微量Mg/F表面梯度渗透改善高电压LiCoO2界面脆弱
王鑫龙, 程真国, 王果, 张晓琨, 向勇, 王欣全
【无机化学学报】doi: 10.11862/CJIC.20230259
采用高温固相法在1 050℃下烧结,制备了LiCoO2低浓度梯度改性样品,分别为LiF掺杂包覆(LCOLF、LCO@LF)和MgF2掺杂包覆(LCOMF、LCO@MF)。通过光电子能谱、透射电子显微镜和电化学技术等表征方法,对比分析材料形貌及电化学性能。结果表明,体相掺杂复合电极中,LCOLF热重测试显示出最优热稳定性,LCOMF晶体中(003)和(104)晶面间距收缩;45℃下1C倍率循环70圈后,LCOLF和LCOMF比容量分别为141.45和166.98 mAh·g-1,循环性能优于LiCoO2。表面包覆复合电极中,LCO@LF和LCO@MF晶粒表面光洁且晶格氧键价都向更高结合能方向增强;LCO@MF构建了坚实且紧密的包覆层,循环70圈后,放电比容量和容量保持率分别为183 mAh·g-1和91.26%(LCO@LF分别为154.38 mAh·g-1和77.54%),循环性能显著优于体相掺杂。
关键词: LiCoO2, 体相掺杂, 表面包覆, LiF, MgF2, 梯度渗透
MFI纳米片沉积层气相转化制备超薄b轴取向沸石膜
陈姣, 李毅, 谢毅, 刁丹丹, 肖强
【无机化学学报】doi: 10.11862/CJIC.20230403
利用乙二胺-水蒸汽进行气相转化(VPT)制备超薄、取向MFI沸石膜,通过将MFI纳米片沉积层转化为致密的沸石膜,实现了膜厚度的有效控制。扫描电子显微镜和X射线衍射表明,制备的沸石膜膜厚度约为280 nm,具有高度b轴取向的致密结构。丁烷异构体双组分分离测试结果表明,在333 K下,等物质的量的正丁烷/异丁烷混合物的正丁烷渗透速率和分离因子分别为1.5×10-7 mol·m-2·s-1·Pa-1和14.8。Na2SiO3作为低聚硅源在MFI沸石纳米片二次生长过程中能够提供硅源和碱度,通过在胺类蒸汽中实现MFI沸石纳米片间的融合生长,进一步提高了膜的取向度和致密性。
关键词: 膜分离, MFI沸石纳米片, 气相转化法, 低聚硅源, 硅酸钠
BiOCl/聚苯胺的制备及其光催化降解罗丹明B性能
张霞, 白羽石, 常熙, 张晗, 张灏昱, 彭利满, 黄姝姝
【无机化学学报】doi: 10.11862/CJIC.20240255
采用原位聚合法制备了氯氧化铋(BiOCl)与聚苯胺(PANI)复合的Ⅱ型异质结光催化剂BiOCl/PANI,并采用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-Vis DRS)和N2吸附-脱附测试等多种技术手段对其进行了表征,考察了BiOCl/PANI在模拟可见光下对罗丹明B (RhB)的光催化降解性能。实验结果表明:BiOCl/PANI催化剂比PANI和BiOCl具有更高的光催化活性,在RhB质量浓度为50 mg·L-1、PANI与BiOCl的物质的量之比为0.02∶1、50 mg·L-1的催化剂条件下,所制备的BiOCl/PANI光催化150 min后,RhB降解率为98.8%,速率常数为0.031 min-1;经过4次循环实验后,RhB降解率从98.8%降低至98.4%,表现出良好的稳定性和可重复利用性。光催化剂BiOCl/PANI实现了电子和空穴对的快速分离,降低了二者在催化剂内部的复合速率,提高了光催化性能。
关键词: 光催化, Ⅱ型异质结, BiOCl/polyaniline, 罗丹明B
B掺杂长余辉室温磷光碳量子点在信息加密与湿度检测中的应用
张越诚, 杨帆, 张诗雨, 马程骏, 田锐, 孙雪花, 李皓瑜, 孙凌波, 马红燕
【无机化学学报】doi: 10.11862/CJIC.20240415
以硼酸与苯甲酸(BZA)为原材料,通过一步热解法合成了B掺杂的长余辉室温磷光碳量子点(B-CQDs-BZA)。采用透射电子显微镜(TEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、紫外可见(UV-Vis)吸收光谱与荧光/磷光发射光谱对B-CQDs- BZA的形貌、结构及发光性能进行表征。结果显示,合成的B-CQDs-BZA主要是由无定形碳构成的尺寸介于2.0~4.5 nm之间的零维碳量子点。B-CQDs-BZA经254与302 nm的紫外光照射后,可呈现出长达20 s的蓝色室温磷光,经测试其磷光寿命长达2.09 s。该方法简单、快速且具有普遍适用性,使用多种原材料均可合成长余辉室温磷光CQDs。基于B-CQDs-BZA卓越的室温磷光发光寿命,我们将B-CQDs-BZA成功应用于时间分辨防伪技术。另外,根据水分子对B-CQDs-BZA的猝灭效应,将其制作成湿度试纸,用来检测环境空气的湿度。
关键词: 室温磷光, 碳量子点, 信息加密, 湿度
(m+n+…)还是[m+n+…]环加成?
杨占会, 许家喜
【大学化学】doi: 10.12461/PKU.DXHX202406032
学术界在表述环加成反应时,(m + n + …)和[m + n + …]环加成混用,不利于准确的学术交流。本文介绍了国际纯粹与应用化学联合会(IUPAC)规定的两种环加成反应表述方式,指明了它们的准确含义和使用环境。
关键词: 有机化学, 环加成反应, 原子个数, 电子个数, 高阶环加成
Research process on radioactive 18F-labelled chemical agents as positron emission tomography imaging probes for tumour detection
Rui WU, Yankun ZHANG, Jiufu LU, Pengfei ZHANG, Yang WANG
【无机化学学报】doi: 10.11862/CJIC.20240387
Malignant tumours always threaten human health. For tumour diagnosis, positron emission tomography (PET) is the most sensitive and advanced imaging technique by radiotracers, such as radioactive 18F, 11C, 64Cu, 68Ga, and 89Zr. Among the radiotracers, the radioactive 18F-labelled chemical agent as PET probes plays a predominant role in monitoring, detecting, treating, and predicting tumours due to its perfect half-life. In this paper, the 18F-labelled chemical materials as PET probes are systematically summarized. First, we introduce various radionuclides of PET and elaborate on the mechanism of PET imaging. It highlights the 18F-labelled chemical agents used as PET probes, including [18F]-2-deoxy-2-[18F]fluoro-D-glucose ([18F]-FDG), 18F-labelled amino acids, 18F-labelled nucleic acids, 18F-labelled receptors, 18F-labelled reporter genes, and 18F-labelled hypoxia agents. In addition, some PET probes with metal as a supplementary element are introduced briefly. Meanwhile, the 18F-labelled nanoparticles for the PET probe and the multi-modality imaging probe are summarized in detail. The approach and strategies for the fabrication of 18F-labelled PET probes are also described briefly. The future development of the PET probe is also prospected. The development and application of 18F-labelled PET probes will expand our knowledge and shed light on the diagnosis and theranostics of tumours.
关键词: 18F, radioactive, imaging, positron emission tomography, labelled, tumour
一种铝基平板孔金属有机骨架用于电子特种气体C3F8的高效分离与回收
方志, 孙亮, 郑铭泽, 申文豪, 黄宏亮, 仲崇立
【无机化学学报】doi: 10.11862/CJIC.20250096
本研究采用溶剂热法制备了一种具有狭缝孔结构的铝基-卟啉金属有机骨架(Al-TCPP)材料,并研究了其对电子特种气体C3F8的吸附分离和回收性能。所合成的Al-TCPP具有狭长平板孔结构,其孔尺寸为0.6 nm×1.1 nm,略微大于C3F8的分子尺寸(0.57 nm×0.52 nm)。同时,Al-TCPP孔道内密布的C—H键与μ-OH基团可与C3F8的F原子形成多重氢键作用位点,进一步增强了对C3F8的亲和力。吸附实验结果表明,在298 K、100 kPa下Al-TCPP对C3F8的吸附量高达96.1 cm3·g-1,而N2吸附量仅为6.1 cm3·g-1,其理想选择性高达244.8,超过了目前已报道的吸附剂材料。同时,C3F8在低压区的吸附热为50.6 kJ·mol-1,远高于N2的16.5 kJ·mol-1。密度泛函理论(DFT)计算表明,Al-TCPP结构中相邻的卟啉单元上的多个H原子可以同时与C3F8的多个F原子形成氢键。穿透实验证实Al-TCPP可以实现C3F8/N2混合物的有效分离,并且通过脱附可以回收获得高纯度的C3F8
关键词: 金属有机骨架, 电子特种气体, 八氟丙烷, 吸附分离
Construction and photocatalytic properties toward rhodamine B of CdS/Fe3O4 heterojunction
Yuan CONG, Yunhao WANG, Wanping LI, Zhicheng ZHANG, Shuo LIU, Huiyuan GUO, Hongyu YUAN, Zhiping ZHOU
【无机化学学报】doi: 10.11862/CJIC.20240219
A simple two-step hydrothermal method synthesized four different CdS/Fe3O4 photocatalysts with varying ratios of mass of CdS to Fe3O4. The composition and morphology of the prepared samples were investigated using X-ray diffraction (XRD), Raman spectrum, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Solid UV reflectance spectra testing found that CdS/Fe3O4 nanocomposites had good light absorption throughout the spectral range, promoting their photocatalytic properties. Under visible light irradiation, CdS/Fe3O4 (2:5) with a mass ratio of 2:5 exhibited excellent photocatalytic performance, with a degradation rate of 98.8% for rhodamine B. Furthermore, after five cycles of photocatalytic degradation reaction, the rhodamine B degradation rate remained at 96.2%, indicating that the photocatalysts have good photocatalytic stability.
关键词: CdS/Fe3O4, photocatalyst, degradation rate, rhodamine B
Corn straw-derived carbon/BiOBr composite: Synthesis and photocatalytic degradation performance for rhodamine B
Jin ZHANG, Yuting WANG, Bin YU, Yuxin ZHONG, Yufeng ZHANG
【无机化学学报】doi: 10.11862/CJIC.20250028
A flower-like BiOBr photocatalyst (CS/BiOBr) was prepared by using the carbon material derived from corn straw (CS) as the carrier. The prepared composites were characterized by X - ray diffraction (XRD), Fourier transform infrared (FIIR) spectra, scanning electron microscope (SEM), X - ray photoelectron spectra (XPS), and UV-Vis diffuse reflectance spectra (UV-Vis DRS). The SEM analyses indicate that the introduction of CS promotes the formation of a unique flower-like structure in BiOBr, which not only optimizes the efficiency of light capture but also increases the specific surface area of BiOBr. The bandgap of the composite was narrower compared with the pure BiOBr. The CS/BiOBr composites exhibited higher photocatalytic activity than pure CS and BiOBr under visible light irradiation, and a higher first-order reaction rate constant (k) of 0.043 7 min-1 than BiOBr (0.014 6 min-1), and exhibited excellent stability and reusability during the cyclic run. The enhanced photocatalytic activity is attributed to the efficient separation of photoinduced electrons and holes. Superoxide radicals and holes were the major active species.
关键词: corn straws, agricultural waste, BiOBr, photocatalysis, rhodamine B
Coordination equilibrium between cyclometalated Pt(Ⅱ) complexs [Pt(κ3-N^C^N′)(CNXyl)]Cl and [Pt(κ2-N^C^N′)(CNXyl)Cl]
Huahong ZHANG, Yang ZHAO, Rui NING, Shuixing WU, Xiaopeng ZHANG
【无机化学学报】doi: 10.11862/CJIC.20250136
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex [Pt(N^C^N′)Cl] with the aryl isocyanide 2,6-dimethylphenyl isocyanide (CNXyl) afforded a mixture of two isomeric species: the ionic complex [Pt(κ3-N^C^N′)(CNXyl)]Cl ([A]Cl) and the molecular complex [Pt(κ2-N^C^N′)(CNXyl)Cl] (B). Isomer B was almost the dominating product. The structures of the isomer B derivatives bearing —CF3 and —Cl substituents on the pyridine ring of the pinene moiety (5B and 7B, respectively) have been confirmed by single-crystal X-ray diffraction, revealing a slightly distorted square planar geometry with trans-NN^C^N′, CNR configuration (The terminal N atom of the κ2-N^C^N′ ligand is trans to the isocyanide ligand CNXyl.). Isomer B is thermodynamically more stable, as confirmed by theoretical calculations.
关键词: coordination equilibrium, cyclometalated Pt(Ⅱ) complex, isocyanide, pinene group

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