Neutral and metallic vs.charged and semiconducting surface layer in acceptor doped CeO_(2)

The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.

Memristive feature and mechanism induced by laser-doping in defect-free 2D semiconductor materials

Memristors as non-volatile memory devices have gained numerous attentions owing to their advantages in storage,in-memory computing, synaptic applications, etc. In recent years, two-dimensional(2D) materials with moderate defects have been discovered to exist memristive feature. However, it is very difficult to obtain moderate defect degree in 2D materials, and studied on modulation means and mechanism becomes urgent and essential. In this work, we realized memristive feature with a bipolar switching and a configurable on/off ratio in a two-terminal MoS_(2) device(on/off ratio ~100), for the first time, from absent to present using laser-modulation to few-layer defect-free MoS_(2)(about 10 layers), and its retention time in both high resistance state and low resistance state can reach 2×10^(4) s. The mechanism of the laser-induced memristive feature has been cleared by dynamic Monte Carlo simulations and first-principles calculations. Furthermore, we verified the universality of the laser-modulation by investigating other 2D materials of TMDs. Our work will open a route to modulate and optimize the performance of 2D semiconductor memristive devices.

Selective core-shell doping enabling high performance 4.6 V-LiCoO_(2)

Constructing robust surface and bulk structure is the prerequisite for realizing high performance high voltage LiCoO_(2)(LCO).Herein,we manage to synthesize a surface Mg-doping and bulk Al-doping coreshell structured LCO,which demonstrates excellent cycling performance.Half-cell shows 94.2%capacity retention after 100 cycles at 3.0-4.6 V(vs.Li/Li^(+))cycling,and no capacity decay after 300 cycles for fullcell test(3.0-4.55 V).Based on comprehensive microanalysis and theoretical calculations,the degradation mechanisms and doping effects are systematically revealed.For the undoped LCO,high voltage cycling induces severe interfacial and bulk degradations,where cracks,stripe defects,fatigue H2 phase,and spinel phase are identified in grain bulk.For the doped LCO,Mg-doped surface shell can suppress the interfacial degradations,which not only stabilizes the surface structure by forming a thin rock-salt layer but also significantly improves the electronic conductivity,thus enabling superior rate performance.Bulk Al-doping can suppress the lattice"breathing"effect and the detrimental H3 to H1-3 phase transition,which minimizes the internal strain and defects growth,maintaining the layered structure after prolonged cycling.Combining theoretical calculations,this work deepens our understanding of the doping effects of Mg and Al,which is valuable in guiding the future material design of high voltage LCO.

Durable hierarchical phosphorus‐doped biphase MoS_(2)electrocatalysts with enhanced H^(*)adsorption

Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.

Unveiling the pressure-driven metal–semiconductor–metal transition in the doped TiS_(2)

Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.

Co-doped BaFe_(2)As_(2) Josephson junction fabricated with a focused helium ion beam

Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation of high-quality iron pnictide Josephson junctions is of great importance.In this work,we have successfully fabricated Josephson junctions from Co-doped BaFe_(2)As_(2)thin films using a direct junction fabrication technique which utilizes high energy focused helium ion beam(FHIB).The electrical transport properties were investigated for junctions fabricated with various He^(+)irradiation doses.The junctions show sharp superconducting transition around 24 K with a narrow transition width of 2.5 K,and a dose correlated foot-structure resistance which corresponds to the effective tuning of junction properties by He^(+)irradiation.Significant J_c suppression by more than two orders of magnitude can be achieved by increasing the He^(+)irradiation dose,which is advantageous for the realization of low noise ion pnictide thin film devices.Clear Shapiro steps are observed under 10 GHz microwave irradiation.The above results demonstrate the successful fabrication of high quality and controllable Co-doped BaFe_(2)As_(2)Josephson junction with high reproducibility using the FHIB technique,laying the foundation for future investigating the mechanism of iron-based superconductors,and also the further implementation in various superconducting electronic devices.

Enhanced stability of FA-based perovskite:Rare-earth metal compound EuBr_(2) doping

It is highly desirable to enhance the long-term stability of perovskite solar cells(PSCs)so that this class of photovoltaic cells can be effectively used for the commercialization purposes.In this contribution,attempts have been made to use the two-step sequential method to dope EuBr_(2)into FAMAPbI_(3)perovskite to promote the stability.It is shown that the device durability at 85℃in air with RH of 20%-40%is improved substantially,and simultaneously the champion device efficiency of 23.04%is achieved.The enhancement in stability is attributed to two points:(ⅰ)EuBr_(2)doping effectively inhibits the decomposition andα-δphase transition of perovskite under ambient environment,and(ⅱ)EuBr_(2)aggregates in the oxidized format of Eu(BrO_(3))_(3)at perovskite grain boundaries and surface,hampering humidity erosion and mitigates degradation through coordination with H_(2)O.

Small but mighty:Empowering sodium/potassium-ion battery performance with S-doped SnO_(2) quantum dots embedded in N,S codoped carbon fiber network

SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish reaction kinetics,low electronic conductivity,and large volume changes during charge and discharge hinder the practical applications of SnO_(2)-based electrodes for SIBs and PIBs.Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges.Herein,S-doped SnO_(2)(S-SnO_(2))quantum dots(QDs)(≈3 nm)encapsulated in an N,S codoped carbon fiber networks(S-SnO_(2)-CFN)are rationally fabricated using a sequential freeze-drying,calcination,and S-doping strategy.Experimental analysis and density functional theory calculations reveal that the integration of S-SnO_(2) QDs with N,S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO_(2)-CFN,and the S doping can increase the conductivity of SnO_(2),thereby enhancing the ion transfer kinetics.The synergistic interaction between S-SnO_(2) QDs and N,S codoped carbon fiber network results in a composite with fast Na+/K+storage and extraordinary long-term cyclability.Specifically,the S-SnO_(2)-CFN delivers high rate capacities of 141.0 mAh g^(−1) at 20 A g^(−1) in SIBs and 102.8 mAh g^(−1) at 10 A g^(−1) in PIBs.Impressively,it delivers ultra-stable sodium storage up to 10,000 cycles at 5 A g^(−1) and potassium storage up to 5000 cycles at 2 A g^(−1).This study provides insights into constructing metal oxide-based carbon fiber network structures for high-performance electrochemical energy storage and conversion devices.

蓝光激发的KMgF_(3)∶Cr^(3+)/Ni^(2+)基透明微晶玻璃超宽带近红外发光

近红外光谱技术在食品科学、信息安全、生物医疗等重大国计民生领域的应用对近红外光源提出了越来越高的要求。研发具有高效超宽带发射的近红外光源因此成为一项重要且迫切的研究课题。本文采用熔融淬火法在氟硅酸盐玻璃体系SiO_(2)-K_(2)CO_(3)-KF·2H_(2)O-MgF_(2)中成功析出了钙钛矿型KMgF_(3)纳米晶体。通过改变玻璃组分和热处理温度可以调控氟化物纳米晶相的析出,得到析晶和透明度最佳的微晶玻璃样品。玻璃中KMgF_(3)纳米晶体为Cr^(3+)和Ni^(2+)提供了稳定的八面体配位和低声子能量发光环境,在450 nm蓝光激发下,基于Cr^(3+)到Ni^(2+)的能量传递实现了Cr^(3+)(700~1200 nm)和Ni^(2+)(1400~1700 nm)双宽带近红外发射,并且双宽带近红外发光强度随离子掺杂浓度而可调变化。荧光光谱和荧光衰减曲线表征证明了Cr^(3+)到Ni^(2+)的能量传递过程,对应的能量传递效率为52.2%,能量传递机制为电子偶极-四极相互作用。研究结果不仅可以为系统掌握透明光学材料的超宽带发光规律提供基础数据,同时有助于设计开发低成本、高效率的近红外宽带光源。

Fe_(3)O_(4)/CS/EDTA对水溶液中Cu^(2+)和Ni^(2+)的吸附研究

分析了自制的Fe_(3)O_(4)/CS/EDTA纳米粒对水溶液中的重金属离子Cu^(2+)和Ni^(2+)的吸附性能和吸附机理。研究了pH值、溶液初始浓度、反应时间等对吸附性能的影响,结合红外、XPS和比表面分析结果确定了参与吸附配位的功能基团及可能发生的络合反应。结果表明:Fe_(3)O_(4)/CS/EDTA对Cu^(2+)和Ni^(2+)的吸附等温线均符合Langmuir模型,对Cu^(2+)的吸附效果要优于Ni^(2+),这可能与Ni^(2+)的离子半径较Cu^(2+)小以及Ni^(2+)与吸附剂形成的金属螯合物的稳定性较Cu^(2+)低有关;Fe_(3)O_(4)/CS/EDTA对Cu^(2+)和Ni^(2+)的吸附机理类似于N·O型螯合剂,并非一般的物理吸附,而是一种以金属离子为中心的吸附螯合。

5%Ag掺杂对MNO_(2)纳米棒和海胆微球形貌及其甲苯氧化性能的影响

采用水热法制备了MNO_(2)纳米棒和海胆微球,并原位掺杂5%Ag制备了Mn-Ag复合氧化物,利用SEM、XRD、BET、Raman等表征技术对其结构进行表征,并考察不同催化剂对甲苯的去除性能。结果表明:(NH_(4))_(2)S_(2)O_(8)的掺入量会对MNO_(2)的形貌产生影响,当其掺入量为2.28 g时,形成MNO_(2)纳米棒,当其掺入量为6.84 g时,形成MNO_(2)海胆微球;MNO_(2)纳米棒掺杂5%的Ag后,形貌未发生变化,但当MNO_(2)海胆微球掺杂5%Ag时,表面的纳米线较MNO_(2)海胆微球有所增长,且出现了缠绕现象,形成了空心鸟巢状结构;5%Ag掺杂后,对MNO_(2)纳米棒和MNO_(2)海胆微球的晶型未产生影响,均为α-MNO_(2),但5%Ag-MNO_(2)纳米棒出现了Mn2O_(3)的衍射峰;MNO_(2)海胆微球较MNO_(2)纳米棒的比表面积、孔径和孔容均增大,且Ag的掺杂进一步提高了MNO_(2)海胆微球的比表面积、孔径和孔容;MNO_(2)海胆微球比MNO_(2)纳米棒具有更好的甲苯去除性能,且5%Ag掺杂后,MNO_(2)海胆微球对甲苯的去除性能达到最好。

Al掺杂对SiO_(2)气凝胶耐高温特性的影响研究

SiO_(2)气凝胶具有成本低、制造工艺简单、化学性质稳定、密度小、超高比表面积等优点,是应用最广泛的高温保温隔热材料。以Si28和Si40为Si源,仲丁醇铝为Al源,乙醇为溶剂,采用酸碱催化、CO_(2)超临界干燥法制备了Al掺杂SiO_(2)气凝胶。结果表明:所得产品高温热处理后均为非晶态无定型结构,无掺杂SiO_(2)气凝胶线收缩率为24.34%,Al掺杂SiO_(2)气凝胶线收缩为14.05%,且在高温热处理后有较大的比表面积和孔体积,说明Al掺杂SiO_(2)气凝胶具有较好的耐高温性能和高温下的绝热性能,这是因为Al元素的掺入使气凝胶在形成过程中产生了很多细小的纳米空洞,热处理过程中Al-Si-O发生化学反应形成双金属氧化物,使气凝胶的氧化物骨架支撑力更强。

掺杂对2H-MoTe_(2)光电特性影响的第一性原理研究

MoTe_(2)是一种非空间反演对称性半导体,由线性偏振光照射,在无偏压条件下可以直接产生光电流,但是非常微弱.掺杂可以改变电子能带结构和降低空间反演对称性,从而有效的增强光电流.本文基于非平衡格林函数-密度泛函理论,采用第一性原理,计算了本征、Nb掺杂、Ti掺杂和W掺杂2H-MoTe_(2)的能带结构、透射谱和光电流.能带结构表明:Nb掺杂使半导体2H-MoTe_(2)能带穿越费米能级,转变为金属特性;Ti和W掺杂减小了2H-MoTe_(2)的带隙,能带没有穿越费米能级,依然为半导体.掺杂都降低2H-MoTe_(2)的反演对称对称性,从本征的D3h转变为Cs.从而在线偏振光的照射下可以有效的提高2H-MoTe_(2)的光电流.同时,发现掺杂可以提高单层2H-MoTe_(2)在低光子能量下的消光比,如Nb和Ti掺杂单层2H-MoTe_(2)分别在光子能量1.1 eV和1.2 eV处取得39.48和28.48的高消光比.这些结果表明掺杂可以有效增强单层2H-MoTe_(2)的光电流和消光比,可以应用于指导2H-MoTe_(2)在光电器件的设计,特别是在红外光探测领域增添了许多可能.

活性炭电极的改性及对Co^(2+),Mn^(2+)和Ni^(2+)的电吸附性能

以商用活性炭(AC)为原料,分别采用磷酸和氢氧化钠改性的方法制备了两种不同的改性活性炭电极材料.采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、Brunauer-Emmett-Teller(BET)测试、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)等手段以及电化学分析方法,对改性前后活性炭材料的表面性质和电化学性能进行了探究.结果表明,H_(3)PO_(4)改性使活性炭的孔隙分布更加密集,NaOH改性使活性炭表面的孔隙结构更加清晰均匀;H_(3)PO_(4)和NaOH改性均使活性炭的比表面积增加.循环伏安测试结果表明,改性前后活性炭电极在低扫描速率下均具备良好的双电层特性,并且两种改性处理均能提高活性炭电极的比电容;当扫描速率为5 mV/s时,未改性、H_(3)PO_(4)以及NaOH改性活性炭电极的比电容分别为36.51,77.25和85.19 F/g.电吸附实验结果证明,两种改性活性炭电极对Co^(2+),Mn^(2+)和Ni^(2+)均有较好的去除效果,电吸附过程均更加符合Langmuir模型,在初始浓度、电压和pH相同的条件下,NaOH改性电极对Co^(2+),Mn^(2+)和Ni^(2+)具有更高的去除率和吸附容量,去除率可分别达到96.84%,94.37%和96.90%,吸附容量分别为140.8,111.4和108.5 mg/g.

pH对δ-MnO_(2)吸附硫酸锰溶液中Co^(2+)、Ni^(2+)的影响

硫酸锰溶液中重金属离子的深度净化,一直是锰行业研究的热点和重点。利用X射线衍射(XRD)、扫描电镜(SEM)和红外光谱(FT-IR)等手段对所制备的δ-MnO_(2)进行表征,利用Visual Minteq软件模拟硫酸锰溶液中Mn、Co和Ni的离子形态随pH的变化关系,研究不同pH条件对δ-MnO_(2)吸附硫酸锰溶液中Co^(2+)、Ni^(2+)的影响。结果表明:δ-MnO_(2)结晶性较差,缺陷和空隙较多,表面羟基丰富。随着硫酸锰溶液pH升高,δ-MnO_(2)对于Co^(2+)和Ni^(2+)吸附率逐渐增加,Co^(2+)比Ni^(2+)更容易被吸附。在低pH下,δ-MnO_(2)吸附效果受结构缺陷和空隙影响,pH高于5时,在表面负电荷和羟基的共同作用下大量吸附Co^(2+)和Ni^(2+),Co^(2+)、Ni^(2+)吸附率最高达到99.98%、89.53%。对吸附后δ-MnO_(2)进行XRD和FT-IR分析进一步验证了吸附机理,为解决锰系电池原材料硫酸锰溶液中重金属杂质离子难去除问题提供一定基础。

改性TiO_(2)在光电协同下处理偶氮染料废水的研究进展

偶氮染料(AZO)是一类难被生物降解的水溶性高分子有机物,近些年来,由于良好的染色性能被广泛应用于印染等相关行业,但AZO废水一旦排入自然水体将会造成重大的环境污染问题。本文主要介绍了不同类型的改性TiO_(2)对AOZ废水的处理效果并分析了作用原理,对比分析了单一TiO_(2)与改性TiO_(2)的优缺点,积极探索改性TiO_(2)催化剂的催化机理,解析金属和非金属掺杂在其中的具体作用,为今后更加精准地控制掺杂金属或者非金属比例、提高催化剂效率提供科学依据和技术支持。

混凝强化型好氧颗粒污泥对Ni^(2+)吸附性能及机理研究

为强化好氧颗粒污泥(AGS)对重金属Ni^(2+)的吸附效能,利用聚合氯化铝(PAC)和天然混凝剂(SNC)的特性培养形成混凝强化型AGS,并探究AGS对Ni^(2+)的吸附性能及机理。结果表明:PAC型和SNC型AGS对Ni^(2+)均具有良好的吸附性能且存在特异性,Ni^(2+)质量浓度为0~25 mg/L时,PAC型AGS吸附效能较优;Ni^(2+)质量浓度为100~150 mg/L时,SNC型AGS吸附性能较优。模型拟合结果表明:混凝强化型AGS对Ni^(2+)的吸附以物理-化学吸附为主,对于吸附量及吸附速率,SNC型AGS均大于PAC型AGS。傅里叶红外变换光谱(FT-IR)结果表明,吸附过程中混凝强化型AGS存在大量羟基、羧基和氨基等基团与Ni^(2+)吸附结合,实现了Ni^(2+)的有效去除;同时,SNC能强化AGS中的官能团,提高吸附性能。

Carbon Doping Triggered Efficient Electrochemical Hydrogen Evolution of Cross-Linked Porous Ru-MoO_(2) Via Solid-Phase Reaction Strategy

The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).

改性多孔硅酸镁纳米材料对废水中Ni^(2+)的吸附性能

将十二烷基磺酸钠(SDS)改性的系列多级孔硅酸镁纳米材料(FMS)用于吸附工业废水中重金属离子Ni^(2+),采用电感耦合等离子发射光谱仪(ICP AES)测定吸附前后溶液中Ni^(2+)的浓度,对所测定的实验数据用动力学和Langmuir吸附模型进行拟合。根据系列改性材料表征数据和实验数据拟合结果,研究系列改性材料的吸附行为及其对Ni^(2+)的吸附效能与吸附材料比表面积、孔结构等性质之间的构效关系。结果表明:孔径和比表面积更大的5 FMS(FMS中添加5%(质量分数)SDS)对Ni^(2+)的平衡吸附量最大,可达231.62 mg/g;所有材料对Ni^(2+)的吸附行为均符合拟二级动力学模型,表明化学吸附在吸附过程中占主导地位;同时所有材料对Ni^(2+)的吸附较好地符合Langmuir吸附模型,即为单分子层均匀吸附,其中5 FMS理论吸附量最大,为280.40 mg/g;该系列材料主要是通过静电吸附、表面金属离子(Mg^(2+))和酸性基团与溶液中Ni^(2+)交换达到去除Ni^(2+)的目的。

Ce掺杂Ni_(2)P纳米片的电子调控促进高效析氧

设计高效非贵金属析氧反应(OER)电催化剂对电化学能量转换具有非常重要的意义.本文通过水热法和煅烧法,成功制备了铈(Ce)掺杂磷化镍(Ni_(2)P)纳米片催化剂Ce-Ni_(2)P.微量Ce掺杂使催化剂表面产生丰富的磷空位,并显著调控了催化剂表面的电子结构,优化了催化活性位的化学价态.得益于Ce掺杂对催化剂表面的电子结构调控,Ce-Ni_(2)P催化剂在碱性电解液中表现出优异的OER性能和长期的稳定性.在50和100 mA/cm^(2)电流密度下,Ce-Ni_(2)P的OER过电位分别为241和281 mV,显著优于Ni_(2)P和商用RuO _(2)的过电位.