Modulating the Optoelectronic Properties of Large,Conjugated, High‐Energy Gap,Quaternary Phosphine Oxide Hosts: Impact of the Triplet‐Excited‐State Location

The purposeful modulation of the optoelectronic properties was realised on the basis of a series of the large, conjugated, phosphine oxide hosts 9,9‐bis‐{4′‐[2‐(diphenylphosphinoyl)phenoxy]biphenyl‐4‐yl}‐9H‐fluorene (DDPESPOF), 9,9‐bis‐{3′‐(diphenylphosphinoyl)‐4′‐[2‐(diphenylphosphinoyl)phenoxy]biphenyl‐4‐yl}‐9H‐fluorene (DDPEPOF), 9‐[4′‐(9‐{4′‐[2‐(diphenylphosphoryl)phenoxy]biphenyl‐4‐yl}‐9H‐fluoren‐9‐yl)biphenyl‐4‐yl]‐9H‐carbazole (DPESPOFPhCz) and 9‐[4′‐(9‐{3′‐(diphenylphosphoryl)‐4′‐[2‐(diphenylphosphoryl)phenoxy]biphenyl‐4‐yl}‐9H‐fluoren‐9‐yl)biphenyl‐4‐yl]‐9H‐carbazole (DPEPOFPhCz). The last two are quaternary with fluorenyls as linking bridges, diphenylphosphine oxide (DPPO) moieties as electron acceptors and diphenylethers and carbazolyls as two different kinds of electron donors. Owing to the fine‐organised molecular structures and the mixed indirect and multi‐insulating linkages, all of these hosts achieve the same first triplet energy levels (T₁) of 2.86 eV for exothermic energy transfer to phosphorescent dopants. The first singlet energy levels (S₁) and the carrier injection/transportation ability of the hosts were accurately modulated, so that DPESPOFPhCz and DPEPOFPhCz revealed extremely similar optoelectronic properties. However, the T₁ state of the former is localised on fluorenyl, whereas the carbazolyl mainly contributes to the T₁ state of the latter. A lower driving voltages and much higher efficiencies of the devices based on DPESPOFPhCz indicated that the chromophore‐localised T₁ state can suppress the quenching effects through realising independent contributions from the different functional groups to the optoelectronic properties and the embedding and protecting effect on the T₁ states by peripheral carrier transporting groups.     

三苯基膦氧基团在合成高性能有机电致发光材料中的应用

有机电致发光技术在通讯、信息、显示和照明等领域显现出巨大的商业应用前景, 十几年来一直是光电信息领域的研究热点之一。相对于无机电致发光材料,有机电致发光材料具有许多优点。近年来,三苯基膦氧基团在合成高性能有机电致发光材料方面的研究吸引了大批研究者的关注。由于磷原子自身性质,可以形成5个共价键,所以膦氧基团极易和其他基团连接形成以其为核的衍生物。由于氧原子具有很强的电负性,这就使膦氧结构高度极化并具有强的吸电子性。吸电子的膦氧基团连接苯环形成的三苯基膦氧单元也具有较强的吸电子性,其对所形成的化合物的能级结构也会产生明显影响。本文从材料合成的角度综述了三苯基膦氧基团在合成高性能有机电致发光材料中的应用方面所取得的最新研究进展,重点介绍了三苯基膦氧基团在合成高性能磷光二极管主体材料、电子传输材料和单分子电致发光材料等方面的应用。最后讨论了三苯基膦氧基团在上述领域应用过程中所存在的问题和功能拓展方向,并对下一步需要研究的热点问题作了展望。     

含三苯基氧磷结构聚芳醚醚酮酮的合成与表征

以苯酚、对二溴苯及苯基磷酰二氯为原料合成出二(4-苯氧基苯基)苯基氧磷(BPOPPO)。 三氯化铝(AlCl₃)为催化剂,通过缩聚反应,BPOPPO与对苯二甲酰氯(TPC)反应制备出一种含有三苯基氧磷结构的聚醚醚酮酮(P-PEEKK)树脂。 采用傅里叶变换红外光谱仪(FT-IR)、差示扫描量热仪(DSC)、热重分析仪(TGA)和广角X射线衍射(WAXD)等技术手段对P-PEEKK树脂的结构和性能进行表征。 结果表明,P-PEEKK树脂属于非晶聚合物,玻璃化转变温度(T_g)较高,为190.5 ℃;热分解温度(T_5%)为515 ℃,耐热性能较好;极限氧指数(LOI)为42,阻燃性能好,为难燃材料;易溶解于氯仿、1,2-二氯乙烷、N,N-二甲基乙酰胺等有机溶剂中,溶解性能较好,便于涂膜加工;拉伸强度为62 MPa,力学性能较好。     

三—（2—甲基氮丙啶）氧化膦异构体的核磁共振和量子化学研究

三-(2-甲基氮丙啶)氧化膦(MAPO)为黄色油状液体,其化学性质活泼,可用作塑料、橡胶及造纸业中高分子化合物的交联剂等。本文对MAPO进行了~1H、~(13)C、~(15)N、~(31)P和~(17)O的核磁共振研究及量子化学计算。结果表明,该化合物存在4种异构体,其中2种为对映体,并得到了这4种异构体的几何构型。     

钾离子影响下凝血酶适配子在氧化石墨烯表面吸附行为的研究

FAM荧光基团标记的凝血酶适配子通过π-π相互作用、疏水作用等分子间相互作用力与氧化石墨烯(GO)结合;通过向反应体系中加入0~50mmol/L K~+,使用荧光分光光度计记录FAM基团的荧光变化,研究凝血酶适配子在氧化石墨烯表面的吸附行为。不存在K~+时,凝血酶适配子以单链形式吸附在氧化石墨烯表面;随着K~+的加入,凝血酶适配子形成G-四聚体结构,脱离氧化石墨烯表面;当K~+浓度从0mmol/L增加到50mmol/L,K~+屏蔽G-四聚体与氧化石墨烯之间的静电斥力,凝血酶适配子重新吸附到氧化石墨烯表面。研究结果证实,K~+影响下,凝血酶适配子在氧化石墨烯表面存在吸附-解吸-再吸附过程。     

P/Rh比对PPh3-Rh/SiO2催化剂上丙烯氢甲酰化反应的影响

研究了P/Kh比对PPh3-Rh/SiO2催化剂上丙烯氢甲酰化反应性能的影响.结果表明,当P/Rh比为15时,丙烯氢甲酰化反应性能最好,丙烯转化率为25.9%,产物丁醛正异比为14,转换频率为241 h-1.PPh3-Rh/SiO2催化剂的固体31P核磁共振结果表明,在合成气气氛下,物理吸附的PPh3能够溢流到Rh/S...     

[NiCl2(dppp)]‐Catalyzed Cross‐Coupling of Aryl Halides with Dialkyl Phosphite,Diphenylphosphine Oxide,and Diphenylphosphine

We present a general approach to C? P bond formation through the cross‐coupling of aryl halides with a dialkyl phosphite, diphenylphosphine oxide, and diphenylphosphane by using [NiCl₂(dppp)] as catalyst (dppp=1,3‐bis(diphenylphosphino)propane). This catalyst system displays a broad applicability that is capable of catalyzing the cross‐coupling of aryl bromides, particularly a range of unreactive aryl chlorides, with various types of phosphorus substrates, such as a dialkyl phosphite, diphenylphosphine oxide, and diphenylphosphane. Consequently, the synthesis of valuable phosphonates, phosphine oxides, and phosphanes can be achieved with one catalyst system. Moreover, the reaction proceeds not only at a much lower temperature (100–120 °C) relative to the classic Arbuzov reaction (ca. 160–220 °C), but also without the need of external reductants and supporting ligands. In addition, owing to the relatively mild reaction conditions, a range of labile groups, such as ether, ester, ketone, and cyano groups, are tolerated. Finally, a brief mechanistic study revealed that by using [NiCl₂(dppp)] as a catalyst, the Ni^II center could be readily reduced in situ to Ni⁰ by the phosphorus substrates due to the influence of the dppp ligand, thereby facilitating the oxidative addition of aryl halides to a Ni⁰ center. This step is the key to bringing the reaction into the catalytic cycle.     

Preparation and Characterization of Ni‐Modified Graphene Oxide Complex as an Efficient Catalyst for the Synthesis of Sulfides via Reaction of Arylhalides with S8 or Thiourea

In this work, complex of Ni‐modified graphene oxide was prepared and characterized using FT‐IR spectroscopy, SEM, XRD, TGA and ICP‐OES techniques. This compound used as an efficient and recoverable catalyst for the C–S coupling reaction using sulfur‐transfer reagents (S₈ or thiourea). The catalyst was easily separated using a simple filtration and reusable without significant loss of their catalytic efficiency.     

电极材料对NPB/Alq3有机电致发光器件性能的影响

采用不同材料作为有机电致发光器件(OELDs)的电极, 制备了基本结构为[阳极/NPB(40 nm)]/Alq3(50 nm)/阴极]的异质结双层器件, 并通过改变OELDs器件的阴极或阳极来研究电极材料对器件光电性能的影响. 研究结果表明, 各器件电流-电压(I-V)关系的基本特征与陷阱电荷限制电流(TCLC)机制的拟合情况相符. 由于有机材料本身能级的无序性以及载流子迁移率对温度和电场的依赖性, 不同电极的载流子注入能力与其功函数并无直接关系. 双层器件中由于空穴传输层的引入, 使得载流子复合区域位于有机层异质结界面处, 降低了金属阴极对激子的猝灭作用, 从而大大提高了器件性能. 此外, 金属电极OLEDs器件结构具有的微腔效应会导致发射光谱的位移和谱峰宽度变窄, 这表明通过对金属电极的表面改性和优化可使器件性能超过常规结构的器件.     

The Facile Deposition of Pt Nanoparticles on Reduced Graphite Oxide in Tunable Aryl Alkyl Ionic Liquids for ORR Catalysts

In this study, we present the facile formation of platinum nanoparticles (Pt-NPs) on reduced graphite oxide (rGO) (Pt-NP@rGO) by microwave-induced heating of the organometallic precursor ((MeCp)PtMe₃ in different tunable aryl alkyl ionic liquids (TAAIL). In the absence of rGO, transmission electron microscopy (TEM) reveals the formation of dense aggregates of Pt-NPs, with primary particle sizes of 2 to 6 nm. In contrast, in the Pt-NP@rGO samples, Pt-NPs are homogeneously distributed on the rGO, without any aggregation. Pt-NP@rGO samples are used as electrode materials for oxygen reduction reaction (ORR), which was assessed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrochemical surface area (ECSA) and mass-specific activity (MA) increase up to twofold, compared with standard Pt/C 60%, making Pt-NP@rGO a competitive material for ORR.     

Influence of NaCl on Cathode Performance of Solid Oxide Fuel Cells

Degradation induced by sodium chloride in air was investigated for (La_0.8Sr_0.2)_0.98MnO₃(LSM) and La_0.6Sr_0.4Co_0.2Fe_0.8O₃(LSCF) cathodes in solid oxide fuel cells(SOFC). Cell performance was measured by volatilizing NaCl to be supplied to the cathode at a constant current density of 200 mA/cm² for up to 100 h. At 800 ℃, an exposure of the cathode to 30 mg/L NaCl caused negligible degradation of LSM at least for 100 h. Slight change in the composition of the cathode materials was observed which may imply the gradual degradation of cell performance for the long-term. In addition, cell performance degradation was compared between 700 ℃ and 900 ℃, being poisoned by 30 mg/L NaCl. Degradation was negligible for LSM cathode, while LSCF cathode showed slightly poor tolerance at 700 ℃ due to the decomposition of the cathode material. Further studies should be done to clarify the long-term influence of NaCl on cathode performance.     

金属、金属氧化物纳米晶催化剂:结构与催化性能关系研究(英文)

金属与金属氧化物纳米晶作为常见催化材料(催化剂、助催化剂或载体),在过去的几十年中引起了人们极大的关注。近年来,纳米催化领域,尤其是纳米晶催化剂的可控制备技术,虽然取得了许多重要的进展,然而,真正理解纳米晶催化剂三性(活性、选择性和稳定性)与其微观结构上的内在联系一直以来都是具有挑战性的科学难题。怎样理解催化反应过程中纳米晶催化剂的活性位点?什么是影响其催化性能的关键因素?如何理解纳米催化的物理化学本质,认识其规律性,提高纳米晶催化剂活性、选择性和稳定性均是纳米催化领域有待解决的重要科学问题。我们课题组针对这些问题和挑战开展了纳米催化研究工作。本文总结了近年来课题组所取得的研究成果。     

十四烷基芳基磺酸盐在大庆油砂上的吸附性能

利用静态吸附实验研究了实验室自制的三种高纯度十四烷基芳基磺酸盐在大庆油砂上的吸附规律,并考察了吸附时间,吸附温度及磺酸盐、NaCl、NaOH、正丁醇的浓度对吸附量的影响.结果表明:吸附量随着磺酸盐浓度的增大逐渐增加后趋于平稳,随着吸附温度和正丁醇体积浓度的降低、NaCl 和NaOH浓度的增加而增大; 磺酸盐活性剂的三种同分异构体中,随两部分碳链长度趋于均等,吸附量下降,且受助剂的影响变小.吸附热力学研究表明,十四烷基芳基磺酸盐在油砂上的吸附等温线服从Langmuir 等温方程,并且计算得到的各参数均能很好地反映磺酸盐在油砂上的吸附特征.吸附动力学研究表明,Elovich 方程能够更好地描述吸附量随时间的变化情况.     

Synthesis and Coordination Properties of Tripodal Ligand on the Triphenylphosphine Oxide Platform with Carbamoyl Side Arms

Abstract

A new tripodal O-donor ligand, tris(2-N,N-dibutylcarbamoylmethoxyphenyl)phosphine oxide (L), was synthesized. This potentially tetradentate ligand L exhibits variable denticity upon complexation with UO₂(NO₃)₂, Nd(NO₃)₃, and Lu(NO₃)₃. The complexes were studied by elemental analysis, IR, and ¹H, ¹³C, and ³¹P NMR spectroscopy.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional text, tables, and figures.]     

Effect of Calcium Oxide Additive on Sorbent for High-Temperature the Performance of Iron Oxide Coal Gas Desulfurization

The effect of calcium oxide additive in iron oxide sorbent for hot gas desulfurization was investigated by XRD and TPR techniques. XRD characterization showed that CaO was highly dispersed after the calcination of sorbents. Calcium sulfate formed in the desulfurization was decomposed and regenerated to CaO by reacting with CO before the next sulfidation process. Calcium participated in every sulfidation/regeneration cycle and contributed to the enhancement of sulfur capacity. The TPR results showed that the reduction temperature of the sorbent increased with the increase of the content of calcium. Calcium played a role of retarding reduction. Therefore, the addition of calcium oxide additive will benefit the utilization of iron oxide sorbent in strongly reducing atmospheres.     

Effect of Calcium Oxide Additive on the Performance of Iron Oxide Sorbent for High-Temperature Coal Gas Desulfurization

The effect of calcium oxide additive in iron oxide sorbent for hot gas desulfurization was investigated by XRD and TPR techniques.XRD characterization showed that CaO was highly dispersed after the calcination of sorbents.Calcium sulfate formed in the desulfurization was decomposed and regenerated to CaO by reacting with CO before the next sulfidation process.Calcium participated in every sulfidation/regeneration cycle and contributed to the enhancement of sulfur capacity.The TPR results showed that the reduction temperature of the sorbent increased with the increase of the content of calcium.Calcium played a role of retarding reduction.Therefore,the addition of calcium oxide additive will benefit the utilization of iron oxide sorbent in strongly reducing atmospheres.     

纳米氧化物对MH/Ni电池负极电化学性能影响的研究

采用纳米氧化铜作为添加剂掺杂制备MH/Ni电池负极, 研究了氧化铜在电极内部的反应机理, 考察了修饰后电极储备容量的变化, 及电极的电化学性能, 并应用EIS方法探讨了电极性能改善的作用机理. 循环伏安测试表明, 氧化铜在首次充电时被还原成铜并沉积在合金颗粒表面. 电化学测试表明, 掺杂后合金电极的电化学性能显著提高. EIS分析表明, 掺杂后合金电极的导电性提高, 电化学活性增强.     

改性氧化石墨烯稳定Pickering乳液法制备高导热相变整体材料

采用表面引发原子转移自由基聚合法(SI-ATRP)改性氧化石墨烯(GO), 并用其稳定Pickering高内相乳液, 一步成型制得高导热氧化石墨烯/石蜡复合整体相变材料. 通过SI-ATRP方法, 在氧化石墨烯表面引入分子刷, 提高GO的分散性, 实现了低GO含量下优异的导热强化效果. 当GO添加量仅为相变复合材料整体的0.4%(质量分数)时, 其热导率(3.968 W?m^-1?K^-1)比纯石蜡的热导率(0.608 W?m^-1?K^-1)有较大提升. 通过测试发现, 在1000次循环后相变材料的泄漏率仅为1.1%~1.3%, 表现出良好的形状稳定性和热可靠性. 制备的新型形状稳定相变材料在温控、 储能应用中具有潜在的用途.     

焙烧温度对Si-Ba-Cs-P复合氧化物催化剂结构及组成和催化性能的影响

Si-Ba-Cs-P复合氧化物催化的单乙醇胺分子内脱水反应极易受催化剂焙烧温度条件变化影响.催化剂采用X射线粉晶衍射(XRD)、程序升温脱附(NH3-TPD)及氮吸附等技术进行表征.在550℃焙烧处理的催化剂,虽然单乙醇胺完全转化,但产品乙烯亚胺选择性却不到10%,催化剂中的物相组成主要为CsBa2(PO3)5晶相及Cs4Ba(PO3)6晶相,孔结构主要为介孔;在700~900℃焙烧处理的催化剂,催化剂酸性及BET比表面积明显下降,催化剂中的物相组成主要为α-Cs4P2O7晶相,孔径逐渐减小,虽然单乙醇胺转化率稍有下降,但产品乙烯亚胺选择性却有很大提高.当焙烧温度为800~900℃时,可在保证单乙醇胺转化率大于80%的前提下,得到高于76%的乙烯亚胺选择性.     

Front Cover: Steric Influence on the Constitution of Beryllium Phosphine Complexes (Eur. J. Inorg. Chem. 29/2023)

The phosphine complexes of beryllium chloride, bromide and iodide, [(PMe₂Ph)₂BeX₂], [(PMePh₂)₂BeX₂] and [(PPh₃)BeX₂]₂ (X=Cl, Br, I) were prepared and characterised with multinuclear NMR spectroscopy. Additionally the molecular structure of dinuclear [(PPh₃)BeCl₂]₂ was determined with single crystal X-ray diffraction techniques. The threshold cone angle of the phosphines, below which two ligands can coordinate to the beryllium dihalide fragments, is between 136° and 145°. Halide-chloride exchange in dichloromethane is observed for [(PPh₃)BeBr₂]₂ and [(PPh₃)BeI₂]₂, which leads to the formation of [(PPh₃)BeCl₂]₂. Due to the relatively low Lewis basicity of PPh₃, it almost exclusively acts as a spectator ligand with only little formation of phosphonium cations.