ICP—AES测定钆镓石榴石中钪、钕、铽、铕、铬

掺Sc、Nd、Cr或掺Tb、Eu的钆镓石榴石(GGG,含Gd-2O_3～54%,Ga_2O_3～46%)是较新的激光晶体材料。化学分析GGG中,少量稀土元素需进行分离,较麻烦,而用ICP法则基体效应小,不需分离,简单准确。本文测定了在0.1%纯GGG中Sc、Nd     

Raman Spectra of Nd:La_3Ga_5SiO_(14) and Nd:La_3Ga_(5.5)Ta_(0.5)O_(14) Crystals

Single crystals of Nd:La_3Ga_5SiO_(14)(NLGS) and Nd:La_3Ga_(5.5)Ta_(0.5)O_(14)(NLGT) were grown by Czochralski method. Both crystals exhibit a langasite structure(space group D23(P321) with Z = 1), whose general formula is A_3BC_2D_3O_(14), where A, B, C and D represent the dodecahedral, octahedral and tetrahedral positions, respectively. The adding of low content of Nd does not change the crystal structure. Although they are isostructural, the distribution of atoms among the symmetric sites is different. While NLGT exhibits a perfect orderly structure, NLGS exhibits an intrinsically disordered structure due to the random distribution of Ga and Si atoms at the C3(2) symmetry sites. To understand what changes occur in the phonon distribution when Ta replaces Si, we recorded and analyzed room temperature polarized Raman spectra. We observe 8A1+18E modes for NLGS and 10A1+13E for NLGT crystals. When Si is substituted by Ta, we observe that the wavenumber of some modes related to vibrations involving Ga and O atoms decreases. This agrees with the fact that the Ga–O bonds are shorter in NLGS than in NLGT.     

碱式邻苯二甲酸氢镧的热分解机理

本文测定了一水合碱式邻苯二甲酸氢镧LaOH(C_8H_5O_1)_2·H_2O的热重(TG)曲线,用红外光谱、气相色谱和质谱法表征了各步热分解产物,研究了其热分解反应机理.整个热分解过程分5步进行:LaOH(C_8H_5O_1)_2·H_2O→La_2(C_8H_4O_4)_3→La_1O(CO_3)_3(C_8H_4O_4)_2→La_2O(CO_3)_2→La_2O_2CO_3→La_2O_3.热分解的气相产物有邻苯二甲酸酐和9,10-蒽醌等.     

基于CuO敏感电极的阻抗型NO_2传感器的多响应信号比较

采用Al掺杂的硅酸镧La_(10)Si_(5.5)Al_(0.5)O_(27)(LSAO)为固体电解质,CuO为敏感材料,构成了阻抗型NO_2传感器。通过X射线衍射和扫描电子显微镜对传感器的结构和形貌进行了表征。采用电化学工作站对分别以模值(|Z|)、相角(Θ)、实部(Z~')和虚部(Z~″)为响应信号的传感器的敏感性能进行了研究。结果表明:以模值(|Z|)、相角(Θ)、实部(Z~')和虚部(Z~″)作为传感器响应信号时,响应值与NO_2浓度均呈现良好的线性关系。在高频下,以相角和虚部作为响应信号的传感器在灵敏度,响应-恢复时间以及稳定性等方面具有更加出色的表现。     

M（Ⅲ）X（Ⅴ）O4型微孔晶体研究：GaPO4—Cn系列的合成与结构

在(0.5～3)R·Ga_2O_3·(1.0～1.5)P_2O_5·(25～100)H_2O体系内,通过150～200℃、1～20天水热晶化合成了12种磷酸镓微孔晶体GaPO_4-C_n(n=1～12)。该晶体经400～500℃下脱模板剂(R)后,对水、乙醇、正己烷、环己烷有不同程度的吸附,对水的吸附等温线具有分子筛的吸附特征,报道了GaPO_4-C_3,-C_4,-C_7的单晶结构分析结果,并结合前人工作对此类新型微孔晶体结构与合成规律的特点进行了探讨。     

镧系化合物的磁化学

本文根据镧系离子基态光谱项的总量子数和Land’e劈裂因子随原子序数的周期变化,阐明了镧系离子的顺磁磁化率和有效磁矩随原子序数的变化规律;对LnF_3、Ln_2O_3、LnP_5O_4和Ln(NO_3)_3·nDMSO等镧系化合物的有效磁矩进行了测量;分别研究和测定了EuF_3+EuF_2,PrGaO_3、CeP_4O_(12)、KCeP_4O_(12)中铕、镨及铈等离子的价态和硝酸钕二苯亚砜晶体的组成;测定了掺钕的钇铝柘榴石激光晶体中钕的含量。     

磷酸盐的添加对甲烷氧化偶联反应镧基催化剂的影响

采用柠檬酸法制备了不同含量磷酸盐修饰的镧基催化剂,考察了磷酸盐的添加对镧基催化剂甲烷氧化偶联反应(OCM)活性的影响,并借助X射线衍射(XRD)、O_2-程序升温脱附(O_2-TPD)及X射线光电子能谱(XPS)等手段对催化剂的理化性质进行了表征.结果表明,随着磷酸盐加入量的增大,催化剂样品的粒径逐渐减少,催化剂的物相由La_2O_3向La_3PO_7和LaPO_4逐步转变.当催化剂的物相由La_2O_3和适量的La_3PO_7构成时,催化剂具有较多的表面缺陷位点数和较大的亲电氧物种/晶格氧物种比值,并呈现出良好的OCM反应性能.     

Synthesis and antibacterial activity of new layered perovskite compounds, AgxNa2-xLa2Ti3O10

Three kinds of new layered perovskite compounds with Ruddlesden-Popper(R-P)phase,Ag_xNa_(2-x)La_2Ti_3O_(10)(x=0.2,0.3 and 0.5),were synthesized by an ion-exchange reaction of Na_2La_2Ti_3O_(10)with AgNO_3 solution.The structures of the compounds were characterized by EDX and XRD,and their antibacterial activity and light-resistance property were evaluated.The results indicated that the molecular formula of Ag_xNa_(2-x)La_2Ti_3O_(10)(x=0.2,0.3 and 0.5)was confirmed,and that the crystalline structure of Na_2La_2Ti_3O_(10)was not obviously affected by exchange of silver ion.The minimum inhibitory concentrations(MICs)of Ag_(0.3)Na_(1.7)La_2Ti_3O_(10)against Escherichia coli(E.coli),Staphylococcus aureus(S.aureus)were 180μg/mL and 240μg/mL, respectively,while its discoloration was not observed after 24 h light ageing test.     

La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3在乙醇水蒸气重整中催化性能研究

用共沉淀法制备了La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物催化剂,用XRD、SEM、TPR、TG等对La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物的晶相结构、还原性能及反应50 h后的La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物表面积碳情况进行了分析,同时用微反色谱装置在不同的反应温度条件下的La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物的初活性、氢气平均选择性和积碳性能进行了探讨。结果表明,La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物在乙醇水蒸气重整反应中具有较好的低温初活性和氢气的选择性,乙醇的平均转化率和氢气的选择性随着反应温度的升高而增大。当温度大于550℃时,转化率增幅不大,氢气的平均选择性在600℃时有所下降。反应温度升高催化剂的积碳量有所增多,积碳主要是不定型碳。     

基于硒化镓纳米片填充的空芯光纤超高二次谐波增强

与传统的光学晶体相比,全光纤功能器件由于和光纤系统的天然兼容性,被认为是下一代集成光学的重要研究方向,吸引了人们的广泛关注。然而,由于二氧化硅固有的中心反演对称性质,光纤中的二阶非线性光学过程仍有待探索,这在可调谐超快激光、全光信号处理、成像和光通信等商业全光纤非线性光学应用中具有重要意义。因此,我们提出了一种新的溶液填充方法,可有效地将具有高非线性的硒化镓纳米片直接沉积在长度达半米的空芯光纤(HCF)的内孔壁上。此外,采用制备的硒化镓纳米片-空芯光纤(GaSe-HCF)作为光频率转换器,其二次谐波(SHG)比嵌入MoS₂的HCF和普通HCF分别提高了2个数量级和3个数量级。我们的研究成果将拓展其它非线性材料在全光纤高端非线性光学和光电子学中的应用,并提供新的制备思路。     

二维铁电材料ABP2X6内在极高的负泊松比

Recently, ferroelectric materials have attracted considerable research attention. In particular, two dimensional (2D) ferroelectric materials have been considered as most crucial for next-generation circuit designs because of their application as novel electric memory devices. However, a 2D ferroelectric material is very rare. The ferroelectric materials with the form ABP₂X₆ (A = Ag, Cu; B = Bi, In; X = S, Se) are of interest because of their ferroelectric property maintained in their ultrathin structures. Within the ABP₂X₆ monolayer, the P―P bonds form the pillars that hold the top and bottom X planes, while the off-center A―B atoms between the X layers induce a spontaneous ferroelectric polarization. If the two off-center A―B sites are equally aligned, this would lead to the appearance of the paraelectric state. Such intriguing structures must impart novel mechanical properties to the materials. Until now, there has been no report on the mechanical properties of monolayer ABP₂X₆. Based on first-principles calculations, we studied the structural, electronic, mechanical as well as the electromechanical coupling properties of monolayer ABP₂X₆ (A = Ag, Cu; B = Bi, In; X = S, Se). We found that they are all semiconductors with wide bandgaps of 2.73, 2.17, 3.00, and 2.31 eV for CuInP₂Se₆, CuBiP₂Se₆, AgBiP₂S₆, and AgBiP₂Se₆, respectively, which are calculated based on the Heyd-Scuseria-Ernzerhof (HSE) exchange correlation functional model. The conduction band minimum is mainly from p orbitals of X and B atoms, whereas the valence band maximum is due to the hybridization of the p orbital of X atoms and the d orbital of A atoms. Moreover, there are three short and three long A/B―X bonds due to the A―B off-center displacement. Together with the d-p orbital hybridization, the main reason for the distorted ferroelectric structure in ABP₂X₆ monolayers is the Jahn-Teller effect. ABP₂X₆ monolayers are predicted to be a new class of auxetic materials with an out-of-plane negative Poisson's ratio, i.e., the values of the negative Poisson's ratio are in the order AgBiP₂S₆ (−0.805) < AgBiP₂Se₆ (−0.778) < CuBiP₂Se₆ (−0.670) < CuInP₂S₆ (−0.060). This is mainly due to the tensile strain applied in the x/y direction enlarging the angle between P―P bonds and top layer X atoms, thereby enhancing the bucking height of monolayer ABP₂X₆. Moreover, external strain has a significant impact on the A―B off-center displacement, rendering an out-of-plane piezoelectric polarization. The values of e₁₃ for CuInP₂S₆, CuBiP₂Se₆, AgBiP₂S₆, AgBiP₂Se₆ monolayers are calculated to be −3.95 × 10⁻¹², −5.68 × 10⁻¹², −3.94 × 10⁻¹², −2.71 × 10⁻¹² C∙m⁻¹, respectively, which are comparable to the only experimentally confirmed 2D out-of-plane piezoelectric Janus system (piezoelectric coefficient = −3.8 × 10⁻¹² C∙m⁻¹). This unusual auxetic behavior, ferroelectric polarization, and the electromechanical coupling in monolayer ABP₂X₆ could potentially lead to enormous technologically important applications in nanoelectronics, nanomechanics, and piezoelectrics.     

新型(4-HBA)SbX5·H2O类钙钛矿单晶及其卤素结构对发光特性的调控(英文)

发光材料因其在照明、显示、成像等方面的广泛应用而备受关注。作为新兴发光材料之一,钙钛矿类材料的研究及报道较多。其中,铅基钙钛矿的研究取得了巨大进展,光致发光量子产率(PLQY)几乎达到了100%。然而,基于铅基钙钛矿化学毒性和低稳定性,在实际应用过程中需要特殊的封装,因而提高了生产成本并限制了其实际应用领域。被广泛关注的锡基钙钛矿的荧光量子产率几乎能达到90%,但Sn²⁺易氧化成Sn⁴⁺,在空气中极不稳定。相较于铅基钙钛矿和锡基钙钛矿,锑基钙钛矿的低化学毒性、高热稳定性等优点突出。此外,锑基钙钛矿的光学性能在过去几年中也取得了很大的进展,有望突破传统钙钛矿应用的局限。在此,我们报道了一系列新型单晶(4-HBA)SbX₅·H₂O (4-HBA为4-羟基苄胺缩写,X为Cl或Br)。利用溶剂热法可制备高质量的(4-HBA)SbBr₅·H₂O、(4-HBA)SbBr₃Cl₂·H₂O和(4-HBA)S...     

共掺稀土离子对Er~(3+)激活中红外激光晶体光谱性能的影响

Er3+掺杂的晶体能够产生2.7~3.0μm波段中红外激光,在激光医疗、光通讯、环境探测和光电对抗等领域具有重要的应用。基于本课题组近年来开展的Er3+激活中红外激光晶体的相关工作,本文综述了共掺稀土离子对Er3+激活晶体光谱性能的影响:包括敏化离子Cr3+、Yb3+等的敏化作用增强了Er3+的特征吸收峰;退激活离子Pr3+、Ho3+等的退激活效应抑制了自终态瓶颈效应;以及共掺Nd3+所起的敏化和退激活双重作用,并对中红外激光的研究趋势和前景进行了展望。     

Research progress on mid-IR nonlinear optical crystals with high laser damage threshold in China

Nonlinear optical (NLO) crystals have been playing an increasingly important role in laser science and technology. The NLO crystals used in the middle infrared (mid-IR) region, compared with the NLO crystals in the other wavelength regions, are still not good enough for the application of high-energy laser. The main defect is that their laser damage thresholds (LDT) are low. Chinese scientists have made a lot of important contributions to the UV and visible NLO crystals. In the last decade, they also did a lot of work on the mid-IR NLO materials. The main purpose of these researches is to increase the LDT and simultaneously balance the other properties. This paper presents a brief summary of their research progress in this topic on three types of materials: chalcogenides, oxides, and halides. The emphasis is put on the design strategy and quality control of the crystals.     

紫外臭氧处理增强溶液法MoO3薄膜的空穴注入能力

空穴注入层对有机发光二极管的性能有重要的影响,尤其是当器件中的空穴传输材料的最高占据分子轨道能级较深的时候。近年来有许多关于新型的溶液法空穴注入材料的研究。在本文中,我们对溶液法MoO₃薄膜使用了三种不同的处理方法来研究其对空穴注入性能的影响,即：在空气中150 ℃退火;在空气中150 ℃退火再紫外臭氧处理(UVO) 15 min;只进行UVO处理15 min。结果发现当MoO₃薄膜在空气中150 ℃退火后,器件的电流最小,空穴注入能力最差。而当MoO₃薄膜经过UVO处理后,器件的电流显著增大,工作电压大幅下降,器件性能接近于蒸镀的MoO₃薄膜的器件。更惊喜的是,这种改善在MoO₃薄膜仅作UVO处理后也可获得。经定量计算发现MoO₃薄膜经过UVO处理后的空穴注入效率能提高到约0.1。XPS分析表明通过UVO处理后,MoO₃薄膜中Mo⁵⁺成分减少并且薄膜表面的富氧吸附物被有效地消除,使得其化学计量基本与蒸镀的MoO₃薄膜相同。基于这种经UVO处理的溶液法MoO₃作为空穴注入层,器件的最大电流效率可达到48.3 cd∙A⁻¹。     

SCN掺杂提高CsPbI3胶体量子点的稳定性和光探测性能

无机卤化物钙钛矿CsPbI₃胶体量子点因其优越的光电性能在光伏和发光器件领域中表现出极大的发展前景。然而,CsPbI₃较差的稳定性阻碍了实际应用。为此,我们采用SCN?离子掺杂CsPbI₃(SCN-CsPbI₃)量子点用于提高量子点的光学性能和稳定性。研究表明,SCN?离子掺杂不仅减少了量子点缺陷、改善了光学性能,还提高了Pb-X键能、量子点结晶质量以及钙钛矿结构稳定性。结果表明,SCN-CsPbI₃量子点的荧光量子产率(PLQY)超过90%,远高于未掺杂原始样品(PLQY为68%)。高的荧光量子产率表明量子点具有较低的缺陷态密度,这归咎于缺陷的减少。空间限制电荷和时间分辨荧光光谱等研究也证实SCN?离子掺杂减少了量子点的缺陷。此外,SCN-CsPbI₃量子点展现出很好的抗水性能,其荧光强度在水中浸泡4 h后依然保持85%的初始值。而未掺杂原始样品的荧光性能很快消失,这是因为水诱导其相变。基于SCN-CsPbI₃量子点的光电探测器表现出宽波域响应(400–700 nm),高的响应率(90 mA·W^?1)和超过1011 Jones的探测度,远高于未掺杂原始量子点探测器的性能(响应率为60 mA·W^?1和探测度为1010 Jones)。     

石墨炔-有机共轭分子复合材料的制备及其储锂性能

发展了基于超分子化学的新方法实现了对石墨炔的原位氮掺杂,通过利用石墨炔与有机共轭分子间强的π–π作用,原位制备了石墨炔/卟吩复合材料薄膜,并用作锂离子电池的负极材料,其比容量增加到了1000 mAh∙g⁻¹,该复合材料表现出优良的倍率性能和循环稳定性,为可控制备掺氮石墨炔复合材料提供了新的思路。     

锂电池磷酸铁锂正极材料的结构与性能相关性的研究进展

磷酸铁锂(LiFePO_4)具有环境友好、价格便宜、安全性能好等优点,作为正极材料已经广泛应用于国内的电动车动力电池中;为了进一步提高电池的性能,需要对影响磷酸铁锂及同类材料(LiMPO_4 (LMP);M=Fe、Mn、Co、Ni及这些元素的混合)电化学性能的因素进行深入研究。本文从材料颗粒体相特征(相结构、掺杂、纳米化、缺陷和锂离子传输机制)、界面结构及在不同的电解质环境下的界面重构和电极结构与锂电池性能的构效关系等方面进行总结,系统化的阐述并总结了影响磷酸铁锂正极材料最新研究进展。     

La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)材料的制备及其上转换发光性质

采用高温固相法制备了La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)荧光粉。通过X射线衍射(XRD)和上转换发射光谱对样品进行了相结构和发光性质表征。XRD实验结果表明:合成的样品为面心立方萤石结构(Fm-3m)的La_(2.4)Mo_(1.6)O_8相。在980 nm红外光激发下,La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)荧光粉发出分别来自Er~(3+)离子的~2H1_(1/2)→~4I_(15/2)、~4S_(3/2)→~4I_(15/2)跃迁的绿光(主峰为548和529 nm)和~4F_(9/2)→~4I_(15/2)跃迁的红光(主峰为670 nm)。进一步地,对样品中可能的上转换发光机制进行了讨论。     

卤化物固态电解质研究进展

全固态电池因其高能量密度和高安全性而成为具有发展前景的下一代储能技术。开发具有高室温离子电导率、优异化学/电化学稳定性、良好正/负极兼容性的固态电解质是实现全固态电池实用化的关键。卤化物固态电解质因其优异的电化学窗口、高正极稳定性、可接受的室温锂离子电导率等优势,受到了广泛的关注。本文通过对近年来卤化物电解质的相关研究进行总结,综述了该类电解质的组成、结构、离子传导路径及制备方法,并分析了金属卤化物电解质的电导率、稳定性特点,归纳了近年来该电解质在全固态电池中具有代表性的应用,并基于以上总结和分析,指出了卤化物固态电解质的研究难点及发展方向。