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.     

双离子液体基多孔炭的制备与电化学性能

以质子型离子液体1-氢-3-乙烯基咪唑硫酸氢盐(HVIm HSO₄)为主炭源,以1-丁基-3-甲基咪唑六氟磷酸盐(BMImPF₆)为助剂,在氮气气氛、1000℃下一步炭化得到氮、磷、硫共掺杂多孔炭.通过N₂吸附-脱附、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、拉曼光谱(Raman)、热重分析(TGA)和X射线光电子能谱(XPS)等技术对多孔炭进行了分析表征.结果表明,多孔炭的孔结构以微孔为主,最高比表面积可达1111 m²/g,其微晶结构中无定形碳和石墨化碳并存;多孔炭中的氮主要以季氮(N-Q)、吡咯氮(N-5)和吡啶氮(N-6)的形式存在,磷以磷-氧(N—O—P)键合形式为主,硫主要以噻吩硫(C—S—C)为主.在6 mol/L KOH溶液、三电极体系中,多孔炭在0. 5 A/g电流密度下的比电容为138 F/g;在10 A/g电流密度下的比电容为100 F/g;在2 A/g电流密度下循环充放电10000次,其比电容保持率为95. 8%,显示出良好的电化学性能.     

Fe掺杂g-C_3N_4的制备及其可见光催化性能

以硝酸铁和三聚氰胺为原料制备不同含铁量的Fe掺杂石墨氮化碳(g-C3N4).采用X射线衍射光谱(XRD)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FT-IR)光谱、电感耦合等离子体-原子发射光谱(ICP-AES)、荧光(PL)光谱、X光电子能谱(XPS)等分析手段对制备的催化剂进行了表征.结果表明,铁以离子形式镶嵌在gC3N4的结构单元中,影响了g-C3N4的能带结构,增加了g-C3N4对可见光的吸收,降低了光生电子-空穴对的复合几率.以染料罗丹明B的降解为探针反应系统研究了不同含铁量对g-C3N4在可见光下催化性能的影响.结果表明,m(Fe)/m(g-C3N4)=0.14%时,制备的Fe掺杂g-C3N4表现出最佳的光催化性能,120 min内罗丹明B的降解率高达99.7%,速率常数达到0.026 min-1,是纯g-C3N4的3.2倍.以叔丁醇、对苯醌、乙二胺四乙酸二钠为自由基(·OH)、自由基(O2-·)和空穴(h+VB)的捕获剂,研究了光催化反应机理.     

溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

In this work, graphitic carbon nitride (g-C₃N₄) with large surface area and many nitrogen vacancies was synthesized by introducing ionic liquid[Bmim]Br as a solvent into the solvothermal post-treatment. X-ray diffraction (XRD), N₂ adsorption, scanning electron microscopy (SEM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), temperature-programmed desorption of N₂ (N₂-TPD), and photoluminescence (PL) spectroscopy were used to characterize the prepared catalysts. The morphology of the as-prepared g-C₃N₄ was markedly changed from an orderless layered structure to nanoparticles with a uniform size distribution of around 30-40 nm after the introduction of[Bmim]Br, leading an increase in surface area from 8.6 to 37.9 m²·g^-1. N₂-TPD, photoluminescence spectra, and density functional theory (DFT) simulations indicated that the nitrogen vacancies not only trapped the photogenerated electrons to enhance their separation rate, but also served as active sites for the adsorption and activation of N₂ molecules. The increased surface area of the as-prepared g-C₃N₄ meant that more nitrogen vacancies were exposed on the surface, leading to a markedly promoted nitrogen photofixation ability. The possible reaction mechanism is proposed.     

Adsorption of CO2 and H2 on Nitrogen-doped Porous Carbon from Ionic Liquid Precursor

Nitrogen-doped mesoporous carbon material was prepared via a simple one-step thermolysis method via the carbonization of ionic liquid, 1-cyanomethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([MCNIm]⁺[Nf₂T]^-). The nanostructure of the resultant carbon material was characterized by X-ray diffraction(XRD) and transmission electron microscopy(TEM) and the types of N-containing groups of the carbon material were investigated by X-ray photoelectron spectroscopy(XPS). The N-content of the carbon material is 18.6%(mass fraction) based on the elemental analysis. The produced mesoporous carbon material was further used as the solid sorbent for H₂ and CO₂. The hydrogen uptake capacity and H₂ isosteric heat of the carbon material were discussed. Furthermore, the nitrogen-containing carbon material as good sorbent shows relatively high adsorption and separation ability for CO₂ from CH₄, for which the heat of CO₂ adsorption(Q_st) is 31.8 kJ/mol. The mesoporous structure and nitrogen functionality make the carbon material with high adsorption capacity and selectivity for CO₂ and ability to store H₂, indicating that this kind of nitrogen-doped carbon material originated from ionic liquids is a promising sorbent material for high-performance separation and adsorption.     

Synthesis and Characterization of [Cu(N-MeIm)4(BF4)2] in Ionic Liquid

A new transition metal complex, [Cu(N-MeIm)₄(BF₄)₂](N-MeIm=N-methylated imidazoles, BF₄= tetrafluoroborate), was synthesized via the solvothermal method in ionic liquid. The ionic liquid acts as thermal decomposition reaction medium, soft temple agent and ligand compound. The central Cu(II) ion is coordinated by four N atoms from four N-methylated imidazole ligands, and the four N-methylated imidazole rings are perpendicular to each other. The crystal structure of [Cu(N-MeIm)₄(BF₄)₂] was determined by single crystal X-ray diffraction. The results of thermogravimetry(TG) and Fourier transform infrared spectrometry(FTIR) analyses were in accordance with that of crystal structure. The complex showed strong ligand-based absorbance with maximum wavelength at 208 and 231 nm, which are attributed to π-π^* transition of the N-methylated imidazole ligands.     

Potential active sites of Mo single atoms for electrocatalytic reduction of N2

Single atom catalysts(SACs) with isolated metal atoms dispersed on supports exhibit distinctive performances for electrocatalysis reactions.The designable realization of well-dispersed single metal atoms is still a great challenge owing to their ease of aggregation.Here,Mo single atomic sites(Mo-N₃C)combined with some ultrasmall Mo₂C/MoN clusters(Mo-SA/Mo₂C-MoN-Cs,mean diameter <2 nm) on nitrogen-doped porous carbon were synthesized via a simple pyrolysis of bimetallic Zn/Mo metalorganic frameworks.X-ray absorption near edge spectra(XANES) in combination with various characterizations show that most of Mo species in sample exist in the form of single sites and the exact structure is Mo-N₃C.Density functional theory(DFT) calculation further shows that as the number of Ncoordination in the Mo-NxC moieties increases,the positive cha rge of Mo atoms increases.The single Mo atoms in Mo-N₃C have the best capability of N₂ adsorption,which may serve as main active sites for further electrochemical N2 reduction.     

离子液体溶胀对煤直接液化残渣结构及热解性能的影响

采用四种相同阴离子不同有机链长阳离子的离子液体([EMIM][MeSO_4]、[BMIM][MeSO_4]、[HMIM][MeSO_4]和[OMIM][MeSO_4])对煤直接液化残渣(DCLR)进行溶胀处理,通过SEM、FT-IR和TG-DTG表征,分析了各离子液体溶胀对煤直接液化残渣溶胀效果、表面形貌、官能团分布、主体结构和热解性能的影响。溶胀结果表明,不同链长离子液体对煤直接液化残渣具有不同的溶胀效果,[HMIM][MeSO_4]对残渣溶胀效果最好,其溶胀度高达1.78。FT-IR表明,不同链长离子液体会不同程度地破坏煤中C-H键,使得脂肪族和芳香族类化合物的相对含量有所差异。由TG-DTG可知,不同链长离子液体溶胀对残渣热解性能的影响具有较大差异,其中,以离子液体[OMIM][MeSO_4]溶胀对残渣的热解最为有利,失重率高达47.5%;而离子液体[BMIM][MeSO_4]溶胀在一定程度上抑制了残渣的热解,其失重率低于未经溶胀处理的残渣。基于Coats-Redfern法的热解动力学分析表明,煤直接液化残渣及其溶胀残渣在低温段(180-480℃)的热解过程均符合二级反应动力学,高温段(480-825℃)均以三级和四级反应动力学为宜。另外,不同链长离子液体溶胀处理明显改变了残渣的热解活化能,其链越长残渣的热解活化能越高。     

纳米银/二维石墨相氮化碳/还原氧化石墨烯复合材料的制备及其光催化降解抗生素

为优化石墨相氮化碳(g-C₃N₄)光催化剂的结构,改善其对污染物的降解性能,本文以三聚氰胺为前驱体,通过高温煅烧和热氧化剥离制备了二维石墨相氮化碳(2D-C₃N₄),并用光还原法一步合成纳米银/二维石墨相氮化碳/还原氧化石墨烯(Ag/2D-C₃N₄/rGO)复合光催化剂。通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)、光致发光光谱(PL)、X射线光电子能谱(XPS)、氮气吸附脱附等温曲线(BET)等对材料进行表征。 以头孢曲松钠为目标污染物,探究pH值、催化剂用量、头孢曲松钠初始浓度等因素对催化剂的吸附、降解性能的影响,并探究降解反应机理。 当pH=6.0,催化剂用量为0.3 g/L,头孢曲松钠初始浓度为10.0 mg/L时,复合材料对头孢曲松钠的降解率可达到89.1%。 催化剂的稳定性较强,具有实际应用价值,可用于处理含头孢类抗生素的废水。     

石墨相氮化碳纳米管的合成及光催化产氢性能

通过硬模板法,采用氰胺前驱物和二氧化硅纳米管(SiO₂-NTs)模板,合成石墨相氮化碳纳米管(CN-NTs)光催化剂。采用扫描电镜(SEM)、透射电镜(TEM)、X射线粉末衍射(XRD)、傅立叶变换红外光谱(FT-IR)、氮气吸附/脱附测试、紫外可见漫反射光谱(UV-Vis DRS)、荧光光谱、热重分析(TGA)等手段对CN-NTs催化剂的结构与性能进行表征。结果表明,CN-NTs的化学组成是石墨相氮化碳(g-C₃N₄),形貌为均匀的纳米管,且是介孔材料。与体相氮化碳(B-CN)和介孔石墨相氮化碳(mpg-CN)相比,CN-NTs的光吸收带边蓝移到440 nm,荧光发射谱的峰强减弱。在可见光(λ>420 nm)照射下,CN-NTs具有较高的光催化分解水活性,产氢速率为58 μmol/h,且表现出良好的光催化活性稳定性和化学结构稳定性。研究结果表明纳米管状结构能有效促进g-C₃N₄半导体激子解离,提高光生电子-空穴的分离效率,进而显著优化g-C₃N₄的光催化产氢性能。     

Synthesis of Gd-N Codoped Porous TiO2 Photocatalyst and Its Enhanced Photocatalytic Activities

Visible-light-active Gd-N codoped porous TiO₂(Gd-N-TiO₂) photocatalyst was fabricated by an evapora-tion-induced self-assembly route using surfactants as structure-directed agents. As-prepared samples were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy(TEM), X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller(BET) method, and ultraviolet-visible absorption spectroscopy. The results indicated that synergistic reaction occurred when codoping with Gd³⁺ and N, which enhanced the light absorption properties of TiO₂. Irregular worm-like particles with wide interparticle spaces were clearly observed by TEM. The average particle size of Gd-N-TiO₂ decreased to ca. 8 nm because co-doping inhibited the particles growth significantly. Thus, the specific surface area of Gd-N-TiO₂(198.7 m²/g) was higher than that of Degussa P25 TiO₂(50 m²/g). Gd-N-TiO₂ exhibited a high photocatalytic activity toward methyl orange degradation under UV-Vis or visible-light irradiation. The Gd-N-TiO₂ catalyst also presented a stable performance without losing activity after four successive photocatalytic experiments. The facile synthesis and excellent activity of Gd-N-TiO₂ indicated its great potential as industrial catalysts for wastewater treatment.