一个各向异性磁稀释杂化钙钛矿系列[CH3NH3][CoxZn1-x(HCOO)3]

Inorganic-organic or hybrid perovskite materials, which are the complementary counterparts of pure inorganic perovskites, can provide many new opportunities in the researches of phase transitions, critical phenomena, and relevant properties, as they combine the characteristics of inorganic and organic components. Therefore, the hybrid perovskites of ammonium metal formate framework are very promising, and their properties have been found to be strongly dependent on the characteristics of the constituent metal ions and/or ammonium ions. Herein, we used solid solution strategies, borrowed from solid state chemistry, to investigate the anisotropic diluted magnetic hybrid perovskite system of [CH₃NH₃][Co_xZn_1-x(HCOO)₃], wherein the B-sites are occupied by the mixed metal ions of Co²⁺ and Zn²⁺. The solid solution compounds of this series in the range x = 0–1 (or the molar percent Co% = 0–100%) were successfully prepared using conventional solution chemistry methods. The resulting compounds were demonstrated to be iso-structural by using both single-crystal and powder X-ray diffraction analyses. The solid solution crystals belong to the orthorhombic space group Pnma, with the cell parameters being a = 8.3015(2)–8.3207(3) Å, b = 11.6574(4)–11.6811(5) Å, c = 8.1315(3)–8.1427(4) Å, and V = 787.89(5)–790.98(7) ų. The perovskite structure consists of a simple cubic anionic metal-formate framework and CH₃NH₃⁺ cations which are located in the framework cavities, with N―H···O hydrogen bonds formed between the framework and the cation. The members of this series showed negligible changes (< 0.4%) in their respective lattice and structural parameters. Thus, the prepared solid solution compounds constitute good molecule-based examples for the study of magnetic dilution under almost the same structural parameters and molecular geometries. Upon dilution, the magnetization per mole of Co at low temperatures and low fields was suppressed by the magnetic anisotropy of Co²⁺ and gradual destruction of the large spin canting between coupled Co²⁺ ions, in contrast to the magnetization enhancement observed in the isotropic diluted system of [CH₃NH₃][Mn_xZn_1-x(HCOO)₃] with the same perovskite structure. The percolation limit was estimated as (Co%)_P = 27(1)% (or x_P = 0.27(1)) from the magnetic data, which was slightly lower than that predicted by the percolation theory for a simple cubic lattice (31%); this trend was due to the strong magnetic anisotropy of the present system. In addition, rare incommensurate phase transitions were primarily detected below ~120 K for the pure Co and Zn members, which may also affect the magnetic properties of the materials.     

一种新型有机质子响应荧光分子的合成在实验教学中的设计与探索

本实验将最新的科研热点——有机发光材料引入实验教学,开发了基于一个荧光分子二甲氨基苯乙烯基苯并噁唑的合成实验,并考查了其质子响应性质。本实验反应温和易控,操作简单,现象明显,绿色环保,并且可以用于模块化教学,拆分成多个环节实验,适合不同学时的实验教学要求,既可培养学生的基本操作,又能激发学生的实验兴趣,锻炼学生的综合能力。     

基于S-型光催化机制CuInS2内嵌中空凹面氮化碳光催化分解H2O制H2（英文）

光催化解离H2O合成H2是绿色可再生的太阳能光子能量转换策略之一.目前,增强光催化材料对太阳能光子的捕获并将之有效利用仍然是一个具有挑战性的课题.光催化解离H2O反应包括三个过程:太阳能光子能量促使光生电子在半导体材料带隙中的跃迁;光生电子定向传输;光生电子与吸附在半导体材料表面的H2O分子发生反应.第一过程需要强的太阳光子捕获能力以产生足够的光生载流子;第二、三过程在动力学上反映了光生载流子在各个竞争过程中能否有效利用的问题,如光生电子迁移与H2O作用的速度很慢(~μs),而电子与空穴的复合速度快(~ps).目前研究者很难协调半导体材料的电学和光学特性以满足光生载流子在热力学和动力学两方面的要求.g-C3N4是由C、N原子通过sp2杂化组成的二维π共轭体系.当g-C3N4结构偏离二维平面时,共轭体系的π电子由凹面迁移到凸面,促使凹、凸面形成表观电势差,有利于电子的定向传输.本文通过卷曲sp2杂化离域均三嗪体系偏离二维平面,得到空心凹面g-C3N4结构,便捷地优化了半导体的电子结构.将CuInS2嵌入生长于空心g-C3N4的凹面,所构成的半导体光催化材料CuInS2@C3N4展现了增强的光捕获能力,以及电子定向传输转移能力.结合XPS、光电流测试、电化学阻抗谱、稳态及瞬态荧光等表征手段揭示空心g-C3N4凹、凸面表观电势差驱动光生电子以S-型光催化作用机制从CuInS2的Cu 2p向g-C3N4的N 1s的路径转移.因而,所构建的CuInS2@C3N4在可见光激发下产氢效率提高到373μmol·h^?1·g^?1,其产氢效率分别是二维平面g-C3N4负载1 wt%Pt和3 wt%Pd效率的1.57倍和1.35倍,表明空心g-C3N4凹、凸面电势差可以显著地促进光生电子分离和利用率,从而提高光催化解离水制氢效率.本文可增强g-C3N4的可持续太阳能转换性能,也适用于其他半导体材料以替代贵金属光催化体系,降低光催化产氢技术成本,促进光催化技术的应用.     

Hybrid Copolymerization via the Combination of Proton Transfer and Ring-opening Polymerization

Phosphazene base,t-BuP2,was employed to catalyze the proton transfer polymerization(PTP)of 2-hydroxyethyl acrylate(HEA),and PTP was further combined with ring-opening polymerization(ROP)to exploit a new type of hybrid copolymerization.The studies on homopolymerization showed that t-BuP2 was a particularly efficient catalyst for the polymerization of HEA at room temperature,giving an excellent monomer conversion.Throughout the polymerization,transesterification reactions were unavoidable,which increased the randomness in the structures of the resulting polymers.The studies on copolymerization showed that t-BuP2 could simultaneously catalyze the hybrid copolymerization via the combination of PTP and ROP at 25°C.During copolymerization,HEA not only provided hydroxyl groups to initiate the ROP ofε-caprolactone(CL)but also participated in the polymerization as a monomer for PTP.The copolymer composition was approximately equal to the feed ratio,demonstrating the possibility to adjust the polymeric structure by simply changing the monomer feed ratio.This copolymerization reaction provides a simple method for synthesizing degradable functional copolymers from commercially available materials.Hence,it is important not only in polymer chemistry but also in environmental and biomedical engineering.     

Modification of porous lignin with metalloporphyrin as an efficient catalyst for the synthesis of cyclic carbonates

Transition Metal Chemistry - The conversion of carbon dioxide into useful chemical raw materials is a necessary development for advancing carbon dioxide capture and storage technology. In this...     

绿色单体二氧化碳参与的新型聚合反应

二氧化碳（CO₂）是一种丰富、廉价、无毒以及可再生的一碳资源,也是一种可用于聚合的绿色单体.基于CO₂的聚合是近年来的研究热点之一.目前广泛报道的是CO₂和环氧单体的聚合反应,经过几十年的发展已经成功实现工业化生产.最近几年,一些CO₂参与的新型聚合反应被陆续报道,这些工作大都通过两种途径实现从CO₂到高分子材料的转变.第一个途径是先将CO₂转化为可以聚合的单体,例如：内酯、环状碳酸酯和2,5-二呋喃甲酸等,再利用开环或者逐步聚合将单体转化为聚合物;另一个途径是直接以CO₂为单体和其他类型单体共聚得到聚合物.这两种途径对于发展CO₂参与的新型聚合反应,拓展CO₂基聚合物种类都具有重要意义.本综述按照CO₂直接还是间接参与聚合反应分类总结了近年来在CO₂制备高分子材料方面的进展,并对未来发展方向进行了简单阐述.     

基于双极性铼配合物的低浓度淬灭电致发光器件

合成了一种含双极性9,9-双(9-乙基咔唑-3-基)-4,5-二氮芴(ECAF)配体的新型三羰基铼配合物Re(CO)3(ECAF)Cl,通过核磁共振氢谱及高分辨质谱对其结构进行了确定。以含有4,5-二氮-9,9-螺二芴(SB)配体的铼配合物Re(CO)3(SB)Cl作为参比物,对比研究了其热稳定性及光电性能。结果表明,与参比物的分解温度(366℃)相比,配合物Re(CO)3(ECAF)Cl有极好的热稳定性(热分解温度419℃)。由于富电子咔唑基团导致的能隙增大,相比参比物的发光波长(572 nm),Re(CO)3(ECAF)Cl的发光波长蓝移至565 nm。Re(CO)3(ECAF)Cl的发光量子效率(39%)稍高于参比物(37%)。以旋涂法制成电致发光器件后,基于Re(CO)3(ECAF)Cl器件的最佳掺杂浓度(质量分数)高达30%,是基于参比物器件的2.4倍,而且开启电压低至2.9 V,明显比参比物器件的4.0 V低,说明ECAF配体能有效抑制发光浓度淬灭,且明显改善了铼配合物的载流子传输性能。基于Re(CO)3(ECAF)Cl器件的最大电流效率及最大外量子效率分别为8.2 cd·A^-1和3.0%,低于参比物器件的9.7 cd·A^-1和3.9%。     

高稳定性水系锌离子电池正极材料MnO2@MgO的制备与性能

采用共沉淀法和热分解法合成了具有核壳结构的MnO2@MgO微球。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等手段对材料进行表征,结果发现包覆MgO不改变MnO2的结构,包覆层由纳米颗粒组成,厚度约为50 nm。电化学性能结果显示,包覆后材料的放电比容量明显提高,在100 mA·g^-1电流密度下,最大放电比容量为274.3 mAh·g^-1,比未包覆材料提高了12.8%。在1000 mA·g^-1电流密度下经过500次循环后,包覆后材料的放电比容量保持率高达84.1%,表现出优异的循环稳定性。MgO包覆层的存在避免了MnO2与电解液之间直接接触,抑制了电极材料在充放电过程中锰的溶解,从而显著提高MnO2的循环性能。     

REAL‐t1, an Effective Approach for t1‐Noise Suppression in NMR Spectroscopy Based on Resampling Algorithm

Summaryof main observation and conclusionIn multidimensional(nD)NMR spectroscopy,t1noise usually appears as ridges along indirect dimen-sions,and affects observation of weak signals.The main source of t1noise is instrumental instability,which causes random variation of FID amplitude during data acquisitions and introduces random noise-like peaks into spectrum after Fourier transformation.A number of efforts have been devoted,in order to develop new method or to improve existing approaches for suppressing t1noise.Herein,we propose a novel t1noise suppression method based on resampling algorithm for data processing,shortenedas REAL-t1.The method was verified using simulated 2D spectra,and NOESY spectra of sucrose and protein GB1,showing that the spectral quality was improved in all cases.The performance of REAL-t1was also compared with another recently pro-posed method,which showed that these two methods provided similar performance while REAL-t1cost much shorter experimental time.     

Synthesis of CF2H‐Containing Oxime Ethers Derivatives from ClCF2H,tert‐Butyl Nitrile and Indoles

Summaryof main observation and conclusion A new and intriguing methodology to access various O-difluoromethylation oxime compounds from CICF2H,TBN and indoles is developed under mild reaction conditions.This strategy can suppress N-difluoromethylation of indoles successfully,in which there are two different active species(:CF2and·NO)while indoles are unprotected,featuringsimple operation and radical involvement.