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.     

532 nm纳秒激光电离产生Xez＋(z ≤ 11)高价离子

利用25 ns脉冲Nd-YAG 532 nm激光,在1011 W•cm－2的光场强度下,研究了Xe原子团簇的激光电离过程,观察到较强的高价离子信号,其中最高价态达＋11.不同脉冲束位置和束源压力的实验表明,仅当激光作用于脉冲束中段时才能观察到高价离子,且高价离子信号强度随束源压力的增加而迅速增强,说明束中大尺寸团簇的存在与高价离子的形成密切相关.通过实验,认为高价离子可能来源于电离原子团簇而形成的纳米尺度等离子体小球对激光光场的共振吸收.     

纳秒强激光电离苯产生高价碳离子的波长效应

The photoionization of seeded benzene beam by 25 ns laser pulse at wavelengths of 266,355 and 1064 nm has been studied by the time-of-flight mass spectrometry. The observed mass spectra at 266 nm and 355 nm at intensities of 1010-1011 W/cm2 indicate a multiphoton ionization and dissociation（MPID）process,in which C+,C2Hx+,C3Hx+,C4Hx+ and C6H6+ are main products. While at 1064 nm laser of similar intensities,the domain ion is C4+ which is produced from Coulomb explosion. The longer wavelength facilities the energy absorption rate during inverse bremsstrahlung,which leads to the resulting wavelength dependence of the multicharged atomic ions.     

Coulomb explosion of nitrogen and oxygen molecules through non-Coulombic states

We have systematically studied Coulomb explosion of nitrogen and oxygen molecules in intense 8 and 24 fs laser pulses. In the experiment, we explicitly separated all explosion pathways through coincident measurements. The high resolution kinetic energy releases (KERs) and the exotic angular distributions of atomic ions provide direct evidence that Coulomb explosion occurs through non-Coulombic states. In the theory, we calculated dissociation potential energy curves (PECs) of nitrogen and oxygen molecules and their multicharged molecular ions using multiconfiguration second-order perturbation theory. The results indicate that Coulomb potentials are close to the accurate PECs of multicharged molecular ions only when the internuclear distance is larger than 3 ?. In comparison with the experimental observations and the theoretical calculations, we determined the internuclear distance when Coulombic explosion occurs. It is near the equilibrium distance of the neutral molecules in the case of 8 fs laser pulses and expands gradually with the increase of the charge state of the molecular ions in the case of 24 fs laser pulses.     

Coulomb explosion of ammonia clusters induced by intense nanosecond laser at 532 and 1064 nm: wavelength dependence of the multicharged nitrogen ions

The Coulomb explosion of ammonia clusters induced by nanosecond laser field with intensity in the range of 10(10)-10(12) W cm(-2) and wavelength of 532 and 1064 nm has been studied. N2+ and N3+ ions are the main multicharged ions at 532 nm, while He-like N5+ ion is the domain multicharged ion at 1064 nm.     

Absorption spectra of e-beam-excited Ne, Ar, and Kr, pure and in binary mixtures

A technique using the broadband emission of a laser plume as probe radiation is applied to record UV-visible (190-510 nm) absorption spectra of Ne, Ar, and Kr, pure and in binary mixtures under moderate e-beam excitation up to 1?MW/cm(3). In all the rare gases and mixtures, the absorption spectra show continuum related to Rg(2) (+) homonuclear ions [peaking at λ～285, 295, and 320 nm in Ne, Ar, and Kr(Ar/Kr), respectively] and a number of atomic lines related mainly to Rg(?)(ms) levels, where m is the lowest principal quantum number of the valence electron. In argon, a continuum related to Ar(2) (?) (λ～325?nm) is also recorded. There are also trains of narrow bands corresponding to Rg(2) (?)(npπ?(3)Π(g))←Rg(2) (?)(msσ?(3)Σ(u) (+)) transitions. All the spectral features mentioned above were reported in literature but have never been observed simultaneously. Although charge transfer to a homonuclear ion of the heavier additive is commonly believed to dominate in binary rare-gas mixtures, it is found in this study that in Ne/Kr mixture, the charge is finally transferred from the buffer gas Ne(2) (+) ion not to Kr(2) (+) but to heteronuclear NeKr(+) ion.     

Absorption Spectrum of Neutral Krypton in the Near Infrared Region

High-resolution absorption spectra of atomic krypton in the range of 11870-12700 cm^?1 were recorded by employing concentration modulation absorption spectroscopy technique with a tunable single-mode cw Ti:Sapphire laser. The krypton atoms were excited to the absorbing energy states by discharge-burning in a mixture of helium and krypton. A total of 120 lines of neutral krypton were observed, among them 33 lines had already been classified in previous studies, 45 lines were newly classi ed with the known energy levels, and 42 lines cannot be classi ed. These unclassified lines indicate that up to now unknown energy levels of Kr must exist. Further, an analysis of the unclassi ed lines to get possible new energy levels with a classi cation program is reported.     

Photoinduced dissociation of electrospray-generated ions in an ion trap/time-of-flight mass spectrometer using a pulsed CO2 laser

An ion trap/time-of-flight (IT/TOF) mass spectrometer was developed and applied to infrared multiphoton dissociation (IRMPD) studies of ions generated by electrospray ionization. A pulsed 10.6- micro m laser beam from a CO(2) laser was used for excitation of trapped ions. Results from IRMPD of peptide ions show that this method provides useful information related to the amino acid sequence of analyzed peptides. Comparative studies show that IRMPD spectra are similar to those obtained using a 266-nm UV laser beam for excitation. However, in contrast to multiple-pulse excitation required at 266 nm, the energy of a single laser pulse in IRMPD is sufficient to induce dissociation of peptide ions. The laser power is practically an exclusive parameter that must be controlled in order to obtain IRMPD spectra that will provide the optimal structural information. It is further demonstrated that the IRMPD IT/TOF technique has the potential to probe the structural features of larger ions that cannot be readily fragmented by collision-induced dissociation (CID). A multiply charged ion of equine cytochrome c is successfully fragmented in a single laser pulse experiment. The IRMPD IT/TOF technique is also shown to be a promising tool for studying dissociation kinetics of peptide and protein ions. Unlike other methods that usually monitor the dissociation ion kinetics in a dissociation time frame of greater than milliseconds, the IT/TOF can promptly detect all product ions generated by the dissociation process, and thus monitor the dissociation process of peptides and proteins in a sub-millisecond time frame. This instrument allows us to determine the dissociation rates of cytochrome c ions using high-energy photoexcitation. It is found that the charge state of the protein ion has a significant effect on dissociation kinetics, which is consistent with that found under low-energy excitation experiments. It is shown that the increase in energy of a laser pulse from 130 to 180 mJ changes the dissociation rate constant for the +12 ion from k = 2.4 x 10(3) x s(-1) to k = 7.3 x 10(4) x s(-1). The +8 ion following excitation at 130 mJ dissociates slower with a rate constant of k = 2.6 x 10(2) x s(-1). The rate difference observed is attributed to conformational differences among the ions with different charge states.     

Energy characteristics and deposition rates of metals from vacuum laser plasma on dielectric substrates

The effect of the energy flux density of a pulsed Kr-F laser on the processes of generation of the laser plasma of tin, palladium and platinum and on the deposition rates of metal films on dielectric substrates in laser ablation have been studied. The use of the differential scheme of probing a laser plasma with Faraday cups and time-of-flight mass spectrometry has made it possible to distinguish, in plasma ion signals, the ranges of singly charged and multicharged ions, which differ in kinetic energy. The film deposition rate depends on both the laser energy flux density and the degree of ionization of the laser plasma.     

Krypton isotopic signature study of the primary coolant of CANDU nuclear power plant

To support interpretation of observed atmospheric krypton radioisotopes, a database of krypton radioisotope in the primary coolant of CANDU reactors has been established. This database is comprised of 40,000 records of high-quality ⁸⁹Kr, ⁸⁷Kr, ⁸⁸Kr and ^85mKr analyses. Records from the database were retrieved by a specifically designed data-mining module and subjected to further analysis. Results from the analysis were subsequently used to study isotopic ratios of observed krypton radioisotopes in the CANDU reactor primary coolant. These studies provided practical information on the characterization of CANDU reactor krypton radioisotope, which can potentially be used to discriminate between reactor effluent and fuel reprocessing for nuclear safeguard ⁸⁵Kr monitoring applications (Kalinowski et al., J Environ Radioact 73:203, 2004). The study also has some potential application to Fissile material cut-off treaty.     

Krypton fixation using KrF2 (III). Entrapment of krypton into zeolite 13x

The KrF₂ - zeolite 13X reaction at ?40 °C results in entrapment of Kr in the zeolite. On heating, a portion of the entrapped Kr is retained up to 500 °C. The Kr loading is more than 8 cc(STP)/g at a storage temperature of 100 °C. The present work has suggested a feasibiltty of the zeolite encapsulation of radioactive krypton by a chemical procedure.