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.     

Formation of thin calcium carbonate films with aragonite and vaterite forms coexisting with polyacrylic acids and chitosan membranes

CaCO3 crystallization on a chitosan membrane was studied using diffusion of (NH4)2CO3 vapors into a CaCl2 solution containing differing added amounts of two polyacrylic acids (PAAs) with molecular weights of ca. 2.0 x 10(3) and ca. 4.5 x 10(4). The coexistence of PAA and the chitosan membranes produced thin CaCO3 island crystals, which developed into a continuous CaCO3 film on the membranes. Continuous CaCO3 films consisting of only aragonite formed on the chitosan membranes at the optimum amount of PAA. When the amount of PAA is not optimum, the polymorph of CaCO3 switches from aragonite to vaterite, and the morphology has a tendency to become an isolated island structure. The formation of the aragonite and vaterite island crystals and the appearance of a range of added PAA suitable for their formation are explained by the action of two parallel phenomena: (a) the high concentration of Ca2+ ions in the chitosan membrane vicinity is achieved by the interaction between the -COO- groups of PAA adsorbed by the -NH3+ groups of the chitosan membrane through an electrostatic force and free Ca2+ ions in the CaCl2 solution, which produces the high supersaturation with CaCO3 in the membrane vicinity during CO2 diffusion; (b) PAA, remaining as mobile carboxylic anions in the CaCO3 solution, inhibits the growth of the CaCO3 island crystals by its adsorption. The CaCO3 supersaturation in the membrane vicinity is controlled by regulating the balance of these phenomena, which leads to the formation of the desired CaCO3 polymorph.     

胆固醇对卵磷脂有序体中生成CaCO3晶型的影响

报道了在卵磷脂、胆固醇、橄榄油、电解质溶液组成的分子有序组合体中,胆固醇的加入影响了有序体的膜结构、表面特性,从而也影响到有序体微环境中所生成的CaCO₃晶体结构。随着胆固醇含量增加,在一定范围内球霰石的相对含量增大;油包水体系中生成的球霰石相对含量远大于水包油体系中生成的球霰石相对含量。     

胆固醇(Cholesterol)嵌入卵磷脂(PC)有序体后对其中CaCO3晶型结构的影响

在PC和Chol/PC有序体中进行CaCO₃沉淀反应,用X射线衍射和扫描电镜方法表征了反应物结构,研究了作为有机模板剂的不同分子有序体对CaCO₃的晶型和形态的指导作用.在反胶束合成中出纳米级CaCO₃颗粒.胆固醇对有序体有显著影响,进而影响此体系中形成的CaCO₃晶型,可诱导生成3种CaCO₃异构体:胶体CaCO₃、球霰石和方解石.方解石含量随胆固醇含量增加减少.     

Formation of stable vaterite with poly(acrylic acid) by the delayed addition method

The crystallization of CaCO3 was examined by changing the addition time of poly(acrylic acid) (PAA) to an aqueous solution of calcium carbonate by selectively interacting with the crystal at different stages during the crystal-forming process. The precipitation of CaCO3 was carried out by a double jet method to prevent heterogeneous nucleation on glass walls, and the sodium salt of PAA was added by a delayed addition method. In the initial presence of PAA in an aqueous solution of calcium carbonate, PAA acted as an inhibitor for the nucleation and growth of crystallization. However, it was found that stable vaterite particles were successfully obtained by delaying the addition of PAA from 1 to 60 min. The vaterite particles were stable in the aqueous solution for more than 30 days, and the CaCO3 particles were formed by a spherulitic growth mechanism. It is suggested that PAA strongly binds with the Ca2+ ion on the surface of CaCO3 particles to stabilize the unstable vaterite form effectively. Upon changing the addition time of PAA, we found that CaCO3 particles were formed through different formation mechanisms in selectively controlled crystallization at different stages during the crystallization process.     

Efficiently stabilized spherical vaterite CaCO3 crystals by carbon nanotubes in biomimetic mineralization

Carbon nanotubes were used to induce the formation of spherical vaterite crystals and stabilize the metastable crystals in the biomimetic mineralization of CaCO3 for the first time. It was found that carboxyl-functionalized multiwalled/single-walled carbon nanotubes (MWNT-COOH/SWNT-COOH) can favor the formation of spherical vaterite crystals and stabilize the crystals. In the presence of CNT-COOH, CaCO3 vaterite crystals with diameters of ca. 1-7 microm coated and embedded with the carbon nanotubes (CNTs) were obtained in 30 min by adding Na2CO3 aqueous solution to the aqueous solution of CaCl2. The spherical vaterite crystals covered by the carboxylic CNTs can exist stably in water for a week. Carboxylic-polymer-functionalized CNTs can also facilitate the formation of spherical vaterite crystals, whereas the formed crystals completely transformed into thermodynamically stable calcite crystals in water within 10 h. "Offline" TEM observations of the mineralization process of CaCO3 in the presence of CNT-COOH or pristine CNTs revealed the stability mechanism of vaterite crystals with carboxylic CNTs. The crystals nucleate at the carboxyl groups of CNT-COOH, grow around the CNTs, and finally form spherical vaterite crystals embedded and covered by the CNTs. The strong interaction between CNT-COOH and crystals together with the strong mechanical strength of CNTs stabilizes the formed vaterite crystals and makes them difficult to dissolve in water. These findings announce that nanomaterials could strongly influence the mineralization of biomineralization matters, which may help us prepare novel biomaterials and bionanomaterials.     

Influence of sodium dodecyl sulfate and static magnetic field on the properties of freshly precipitated calcium carbonate

Properties of calcium carbonate precipitated from aqueous solutions of CaCl(2) and Na(2)CO(3) in the presence of sodium dodecyl sulfate (SDS) and S-S 0.1 T magnetic field (MF) were studied. The nucleation and precipitation processes of CaCO(3) were investigated by pH and zeta potential measurements at 20 +/- 1 degrees C up to 2 h after mixing the solutions. Also the amounts of calcium carbonate deposited on the glass surfaces and its structure were examined. It was found that SDS influences the kinetics of precipitation, crystallographic forms, and crystal size of CaCO(3). The SDS effects are more pronounced in MF presence. A small amount of SDS accelerates transformation of vaterite into calcite, whereas increasing surfactant concentration moderates such a transformation. On the other hand, in all the systems, MF in the presence of SDS causes a slower transformation of vaterite into calcite. These effects are reflected in pH and zeta potential changes, although there is no clear dependence between the SDS amount present during the precipitation and changes of the parameters investigated. It seems that MF effect is most significant at a defined optimal SDS concentration. The results, however, do not allow suggestion of any detailed mechanism of the field interaction.     

Controlling the polymorph and morphology of CaCO3 crystals using surfactant mixtures

Inspired by mineralization in biological organisms, fabrication of higher ordered CaCO(3) crystals modified by surfactants has received much attention. In our present work, mixed surfactants of hexadecyl(trimethyl)azanium bromide and sodium dodecyl sulfate were used to mediate the nucleation and growth of CaCO(3) crystals. When the concentration of sodium dodecyl sulfate in the solution is constant (0.1 mM), the polymorph of CaCO(3) crystals changed from pure vaterite to pure aragonite with increase of the ratio of hexadecyl(trimethyl)azanium bromide to sodium dodecyl sulfate. Various morphologies of vaterite and aragonite were obtained. Based on the time-resolved experiments, we suggest that the flower-like CaCO(3) formed via aggregation of hexagon-like vaterite induced by the surfactants. More importantly, we realized that a cluster-shaped morphology of aragonite was produced through the nucleation of aragonite at the surfaces of the hexagon-like vaterite.     

卵磷脂有序体中碳酸钙超微颗粒的研究

近些年来，国内外对超微颗粒的研究正处方兴未艾，由于纳米级材料与大块物质的特性截然不同，引起了国内外科学工作者的关注，试图用各种方法制备各种超微颗粒．在有序体中制备铂、佬、金、银、锅等超微颗粒已有文献介绍山，在表面活性剂AOT与水形成的有序体中制各碳酸钙超细颗粒也有报导问，用脂质体合成某些超微颗粒的工作也有文章发表［3］．但是由卵磷脂（PC）与水组成人。膜体系制备碳酸钙超微颗粒尚未见到报导．我们根据分子有序组合体具有”隔室化”作用，形成纳米级空间的思路，采用PC－H。0有序体系作为生成碳酸钙的反应场所．…     

利用室温固态反应制备球霰石型CaCO3粒子

合成形态、大小及结构可人为调控的无机材料是现代材料科学的重要研究方向[1]. 借助于各类有机添加剂及模板剂的调控作用, 可利用溶液合成方法制备出形貌与结构受到有效调控的无机粒子[2,3]. 室温固态化学反应已被成功地应用于多种无机纳米粒子[4]及纳米线[5]的合成, 并显示出高效、节能、无污染和操作简便等优点, 因而在材料合成领域具有应用前景[6].     

Crystallization and Transformation Mechanism of Calcium Carbonate Polymorphs and the Effect of Magnesium Ion

The crystallization of calcium carbonate was carried out by mixing CaCl(2) and Na(2)CO(3) solutions. The morphology of precursor formed prior to the nucleation of the polymorphous crystals (calcite and vaterite) varies depending on the feed concentration. The faster nucleation rate of polymorphous crystals in 0.2 mol/L than in 0.05 mol/L solution results in the prompt disappearance of the precursor at 0.2 mol/L. In 0.05 mol/L solutions the lifetime of the precursor is relatively long. The crystallization fraction of vaterite increases with the feed concentration and decreases with the addition rate of Na(2)CO(2) solution. Vaterite takes on the various morphologies of the aggregates of the primary flocculation body (spherulite) depending on the crystallization conditions. Vaterite transforms to calcite by a direct solution-mediated mechanism. During crystallization the concentration attains a stationary value, which increases with the feed concentration and decreases with the addition rate of Na(2)CO(2) solution. This may be due to the crystal size decrease expected from the Gibbs-Kelvin equation. Magnesium ion suppresses the transformation of vaterite by inhibiting the growth of the calcite. Magnesium ion is selectively included in calcite and causes the increase of the attained concentration and the remarkable change in the morphology of calcite especially in 0.05 mol/L solution. Copyright 2001 Academic Press.