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.     

Ga对在AlN衬底上直接生长石墨烯的远程催化

通过镓(Ga)远程催化,采用化学气相沉积(CVD)方法在氮化铝(AlN)衬底上直接生长石墨烯薄膜.研究了生长温度、催化剂距离对石墨烯生长及其光学性质和电学性质的影响规律.结果表明,在生长温度1070℃下可以制备厚度约为5层的石墨烯薄膜, Ga周围1.4 cm范围内可以得到厚度均匀的石墨烯薄膜.通过透光率和方阻表征了石墨烯的光学和电学性质,结果表明, 400～800 nm波长范围内石墨烯薄膜透光率可达90%以上,方阻约为230Ω/.第一性原理计算结果表明,石墨烯仍保持金属性, AlN衬底对石墨烯有吸附掺杂作用,可有效降低石墨烯的方阻,改善石墨烯和衬底的电学接触.     

柔性透明石墨烯膜制备及导电性能研究

本文通过液相化学还原和热还原联合作用制备了柔性透明导电石墨烯膜.阳极氧化铝(AAO)模板在制备过程中既作为抽滤的滤网,又作为热还原处理时支撑石墨烯膜的衬底,制成的柔性透明石墨烯膜对波长为540—840 nm的可见光透光率为80%,面电阻为850 Ω/平方,这与化学气相沉积法制备的石墨烯膜(280—770 Ω/平方)相近,而低于溶液法制备的石墨烯膜(通常是10³—10⁴ Ω/平方).     

基于混合溶剂有机电解液的超低温孔洞石墨烯超级电容

适用于极低温环境的石墨烯超级电容具有广阔的应用前景。然而,由于片层间严重的堆叠团聚,目前石墨烯超级电容的低温储能性能并不理想。本文使用H₂O₂氧化刻蚀法制备了孔洞石墨烯(rHGO),将传统有机溶剂碳酸丙烯酯(PC)和低凝固点溶剂甲酸甲酯(MF)混合制备了混合溶剂有机电解液,组装获得了能够在-60 ℃极低温环境下稳定工作的超级电容。结果表明,该超级电容在-60 ℃下的比电容为106.2 F·g^-1,相对于常温电容(150.5 F·g^-1)的性能保持率高达70.6%,显著优于未做处理的石墨烯(52.3%)以及文献中的其他石墨烯材料。得益于孔洞化形貌中丰富的介孔和大孔所形成的离子传输通道和缩短的离子传输路径,孔洞石墨烯内的离子扩散阻抗远小于普通石墨烯,且受温度降低的影响更小。在-60 ℃的极低温条件下,该超级电容表现出26.9 Wh·kg^-1的最大能量密度和18.7 kW·kg^-1的最大功率密度,优于传统碳材料的低温超级电容性能。-60 ℃时在5 A·g^-1电流密度下循环充放电10000次后电容保持率达89.1%,具有良好的低温循环稳定性。     

柔性复合织物电极Graphene/Cotton和MnO2/Graphene/Cotton的合成及在电化学电容器中的应用

通过热还原法成功地制备出了柔性复合织物电极石墨烯/棉布(graphene/cotton)。热还原条件对电极的导电性能具有较大的影响。导电柔性织物电极graphene/cotton特有的多级结构使其既有利于进一步负载膺电容材料,又有利于电子和电解质离子的传输与扩散。通过电化学沉积方法,利用导电柔性织物电极graphene/cotton进一步制备出了电极MnO₂/graphene/cotton。利用扫描电子显微镜(SEM),傅里叶变换红外(FTIR)光谱,四探针测试法等表征技术对电极的结构进行了较为详细的表征。结果表明电极MnO₂/graphene/cotton的比电容可以达到536 F·g^-1。良好的电化学性能和柔性使得此类电极在柔性储能材料应用中具有极大的应用前景。     

Graphene arrested in laponite-water colloidal glass

Graphene production in water from graphite sources is an important technological route toward harvesting the unique properties of this material. Graphene forms thermodynamically unstable dispersions in water, limiting the use of this solvent due to aggregation. We show that graphene-water dispersions can be controlled kinetically to produce graphene by using laponite clay. Laponite exhibits rapid gelation kinetics when dispersed in water above its gelation concentration, allowing graphene aggregation to be halted after exfoliation in water at ambient conditions. The transparency of laponite colloidal glass and films is important in examining the extent of graphene exfoliation.     

石墨烯电子器件的研究进展

石墨烯是一种sp²杂化的平面类蜂窝型二维结构材料,特殊的结构赋予其许多优良的性能,如导电、导热性能好,载流子迁移率高和透射性好等,使其在电子器件领域表现出巨大潜力。 本文从石墨烯在三维集成电路中的应用、石墨烯场效应晶体管、石墨烯有机发光二极管及化学传感器四方面综述了石墨烯电子器件的研究进展及现状。     

石墨烯纤维材料的化学气相沉积生长方法

石墨烯纤维材料是以石墨烯为主要结构基元沿某一特定方向组装而成或由石墨烯包覆纤维状基元形成的宏观一维材料。根据组成基元的不同可将石墨烯纤维材料分为石墨烯纤维和石墨烯包覆复合纤维。石墨烯纤维材料在一维方向上充分发挥了石墨烯高强度、高导电、高导热等特点,在智能纤维与织物、柔性储能器件、便携式电子器件等领域具有广阔的应用前景。随着化学气相沉积(Chemical Vapor Deposition,CVD)制备石墨烯薄膜技术的发展,CVD技术也逐渐应用于石墨烯纤维材料的制备。利用CVD法制备石墨烯纤维可避免传统纺丝工艺中繁琐的氧化石墨烯(Graphene Oxide,GO)还原过程。同时,通过CVD法直接将石墨烯沉积至纤维表面可以保证石墨烯与纤维基底之间强的粘附作用,提高复合纤维的稳定性,同时可实现对石墨烯质量的有效调控。本文综述了石墨烯纤维材料的CVD制备方法,石墨烯纤维材料优异的力学、电学、光学性质及其在智能传感、光电器件、柔性电极等领域的应用,并展望了CVD法制备石墨烯纤维材料未来的发展方向。     

La2CuO4阴极薄膜的相转变及其对电化学性能的影响

通过调控薄膜的沉积条件,探索La₂CuO₄的晶体结构对电化学性质的影响。采用脉冲激光沉积设备在YSZ(100)单晶基底上沉积一系列La₂CuO₄薄膜,通过调节沉积时的氧压,制备了不同晶体结构的La₂CuO₄薄膜。 研究表明,沉积氧压的变化使薄膜晶体结构发生相转变,从T'相→T^*相→T相。 T'相为沿着c轴择优生长的单晶四方相,且表现出较大的界面极化电阻,在850 ℃的R_p值为2.351 Ω·cm²。 T^*相为T'相和T相的混合相,在850 ℃的电阻值介于T'相和T相之间。 T相为正交相,相对于其它相结构表现出较低的界面极化电阻,沉积氧压为26.60 Pa下制备的T相在850 ℃的电阻值为0.783 Ω·cm²,比T'相的电阻值低近67%。 并且,正交相表面有相对较高的氧空位浓度,有利于氧气的吸附和扩散,加速了阴极的氧还原反应。 因此,具有正交对称性的La₂CuO₄的电化学性质优于其它对称性。 这一结果也表明可以通过改变薄膜材料的晶体结构,降低界面极化电阻,提高阴极薄膜的电化学性能。     

Vanadium(IV) oxide thin films on glass and silicon from the atmospheric pressure chemical vapour deposition reaction of VOCl3 and water

The dual source atmospheric pressure chemical vapour deposition (APCVD) reaction of VOCl₃ and H₂O was used to prepare thin films of vanadium oxides on glass and silicon substrates. The thin films were characterised by X-ray diffraction, Raman spectroscopy X-ray photoelectron spectroscopy and scanning electron microscopy. At reactor temperatures above 600 °C with a gas-phase excess of water over VOCl₃, vanadium(IV) oxide thin films were produced which show a thermochromic transition temperature of 67 °C. The APCVD process is directly compatible with high throughput float-glass production enabling the use of a thin film of VO₂ as an intelligent window coating. With reactor temperatures below 600 °C or with a gas-phase excess of VOCl₃ over water, V₂O₅ thin films were produced. Vanadium(IV) oxide thin films could also be prepared on silicon substrates from the APCVD reaction of VOCl₃ and H₂O, which opens up further technological applications for the APCVD of VO₂ thin films.     

Thick titanium dioxide films for semiconductor photocatalysis

Thick paste TiO₂ films are prepared and tested for photocatalytic and photoinduced superhydrophilic (PSH) activity. The films are effective photocatalysts for the destruction of stearic acid using near or far UV and all the sol–gel films tested exhibited a quantum yield for this process of typically 0.15%. These quantum yields are significantly greater (4–8-fold) than those for titania films produced by an APCVD technique, including the commercial self-cleaning glass product Activ™. The films are mechanically robust and optically clear and, as photocatalysts for stearic acid removal, are photochemically stable and reproducible. The kinetics of stearic acid photomineralisation are zero order with an activation energy of ca. 2.5 kJ mol⁻¹. All titania films tested, including those produced by APCVD, exhibit PSH. The light-induced fall, and dark recovery, in the water droplet contact angle made with titania paste films are similar in profile shape to those described by others for thin titania films produced by a traditional sol–gel route.