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.     

On-line determination of palladium by flame atomic absorption spectrometry coupled with a separation/preconcentration minicolumn containing a new sorbent

A method was developed for the on-line determination of palladium in complex matrices with flame atomic absorption spectrometry (FAAS) using Amberlite XAD-16 resin functionalized with 2-[2-(5-thiol-1,3,4-thiadiazolyl)]-azonaphthol (TTAN) reagent. Optimum experimental conditions such as pH of sample, type of eluent, amount of resin, volumes of sample and eluent solution, flow rates of sample and eluent, and effect of interfering ions were established. A 0.1?mol?L^?1 thiourea solution in 0.5?mol?L^?1 HCl was used as the eluent and subsequently transportation the analyte ions into the nebulizer–burner system for atomization. The synthesized chelating resin material showed excellent chemical and mechanical resistance, fast adsorption kinetics permitting the use of high sample flow rates without significant losses of retention efficiency. The detection limit of the method was 1.5?µg?L^?1 while the relative standard deviation (RSD%) was 2.4% at 0.1?mg?L^?1 Pd(II) level. The developed method was successfully applied to the determination of palladium in the catalytic converter and water samples.     

Column solid-phase extraction with Chromosorb-102 resin and determination of trace elements in water and sediment samples by flame atomic absorption spectrometry

A column, solid-phase extraction (SPE), preconcentration method was developed for determination of Bi, Cd, Co, Cu, Fe, Ni and Pb ions in drinking water, sea water and sediment samples by flame atomic absorption spectrometry. The procedure is based on retention of analytes in the form of pyrrolidine dithiocarbamate complexes on a short column of Chromosorb-102 resin from buffered sample solution and then their elution from the resin column with acetone. Several parameters, such as pH of the sample solution, amount of Chromosorb-102 resin, amount of ligand, volume of sample and eluent, type of eluent, flow rates of sample and eluent, governing the efficiency and throughput of the method were evaluated. The effects of divers ions on the preconcentration were also investigated. The recoveries were >95%. The developed method was applied to the determination of trace metal ions in drinking water, sea water and sediment samples, with satisfactory results. The 3σ detection limits for Cd, Cu, Fe, Ni and Pb and were found to be as 0.10, 0.44, 11, 3.6, and 10 μg l⁻¹, respectively. The relative standard deviation of the determination was <10%. The procedure was validated by the analysis of a standard reference material sediment (GBW 07309) and by use of a method based on coprecipitation.     

Ion chromatographic system with a novel switching suppression device

Ion chromatography (IC) has been a powerful tool for measuring ionic species in environmental samples such as tap, river and drain waters. Suppressor modules (membrane and disposable column types) have been used for reducing the background of a baseline. A new type of suppressor device, which has a suppressor resin and switching valve was developed. Fresh ionic resin is introduced into a groove for each analysis to perform the suppression of the working eluent. The eluent composition for obtaining higher sensitivity and better resolutions among ionic species and carbonate ion was also investigated. Although carbonate buffers are used for ion separation in general, the separation of carbonate ion from other ions was not achieved. A borate eluent resulted in good resolutions and higher sensitivity. A new column was also developed for obtaining higher column efficiency and resolution. The optimization of anion separation using a new IC system (IC-2001) that consists of a new suppressor device, an anion-exchange column (TSKgel SuperIC-Anion, 150x4.6 mm), an autosampler, a conductivity cell and a pump in a compact module is described.     

用大孔吸附树脂分离利血平

以利血平的吸附量和解吸率为指标,筛选大孔吸附树脂.研究吸附和解吸的优化条件,并考察选定树脂的吸附等温线、吸附动力学、吸附和解吸性能.结果表明,将催吐萝芙木根粉浸提液蒸去乙醇且不调pH(pH 1)进行吸附,HZ-818型大孔吸附树脂对利血平的吸附量可达到9.34mg/mL.使用工业乙醇-水(80:20,pH 1.0)为解吸剂,解吸率可达99.3%.该树脂的吸附符合Langmuir吸附等温方程.吸附前期,吸附速度较快,以后速度减慢.HZ-818型树脂对利血平的吸附量大,解吸率高,通过大孔树脂吸附和解吸,利血平浓度提高50倍以上,适宜于工业化生产.     

Preconcentration and separation with Amberlite XAD-4 resin; determination of Cu, Fe, Pb, Ni, Cd and Bi at trace levels in waste water samples by flame atomic absorption spectrometry

A method for the preconcentration of Cu, Fe, Pb, Ni, Cd and Bi as their diethyldithiocarbamate chelates was proposed using a column filled with Amberlite XAD-4 resin. The retained analytes on the resin were recovered with a small volume of acetone. The metal ions in the effluent were determined by a flame atomic absorption spectrometer. Different factors including pH of sample solution, sample volume, amount of XAD-4 resin, amount of ligand, eluent volume and matrix effects for preconcentration were examined. The recoveries for the analytes under the optimum working conditions were higher than 95%. The relative standard deviations of the determinations were below 9%. The limits of detection (3 s, n=20) for analytes were found to be between 4 and 23 mug l(-1). The proposed method was applied to the analysis of some waste waters from the organized industrial region of Kayseri.     

Optimization of a new resin, Amberlyst 36, as a solid-phase extractor and determination of copper(II) in drinking water and tea samples by flame atomic absorption spectrometry

A new simple and reliable method has been developed to separate and preconcentrate trace copper ion in drinking water and tea samples for subsequent measurement by flame atomic absorption spectrometry (FAAS). The copper ions are adsorbed quantitatively during passage of aqueous solutions through Amberlyst 36 cation exchange resin. After the separation and preconcentration stage, the analyte was eluted with a potassium cyanide solution and determined by FAAS. Different factors including pH of sample solution, sample volume, amount of resin, flow rate of aqueous solution, volume and concentration of eluent, and matrix effects for preconcentration were examined. The analytical figures of merit for the determination of copper are as follows: analytical detection limit (3 sigma), 0.26 microg/L; precision (RSD), 3.1% for 100 microg/L; enrichment factor, 200 (using 1000 mL of sample solution and 5 mL of eluent); time of analysis, 3.5 h (for obtaining enrichment factor of 200); capacity of resin, 125 mg/g. The method was applied for copper determination by FAAS in tap water, commercial natural spring water, commercial treated drinking water, and commercial tea bag sample. The accuracy of the method is confirmed by analyzing tea leaves (GBW 07605). The results demonstrated good agreement with the certified values.     

Retention behaviour of strong acid anions in ion-exclusion chromatography on sulfonate and carboxylate stationary phases

Some factors influencing the retention of strong-acid anions on ion-exclusion columns were investigated using columns with sulfonate and carboxylate functional groups. The nature of the functional group on the resin, the eluent pH and the eluent ionic strength all significantly affected the retention and separation of these analytes. Retention was observed for all strong-acid anions over the eluent pH range 2.2-5.7 and increased with both decreasing eluent pH and increasing eluent ionic strength. Some separation of strong-acid anions was possible when using a resin with carboxylate functional groups. It has also been demonstrated that strong-acid anions are poor markers of column void volume for ion-exclusion chromatography. A more accurate value was obtained using the neutral polymeric material dextran blue. When using eluents of low ionic strength, poor or fronted peak shapes were observed. A mechanism for these observations is proposed that relates the shape to ionic strength changes across the peak. A system peak was encountered under most experimental conditions. The properties of this peak are discussed and a cause for the system peak postulated.     

A modified lead–matrix separation procedure shown for lead isotope analysis in Trojan silver artefacts as an example

A modified Pb–matrix separation procedure using NH₄HCO₃ solution as eluent has been developed and validated for determination of Pb isotope amount ratios by thermal ionization mass spectrometry. The procedure is based on chromatographic separation using the Pb·Spec resin and an in-house-prepared NH₄HCO₃ solution serving as eluent. The advantages of this eluent are low Pb blanks (<40 pg?mL^?1) and the property that NH₄HCO₃ can be easily removed by use of a heating step (>60 °C). Pb recovery is >95 % for water samples. For archaeological silver samples, however, the Pb recovery is reduced to approximately 50 %, but causes no bias in the determination of Pb isotope amount ratios. The validated procedure was used to determine lead isotope amount ratios in Trojan silver artefacts with expanded uncertainties (k?=?2) <0.09 %.     

Unique elution behavior of bromide and nitrate in anion-exchange chromatography using aqueous potassium chloride eluent containing cadmium or zinc ion

In anion-exchange chromatography using a high-concentration eluent and high-capacity ion-exchange resin, the effect of the countercation contained in the eluent was investigated. Cadmium(II) and zinc(II) ions were examined as additives in an aqueous potassium chloride eluent. The addition of these cations resulted in a reversed elution order of bromide and nitrate, as compared with conventional anion-exchange chromatography. The separation factor for these two anions increased as the cadmium concentration in the eluent was increased. Zinc(II) ion was also effective, but a relatively high concentration was necessary.     

Evaluation of different electrolyte systems and on-line preconcentrations for the analysis of haloacetic acids by capillary zone electrophoresis

The separation of various carboxylic acids was performed on a polymethacrylate-based weakly acidic cation-exchange resin (TSKgel OApak-A) using ion-exclusion chromatography under the acidic elution conditions. When a diluted sulfuric acid solution was used as the eluent, highly sensitive conductimetric detection of carboxylic acids was achieved without increasing the background conductance of the eluent. This method was more sensitive than using benzoic acid eluent and enabled a good resolution of dicarboxylic as well as monocarboxylic acids. The addition of 5–20% methanol to the eluent considerably reduced the retention times of carboxylic acids with hydrophobic nature.