共聚改性g-C3N4-N可见光催化降解RhB的研究

染料废水的排放对人类健康和生态系统构成严重威胁,光催化技术因其操作简单、绿色环保等优点在解决环境污染问题上已显示出巨大的潜力。类石墨相氮化碳（g-C₃N₄）由于成本低且具有良好的化学稳定性,被认为是光催化领域最有前景的新型光催化剂之一,但由于单一g-C₃N₄的比表面积小、可见光吸收能力低、光生电子-空穴复合率高影响了其光催化性能。以邻氨基苯甲腈和尿素为原料,通过高温共聚改性制备高催化活性的g-C₃N₄-N光催化剂,研究g-C₃N₄-N在不同pH值、g-C₃N₄-N投加量和RhB溶液浓度条件下对RhB光催化降解的影响,并结合红外光谱、XRD、BET、UV-Vis对g-C₃N₄-N光催化降解RhB的机理和染料降解路径进行解析。结果表明,经共聚改性制备的碳化氮为类石墨型纯相g-C₃N₄-N,具有稳定的光催化活性、大的比表面积和多孔结构,在初始pH值为3时,加入50 mg的g-C₃N₄-N在可见光条件下光催化降解10 mg·L-1 的RhB可达到最好的光催化降解效果,RhB在暗反应30 min内的吸附去除率可达30%左右,120 min的去除率达到97.7%。在光催化作用下,g-C₃N₄-N将吸附在光催化剂表面的罗丹明B分子通过快速N-脱乙基过程形成DER、EER和AR等大分子中间体,它们在空穴与·OH和·O-₂作用下,共轭结构裂解、开环,生成丁二酸、间苯二酚、丙酸等小分子,脱除的乙基被逐步氧化为乙二醇,这些小分子可以被转化为CO₂和H₂O。     

In situ formed FeS2@CoS cathode for long cycling life lithium-ion battery

Pyrite FeS₂ exhibits an ultrahigh energy density (1671 W·h·kg^-1, for the reaction of FeS₂+4Li=Fe+2Li₂S) in secondary lithium-ion batteries, but its poor cycling stability, huge volume expansion, the shuttle effect of polysulfides, and slow kinetic properties limit its practical application. In this work, we synthesize a composite structure material CoS on FeS₂ surface (FeS_x@CoS, 1 < x ≤ 2) by using a cobalt-containing MOF to improve its cycle stability. It is found that CoS inhibits the side reactions and adsorbs polysulfides. As a result, the modified FeS₂ shows a higher discharge capacity of 577 mA·h·g^-1 (919 W·h·kg^-1) after 60 cycles than 484 mA·h·g^-1 (778 W·h·kg^-1) of bare pyrite FeS₂. This efficient strategy provides a valuable step toward the realization of high cycling stability FeS₂ cathode materials for secondary lithium-ion batteries and enriches the basic understanding of the influence of FeS₂ interfacial stability on its electrochemical performances.     

硅钨酸晶体合成和谱学研究及与罗丹明B复合反应探索

通过水热法合成新型硅钨酸化合物[Cu(en)₂(H₂O)]_n{[Cu(en)₂] [SiW₁₂O_39.5]}_n(OH)_n·n(en)。化合物属于三斜晶系,P空间群,呈一维双链结构,配体与簇阴离子间的氢键构成二维层状结构,层与层之间通过游离的乙二胺（en）分子、羟基与簇阴离子间的强氢键作用连结成三维超分子。利用X射线粉末衍射、红外光谱、磁微扰及热微扰下的二维红外光谱、固体紫外可见漫反射光谱和热重分析等方法对化合物进行研究。X射线粉末衍射（XRD）显示,化合物测试谱图和单晶结构数据模拟谱图主要峰位重合,峰形基本一致,表明合成的化合物较纯。红外光谱（FTIR）显示,在1 100~700 cm-1,出现了饱和Keggin结构4个特征振动吸收峰,3 600~3 300 cm-1处ν_as(O-H)吸收峰由于形成氢键峰出现了宽化;5~50mT磁场变化下的2D-IR COS显示,890,800和780 cm-1处较强的磁响应峰分别为ν_s(W═O_d),ν(W-O_b-W)和ν(W-O_c-W),这是由于磁性粒子Cu与簇阴离子上的端氧配位导致钨氧骨架伸缩振动时偶极矩随磁场发生变化;50~120 ℃热微扰2D-IR COS显示,920 cm-1处出现很强的ν_as(W═O_d)响应峰,762 cm-1处的ν(W-O_b-W)和748 cm-1处的ν(W-O_c-W)响应峰相对较弱,验证了结构分析中簇笼上端氧形成的氢键比桥氧的氢键多,强氢键作用导致整个簇阴离子骨架对热响应敏感;固体紫外-可见漫反射（UV-Vis DRS）光谱表明,化合物分别在309和558 nm处出现了O→W的LMCT跃迁和Cu2+的d→d跃迁。热重分析（TGA）显示,失重过程分为3个阶段,第1阶段主要失去游离的乙二胺分子和羟基,第2阶段失去配位乙二胺和配位水,第3阶段540 ℃后,钨氧簇骨架开始坍塌。探讨不同pH条件下化合物与染料罗丹明B（RhB）的复合反应情况,实验表明强酸性条件有利于复合反应,生成紫色复合物沉淀,在pH 1时绘制RhB的标准浓度曲线,并利用紫外吸收光谱检测复合反应后试液中残余的RhB的吸光度,通过进一步计算得出RhB与化合物复合反应的最佳配比为4∶1,为去除工业废水中难以降解的有机污染物RhB提供了新的途径,显示了化合物的潜在应用前景。     

CdTe量子点与罗丹明B水溶液体系下的双光子激发荧光共振能量转移

采用时间分辨荧光光谱技术研究了在双光子激发下不同尺寸的量子点与罗丹明B 之间的荧光共振能量转移. 研究结果表明, 在800 nm的双光子激发条件下, 体系间能量转移效率随着供体吸收光谱与受体荧光光谱的光谱重叠程度增加而增加; 理论分析表明, 供体和受体间的Förster半径增加是导致其双光子能量转移效率增大的物理原因. 同时, 研究了罗丹明B浓度对荧光共振能量转移效率的影响. 研究结果表明, 量子点的荧光寿命随着罗丹明B浓度的增加而减小; 量子点与罗丹明B之间的荧光共振能量转移效率随着罗丹明B浓度的增加而增加; 当罗丹明B浓度为3.0×10^-5 mol·L^-1时, 双光子荧光共振能量转移效率为40.1%.     

Synthesis and sonocatalytic property of rod-shape Sr(OH)2·8H2O

A novel rod-shape sonocatalyst Sr(OH)₂·8H₂O was prepared by a facile precipitation method, and characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and UV–vis absorption spectroscopy. Comparative sonocatalytic degradation experiments were carried out in different conditions under ultrasonic irradiation by using rhodamine B (RhB) as the model substrate, indicating that Sr(OH)₂·8H₂O was highly sonocatalytic. Total organic carbon experiment demonstrated Sr(OH)₂·8H₂O with mass mineralization of organic carbon. The effects of catalyst amount, initial RhB concentration and ultrasonic energy of degradation were investigated, and the sonocatalyst could be reused 5 times without significant loss of activity. Furthermore, the potent degrading capability was ascribed to ultrasonic cavitation producing flash light/energy which generated radicals (e.g., OH) with high oxidation activity.     

High-sensitive phototransistor based on vertical HfSe2/MoS2 heterostructure with broad-spectral response

Van der Waals heterostructures based on the two-dimensional (2D) semiconductor materials have attracted increasing attention due to their attractive properties. In this work, we demonstrate a high-sensitive back-gated phototransistor based on the vertical HfSe₂/MoS₂ heterostructure with a broad-spectral response from near-ultraviolet to near-infrared and an efficient gate tunability for photoresponse. Under bias, the phototransistor exhibits high responsivity of up to 1.42×10³ A/W, and ultrahigh specific detectivity of up to 1.39×10¹⁵ cm·Hz^1/2·W^-1. Moreover, it can also operate under zero bias with remarkable responsivity of 10.2 A/W, relatively high specific detectivity of 1.43×10¹⁴ cm·Hz^1/2·W^-1, ultralow dark current of 1.22 fA, and high on/off ratio of above 10⁵. These results should be attributed to the fact that the vertical HfSe₂/MoS₂ heterostructure not only improves the broadband photoresponse of the phototransistor but also greatly enhances its sensitivity. Therefore, the heterostructure provides a promising candidate for next generation high performance phototransistors.     

用Na2O2-DMSO体系产生O2·的ESR研究

提出了Na₂O₂的二甲基亚砜(DMsO)/H₂O溶液中产生超氧阴离子自由基(O₂^·)的新方法,用电子自旋共振仪(ESR)可直接检测到很强的O₂^·信号,研究了反应的条件及其O₂^·信号的特性,并用该法考察了茶多酚等清除剂对于超氧阴离子自由基的清除作用。结果表明本体系是产生O₂^·的有效方法,可用于超氧阴离子自由基清除剂的研究。     

以二氧化钛前驱体为基的电流变液的成分分析和机理研究

制备了二氧化钛前驱体粉体, 它具有优良的巨电流变效应, 但不含一水草酸钙的成分. 通过X射线衍射谱、扫描电子显微镜、电感耦合等离子体光谱仪和热失重-质谱联用仪等一系列实验手段, 对二氧化钛前驱体粉体进行了表征, 发现它是非晶形态的纳米粉体, 其主要成分为TiOC₂O₄·2H₂O和TiO(OH)₂. 由二氧化钛前驱体配置的电流变液具有与钛酸钙前驱体电流变液类似的温度特征, 即 当处理温度超过160℃后, 电流变液的屈服强度会逐渐降低, 至200℃后, 巨电流变效应完全消失. 通过对比分析发现, 伴随上述巨电流变效应消失过程的化学反应是TiOC₂O₄·2H₂O 在加热过程中失去了结晶水. 这些特征在所有钛酸盐系列的电流变液中均可观察到, 因此我们推断TiOC₂O₄·2H₂O是钛酸盐系列巨电流变液中的关键物质. 关键词： 电流变液 钛酸盐 极性分子     

Mn2+, Pb2+共掺杂ZnS纳米材料制备及光致发光

采用聚乙烯基吡咯烷酮(PVP)为表面包覆剂,在室温大气条件下的水溶液中制备了ZnS:Mn,Pb纳米晶。讨论了Mn²⁺和Pb²⁺掺杂量对ZnS纳米发光材料光致发光强度的影响,确定了Mn²⁺和Pb²⁺掺杂量相对于Zn²⁺的最佳的量的比,并对其发光机理进行了初步的探讨。     

铜-钼源漏电极对非晶氧化铟镓锌薄膜晶体管性能的改善

在铜(Cu)和非晶铟镓锌氧化物(a-IGZO)之间插入30 nm厚的钼(Mo)接触层, 制备了具有Cu-Mo源漏电极的a-IGZO薄膜晶体管(TFT). Mo接触层不仅能够抑制Cu与a-IGZO有源层之间的扩散, 而且提高了Cu电极与玻璃基底以及栅极绝缘层的结合强度. 制备的Cu-Mo结构TFT与纯Cu 结构TFT相比, 具有较高的迁移率(～9.26 cm²·V^-1·s^-1)、更短的电流传输长度(～0.2 μm)、更低的接触电阻(～1072 Ω)和有效接触电阻率(～1×10^-4Ω·cm²), 能够满足TFT 阵列高导互联的要求.     

BiVO4/TiO2 heterojunction with rich oxygen vacancies for enhanced electrocatalytic nitrogen reduction reaction

The large-scale production of ammonia mainly depends on the Haber–Bosch process, which will lead to the problems of high energy consumption and carbon dioxide emission. Electrochemical nitrogen fixation is considered to be an environmental friendly and sustainable process, but its efficiency largely depends on the activity and stability of the catalyst. Therefore, it is imperative to develop highefficient electrocatalysts in the field of nitrogen reduction reaction (NRR). In this paper, we developed a BiVO₄/TiO₂ nanotube (BiVO₄/TNT) heterojunction composite with rich oxygen vacancies as an electrocatalytic NRR catalyst. The heterojunction interface and oxygen vacancy of BiVO₄/TNT can be the active site of N₂ dynamic activation and proton transition. The synergistic effect of TiO₂ and BiVO₄ shortens the proton transport path and reduces the over potential of chemical reaction. BiVO₄/TNT has high ammonia yield of 8.54 μg·h⁻¹·cm⁻² and high Faraday efficiency of 7.70% in −0.8 V vs. RHE in 0.1 M Na₂SO₄ solution.     

邻啡啰啉─吡啶2,6二甲酸铕二、三元配合物的NMR研究

报道了稀上铕(Eu³⁺)与吡啶-2,6-二甲酸(H₂DPC)及邻啡啉(Phen)形成的二元和三元固体配合物的制备.对它们进行了元素分析,确定该配合物的组成为二元Na₃[Eu(DPC)₃]·2H₂O和三元NaEu(DPC)₂·4H₂O,对上述配合物的结构作了核磁共振氢谱(¹H NMR)、碳谱(¹³CNMR)和氮谱(¹⁴N NMR)及红外光谱(IR)的研究.吡啶-2,6-二甲酸中的羧基以单齿配位(整个分子为三齿配位),二、三元配合物中铕的配位数分别为9和8.     

Co$lt;sub$gt;2$lt;/sub$gt;SnO$lt;sub$gt;4$lt;/sub$gt;/Graphene复合材料的制备与电化学性能研究

实验首先采用改进的Hummers法制备氧化石墨,然后以氧化石墨烯为前驱体,通过水热法将锡酸钴纳米颗粒均匀镶嵌在石墨烯薄膜基片上,最终获得Co₂SnO₄/Graphene镶嵌复合材料. 采用X射线衍射（XRD）、扫描电子显微镜（SEM）对材料的结构和形貌进行表征,通过恒电流充放电（CC）、循环伏安法（CV）与交流阻抗法（EIS）测试了材料的电化学性能. 实验结果表明,石墨烯良好的分散性及较高的电子导电率,可以提高锡酸钴材料的电化学性能,材料首次可逆容量达到1415.2 mA·h/g,50次循环后仍能保持469.7 mA·h/g的放电比容量. 关键词： 2SnO₄')" href="#">Co₂SnO₄ 石墨烯 电化学性能 锂离子电池     

稀土离子Ce,Tb掺杂硼磷酸锶荧光粉的发光性质

采用高温固相法合成了2SrO·0.25B₂O₃·0.75P₂O₅:RE³⁺(RE=Ce,Tb)荧光粉。研究了其中Ce³⁺,Tb³⁺的光谱性质,Ce³⁺和Tb³⁺共掺杂时的能量传递效率,以及Ce³⁺和Tb³⁺的动力学过程。发现在共掺杂的样品中,Tb³⁺的⁵D₄→⁷F₅绿色发射比Tb³⁺单掺杂样品中的绿色发射有显著的提高。当Tb³⁺的含量从1%增加到8%时,Ce³⁺→Tb³⁺的能量传递效率逐渐增加至70%。通过动力学研究,在Ce³⁺和Tb³⁺共掺杂的样品中,提高Tb³⁺的浓度,Ce³⁺的寿命减小。此外,Ce³⁺离子寿命的倒数与Tb³⁺的浓度之间很好地符合线性函数关系,经过拟合Ce³⁺离子的电子跃迁速率和Ce³⁺→Tb³⁺的能量传递速率分别为5.1×10^-2和1.34ns^-1·mol^-1。Tb³⁺的⁵D₄→⁷F₅跃迁的衰减曲线很好地遵守指数式衰减,并且随着Ce³⁺的掺杂浓度提高,Tb³⁺的⁵D₄→⁷F₅寿命增加。结果表明在共掺杂的2SrO·0.25B₂O₃·0.75P₂O₅材料中存在Ce³⁺到Tb³⁺的有效能量传递,这种材料在541nm处有着较强的绿光发射,所以将在发光以及显示领域有潜在的应用前景。     

Fabrication and characterization of the normally-off N-channel lateral 4H–SiC metal–oxide–semiconductor field-effect transistors

In this paper, the normally-off N-channel lateral 4H–Si C metal–oxide–semiconductor field-effect transistors(MOSFFETs) have been fabricated and characterized. A sandwich-(nitridation–oxidation–nitridation) type process was used to grow the gate dielectric film to obtain high channel mobility. The interface properties of 4H–Si C/SiO_2 were examined by the measurement of HF I–V, G–V, and C–V over a range of frequencies. The ideal C–V curve with little hysteresis and the frequency dispersion were observed. As a result, the interface state density near the conduction band edge of 4H–Si C was reduced to 2 × 10~(11) e V~(-1)·cm~(-2), the breakdown field of the grown oxides was about 9.8 MV/cm, the median peak fieldeffect mobility is about 32.5 cm~2·V~(-1)·s~(-1), and the maximum peak field-effect mobility of 38 cm~2·V~(-1)·s~(-1) was achieved in fabricated lateral 4H–Si C MOSFFETs.     

Fe+注入植物种子射程实验的Monte-Carlo仿真

研究表明,TRIM程序运算结果与实验测量离子注入种子的射程分布数据相差甚远.本文根据种子微结构的特点,综合考虑多种因素,设计种子微结构模型和运算程序,用Monte-Carlo仿真不同能量（110 keV,20 keV,200 keV）、不同注量（2×10¹⁶ ions·cm^-2,5×10¹⁶ ions·cm^-2,10¹⁷ ions·cm^-2,2×10¹⁷ ions·cm^-2）的Fe⁺注入花生、彩棉、小麦种子的射程分布,结果显示本设计程序仿真的结果与实验测量数据较为吻合.所获得的注入离子与种子微结构相互作用的随机抽样模拟运算方法,为离子注入与生命体相互作用的理论研究提供新的思路.     

碳量子点/罗丹明B分子复合体系中的能量和电子转移过程研究

本文采用荧光光谱结合稳态和瞬态吸收光谱技术,研究了碳量子点(CQDs)/罗丹明B(RhB)分子复合体系o-CQDs/RhB和m-CQDs/RhB中的能量转移和电子转移过程以及它们之间的关系. 研究发现在能量转移效率为73.2%的o-CQDs/RhB体系中,电子转移过程可以忽略;而在能量转移效率低于33.5%的m-CQDs/RhB体系中,电子转移过程则较为显著. 在这个由碳量子点和染料分子组成的典型复合体系中所揭示的能量转移与电子转移过程之间的内联关系,将为与激子猝灭相关的应用提供有用的视角.     

Etching mask optimization of InAs/GaSb superlattice mid-wavelength infared 640×512 focal plane array

In this paper we focused on the mask technology of inductively coupled plasma(ICP) etching for the mesa fabrication of infrared focal plane arrays(FPA).By using the SiO_2 mask,the mesa has higher graphics transfer accuracy and creates less micro-ripples in sidewalls.Comparing the IV characterization of detectors by using two different masks,the detector using the SiO_2 hard mask has the R_0A of 9.7×10~6 Ω·cm~2,while the detector using the photoresist mask has the R_0A of3.2 × 10~2 Ω·cm~2 in 77 K.After that we focused on the method of removing the remaining SiO_2 after mesa etching.The dry ICP etching and chemical buffer oxide etcher(BOE) based on HF and NH4 F are used in this part.Detectors using BOE only have closer R_0A to that using the combining method,but it leads to gaps on mesas because of the corrosion on AlSb layer by BOE.We finally choose the combining method and fabricated the 640×512 FPA.The FPA with cutoff wavelength of 4.8 μm has the average R_0A of 6.13 × 10~9 Ω·cm~2 and the average detectivity of 4.51 × 10~9 cm·Hz~(1/2).W~(-1)at 77 K.The FPA has good uniformity with the bad dots rate of 1.21%and the noise equivalent temperature difference(NEDT) of 22.9 mK operating at 77 K.     

一种新型基底上右旋肉碱的表面增强拉曼光谱研究

在聚乙烯吡咯烷酮(PVP)存在下,用多元醇还原硝酸银,Cu(NO₃)₂作为保护剂,快速有效的合成大量银纳米线,并优化了反应条件,得到结构均一、分散性较好的银纳米线。以罗丹明B为探针分子检测了该银纳米基底的表面增强效应,结果表明该基底对罗丹明B的表面增强效果明显,其表面增强因子可达6.4×105。文中利用这种基底得到了右旋肉碱的表面增强拉曼光谱(SERS),与其固体常规拉曼光谱(NRS)和10-3 mol·L-1水溶液的拉曼光谱对比,并对各自的峰位进行了归属。右旋肉碱固体在3 100～2800和1 700～200 cm-1处有明显拉曼振动峰,在右旋肉碱的表面增强拉曼光谱中,1700～200 cm-1处的峰得到了明显的增强。经分析,右旋肉碱分子与银纳米基底呈180°。本文还用合成的纳米银基底得到了不同浓度右旋肉碱溶液的表面增强拉曼光谱,其最低检测浓度为10-6 mol·L-1。右旋肉碱是一种重要的心血管药物,本文为其研究提供了较全面的拉曼光谱信息,为右旋肉碱的快速、特征、痕量监测提供了有力依据,也为进一步研究右旋肉碱的药理学提供了重要参考。     

Boron diffusion in bcc-Fe studied by first-principles calculations

The diffusion mechanism of boron in bcc-Fe has been studied by first-principles calculations. The diffusion coefficients of the interstitial mechanism, the B–monovacancy complex mechanism, and the B–divacancy complex mechanism have been calculated. The calculated diffusion coefficient of the interstitial mechanism is D_0= 1.05 ×10~(-7)exp(-0.75 e V/k T) m~2· s~(-1), while the diffusion coefficients of the B–monovacancy and the B–divacancy complex mechanisms are D_1= 1.22 × 10~(-6)f1exp(-2.27 e V/k T) m~2· s~(-1)and D_2≈ 8.36 × 10~(-6)exp(-4.81 e V/k T) m~2· s~(-1), respectively. The results indicate that the dominant diffusion mechanism in bcc-Fe is the interstitial mechanism through an octahedral interstitial site instead of the complex mechanism. The calculated diffusion coefficient is in accordance with the reported experiment results measured in Fe–3%Si–B alloy(bcc structure). Since the non-equilibrium segregation of boron is based on the diffusion of the complexes as suggested by the theory, our calculation reasonably explains why the non-equilibrium segregation of boron is not observed in bcc-Fe in experiments.