Zn^(2+)和TiO_(2)合金化过程中不同成分占比对薄膜结构和光催化性能的影响

使用溶胶-凝胶法在单晶硅衬底上制备一批不同Zn^(2+)成分调节的TiO_(2)薄膜,观测Zn^(2+)和TiO_(2)合金化过程中光学和光催化性能的变化.X射线衍射光谱仪用于观测在合金化过程中薄膜的晶体结构变化并追踪ZnTiO_(3)化合物的形成.扫描电子显微镜、原子力显微镜用于观测合金化过程中因TiO_(2)晶格对Zn^(2+)溶解度有限而导致薄膜表面出现大量孔洞的现象.X射线光电子能谱和光学带隙用于观测Zn^(2+)与TiO_(2)合金化过程中电子结构层面的变化.最后,通过降解亚甲基蓝(MB)溶液,表明少量Zn^(2+)掺杂完全溶解在TiO_(2)中,并破坏TiO_(2)结晶质量.在Zn^(2+)的成分占比继续提高至15%的过程中,XPS峰形拟合结果验证了TiO_(2)对Zn^(2+)的溶解度有限,导致薄膜出现大量孔洞结构,薄膜的活性比表面积得以提升,同时Zn^(2+)可以有效地捕获光生e^(-)/h^(+).为了继续观察Zn^(2+)浓度对TiO_(2)的影响,将Zn^(2+)的浓度提升至40%,观察Zn^(2+)与TiO_(2)合金化过程中的现象.表明化合物ZnTiO_(3)的出现可以充当e^(-)/h^(+)的复合中心以及TiO_(2).占比的大幅下降导致合金化之后的薄膜光催化效率逐渐下降.

Plasma-assisted aerogel interface engineering enables uniform Zn^(2+)flux and fast desolvation kinetics toward zinc metal batteries

The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.

基于不同荧光发色基团的Zn^(2+)荧光探针的研究进展

荧光光谱法具有灵敏度高、选择性好、检出限低以及操作简单等特点,设计合成特异性识别和检测Zn^(2+)的荧光探针对化学、生物学、临床医学等研究具有十分重要的意义。以近年来文献报道的Zn^(2+)荧光探针为例,综述了基于不同荧光发色基团的Zn^(2+)荧光探针的作用机制、应用与发展前景,为Zn^(2+)荧光探针研究提供了参考(引用文献44篇)。

Self-assembled S-scheme In_(2.77)S_(4)/K^(+)-doped g-C_(3)N_(4)photocatalyst with selective O_(2) reduction pathway for efficient H_(2)O_(2) production using water and air

The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.

Sn-doped BiOCl nanosheet with synergistic H^(+)/Zn^(2+)co-insertion for“rocking chair”zinc-ion battery

The development of insertion-type anodes is the key to designing“rocking chair”zinc-ion batteries.However,there is rare report on high mass loading anode with high performances.Here,{001}-oriented Bi OCl nanosheets with Sn doping are proposed as a promising insertion-type anode.The designs of cross-linked CNTs conductive network,{001}-oriented nanosheet,and Sn doping significantly enhance ion/electron transport,proved via experimental tests and theoretical calculations(density of states and diffusion barrier).The H^(+)/Zn^(2+)synergistic co-insertion mechanism is proved via ex situ XRD,Raman,XPS,and SEM tests.Accordingly,this optimized electrode delivers a high reversible capacity of 194 m A h g^(-1)at 0.1 A g^(-1)with a voltage of≈0.37 V and an impressive cyclability with 128 m A h g^(-1)over 2500 cycles at 1 A g^(-1).It also shows satisfactory performances at an ultrahigh mass loading of 10 mg cm^(-2).Moreover,the Sn-Bi OCl//MnO_(2)full cell displays a reversible capacity of 85 m A h g^(-1)at 0.2 A g^(-1)during cyclic test.

Zn^(2+)/Zn和Fe^(3+)/Fe^(2+)的电化学行为及其在液流电池中的应用

锌铁液流电池采用成本低廉的锌、铁元素作为活性物质,有望成为下一代高性价比储能电池。本文利用循环伏安法测试锌、铁离子在碳毡电极表面的电化学活性,计算Zn^(2+)/Zn与Fe^(3+)/Fe^(2+)的扩散系数与反应速率常数。结果表明,锌离子与铁离子在多孔碳毡上具有良好的电化学性能,可以作为锌铁液流电池的活性物质。充放电测试结果表明,锌铁液流电池的充放电性能良好,它具有较高的电流效率、电压效率和能量效率。

连续识别Zn^(2+)和草甘膦荧光探针的合成与应用

以2-巯基苯并噻唑为原料,设计合成了一种结构简单的苯并噻唑类荧光探针2-[2-(苯并噻吩-2-基亚甲基)肼基]苯并噻唑(简称NSS),并通过FTIR、HRMS、^(1)HNMR、^(13)CNMR对其结构进行了表征。荧光光谱表明,在二甲基亚砜中,探针NSS实现了Zn^(2+)的“关-开”型检测,具有响应时间短(30 s)、特异性强、抗干扰性强等优点。探针NSS荧光强度与Zn^(2+)浓度(0~11μmol/L)呈现良好的线性关系,检出限达19.1 nmol/L,并与Zn^(2+)形成物质的量比为1∶1的络合物。同时,络合物NSS-Zn^(2+)对草甘膦呈现特异性的荧光猝灭响应,猝灭率达99.4%,检出限16.0 nmol/L(2.71 ng/mL),且不受其他有机磷农药的干扰。

Zn^(2+)与腐殖酸钠组合抑制剂对萤石、方解石浮选分离的影响及机理研究

常见的方解石型萤石矿由于方解石与萤石表面物理化学性质相似,两者的浮选分离较为困难。本文研究了ZnSO_(4)·7H_(2)O与腐殖酸钠组合抑制剂对萤石和方解石选择性分离浮选的影响,通过吸附量测定、XPS检测、红外光谱分析以及溶液化学计算进行了机理分析。实验结果表明,相比于单一腐殖酸钠抑制剂,当使用腐殖酸钠与ZnSO_(4)·7H_(2)O质量比为3∶1的组合抑制剂且其用量为20 mg/L、油酸钠用量为1.5×10^(-4)mol/L、pH为7的条件下,可使萤石、方解石浮选回收率之差由41.8百分点提高到70.31百分点。腐殖酸钠与Zn^(2+)发生化学反应生成的腐殖酸锌与单一抑制剂相较方解石表面腐殖酸根吸附量有所提高;而萤石表面腐殖酸根吸附量减少,更多活性位点与油酸钠结合,油酸钠的吸附量提高,进而提高了组合抑制剂在两种矿物表面的选择性吸附,最终达到浮选分离的目的。

Fabrication of Gd_(2)O_(3)-doped CeO_(2)thin films through DC reactive sputtering and their application in solid oxide fuel cells

Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.

Zn^(2+)-Ni^(2+)-Al^(3+)-类水滑石@Al薄膜制备及其光催化性能

含过渡金属元素的类水滑石(LDHs)材料在可见光催化领域显示了广泛应用前景.然而LDHs粉末在催化反应中难回收、易流失,不利于材料的循环利用.以铝板为基体,通过原位生长技术在基体表面原位生长Zn^(2+)-Ni^(2+)-Al^(3+)-LDHs,开辟制备Zn^(2+)-Ni^(2+)-Al^(3+)-LDHs@Al材料的新方法.研究表明,Zn^(2+)-Ni^(2+)-Al^(3+)LDHs薄膜在铝基底纵向生长,具有高取向性.LDHs结晶度较高,片层结构规整,极大暴露了LDHs催化活性较高的层板边缘.该薄膜材料具有较低禁带宽度、较高可见光催化活性.Zn^(2+)-Ni^(2+)-Al^(3+)-LDHs@Al能够有效降解甲基橙(MO)有机染料废水,多次循环后对染料的降解率可达98%.该材料极大的增强了对光的利用率,促进了光生电子和空穴对的分离和转移,提高了材料光催化活性,推动和强化了LDHs材料的循环利用及综合处理废水的能力,提高了其应用价值和应用范围,为LDHs材料的开发、设计及应用提供了新思路.

一种基于联萘酚和(R,R)-Salen的高分子荧光探针的合成及对Zn^(2+)的识别研究

利用Sonogashira偶联反应设计合成了一种含有联萘酚和(R,R)-Salen单元的共轭高分子荧光探针P-1,并通过核磁共振氢谱表征了其结构。荧光光谱分析实验结果表明,高分子荧光探针P-1对Zn^(2+)具有高选择性识别,表现出明显的荧光增强,检测限可达到28.11 nmol·L^(-1),因此,高分子荧光探针P-1也具有较高的灵敏度。

Boosting Zn^(2+)kinetics via the multifunctional pre-desolvation interface for dendrite-free Zn anodes

Aqueous zinc ion batteries(AZIBs)are an advanced secondary battery technology to supplement lithiumion batteries.It has been widely concerned and developed recently based on the element abundance and safety advantages.However,AZIBs still suffer from serious problems such as dendrites Zn,hydrogen evolution corrosion,and surface passivation,which hinder the further commercial application of AZIBs.Herein,an in-situ ZnCr_(2)O_(4)(ZCO)interface endows AZIBs with dendrite-free and ultra-low polarization by realizing Zn^(2+)pre-desolvation,constraining H2O-induced corrosio n,and boosting Zn^(2+)transport/deposition kinetics.The ZCO@Zn anode harvests an ultrahigh cumulative capacity of~20000 mA h cm^(-2)(cycle time:over 4000 h)at a high current density of 10 mA cm^(-2),indicating excellent reversibility of Zn deposition,Such superior performance is among the best cyclability in AZIBs.Moreover,the multifunctional ZCO interface improves the Coulombic efficiency(CE)to 99.7%for more than 2600 cycles.The outstanding electrochemical performance is also verified by the long-term cycle stability of ZCO@Zn//α-MnO_(2) full cells.Notably,the as-proposed method is efficient and low-cost enough to enable mass production.This work provides new insights into the uniform Zn electrodeposition at the scale of interfacial Zn^(2+)predesolvation and kinetics improvement.

焙烧镁铝类水滑石对Cd^(2+)、Cu^(2+)、Zn^(2+)的吸附性能研究

通过控制变量法考察温度、浓度对焙烧镁铝类水滑石得到的层状双金属氧化物(LDO)吸附Cd^(2+)、Cu^(2+)、Zn^(2+)单一离子及其共存体系的影响。结果表明,LDO对单一离子吸附效果均较好,温度升高,有利于LDO吸附Cd^(2+)、Cu^(2+)、Zn^(2+);Cu^(2+)-Cd^(2+)、Cd^(2+)-Zn^(2+)共存时,LDO吸附效果为Cu^(2+)> Cd^(2+)、Zn^(2+)> Cd^(2+);三者共存时,LDO吸附效果为Cu^(2+)> Zn^(2+)> Cd^(2+)。

光谱法研究Zn^(2+)与TEVp之间的相互作用

为了探究金属离子对TEVp结构和功能的影响,促进TEVp在去除重组蛋白融合标签中的应用,采取荧光光谱、圆二色谱等光谱方法研究TEVp与Zn^(2+)之间的相互作用。紫外光谱及内源荧光实验结果表明,TEVp与Zn^(2+)的相互作用为静态淬灭机制。同步荧光光谱、三维荧光光谱以及圆二色谱实验结果表明,TEVp与Zn^(2+)的结合会引起蛋白构象发生改变,导致TEVp的β-折叠结构降低,α-螺旋结构增加,蛋白色氨酸残基微环境发生改变,造成疏水性增强、极性减弱。

Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene

Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.

淡水小球藻清除Cu^(2+)、Cd^(2+)、Zn^(2+)污染能力的研究

用接种密度(n/mL-1)为498×104的淡水小球藻对含Cu2+、Cd2+、Zn2+的水体分别处理,观察了藻细胞对上述3种离子的清除能力,并用金鱼存活检测了结果。结果表明:(1)淡水小球藻对不同密度的Cu2+、Cd2+、Zn2+都有清除能力,Cu2+的密度在0.094~0.484 mol/L时,清除率为61%~84.5%;Cd2+的密度在0.053~0.32mol/L时,清除率为45.90%~78.20%;Zn2+的密度在0.077~0.466 mol/L时,清除率为61.80%~84.80%。(2)淡水小球藻Cu2+、Cd2+和Zn2+良好工作浓度分别为0.094~0.484 mol/L、0.053~0.32 mol/L和0.077~0.466mol/L。其中,Zn2+的清除能达到国家污染物排放的二级标准。

重金属Zn^(2+)、Cd^(2+)对青蛤幼贝的致毒效应

采用静态急性毒性试验的方法,研究了96h内海水中重金属离子Zn2+、Cd2+的不同浓度及其交互作用对青蛤幼贝存活的影响。结果表明:Zn2+和Cd2+对青蛤幼贝的96h LC50和安全浓度分别为160mg/L、14mg/L和1.60mg/L、0.14mg/L;而二种离子的交互作用表现为二者间存在拮抗作用,其中,Zn2+的毒性略大于Cd2+。

幼刺参不同部位对Zn^2＋、Cu^2＋的蓄积动力学研究

以幼刺参为实验材料,在10℃、15℃、20℃条件下测定其体壁、消化道及呼吸树中Zn2+、Cu2+的蓄积量、蓄积速率及浓缩系数。研究发现,10℃时,Zn2+于第8 d在刺参体壁、消化道达到蓄积顶点,最大蓄积量分别为245.48×10-6和973.35×10-6;Cu2+于15℃,第8 d在幼刺参体壁和消化道达到最大蓄积量,分别为9.34×10-6和59.65×10-6;20℃时,Cu2+于第8d在呼吸树达到最大蓄积量,为622.37×10-6。研究表明,刺参消化道对Zn2+的蓄积大于体壁的蓄积,刺参呼吸树对Cu2+的蓄积大于消化道和体壁的蓄积。同时,温度显著影响Zn2+、Cu2+的蓄积。为了更好地理解Zn2+、Cu2+不同温度下在幼参体内的蓄积过程,本研究采用经典的非线性最小二乘估计原理构建数学模型,很好地模拟了重金属在不同的组织中随时间变化的动力学过程。

Cu^(2+)、Cd^(2+)、Zn^(2+)对两种单胞藻的毒害作用

分别用不同浓度 (c =0 .0 1～ 2 .34mmol/L)的Cu2 + 、Cd2 + 、Zn2 + 处理亚心型大扁藻 (Plztymonassp.)和小球藻(Chlorelavulagris) ,观察了重金属离子对其生长、呼吸及其被富集的情况 .结果表明 :① 3种离子的毒性强度的顺序为Cu2 + >Cd2 + >Zn2 + ;亚心型大扁藻的耐受力大于小球藻 ;②Cu2 + 对生长的抑制最强 ,两种藻的c(EC50 ,72h)分别为 0 .2 11mmol/L和 0 .2 89mmol/L ;Cd2 + 对生长的抑制稍弱 ,两种藻的c(EC50 ,72h)分别为 0 .4 38mmol/L和 0 .2 4 1mmol/L ;Zn2 + 对生长的抑制最弱 ,其c(EC50 ,72h)分别为 0 .75 4mmol/L和 0 .30 8mmol/L ;③在c(EC50 )毒害浓度下 ,两种单胞藻均提前进入生长静止期 ,缩短了种群生长周期 ;呼吸作用先增强后降低 ;④在c(EC50 )毒害浓度下 ,两种藻对Cu2 + 、Zn2 + 的富集量为 4 5 82～ 4 12 83.7mgkg-1,对Cd2 + 的富集量 5 0 0～ 2 72 3.6mgkg-1.图 2表 3参

Zn^(2+)胁迫对小麦幼苗生理活性影响的研究

以郑州9023为供试材料,采用室内水培方法,研究了不同浓度Zn2(+0、30、60、120、240、360mg·L-1)对小麦幼苗生理活性的影响,初步阐明了Zn2+对小麦幼苗的毒害机理。结果表明,在Zn2+胁迫下,随处理浓度的升高,小麦幼苗叶片中超氧阴离子自由基(O·2-)含量、丙二醛(MDA)含量、可溶性糖含量、抗坏血酸过氧化物酶(APX)及过氧化物酶(POD)活性均呈上升趋势,超氧化物歧化酶(SOD)活性呈先下降后上升的趋势;抗坏血酸(ASA)含量、过氧化氢酶(CAT)活性均呈现先上升后下降的趋势,可溶性蛋白和叶绿素含量呈下降趋势。对SOD、POD、CAT同工酶的聚丙烯酰胺凝胶电泳结果分析表明,正常情况下,小麦幼苗叶片主要表达Rf值(相对迁移率)分别为0.98、0.96、0.9、0.8、0.6、0.48的6条SOD同工酶带;POD同工酶带主要分为5区,至少包括10条同工酶酶带;CAT主要表达2条同工酶带。浓度小于120mg·L-1的Zn2+抑制SOD同工酶的表达,促进CAT同工酶的表达,浓度大于240mg·L-1的Zn2+促进SOD同工酶的表达,抑制CAT同工酶的表达,Zn2+诱导小麦幼苗中POD同工酶的表达。Zn2+没有诱导新的CAT、SOD和POD同工酶的表达。