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.     

酵母对抑制剂耐受的系统分析

纤维素生产乙醇的关键问题之一是水解产生的抑制性物质对乙醇发酵具有明显的抑制效应,因而引起了国内外研究者的广泛关注.研究发现,在抑制剂存在下,酵母在基因表达水平,蛋白水平和代谢物水平都有相应的耐受响应,且这些响应错综复杂.从系统角度运用组学的方法研究这一体系将有助于全面深入了解酵母的耐受机制.本文综述了系统研究的思路和方法在酵母对抑制剂耐受方面的研究状况;对主要研究手段和成果进行了回顾;并对酵母发酵乙醇系统分析的前景进行了展望.     

Miniaturized electrochemical sensors and their point-of-care applications

Most of the current analytical methods depend largely on laboratory-based analytical techniques that require expensive and bullky equipment,potentially incur costly testing,and involve lengthy detection processes.With increasing requirements for point-of-care testing(POCT),more attention has been paid to miniaturized analytical devices.Miniaturized electrochemical(MEC)sensors,including different material-based MEC sensors(such as DNA-,paper-,and screen electrode-based),have been in strong demand in analytical science due to their easy operation,portability,high sensitivity,as well as their short analysis time.They have been applied for the detection of trace amounts of target through measuring changes in electrochemical signal,such as current,voltage,potential,or impedance,due to the oxidation/reduction of chemical/biological molecules with the help of electrodes and electrochemical units.MEC sensors present great potential for the detection of targets including small organic molecules,metal ions,and biomolecules.In recent years,MEC sensors have been broadly applied to POCT in various fields,including health care,food safety,and environmental monitoring,owing to the excellent advantages of electrochemical(EC)technologies.This review summarized the state-of-the-art advancements on various types of MEC sensors and their applications in POCT.Furthermore,the future perspectives,opportunities,and challenges in this field are also discussed.     

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.     

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.     

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.     

Rotationally Resolved Vacuum Ultraviolet Pulsed Field Ionization-Photoelectron Vibrational Bands for H2+(X2§+g,v+=0-18)

We have obtained a rotationally resolved vacuum ultraviolet pulsed ˉeld ionization-photoelectron (VUV-PFI-PE) spectrum of H2 in the energy range of 15.30-18.09 eV, covering the ionization transitions H2+(X2§+g ,v+=0-18, N+=0-5)?H2(X1§+g , v00=0, J00=0-4). The assignment of the rotational transitions resolved inthe VUV-PFI-PE vibrational bands for H2+(X2§+g , v+=0-18) and their simulation using the Buckingham-Orr-Sichel (BOS) model are presented. Only the ￠N=N+?J00=0 and §2 rotational branches are observed in the VUV-PFI-PE spectrum of H2. However, the vibrational band is increasingly dominated by the 4N=0 rotational branch as v+ is increased. The BOS simulation reveals that the perturbation of VUV-PFI-PE rotational line intensities by near-resonance autoionizing Rydberg states is minor at v+?6 and decreases as v+ is increased. Thus, the rotationally resolved PFI-PE bands for H2+(v+?6) presented here providereliable estimates of state-to-state cross sections for direct photoionization of H2, while the rotationally resolved PFI-PE bands for H2+(v+·5) are useful data for fundamental understanding of the near resonance autoionizing mechanism. On the basis of the rovibrational assignment of the VUV-PFI-PE spectrum of H2, the ionization energies for the formation of H2+(X2§+g , v+=0-18, N+=0-5) from H2+(X1§+g , v00=0,J00=0-4), the vibrational constants (!e, !e?e, !eye, and !eze), the rotational constants (Bv+, Dv+, Be,and ?e), and the vibrational energy spacings ￠G(v++1/2) for H2+(X2§+g , v+=0-18) are determined. With a signiˉcantly higher photoelectron energy resolution achieved in the present study, the precisions of these spectroscopic values are higher than those obtained in the previous photoelectron studies. As expected, the spectroscopic results for H2+(X2§+g , v+=0-18) derived from this VUV-PFI-PE study are in excellent agreement with high-level theoretical predictions.     

Vacuum ultraviolet-infrared photo-induced Rydberg ionization spectroscopy: C-H stretching frequencies for trans-2-butene and trichloroethene cations

We have demonstrated the two-color vacuum ultraviolet (VUV)-infrared (IR) photoinduced Rydberg ionization (PIRI) experiment. Trichloroethene (ClCH=CCl2) and trans-2-butene (trans-CH3CH=CHCH3) were prepared in Rydberg states in the range of effective principal quantum number n* approximately 7-93 by VUV excitation prior to IR-induced autoionization. The observed VUV-IR-PIRI spectra are found to be independent of n*, suggesting that the electron Rydberg orbital is conserved, i.e., the Rydberg electron is behaving as a spectator during the excitation process. The observed IR active C-H stretching vibrational frequencies nu12+ = 3072+/-5 cm(-1) for ClCH=CCl2+ and nu23+ =2908+/-3 cm(-1), nu25+ =2990+/-10 cm(-1) and nu30+ =3022+/-10 cm(-1) for trans-CH3CH=CHCH3+ are compared with predictions based on ab initio quantum-chemical procedures and density functional calculations.     

Rotationally resolved vacuum ultraviolet pulsed field ionization-photoelectron vibrational bands for HD+(X 2Sigmag+,v+=0-20)

The authors have obtained rotationally resolved vacuum ultraviolet pulsed field ionization-photoelectron (vuv-PFI-PE) spectrum of HD in the photon energy range of 15.29-18.11 eV, covering the ionization transitions HD+(X 2Sigmag+,v+=0-21,N+)<--HD(X 1Sigmag+,v"=0,J"). The assignment of rotational transitions resolved in the vuv-PFI-PE vibrational bands for HD+(X 2Sigmag+,v+=0-20) and their simulation using the Buckingham-Orr-Sichel (BOS) model are presented. Rotational branches corresponding to the DeltaN=N+-J"=0, +/-1, +/-2, +/-3, and +/-4 transitions are observed in the vuv-PFI-PE spectrum of HD. The BOS simulation shows that the perturbation of vuv-PFI-PE rotational line intensities due to near resonance autoionization is very minor at v+>or=5 and decreases as v+ is increased. Thus, the rotationally resolved PFI-PE bands for HD+(v+>or=5) presented here provide reliable estimates of state-to-state cross sections for direct photoionization of HD, while the rotationally resolved PFI-PE bands for HD+(v+<5) are useful data for fundamental understanding of the near resonance autoionizing mechanism. On the basis of the rovibrational assignment of the vuv-PFI-PE bands, the ionization energies for the formation of HD+(X 2Sigmag+,v+=0-20,N+) from HD(X 1Sigmag+,v"=0,J") and the vibrational constants (omegae, omegaechie, omegaeye, and omegaeze), the rotational constants (Be and alphae), the vibrational energy spacings, and the dissociation energy for HD+(X 2Sigmag+) are determined. As expected, these values are found to be in excellent agreement with high level theoretical predictions.     

气相CBr2 自由基的产生及激光诱导荧光色散谱研究

利用双层流动反应管作为束源,研究了F与CH2Br2反应生成的CBr2和Br2的气相激光诱导荧光色散谱,将得到的谱线分别指定为CBr2的(0,13,0)→(0,v2″,0)(v2″=1～6)跃迁和Br2的 3Π+u→ 1Σ+g跃迁,从光谱中首次得到气相CBr2自由基基态弯曲振动频率ν2″=215 cm-1,实验确认了CBr2自由基和Br2是F+CH2Br2过程多步反应的产物.     

A combined VUV synchrotron pulsed field ionization-photoelectron and IR-VUV laser photoion depletion study of ammonia

The synchrotron based vacuum ultraviolet-pulsed field ionization-photoelectron (VUV-PFI-PE) spectrum of ammonia (NH(3)) has been measured in the energy range 10.12-12.12 eV using a room-temperature NH(3) sample. In addition to extending the VUV-PFI-PE measurement to include the v(2)(+) = 0, 10, 11, 12, and 13 and the v(1)(+) + nv(2)(+) (n = 4-9) vibrational bands, the present study also reveals photoionization transition line strengths for higher rotational levels of NH(3), which were not examined in previous PFI-PE studies. Here, v(1)(+) and v(2)(+) represent the N-H symmetric stretching and inversion vibrational modes of the ammonia cation (NH(3)(+)), respectively. The relative PFI-PE band intensities for NH(3)(+)(v(2)(+)=0-13) are found to be in general agreement with the calculated Franck-Condon factors. However, rotational simulation indicates that rotational photoionization transitions of the P-branches, particularly those for the lower v(2)(+) PFI-PE bands, are strongly enhanced by forced rotational autoionization. For the synchrotron based VUV-PFI-PE spectrum of the origin band of NH(3)(+), rotational transition intensities of the P-branch are overwhelming compared to those of other rotational branches. Similar to that observed for the nv(2)(+) (n = 0-13) levels, the v(1)(+) + nv(2)(+) (n = 4-9) levels are found to have a positive anharmonicity constant; i.e., the vibrational spacing increases as n is increased. The VUV laser PFI-PE measurement of the origin band has also been made using a supersonically cooled NH(3) sample. The analysis of this band has allowed the direct determination of the ionization energy of NH(3) as 82158.2 +/- 1.0 cm(-1), which is in good accord with the previous PFI-PE and photoionization efficiency measurements. Using the known nd(v(2)(+)=1,1(0)<--0(0)) Rydberg series of NH(3) as an example, we have demonstrated a valuable method based on two-color infrared-VUV-photoion depletion measurements for determining the rotational character of autoionizing Rydberg states.     

Combined vacuum ultraviolet laser and synchrotron pulsed field ionization study of CH2BrCl

The pulsed field ionization-photoelectron (PFI-PE) spectrum of bromochloromethane (CH2BrCl) in the region of 85,320-88,200 cm-1 has been measured using vacuum ultraviolet laser. The vibrational structure resolved in the PFI-PE spectrum was assigned based on ab initio quantum chemical calculations and Franck-Condon factor predictions. At energies 0-1400 cm-1 above the adiabatic ionization energy (IE) of CH2BrCl, the Br-C-Cl bending vibration progression (nu1+=0-8) of CH2BrCl+ is well resolved and constitutes the major structure in the PFI-PE spectrum, whereas the spectrum at energies 1400-2600 cm-1 above the IE(CH2BrCl) is found to exhibit complex vibrational features, suggesting perturbation by the low lying excited CH2BrCl+(A 2A") state. The assignment of the PFI-PE vibrational bands gives the IE(CH2BrCl)=85,612.4+/-2.0 cm-1 (10.6146+/-0.0003 eV) and the bending frequencies nu1+(a1')=209.7+/-2.0 cm-1 for CH2BrCl+(X2A'). We have also examined the dissociative photoionization process, CH2BrCl+hnu-->CH2Cl++Br+e-, in the energy range of 11.36-11.57 eV using the synchrotron based PFI-PE-photoion coincidence method, yielding the 0 K threshold or appearance energy AE(CH2Cl+)=11.509+/-0.002 eV. Combining the 0 K AE(CH2Cl+) and IE(CH2BrCl) values obtained in this study, together with the known IE(CH2Cl), we have determined the 0 K bond dissociation energies (D0) for CH2Cl+-Br (0.894+/-0.002 eV) and CH2Cl-Br (2.76+/-0.01 eV). We have also performed CCSD(T, full)/complete basis set (CBS) calculations with high-level corrections for the predictions of the IE(CH2BrCl), AE(CH2Cl+), IE(CH2Cl), D0(CH2Cl+-Br), and D0(CH2Cl-Br). The comparison between the theoretical predictions and experimental determinations indicates that the CCSD(T, full)/CBS calculations with high-level corrections are highly reliable with estimated error limits of <17 meV.     

Effect of Vibrational Angular Momentum on the Lifetime of CS21B2(1Σ)State

Predissociation lifetimes of totally 13 vibrational levels in the 1B2 state of jet-cooled CS2 have been determined by simulating the rotational band contours of the PHOFEX spectrum in the range of 209. 5 ～ 216 nm, where the PHOFEX spectrum was obtained by monitoring the laser-induced fluorescence of CS fragment via the Q band head excitation of（A 1Π,v' = 0）&（X 1Σ + ,v" = 0）transition. In order to investigate the influence of vibrational angular momentum quantum number K of the excited 1B2 （ 1Σ + U ）state,the nozzle was heated to increase the hot-band transition intensities. The results indicate that,for levels with the same vibrational quantum number but different K numbers in the 1B2 （ 1Σ + u ）state of CS2 ,the lifetime decreases with the increasing of quantum number K, suggesting that the dissociation could be accelerated by K number.     

Infrared vacuum-ultraviolet laser pulsed field ionization-photoelectron study of CH3Br+ (X(2)E(3/2))

By preparing methyl bromide (CH3Br) in selected rotational levels of the CH3Br(X(1)A1; v1 = 1) state with infrared (IR) laser excitation prior to vacuum-ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) measurements, we have observed rotationally resolved photoionization transitions to the CH3Br(+)(X(2)E(3/2); v1(+) = 1) state, where v1 and v1(+) are the symmetric C-H stretching vibrational mode for the neutral and cation, respectively. The VUV-PFI-PE origin band for CH3Br(+)(X(2)E(3/2)) has also been measured. The simulation of these IR-VUV-PFI-PE and VUV-PFI-PE spectra have allowed the determination of the v1(+) vibrational frequency (2901.8 +/- 0.5 cm(-1)) and the ionization energies of the origin band (85 028.3 +/- 0.5 cm(-1)) and the v1(+) = 1 <-- v1 = 1 band (84 957.9 +/- 0.5 cm(-1)).     

Quantum defect theory of dipole and vibronic mixing in Rydberg states of CaF

The Rydberg spectra of CaF combine the simplicity of a single electron outside a doubly closed-shell Ca2+F- ion core with the exceptional polarity of the ion core. A global multichannel quantum defect (MQDT) fit to 612 previously assigned levels, 507 from n approximately = 12-18, N=0-14, v+=1, 97 from n approximately = 9-10, N=0-14, v+=2, and 8 from n approximately = 7, N=3-10, v+=3, produces the complete L=0-3 quantum defect matrix mu (with the exception of one element) and 19 of 20 elements of the partial differentialmu/differentialR matrix, as well as the molecular constants of the CaFX 1sigma+ state [omega(e)+=694.58(14), omega(e)x(e+)=2.559(40), B(e+)=0.373 07(16) cm(-1), and the v=0, N=0 to v(+)=0, N(+)=0 ionization energy, 46,996.40(8) cm(-1)]. This experimentally determined mu(R) matrix is unusual in the completeness of its representation of the spectrum of both core-penetrating and nonpenetrating Rydberg series, including both local perturbations and vibrational autoionization rates, as well as all dynamical processes encoded in the spectrum that result from the scattering (at negative energy) of the Rydberg electron off the Ca2+F- ion core. The MQDT theory is presented in a form that clarifies the relationships of the reaction (K) and phase (P) matrices of MQDT to effective Hamiltonian models for local interactions between accidentally near degenerate levels. In particular, a Hund's case (b) like representation of the Hamiltonian is described in which the rovibronic K matrix is diagonalized and the P matrix, which contains information about the v+, N+ eigenstates of the ion, becomes nondiagonal.     

A vacuum-ultraviolet laser pulsed field ionization-photoelectron study of sulfur monoxide (SO) and its cation (SO+)

Vacuum ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) spectroscopy has been applied to the study of the sulfur monoxide radical (SO) prepared by using a supersonically cooled radical beam source based on the 193 nm excimer laser photodissociation of SO(2). The vibronic VUV-PFI-PE bands for the photoionization transitions SO(+)(X(2)Π(1∕2); v(+) = 0) ← SO(X(3)Σ(-); v = 0); and SO(+)((2)Π(3∕2); v(+) = 0) ← SO(X(3)Σ(-); v = 0) have been recorded. On the basis of the semiempirical simulation of rotational branch contours observed in these PFI-PE bands, we have obtained highly precise ionization energies (IEs) of 83,034.2 ± 1.7 cm(-1) (10.2949 ± 0.0002 eV) and 83,400.4 ± 1.7 cm(-1) (10.3403 ± 0.0002 eV) for the formation of SO(+)(X(2)Π(1∕2); v(+) = 0) and SO(+)((2)Π(3∕2); v(+) = 0), respectively. The present VUV-PFI-PE measurement has enabled the direct determination of the spin-orbit coupling constant (A(0)) for SO(+)(X(2)Π(1∕2,3∕2)) to be 365.36 ± 0.12 cm(-1). We have also performed high-level ab initio quantum chemical calculations at the coupled-cluster level up to full quadruple excitations and complete basis set (CBS) extrapolation. The zero-point vibrational energy correction, the core-valence electronic correction, the spin-orbit coupling, and the high-level correction are included in the calculation. The IE[SO(+)(X(2)Π(1∕2,3∕2))] and A(0) predictions thus obtained are found to be in remarkable agreement with the experimental determinations.