等浓度的氯化铵和硫酸铵溶液哪个pH高

有中学化学参考资料题:0.10 mol/L的NH4Cl和(NH4)2SO4溶液哪个pH值高?这似乎是个中学生可做的简单题目,仔细考虑不是如此.如果简单地认为盐酸和硫酸都是强酸,而硫酸是二元酸,硫酸铵溶液中铵盐浓度为0.20 mol/L,那么NH4Cl溶液pH高,那是不妥的.硫酸是二元酸,第一个氢离子能完全电离,第二个氢离子部分电离,如此考虑情况怎么样呢?是不是答案发生变化?这要通过计算来说明.     

Enhanced efficiency and stability in Sn-based perovskite solar cells with secondary crystallization growth

The conversion efficiencies reported for Tin(Sn)halide-based perovskite solar cells(PSCs)fall a large gap behind those of lead halide-based PSCs,mainly because of poor film quality of the former.Here we report an efficient strategy based on a simple secondary crystallization growth(SCG)technique to improve film quality for tin halide-based PSCs by applying a series of functional amine chlorides on the perovskite surface.They were discovered to enhance the film crystallinity and suppress the oxidation of Sn²⁺remarkably,hence reduce trap state density and non-irradiative recombination in the absorber films.Furthermore,the SCG film holds the band levels matching better with carrier transport layers and herein favoring charge extraction at the device interfaces.Consequently,a champion device efficiency of 8.07% was achieved alo ng with significant enhancements in VOC and JSC,in contrast to 5.35% of the control device value.Moreover,the SCG film-based devices also exhibit superior stability comparing with the control one.This work explicitly paves a novel and general strategy for developing high performance lead-free PSCs.     

Energy level engineering of charge selective contact and halide perovskite by modulating band offset:Mechanistic insights

Mixed cation and anion based perovskites solar cells exhibited enhanced stability under outdoor conditions,however,it yielded limited power conversion efficiency when TiO₂ and Spiro-OMeTAD were employed as electron and hole transport layer(ETL/HTL)respectively.The inevitable interfacial recombination of charge carriers at ETL/perovskite and perovskite/HTL interface diminished the efficiency in planar(n-i-p)perovskite solar cells.By employing computational approach for uni-dimensional device simulator,the effect of band offset on charge recombination at both interfaces was investigated.We noted that it acquired cliff structure when the conduction band minimum of the ETL was lower than that of the perovskite,and thus maximized interfacial recombination.However,if the conduction band minimum of ETL is higher than perovskite,a spike structure is formed,which improve the performance of solar cell.An optimum value of conduction band offset allows to reach performance of 25.21%,with an open circuit voltage(VOC)of 1231 mV,a current density JSC of 24.57 mA/cm² and a fill factor of 83.28%.Additionally,we found that beyond the optimum offset value,large spike structure could decrease the performance.With an optimized energy level of Spiro-OMeTAD and the thickness of mixed-perovskite layer performance of 26.56% can be attained.Our results demonstrate a detailed understanding about the energy level tuning between the charge selective layers and perovskite and how the improvement in PV performance can be achieved by adjusting the energy level offset.     

A new strategy to access Co/N co-doped carbon nanotubes as oxygen reduction reaction catalysts

Carbon nanotubes(CNTs),as one-dimensional nanomaterials,show great potential in energy conversion and storage due to their efficient electrical conductivity and mass transfer.However,the security risks,time-consuming and high cost of the preparation process hinder its further application.Here,we develop that a negative pressure rather than a following gas environment can promote the generation of cobalt and nitrogen co-doped CNTs(Co/N-CNTs) by using cobalt zeolitic imidazolate framework(ZIF-67) as a precursor,in which the negative pressure plays a key role in adjusting the size of cobalt nanoparticles and stimulating the rearragement of carbon atoms for forming CNTs.Importantly,the obtained Co/N-CNTs,with high content of pyridinic nitrogen and abundant graphitized structure,exhibit superior catalytic activity for oxygen reduction reaction(ORR) with half-wave potential(E_1/2) of 0.85 V and durability in terms of the minimum current loss(2%) after the 30,000 s test.Our development provides a new pathway for large-scale and cost-effective preparation of metal-doped CNTs for various applications.     

Recent Advances of Pure Organic Room Temperature Phosphorescence Materials for Bioimaging Applications

Bioimaging,as a powerful and helpful tool,which allows people to investigate deeply within living organisms,has contributed a lot for both clinical theranostics and scientific research.Pure organic room temperature phosphorescence(RTP)materials with the unique features of ultralong luminescence lifetime and large Stokes shift,can efficiently avoid biological autofluorescence and scattered light through a time-resolved imaging modality,and thus are attracting increasing attention.This review classifies pure organic RTP materials into three categories,including small molecule RTP materials,polymer RTP materials and supramolecular RTP materials,and summarizes the recent advances of pure organic RTP materials for bioimaging applications.     

Stabilizing High-voltage Cathode Materials for Next-generation Li-ion Batteries

The pressing demand for high-energy/power lithium-ion batteries requires the deployment of cathode materials with higher capacity and output voltage.Despite more than ten years of research,high-voltage cathode mate-rials,such as high-voltage layered oxides,spinel LiNi0.5Mn1.5O4,and high-voltage polyanionic compounds still cannot be commercially viable due to the instabilities of standard electrolytes,cathode materials,and cathode electrolyte interphases under high-voltage operation.This paper summarizes the recent advances in addressing the surface and interface issues haunting the application of high-voltage cathode materials.The understanding of the limitations and advantages of different modification protocols will direct the future endeavours on advancing high-energy/power lithium-ion batteries.     

Conformational Properties of Comb-shaped Polyelectrolytes with Negatively Charged Backbone and Neutral Side Chains Studied by a Generic Coarse-grained Bead-and-Spring Model

A generic coarse-grained bead-and-spring model,mapped onto comb-shaped polycarboxylate-based(PCE)superplasticizers,is developed and studied by Langevin molecular dynamics simulations with implicit solvent and explicit counterions.The agreement on the radius of gyration of the PCEs with experiments shows that our model can be useful in studying the equilibrium sizes of PCEs in solution.The effects of ionic strength,side-chain number,and side-chain length on the conformational behavior of PCEs in solution are explored.Single-chain equilibrium properties,including the radius of gyration,end-to-end distance and persistenee length of the polymer backbone,shape-asphericity parameter,and the mean span dimension,are determined.It is found that with the increase of ionic strength,the equilibrium sizes of the polymers decrease only slightly,and a linear dependenew of the persistence length of backbone on the Debye screening length is found,in good agreement with the theory developed by Dobrynin.Increasing side-chain numbers and/or side-chain lengths increases not only the equilibrium sizes(radius of gyration and mean span)of the polymer as a whole,but also the persistence length of the backbone due to excluded volume interactions.     

Suppressing trap states and energy loss by optimizing vertical phase distribution through ternary strategy in organic solar cells

Suppressing the trap-state density and the energy loss via ternary strategy was demonstrated.Favorable vertical phase distribution with donors(acceptors)accumulated(depleted)at the interface of active layer and charge extraction layer can be obtained by introducing appropriate amount of polymer acceptor N2200 into the systems of PBDB-T:IT-M and PBDB-TF:Y6.In addition,N2200 is gradiently distributed in the vertical direction in the ternary blend film.Various measurements were carried out to study the effects of N2200 on the binary systems.It was found that the optimized morphology especially in vertical direction can significantly decrease the trap state density of the binary blend films,which is beneficial for the charge transport and collection.All these features enable an obvious decrease in charge recombination in both PBDB-T:IT-M and PBDB-TF:Y6 based organic solar cells(OSCs),and power conversion efficiencies(PCEs)of 12.5%and 16.42%were obtained for the ternary OSCs,respectively.This work indicates that it is an effective method to suppress the trap state density and thus improve the device performance through ternary strategy.     

Three-dimensionalization via control of laser-structuring parameters for high energy and high power lithium-ion battery under various operating conditions

Laser-structuring is an effective method to promote ion diffusion and improve the performance of lithium-ion battery(LIB)electrodes.In this work,the effects of laser structuring parameters(groove pitch and depth)on the fundamental characteristics of LIB electrode,such as interfacial area,internal resistances,material loss and electrochemical performance,are investigated,LiNi_0.5Co_0.2Mn_0.3O₂ cathodes were structured by a femtosecond laser by varying groove depth and pitch,which resulted in a material loss of 5%-14%and an increase of 140%-260%in the in terfacial area between electrode surface and electrolyte.It is shown that the importance of groove depth and pitch on the electrochemical performance(specific capacity and areal discharge capacity)of laser-structured electrode varies with current rates.Groove pitch is more im porta nt at low current rate but groove depth is at high curre nt rate.From the mapping of lithium concentration within the electrodes of varying groove depth and pitch by laser-induced breakdown spectroscopy,it is verified that the groove functions as a diffusion path for lithium ions.The ionic,electronic,and charge transfer resistances measured with symmetric and half cells showed that these internal resistances are differently affected by laser structuring parameters and the changes in porosity,ionic diffusion and electronic pathways.It is demonstrated that the laser structuring parameters for maximum electrode performance and minimum capacity loss should be determined in consideration of the main operating conditions of LIBs.     

Mesh-like vertical structures enable both high areal capacity and excellent rate capability

In order to balance electrochemical kinetics with loading level for achieving efficient energy storage with high areal capacity and good rate capability simultaneously for wearable electronics,herein,2 D meshlike vertical structures(NiCo_2 S_4@Ni(OH)_2) with a high mass loading of 2.17 mg cm^-2 and combined merits of both 1 D nanowires and 2 D nanosheets are designed for fabricating flexible hybrid supercapacitors.Particularly,the seamlessly interconnected NiCo_2 S_4 core not only provides high capacity of 287.5 μAh cm^-2 but also functions as conductive skeleton for fast electron transport;Ni(OH)_2 sheath occupying the voids in NiCo_2 S_4 meshes contributes extra capacity of 248.4 μAh cm^-2;the holey features guarantee rapid ion diffusion along and across NiCO_2 S_4@Ni(OH)_2 meshes.The resultant flexible electrode exhibits a high areal capacity of 535.9 μAh cm^-2(246.9 mAh g^-1) at 3 mA cm^-2 and outstanding rate performance with 84.7% retention at 30 mA cm^-2,suggesting efficient utilization of both NiCo_2 S_4 and Ni(OH)_2 with specific capacities approaching to their theoretical values.The flexible solid-state hybrid device based on NiCo_2 S_4@Ni(OH)_2 cathode and Fe_2 O_3 anode delivers a high energy density of 315 μWh cm^-2 at the power density of 2.14 mW cm^-2 with excellent electrochemical cycling stability.     

1-丁腈-3-甲基咪唑双三氟甲基磺酸亚胺的性质

制备了功能化离子液体1-丁腈-3-甲基咪唑双三氟甲基磺酸亚胺。在T为283.15-353.15 K温度范围内,测定了该功能化离子液体的密度、动力粘度、电导率及折光率。讨论了亚甲基的增减对该类功能化离子液体的密度、动力粘度、电导率及折光率等性质的影响,并与传统咪唑类、吡啶类离子液体物理化学性质的变化趋势进行了对比。通过经验方程计算了该功能化离子液体的热膨胀系数、分子体积、标准摩尔熵及晶格能等热力学性质参数。讨论了Vogel-Fulcher-Tamman (VFT)方程和Arrhenius方程的适用性,得出VFT方程适用于该功能化离子液体,而Arrhenius方程并不适用。有关研究对新型离子液体的合成及其工业化的应用具有十分重要的意义。     

The physicochemical properties of some imidazolium-based ionic liquids and their binary mixtures

The density, viscosity and conductivity of ionic liquids (ILs), 1-octyl-3-methylimidazolium tetrafluoroborate ([omim][BF4]), 1-octyl-3-methylimidazolium chloride ([omim][Cl]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim] BF4]), 1-hexyl- 3-methylimidazolium chloride ([hmim][Cl]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF6]), and the [omim][BF4] + [omim][Cl], [hmim][BF4] + [hmim][Cl], and [hmim][PF6] + [hmim][Cl] binary mixtures were studied at dif- ferent temperatures. It was demonstrated that the densities of both the neat ILs and their mixtures varied linearly with temper- ature. The density sensitivity of a binary mixture is between those of the two components. The excess molar volumes (VE) of [hmim][BF4] + [hmim][Cl] and [hmim][PF6] + [hmim][Cl] mixtures are positive in the whole composition range. For [omim][BF4] + [omim][Cl], the VE is also positive in the [omim][Cl]-rich region, but is negative in the [omim][BF4]-rich re- gion. The viscosity or conductivity of a mixture is in the intermediate of those of the two neat ILs. For all the neat ILs and the binary mixtures studied, the order of conductivity is opposite to that of the viscosity. The Vogel-Tammann-Fulcher (VTF) equations can be used to fit the viscosity and conductivity of all the neat ILs and the binary mixtures. The neat ILs and their mixtures obey the Fractional Walden Rule very well, and the values of the Walden slopes are all smaller than unit, indicating obvious ion associations in the neat ILs and the binary mixtures.     

离子液体[Cnpy][NTf2] (n=2, 4, 5)的动力粘度和电导率

在298.15-338.15 K和283.15-338.15 K温度范围内,分别测量了N-烷基吡啶双三氟甲磺酸亚胺(烷基链分别为:乙基、丁基、戊基)三种疏水型离子液体的动力粘度和电导率.利用Arrhenius 方程和Fulcher 方程将测量的动力粘度和电导率对温度拟合,得到了动力粘度和电导率随温度变化方程式.从电导率和密度计算出了上述三种离子液体在283.15-338.15 K温度范围内的摩尔电导率.应用Walden 规则,描述了动力粘度与摩尔电导率之间的关系.     

质子型离子液体N,N-二甲基乙醇胺丙酸盐的密度、粘度及电导率

在283.15-333.15 K温度范围内, 测量了质子型离子液体N,N-二甲基乙醇胺丙酸盐(DMEOAP)的密度、粘度及电导率. 讨论了温度对密度、粘度和电导率等物理化学参数的影响. 通过经验和半经验方程得到了该离子液体的热膨胀系数、分子体积、标准摩尔熵及晶格能等热力学性质参数. 由电导率和密度计算出了该离子液体的摩尔电导率. 利用Vogel-Fulcher-Tamman (VFT)方程, 将测量的动力粘度和电导率对温度拟合, 得到了动力粘度和电导率随温度变化方程式.并通过Walden规则, 建立了粘度与摩尔电导率之间的联系.     

[C3mim][NTf2]/DEC/[Li][NTf2]体系的基础性质

The hydrophobic ionic liquid (IL) 1-propyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C₃mim][NTf₂]) was synthesized according to traditional methods. By adding different amounts of diethyl carbonate (DEC) solvent and lithium bis[(trifluoromethyl)sulfonyl]imide ([Li][NTf₂]) salt to [C₃mim][NTf₂] IL, eight solution systems were prepared. First, the thermodynamic properties of the eight solution systems were characterized by differential scanning calorimetry (DSC). The semi-stable temperature of the system gradually disappeared with increasing lithium salt content, but the melting point temperature was not apparent in the experiment. These results indicate that DEC and lithium salts can dissolve in ILs within the tested temperature range. The basic properties of the eight systems, including thermodynamic and dynamic properties, were systematically studied at different temperatures. The variation in the self-diffusion coefficient of lithium ion ([Li]⁺) as a function of DEC concentration, density changes, viscosity, conductivity, and the viscosity/conductivity activation energy of the eight systems was calculated by the Vogel Fulcher Taman (VFT), Final Vogel Fulcher Taman (FVFT), and Arrhenius equations. The effect of temperature on the properties of the system was studied in detail. Within the temperature range measured herein, the deviation between the fitting equation and experimental value was small. Consequently, these equations were successfully used to calculate the properties of the system at various temperatures. All fitting parameters of the corresponding equations are provided herein. The viscosity for all systems decreased rapidly with increasing temperature, which increased the conductivity. Based on these experiments, the influence of DEC on the system microstructure was discussed in the context of the molecular dynamics simulation results. In particular, the interaction between [Li]⁺ and [NTf₂]^-/DEC was examined. In all solution systems, [NTf₂]^- coordinates to [Li]⁺ through only the O atom and not the N atom. Radial distribution function (RDF) analysis showed that the interaction between [Li]⁺ and [NTf₂]^- weakened with increasing DEC concentration. DEC molecules were observed in the first solvation layer of [Li]⁺ coordinating to [Li]⁺ through the carbonyl O atom. Although the interaction between [Li]⁺ and DEC was weakened, competition between [NTf₂]^- and DEC in the first solvation layer of [Li]⁺ was observed by the coordination number analysis of the O atom around [Li]⁺. Therefore, the introduction of DEC is beneficial for Li⁺ diffusion, which is consistent with the experimental results.     

四种深共融溶剂的性质:密度、电导率、动力粘度及折光率

制备了四种四丁基氯化铵类深共融溶剂,包括四丁基氯化铵:丙酸[TBAC:2PA]、四丁基氯化铵:乙二醇[TBAC:2EG]、四丁基氯化铵:聚乙二醇[TBAC:2PEG]、四丁基氯化铵:苯乙酸[TBAC:2PAA].在288.15-338.15 K温度范围内,测定了它们的密度、电导率、动力粘度及折光率.讨论了温度对密度、电导率、动力粘度及折光率等性质的影响.通过经验方程估算了深共融溶剂的热膨胀系数、分子体积、标准摩尔熵及晶格能等热力学性质参数.利用Vogel-Fulcher-Tamman (VFT)方程和Arrhenius方程,将测量的电导率和动力粘度对温度拟合,得到了动力粘度和电导率随温度变化方程式.有关研究对深共融溶剂的工业化应用具有重要意义.     

Physical and CO2-Absorption Properties of Imidazolium Ionic Liquids with Tetracyanoborate and Bis(trifluoromethanesulfonyl)amide Anions

Ionic liquids with tetracyanoborate ([TCB]^?) and bis(trifluoromethanesulfonyl)amide ([Tf₂N]^?) anions generally have low viscosities and high CO₂ capacities, and thus they are attractive solvents for CO₂-related applications. Herein, we have investigated physical and CO₂-absorption properties of 1-ethyl-3-methylimidazolium tetracyanoborate ionic liquid ([emim][TCB]) to discuss the anion effects of [TCB]^? in comparison with the previous results of [emim][Tf₂N]. The density, viscosity, electrical conductivity, and isobaric molar heat capacity were measured as a function of temperature at atmospheric pressure. [emim][TCB] has both lower density and isobaric molar heat capacity than [emim][Tf₂N]. [emim][TCB] shows superior transport properties (lower viscosity and higher electrical conductivity) compared to [emim][Tf₂N], whereas the Walden plots of molar conductivity against fluidity (reciprocal of viscosity) have smaller values in [emim][TCB] than in [emim][Tf₂N] at certain fluidities. The high-pressure CO₂ solubilities were also determined in [emim][TCB]. The mole fraction scaled solubility of CO₂ in [emim][TCB] is slightly larger than that in [emim][Tf₂N] at certain pressures and temperatures. The former ionic liquid shows much higher molarity scaled solubility of CO₂ than the latter because of the smaller molar volume. It is suggested that both anions have similar strength of intermolecular interaction with CO₂ and comparable changes in the solvent structure between neat and CO₂ solution, in view of the thermodynamic parameters of dissolution.     

Synthesis of room-temperature ionic liquids with the weakly coordinating [Al(ORF)4]- anion (RF=C(H)(CF3)2) and the determination of their principal physical properties

A large series of ionic liquids (ILs) based on the weakly coordinating alkoxyaluminate [Al(hfip)(4)](-) (hfip: hexafluoroisopropoxy) with classical as well as functionalized cations were prepared, and their principal physical properties determined. Melting points are between 0 ([C(4)MMIM][Al(hfip)(4)]) and 69 °C ([C(3)MPip][Al(hfip)(4)]); three qualify as room-temperature ILs (RTILs). Crystal structures for six ILs were determined; their structural parameters and anion-cation contacts are compared here with known ILs, with a special focus on their influence on physical properties. Moreover, the biodegradability of the compounds was investigated by using the closed-bottle and the manometric respirometry test. Temperature-dependent viscosities and conductivities were measured between 0 and 80 °C, and described by either the Vogel-Fulcher-Tammann (VFT) or the Arrhenius equations. Moreover, conductivities and viscosities were investigated in the context of the molecular volume, V(m). Physical property-V(m) correlations were carried out for various temperatures, and the temperature dependence of the molecular volume was analyzed by using crystal structure data and DFT calculations. The IL ionicity was investigated by Walden plots; according to this analysis, [Al(hfip)(4)](-) ILs may be classified as "very good to good ILs"; while [C(2)MIM][Al(hfip)(4)] is a better IL than [C(2)MIM][NTf(2)]. The dielectric constants of ten [Al(hfip)(4)](-) ILs were determined, and are unexpectedly high (ε(r)=11.5 to 16.8). This could be rationalized by considering additional calculated dipole moments of the structures frozen in the solid state by DFT. The determination of hydrogen gas solubility in [Al(hfip)(4)](-) RTILs by high-pressure NMR spectroscopy revealed very high hydrogen solubilities at 25 °C and 1 atm. These results indicate the significant potential of this class of ILs in manifold applications.     

Effect of water and organic solvents on the ionic dissociation of ionic liquids

The effect of water and several organic solvents on the density, viscosity, and conductivity of ionic liquids (ILs) 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), 1-n-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), and 1-n-butyl-3-methylimidazolium trifluoroacetate ([bmim][CF3CO2]) was studied at 298.15 K in wide composition ranges. The density, viscosity, and conductivity of the three neat ILs were also determined at various temperatures. Upon the basis of the molar conductivity of the mixtures and that of the neat ILs of the same viscosity, the degree of dissociation of ILs in the solutions was investigated. It can be deduced that the organic solvents enhance the ionic association of the ILs, the effect depending on the solvent dielectric constant, while water promotes dissociation significantly due to its high dielectric constant and its ability to form strong hydrogen bonds with the anions of the ILs.