.
文摘Dislocation structures in polycrystalline Ni 3Al alloy doped with palladium deformed at room temperature have been investigated by transmission electron microscopy. The structure consists mainly of dislocations dissociated into a /2〈011〉 super partials bounding an anti phase boundary (APB). Dislocations dissociated into a /3〈112〉 super Shockley partials bounding a superlattice intrinsic stacking fault (SISF) are also common debris. The majority of the SISFs are truncated loops, i.e. the partials bounding the SISF are of similar Burgers vector. These faulted loops are generated from APB coupled dislocations, according to a mechanism for formation of SISFs proposed by Suzuki et al , and recently modified by Chiba et al . The APB energies for {111} and {010} slip planes are measured to be 144±20 mJ/m 2 and 102±11 mJ/m 2 respectively, and the SISF energy has been estimated to be 12 mJ/m 2 in this alloy. It is concluded that the dislocation structure in Ni 74.5 Pd 2Al 23.5 alloy deformed at room temperature is similar to that in binary Ni 3Al, and the difference in fault energies between these two alloys is small. Thus, it seems unlikely that the enhancement of ductility of Ni 74.5 Pd 2Al 23.5 results from only such a small decrease of the ordering energy of the alloy. SISF bounding dislocations also have no apparent influence on the ductilization of Ni 74.5 Pd 2Al 23.5 alloy.
基金Supported by the National Natural Science Foundation of China(51436003,51822603,51576025)the National Key Research and Development Program of China(2017YFC0307303,2016YFC0304001)+1 种基金the Fok Ying Tong Education Foundation for Young Teachers in the Higher Education Institutions of China(161050)the Fundamental Research Funds for the Central Universities of China(DUT18ZD403)
文摘Methane hydrate is considered as a potential energy source in the future due to its abundant reserves and high energy density.To investigate the influence of initial hydrate saturation,production pressure,and the temperature of thermal stimulation on gas production rate and cumulative gas production percentage,we conducted the methane hydrate dissociation experiments using depressurization,thermal stimulation and a combination of two methods in this study.It is found that when the gas production pressures are the same,the higher the hydrate initial saturation,the greater change in hydrate reservoir temperature.Therefore,it is easier to appear the phenomenon of icing and hydrate reformation when the hydrate saturation is higher.For example,the reservoir temperature dropped to below zero in depressurization process when the hydrate saturation was about 37%.However,the same phenomenon didn’t appear as the saturation was about 12%.This may be due to more free gas in the reservoir with hydrate saturated of 37%.We also find that the temperature variation of reservoir can be reduced effectively by combination of depressurization and thermal stimulation method.And the average gas production rate is highest with combined method in the experiments.When the pressure of gas production is 2 MPa,compared with depressurization,the average of gas production can increase 54%when the combined method is used.The efficiency of gas production is very low when thermal stimulation was used alone.When the temperature of thermal stimulation is 11℃,the average rate of gas production in the experiment of thermal stimulation is less than 1/3 of that in the experiment of the combined method.
基金Supported by the Key Program of National Natural Science Foundation of China(51736009)the Natural Science Foundation of Guangdong Province of China(2017A030313301)+4 种基金the Special project for marine economy development of Guangdong Province(GDME-2018D002)the National Key R&D Program of China(2016YFC0304002,2017YFC0307306)the Science and Technology Apparatus Development Program of the Chinese Academy of Sciences(YZ201619)the National Natural Science Foundation of China(51476147,51879254)the Frontier Sciences Key Research Program of the Chinese Academy of Sciences(QYZDJ-SSW-JSC033)
文摘The methane hydrate formation and the methane hydrate dissociation behaviors in montmorillonite are experimentally studied. Through the analyses of the microstructure characteristic, the study obtains the porous characteristic of montmorillonite. It is indicated that methane hydrate in montmorillonite forms the structure I (si) crystal. Meanwhile, molecular dynamics simulation is carried out to study the processes of the methane hydrate formation and the methane hydrate dissociation in montmorillonite. The microstructure and microscopic properties are analyzed. The methane hydrate formation and methane hydrate dissociation mechanisms in the montmorillonite nanopore and on the montmorillonite surface are expounded. Combining the experimental and simulating analyses, the results indicate the methane hydrate formation and methane hydrate dissociation processes have little influence upon the crystal structure of porous media from either micro- or macro-analysis. It is beneficial to the fundamental researches on the exploitation and security control technologies of natural gas hydrate in deep-sea sediments.
基金Project supported by the National Natural Science Foundation of China(Nos.11732011,11672205,and 11332007)the National Key Research and Development Program of China(No.2016YFA0401200)
文摘The effects of air dissociation on ?at-plate hypersonic boundary-layer ?ow instability and transition prediction are studied. The air dissociation reactions are assumed to be in the chemical equilibrium. Based on the ?at-plate boundary layer, the ?ow stability is analyzed for the Mach numbers from 8 to 15. The results reveal that the consideration of air dissociation leads to a decrease in the unstable region of the ?rst-mode wave and an increase in the maximum growth rate of the second mode. High frequencies appear earlier in the third mode than in the perfect gas model, and the unstable region moves to a lower frequency region. When the Mach number increases, the second-mode wave dominates the transition process, and the third-mode wave has little effect on the transition. Moreover, when the Mach number increases from 8 to 12, the N-factor envelope becomes higher, and the transition is promoted. However, when the Mach number exceeds 12, the N-factor envelope becomes lower, and the transition is delayed. The N-factor envelope decreases gradually with the increase in the altitude or Mach number.
基金supported by the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.18KJA140002)National Natural Science Foundation of China(Nos.11564040,21763027)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX18_1015)College Students’ Practice Innovation Training Program of Nuist(No.201810300033Z)
文摘Disulfur dichloride is a hazardous substance, which is irritating to the eyes. It is significant to study the physical and dissociation properties under external electric fields. The bond length, energy, dipole moment, orbital energy level distribution, infrared spectra and dissociation properties of disulfur dichloride molecule under different external fields are obtained by using the density functional theory at the B3LYP/6-311++G(d, p) basis set level. In addition, ultraviolet-visible absorption spectra of the molecule in different electric fields are studied with configuration interaction-single excitation(CIS)/6-311++G(d, p) method. According to the results, it has been found that as the electric field exerted along the positive direction of the z-axis increases, the two sulfur-chlorine(S-Cl) bond lengths become longer and tend to break, while the sulfur-sulfur(S-S) bond length becomes shorter and the energy gap decreases. The infrared spectrum and ultraviolet-visible absorption spectra both exhibit red shift under electric field. Moreover, by scanning the potential energy surface of disulfur dichloride about S-Cl bond, the dissociation barrier decreases with the increase of positive electric field. When the external electric field arrives at 0.040 atomic units, the barrier disappears, meaning the dissociation of disulfur dichloride. The present results offer an important reference to further study of disulfur dichloride.
基金Supported by the Program for Changjiang Scholars,and the National Natural Science Foundation of China under Grant Nos 40972196 and 41172263.
文摘Density functional theory is used to investigate the adsorption,diffusion,and dissociation of H_(2)O on kaolinite(001)surface.It is found that the preferred adsorption sites on the kaolinite(001)surface for H_(2)O are the threefold hollow sites with the adsorption energies ranging from 1.06 to 1.15 eV.H_(2)O does not adsorb on the six-fold hollow site of the aluminium(001)face of the third layer of kaolinite,implying that it is difficult for water molecules to penetrate the ideal kaolinite(001)surface.In addition,we calculate the energetic barriers for the diffusion of H_(2)O between the most stable and next most stable adsorption sites,which range from 0.073 to 0.129eV.The results also show that H_(2)O molecules are easy to diffuse on kaolinite(001)surface.Finally,our study indicates that no dissociation state exists for the H_(2)O on kaolinite(001)surface.
文摘BACKGROUND Most Mahaim fibers are right free-wall atriofascicular accessory pathways with only antegrade conduction.Concealed Mahaim fiber is not very rare;however,concealed nodoventricular fiber is a very rare kind of retrograde accessory pathway in supraventricular tachycardia with atrioventricular(AV)dissociation.Only a few cases about successful ablation of the nodoventricular accessory pathway have been reported.We describe the case of a 32-year-old woman who underwent an electrophysiology study and radiofrequency(RF)ablation of a rare narrow QRS tachycardia with AV dissociation.CASE SUMMARY A 32-year-old woman with a history of paroxysmal palpitation was admitted to our hospital for RF ablation.Electrocardiography revealed a narrow QRS complex tachycardia with the same morphology in sinus rhythm.Echocardiography showed no structural heart disease.A right-sided concealed AV accessory pathway and a right-sided concealed nodoventricular accessory pathway were involved in the orthodromic atrioventricular reciprocating tachycardia.His bundle-ventricular interval during tachycardia was the same as that in sinus rhythm.The tachycardia could be initiated and entrained by ventricular pacing.Premature right ventricular stimulus introduced during the His-bundle refractory period when tachycardia occurred was able to advance the next atrial potential.The earliest atrial activation was mapped near the proximal slow AV nodal pathway.RF ablation of both accessary pathways was successfully performed under the guidance of a three-dimensional mapping system by recording the earliest retrograde atrial potential,and tachycardia could no longer be induced.CONCLUSION Narrow QRS tachycardia with AV dissociation is inducible by concealed nodoventricular fiber and ablated by recording the earliest retrograde atrial potential.
基金National Natural Science Foundation of China(29976040),Natural Science Foundation of AnhuiProvince(99045431),Foundation of Environments and Resources of USTC and Youth Foundation of USTC.
文摘The water dissociation mechanism on a bipolar membrane under the electrical field was investigated and characterized in terms of ionic transport and limiting current density. It is considered that the depletion layer exists at the junction of a bipolar membrane, which is coincided with the viewpoint of the most literatures, but we also consider that the thickness and conductivity of this layer is not only related with the increase of the applied voltage but also with the limiting current density. Below the limiting current density, the thickness of the depletion layer keeps a constant and the conductivity decreases with the increase of the applied voltage; while above the limiting current density, the depletion thickness will increase with the increase of the applied voltage and the conductivity keeps a very low constant. Based on the data reported in the literatures and independent determinations, the limiting current density was calculated and the experimental curves Ⅰ-Ⅴ in the two directions were
文摘In this work,several experiments were conducted at isobaric and isothermal condition in a CSTR reactor to study the kinetics of methane hydrate formation and dissociation.Experiments were performed at five temperatures and three pressure levels(corresponding to equilibrium pressure).Methane hydrate formation and dissociation rates were modeled using mass transfer limited kinetic models and mass transfer coefficients for both formation and dissociation were calculated.Comparison of results,shows that mass transfer coefficients for methane hydrate dissociation are one order greater than formation conditions.Mass transfer coefficients were correlated by polynomials as relations of pressure and temperature.The results and the method can be applied for prediction of methane production from naturally occurring methane hydrate deposits.
基金supported by the National Natural Science Foundation of China[Grand numbers:52104069,51874323,U20B6005]China Postdoctoral Science Foundation[Grand number:2022M713460]Science Foundation of China University of Petroleum,Beijing[Grand number:2462020YXZZ045]。
文摘Understanding the kinetics and viscosity of hydrate slurry in gas-water-sand system is of great significance for the high-efficiency and high-safety development of natural gas hydrates.The effect of micronsized sands with various concentrations and particle sizes on the hydrate formation,dissociation,and viscosity in gas-water-sand system are investigated in this work.The experimental results show that the hydrate induction time in the sandy system is slightly prolonged compared to the pure gas-water system,and the inhibition effect first strengthens and then weakens as the sand concentration increases from0 wt%to 5 wt%.Besides,the difference of hydrate formation amount in various cases is not obvious.The concentration and particle size of sand have little effect on the kinetics of hydrate formation.Both promoting and inhibiting effects on hydrate formation have been found in the sandy multiphase fluid.For the viscosity characteristics,there are three variations of hydrate slurry viscosity during the formation process:Steep drop type,S-type and Fluctuation type.Moreover,appropriate sand size is helpful to reduce the randomness of slurry viscosity change.Meanwhile,even at the same hydrate volume fraction,the slurry viscosity in the formation process is significantly higher than that in dissociation process,which needs further research.This work provides further insights of hydrate formation,dissociation,and viscosity in gas-water-sand system,which is of great significance for safe and economic development of natural gas hydrates.
基金the financial support from the National Natural Science Foundation of China(Grant Nos.U1610103,21805169 and 21978156)Shandong Provincial Natural Science Foundation,China(Grant No.ZR2018BB069)Project of Shandong Province Higher Educational Young Innovative Talent Introduction and Cultivation Team(Hydrogen energy chemistry innovation team)。
文摘Density functional theory(DFT)calculations have been performed to investigate the hydrogen dissociation and diffusion on Mg(0001)surface with Ni incorporating at various locations.The results show that Ni atom is preferentially located inside Mg matrix rather than in/over the topmost surface.Further calculations reveal that Ni atom locating in/over the topmost Mg(0001)surface exhibits excellent catalytic effect on hydrogen dissociation with an energy barrier of less than 0.05 eV.In these cases,the rate-limiting step has been converted from hydrogen dissociation to surface diffusion.In contrast,Ni doping inside Mg bulk not only does little help to hydrogen dissociation but also exhibits detrimental effect on hydrogen diffusion.Therefore,it is crucial to stabilize the Ni atom on the surface or in the topmost layer of Mg(0001)surface to maintain its catalytic effect.For all the case of Ni-incorporated Mg(0001)surfaces,the hydrogen atom prefers firstly immigrate along the surface and then penetrate into the bulk.It is expected that the theoretical findings in the present study could offer fundamental guidance to future designing on efficient Mg-based hydrogen storage materials.
文摘The dissociation of a [1-01] superdislocation in Ni 3Al was studied by computer simulation techniques using the embedded atom method (EAM). Three types of dissociation were obtained, depending on the initial position of elastic centers of the superdislocation. One is the stable planar dissociation that the superdislocation dissociates on only one {111} plane into a pair of 1/2[1-01] superpartials separated by antiphase boundary (APB). Another stable dissociation is that it occurs on two adjacent {111} planes joined by an intersecting {111} or (010) plane. The metastable one is that the dissociation occurs in T shape: the superdislocation dissociates on two intersecting {111} planes into three partials: one 1/2[1-01] partial and two widely separated 1/6〈112〉 Shockley partials with a complex stacking fault (CSF) in between.
基金the funding by the State Key Project (Grant Nos. 2012CB224802 and 2012BAE05B03)by the Technology Development Project of SINOPEC (S112101)
文摘A DFT study of H2 dissociation on a series of Mo x S y clusters was performed, including homolytic and heterolytic dissociation. The preference for the two pathways on these models show much difference, as the Mo coordination number increases, the homolytic dissociation becomes easier, whereas the heterolytic dissociation becomes more difficult. Furthermore, frontier orbital theory was used to analyze the dissociation mechanisms of these two pathways. It was found that the symmetry and energy gap of Mo x S y's HOMO and H2's LUMO are the decisive factors in H2 activation.
基金supported by the National Natural Science Foundation of China(21875292 and 51902103)Hunan Provincial Natural Science Foundation(2019JJ50037 and 2021JJ30087)+1 种基金Natural Science Foundation of Guangdong Province(2020A1515010798)the Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy(2020CB1007)。
文摘Nickel molybdate(NiMoO_(4))attracts superior hydrogen desorption behavior but noticeably poor for efficiently driving the hydrogen evolution reaction(HER)in alkaline media due to the sluggish water dissociation step.Herein,we successfully accelerate the water dissociation kinetics of NiMoO_(4)for prominent HER catalytic properties via simultaneous in situ interfacial engineering with molybdenum dioxide(MoO_(2))and doping with phosphorus(P).The as-synthesized P-doped NiMoO_(4)/MoO_(2)heterostructure nanorods exhibit outstanding HER performance with an extraordinary low overpotential of-23 m V at a current density of 10 m A cm^(-2),which is highly comparable to the performance of the state-of-art Pt/C coated on nickel foam(NF)catalyst.The density functional theory(DFT)analysis reveals the enhanced performance is attributed to the formation of MoO_(2)during the in situ epitaxial growth that substantially reduces the energy barrier of the Volmer pathway,and the introduction of P that provides efficient hydrogen desorption of Ni MoO_(2).This present work creates valuable insight into the utilization of interfacial and doping systems for hydrogen evolution catalysis and beyond.
