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Zr‐MOF nanosheets featuring benzothiadiazoles enable efficient visible light driven photooxidation of sulfides and amines 以苯并噻二唑为特征的 Zr-MOF 纳米片能在可见光驱动下实现硫化物和胺的高效光氧化反应
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-16 DOI: 10.1002/cnma.202400302
Yuan-Zhi Tan, Yu-Qing Zhao, Xing-Yu Zhou, Ying-Mei Zhao, Bi-Fu Luo, Hai-Xing Li, Jin-Liang Zhuang
Ultrathin zirconium‐based metal–organic framework (MOF) nanosheets, embedded with photochromic units, are expected to be highly efficient heterogeneous photocatalysts, thanks to their rich catalytic sites, short diffusion paths, and effective separation of photogenerated charge carriers. Herein, we reported the synthesis of novel Zr‐MOF nanosheets (Zr‐BTDB) through a solvothermal synthesis that integrates benzothiadiazole (BTz) as a photochromic moiety within the framework of MOF. The Zr‐BTDB nanosheets processes a [Zr12(μ3‐O)8(μ3‐OH)8(μ2‐OH)6] cluster with hcp topology. Importantly, Zr‐BTDB nanosheets exhibit excellent photocatalytic activity for the photooxidation of sulfides and amines at room temperature under blue light irradiation. Notably, these nanosheets maintain their photocatalytic activity and selectivity for up to five cycles without significant loss of activity and crystallinity. Systematical catalytic reactions revealed that the Zr‐BTDB nanosheets enable the generation of singlet oxygen (1O2) and superoxide radical (O2•–) under visible light irradiation, which is critical reactive oxygen species for the photooxidation of sulfides and benzylamines. Our work represents a straightforward route for the preparation of ultrathin, water stable, and visible‐light‐activated Zr‐MOF nanosheets, offering new potentials for the selective photooxidation of sulfides and amines in an eco‐friendly way.
嵌入光致变色单元的超薄锆基金属有机框架(MOF)纳米片具有丰富的催化位点、较短的扩散路径和有效分离光生电荷载流子的特性,有望成为高效的异相光催化剂。在此,我们报道了通过溶热合成法合成新型 Zr-MOF 纳米片(Zr-BTDB)的过程,该方法在 MOF 框架内整合了苯并噻二唑(BTz)作为光致变色分子。Zr-BTDB 纳米片形成了具有 hcp 拓扑结构的[Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6]簇。重要的是,Zr-BTDB 纳米片在室温蓝光照射下对硫化物和胺的光氧化表现出卓越的光催化活性。值得注意的是,这些纳米片在保持光催化活性和选择性长达五个周期后,其活性和结晶度都没有明显下降。系统催化反应表明,在可见光照射下,Zr-BTDB 纳米片能够生成单线态氧(1O2)和超氧自由基(O2--),而单线态氧和超氧自由基是硫化物和苄胺光氧化反应的关键活性氧。我们的工作为制备超薄、水稳定和可见光激活的 Zr-MOF 纳米片提供了一条直接的途径,为以生态友好的方式选择性光氧化硫化物和胺提供了新的潜力。
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引用次数: 0
Conversion of 5-Hydroxymethylfurfural and Carbohydrates to 2,5-Diformylfuran Over MoOx/Biochar Catalysts 在支撑的钼基催化剂上将 5-羟甲基糠醛和碳水化合物转化为 2,5-二甲酰呋喃
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-15 DOI: 10.1002/cnma.202400351
Delong Yang, Ziting Du, Dr. Jinhang Dai, Qingya Cao, Prof. Zhaobao Xiang, Prof. Gang Chen, Dr. Fukun Li

Here, a series of nitrogen-doped carbon (NC) supported transition metal oxide catalysts were prepared by pyrolysis of chitosan-metal salt mixtures for the efficient synthesis 2,5-diformylfuran (DFF) from 5-hydroxymethylfurfural (HMF) and fructose. Among them, supported molybdenum-based species on nitrogen-doped carbon (Mo/NC) exhibited excellent activity and selectivity for selective oxidation of HMF to DFF. The presence of nitrogen species reduces the electron cloud density around the Mo species, thereby improving the catalytic activity. Moreover, the interaction between active MoO2 species on the catalyst surface and NC ensured the stability of the catalyst, resulting in no significant loss of activity after four catalytic cycles. 99.5 % and 55.1 % yields of DFF with full conversion were obtained from HMF and fructose respectively over Mo/NC-chitosan-600 in DMSO under ambient air. In order to enhance DFF yield from fructose, sulfonate groups were introduced into Mo/NC-chitosan-600 catalyst, leading to the highest DFF yield of 70.2 %. In addition, this catalyst also allowed 10.0%, 22.9% and 33.3% DFF yields from glucose, sucrose and inulin, respectively.

本文通过热解壳聚糖-金属盐混合物制备了一系列氮掺杂碳(NC)支撑过渡金属氧化物催化剂,用于从 5- 羟甲基呋喃(HMF)和果糖高效合成 2,5-二甲酰呋喃(DFF)。其中,掺氮碳(Mo/NC)上的钼基支撑物在选择性氧化 HMF 到 DFF 的过程中表现出优异的活性和选择性。氮元素的存在降低了钼元素周围的电子云密度,从而提高了催化活性。此外,催化剂表面的活性 MoO2 物种与 NC 之间的相互作用确保了催化剂的稳定性,使催化剂在经过四个催化循环后活性没有明显下降。在环境空气中,Mo/NC-壳聚糖-600 在 DMSO 中分别从 HMF 和果糖中获得了 99.5% 和 55.1% 的完全转化的 DFF 产率。为了提高果糖的 DFF 收率,在 Mo/NC-chitosan-600 催化剂中引入了磺酸基团,从而获得了最高的 70.2% DFF 收率。此外,这种催化剂还能使葡萄糖、蔗糖和菊粉的 DFF 产率分别达到 10.0%、22.9% 和 33.3%。
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引用次数: 0
Quantitative and Ultrasensitive Detection of Four Inflammatory Biomarkers by Gold Nanoparticle-Based Paper Sensor 基于金纳米粒子的纸质传感器对四种炎症生物标记物进行定量和超灵敏检测
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-15 DOI: 10.1002/cnma.202400118
Liya Ye, Aihong Wu, Liqiang Liu, Hua Kuang, Chuanlai Xu, Xinxin Xu

Due to the complexity and diversity of infectious diseases, diagnosis based solely on symptoms and imaging manifestations is associated with a high rate of misdiagnosis, so it is particularly important to find reliable and accurate biomarkers. Four inflammatory biomarkers (CRP, IL-6, PCT and SAA) have different manifestations and roles in different infectious diseases and stages of infection, and the diagnosis and identification of infectious diseases can be realized through quantitative analysis of these four biomarkers simultaneously. In this study, we developed a colloidal gold nanoparticle (AuNP)-based multiplex LFA strip using eight highly-sensitive monoclonal antibodies that simultaneously detected CRP, IL-6, PCT and SAA in serum within 15 min. And quantitative analysis was achieved with a portable strip reader, the LODs were 2.5 μg/mL, 25.3 pg/mL 0.87 ng/mL and 8.8 μg/mL for CRP, IL-6, PCT and SAA, while detection ranges were 2.5–200 μg/mL, 25.3–8000 pg/mL 0.87–100 ng/mL and 8.8–200 μg/mL. Moreover, the quantitative colloidal gold assay correlated well with the results of a chemiluminescence immunoassay when testing clinical serum samples. Our developed method was reliable and accurate according to the recovery test results. Therefore, the strip can be used as an alternative method for the simultaneous monitoring of CRP, IL-6, PCT and SAA in serum samples.

四种炎症生物标志物(CRP、IL-6、PCT 和 SAA)在不同的感染性疾病和感染阶段有不同的表现和作用,通过同时定量分析这四种生物标志物可以实现对感染性疾病的诊断和鉴别。本研究开发了一种基于胶体金纳米颗粒(AuNP)的多重 LFA 检测试纸条,使用八种高灵敏度的单克隆抗体,可在 15 分钟内同时检测血清中的 CRP、IL-6、PCT 和 SAA。CRP、IL-6、PCT 和 SAA 的检测限分别为 2.5 μg/mL、25.3 pg/mL 0.87 ng/mL 和 8.8 μg/mL,检测范围分别为 2.5-200 μg/mL、25.3-8000 pg/mL 0.87-100 ng/mL 和 8.8-200 μg/mL。此外,在检测临床血清样本时,胶体金定量检测法与化学发光免疫分析法的结果具有良好的相关性。根据回收率测试结果,我们开发的方法是可靠和准确的。因此,该试剂条可作为同时监测血清样本中 CRP、IL-6、PCT 和 SAA 的替代方法。
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引用次数: 0
Self-Assembled Bioinspired Short Metallopeptide Nanostructures for Plausible Biomedical Applications 自组装生物启发短金属肽纳米结构的合理生物医学应用
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-14 DOI: 10.1002/cnma.202400098
Shruti Sharma, Aanand Kautu, Dr. Nikunj Kumar, Narayan Swain, Vikas Kumar, Dr. Ramesh Singh, Dr. Khushboo Kesharwani, Dr. Narendra Singh, Dr. Puneet Gupta, Dr. Khashti Ballabh Joshi

Metal chelation, characterized by its precise interactions with diverse functional groups, assumes a pivotal role in providing structural stability and generating reactive centers within metalloproteins and metallopeptides. This, in turn, orchestrates the architecture and functionality of various biological processes in living organisms. In our biomimetic approach inspired by the intricacies of natural metallopeptides, we have purposefully designed pyridine-bis-tyrosine, a concise Metallopeptide Conjugate (sMPC). Demonstrating the capacity to form complexes with various bioactive metal ions, sMPC emerges as a promising tool for advancing our understanding of metal-binding proteins and catalyzing the development of cutting-edge biotechnological materials and technologies. Our investigations underscore the hierarchical self-assembly of these abridged conjugates into toroidal to vesicle nanostructures, influenced by concentration, and their susceptibility to spatial manipulation through metal ion coordination with functional groups. These biocompatible metal peptide complexes and their resultant nanomaterials present specific potential as exceptional therapeutic agents to address problems associated with metal ion deficiencies, offering a facile and low-cost alternative to traditional metallodrugs.

金属螯合的特点是能与各种功能基团发生精确的相互作用,在提供结构稳定性以及在金属蛋白和金属肽中产生反应中心方面发挥着关键作用。这反过来又协调了生物体内各种生物过程的结构和功能。受天然金属肽复杂性的启发,我们采用仿生方法,有目的地设计了吡啶-双酪氨酸--一种简明金属肽共轭物(sMPC)。sMPC 具有与各种生物活性金属离子形成复合物的能力,是一种很有前途的工具,可促进我们对金属结合蛋白的了解,并推动尖端生物材料和技术的发展。我们的研究强调了这些节段共轭物在浓度影响下分层自组装成环状到囊状纳米结构的过程,以及它们通过金属离子与功能基团配位进行空间操纵的易感性。这些具有生物兼容性的金属肽复合物及其产生的纳米材料具有特殊的治疗潜力,可以解决与金属离子缺乏有关的问题,为传统金属药物提供了一种简便、低成本的替代方法。
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引用次数: 0
Metal-Support Interaction Boosts Au Catalysts for Hydrogen Evolution-Coupled Ethanol Electro-Oxidation Reaction 金属与支撑物的相互作用促进了金催化剂在氢气进化耦合乙醇电氧化反应中的应用
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1002/cnma.202400267
Yiquan Yin, Dr. Fangwei Gu, Yuxin Wang, Chengjin Chen, Yongsheng Wang, Prof. Wei Zhu, Prof. Zhongbin Zhuang

Electrochemical hydrogen and acetate cogeneration from ethanol is a promising green hydrogen production technique with low hydrogen production energy consumption and high profitability. However, the poor catalytic stability of the anodic ethanol electro-oxidation reaction (EOR) retards the device application. We adopted a metal support interaction strategy to reinforce small-sized Au active sites using cuprous sulfide supports. The Au−Cu2–xS/C showed a superior activity of 1055 mA mgAu−1 at 1.1 V vs. RHE and retained the high activity in the chronopotentiometric test, surpassing the Au/C catalyst. It was demonstrated that the Cu2–xS support facilitated the formation of Au−OH and prevented the gold sites from aggregation, leading to high activity and stability for EOR. Finally, an electrochemical cogeneration electrolyzer assembled with the Au−Cu2–xS/C anodic catalyst continuously ran for over 100 hours, suggesting the device‘s applicability.

利用乙醇进行电化学制氢和醋酸联产是一种前景广阔的绿色制氢技术,具有制氢能耗低、收益高的特点。然而,阳极乙醇电氧化反应(EOR)的催化稳定性较差,阻碍了该装置的应用。我们采用金属支撑相互作用策略,利用硫化亚铜支撑强化小尺寸金活性位点。Au-Cu2-xS/C 在 1.1 V 对 RHE 时显示出 1055 mA mgAu-1 的卓越活性,并在计时电位测试中保持了高活性,超过了 Au/C 催化剂。研究表明,Cu2-xS 支持物促进了 Au-OH 的形成,并阻止了金位点的聚集,从而提高了 EOR 的活性和稳定性。最后,使用 Au-Cu2-xS/C 阳极催化剂组装的电化学热电联产电解槽连续运行了 100 多个小时,表明了该装置的适用性。
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引用次数: 0
Fast, Simple, and Cost-Effective Fabrication of High-Performance Thermoelectric Ag2Se through Low-Temperature Hot-Pressing 通过低温热压快速、简单、经济高效地制造出高性能热电Ag2Se
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1002/cnma.202400319
Jariya Lasiw, Teerasak Kamwanna, Supree Pinitsoontorn

Silver selenide (Ag2Se) is a promising thermoelectric material for near-room temperature applications. This study proposes a fast, simple, and cost-effective method for producing high thermoelectric performance bulk Ag2Se. Ag2Se powders were synthesized from Ag and Se powders via a one-hour wet ball milling process, followed by the fabrication of bulk pellets through low-temperature hot-pressing (130–250 °C) with a mere 0.5-hour holding time. Both Ag2Se powders and bulk pellets exhibited a single phase of Ag2Se with an orthorhombic structure. Moreover, uniform compositional distribution with the stoichiometric Ag : Se ratio was observed in all samples. Microstructural analysis revealed distinct grain boundaries in samples hot-pressed below 190 °C, transitioning to grain coalescence was at 190 °C and 250 °C. The thermoelectric and transport measurements demonstrated that the electrical conductivity decreased and the Seebeck coefficient increased with hot-pressing temperatures from 130 °C and 190 °C primarily due to reduced carrier concentrations. Thermal conductivity decreased with increasing hot-pressing temperatures up to 190 °C, attributed to the weak chemical bonding of Ag2Se and the presence of defects. This combination resulted in a peak zT over 1.0 at 300 K, with an average zT close to 1.0 from 300 to 380 K. In comparison to other reported synthesis methods, the present approach offers significantly reduced processing time, simplicity, and cost-effectiveness. Despite lower temperatures and shorter processing times, the method produces Ag2Se with zT values comparable to more intricate techniques. This fabrication route holds the potential for scalable mass production in the future.

硒化银(Ag2Se)是一种很有前途的近室温应用热电材料。本研究提出了一种快速、简单、经济高效的方法来生产高热电性能的块状 Ag2Se。通过一个小时的湿球磨工艺,从Ag和Se粉末中合成出Ag2Se粉末,然后通过低温热压(130-250 °C)制造出块状颗粒,保温时间仅为0.5小时。Ag2Se 粉末和块状颗粒都呈现出单相正交β-Ag2Se 相,成分分布均匀。微观结构分析表明,在 190 ℃ 以下热压的样品中晶界明显,在 190 ℃ 和 250 ℃ 时过渡到晶粒凝聚。热电和传输测量表明,随着热压温度从 130 ℃ 升至 190 ℃,电导率降低,塞贝克系数升高,这主要是由于载流子浓度降低。热导率随着热压温度的升高而降低,直到 190 ℃,这归因于 Ag2Se 的弱化学键和缺陷的存在。尽管温度较低,加工时间较短,但该方法生产出的 Ag2Se 的 zT 值可与更复杂的技术相媲美。
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引用次数: 0
Highly Sensitive Two-Dimensional Ruddlesden-Popper Perovskites for Thermochromic Smart Windows 用于热致变色智能窗的高灵敏度二维 Ruddlesden-Popper Perovskites
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-11 DOI: 10.1002/cnma.202400306
Ruijie Han, Qi Yue, Yingjie Cao, Duo Wei, Xiaolin Liu, Jia Lin

With the growing demand for high-performance smart windows, the discover of a class of thermochromic materials with reversible cycling and rapid response characteristics has become urgent. In this work, we have uncovered a two-dimensional (2D) Ruddlesden-Popper (RP) phase halide perovskite, (PMA)2MAPb2I7−xClx, where PMA=C6H5CH2NH3 and MA=CH3NH3, exhibiting exceptional reversible thermochromic properties. The 2D RP phase perovskite thin film features a low transition temperature (Tc=30 °C from the hydrated state to the hot state, along with a fast transition time of 40 s. Furthermore, the addition of 0.5 times excess MAI significantly enhances the visible light transmittance of the hydrated state. Characteristic hydration peaks in X-ray diffraction patterns and O−H bond absorption peaks Fourier-transform infrared spectra are observed in the thin film in its hydrated state, which disappear in the hot state, validating its reversible thermochromic properties. Additionally, a solar cell based on the thermochromic 2D RP phase thin film achieves a power conversion efficiency of 2.31 %, offering a promising solution for advanced smart window technologies.

随着人们对高性能智能窗户的需求日益增长,发现一类具有可逆循环和快速响应特性的热致变色材料已成为当务之急。在这项工作中,我们发现了一种二维(2D)Ruddlesden-Popper(RP)相卤化物包晶体--(PMA)2MAPb2I7-xClx,其中 PMA = C6H5CH2NH3,MA = CH3NH3,表现出优异的可逆热致变色特性。这种二维 RP 相包晶石薄膜从水合态到热态的转变温度低至 30 °C,转变时间短至 40 秒。此外,添加 0.5 倍过量的 MAI 能显著提高水合态的可见光透射率。在水合态薄膜的 X 射线衍射图谱中可以观察到特征性的水合峰,在傅立叶变换红外光谱中可以观察到 O-H 键吸收峰,这些峰在热态时消失,从而验证了其可逆热致变色特性。此外,基于热致变色二维 RP 相薄膜的太阳能电池实现了 2.31% 的功率转换效率,为先进的智能窗户技术提供了一种前景广阔的解决方案。
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引用次数: 0
Rapid Colorimetric Detection of Ca(II) Based on Surface Plasmon Resonance Absorbances of 5-PBA@AuNPs Sensor 基于 5-PBA@AuNPs 传感器表面等离子共振吸光率的 Ca(II) 快速比色检测技术
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-09 DOI: 10.1002/cnma.202400305
Jingyi Ma, Guona Li, Xueqi Duan, Jin-Peng Xue, Xing Li, Yun Li

Calcium ions (Ca2+) are essential for a myriad of physiological functions, including excitability, neurotransmitter release, gene transcription, cell proliferation, synaptic plasticity, and hormone secretion. Consequently, the detection of Ca2+ concentrations in water is of fundamental and practical significance. In this study, a novel method for the simple, visual, and rapid colorimetric detection of Ca2+ is introduced, leveraging the surface plasmon resonance (SPR) absorbances of gold nanoparticles (AuNPs) modified with 5-Pyrimidinylboronic acid (5-PBA). A color change from wine-red to gray-blue was observed with increasing concentrations of Ca2+, indicative of the agglomeration of AuNPs. This agglomeration displayed favorable anti-interference properties and selectivity. The limits of detection (LOD) were determined to be 0.08 mM by the unaided eye and 3.29 μM by UV-visible spectroscopy. Moreover, an excellent linear relationship (R2=0.9879) was maintained within the Ca2+ concentration range of 0.0 to 0.5 mM. These results suggest that AuNPs modified with 5-PBA are suitable for the quantitative determination of Ca2+. Subsequent testing on actual samples confirmed that this new method could be effectively applied to the monitoring of Ca2+ in water.

钙离子(Ca2+)对多种生理功能至关重要,包括兴奋性、神经递质释放、基因转录、细胞增殖、突触可塑性和激素分泌。因此,检测水中的 Ca2+ 浓度具有重要的现实意义。本研究利用 5-嘧啶基硼酸(5-PBA)修饰的金纳米粒子(AuNPs)的表面等离子体共振(SPR)吸光度,介绍了一种简单、直观、快速的比色法检测 Ca2+。随着 Ca2+ 浓度的增加,观察到颜色从酒红色变为灰蓝色,这表明 AuNPs 发生了团聚。这种团聚显示出良好的抗干扰性能和选择性。检测限(LOD)经肉眼测定为 0.08 mM,经紫外可见光谱测定为 3.29 μM。此外,在 0.0 至 0.5 mM 的 Ca2+ 浓度范围内,保持了良好的线性关系(R2 = 0.9879)。这些结果表明,用 5-PBA 修饰的 AuNPs 适用于 Ca2+ 的定量测定。随后的实际样品测试证实,这种新方法可有效地用于监测水中的 Ca2+。
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引用次数: 0
Copper(I) Induced Phase Transition and 1D Growth in Cesium Lead Bromide Cubic Nanocrystals 铜(I)诱导的溴化铯铅立方纳米晶体的相变和一维生长
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-09 DOI: 10.1002/cnma.202400270
Fency Sunny, Pratap Mane, Brahmananda Chakraborty, Nandakumar Kalarikkal, Subila Kurukkal Balakrishnan

Lead halide perovskites have been explored ardently in the past decade owing to their excellent photophysical properties. High-temperature cation exchange reactions have been employed to improve the stability and performance in perovskite lattice, but lacks control over size, shape, and stoichiometry. Herein, the solution phase interaction of cesium lead bromide (CsPbBr3) nanocrystals with monovalent and bivalent copper ions, under ambient conditions is systematically investigated. The introduction of Cu1+ explicitly initiates a one-dimensional growth with a distinct phase transition, that is from cubic to orthorhombic, while Cu2+ induces a partial exchange with Pb2+ with no phase change. DFT calculations suggest that Cu1+ induces structural distortion via Cs1+ substitution, altering the Goldschmidt tolerance factor and perovskite octahedral tilting, leading to the phase transition. Additionally, the oleic acid/amine ligands used to stabilize the nanocrystals, are preferentially etched away to form complexes with Cu1+, initializing an oriented growth of the nanocubes to nanorods. A mechanistic investigation of the evolution of the nanorods gave insights on tuning the tolerance factor via room temperature modifications and cation exchanges in perovskites for anisotropy and morphology tuning. This effortlessly obtained perovskite nanorods with Cu1+ could find effective applications in optoelectronics, and as novel photocatalysts.

由于卤化铅包晶石具有优异的光物理特性,在过去十年中,人们一直在对其进行积极探索。人们采用高温阳离子交换反应来提高包晶晶格的稳定性和性能,但缺乏对尺寸、形状和化学计量的控制。本文系统地研究了纳米溴化铯铅(CsPbBr3)晶体在环境条件下与一价和二价铜离子的溶液相相互作用。Cu1+ 的引入明确地启动了一维生长,并产生了明显的相变,即从立方到正方的转变,而 Cu2+ 则诱导了与 Pb2+ 的部分交换,但没有相变。DFT 计算表明,Cu1+ 通过 Cs1+ 取代引起结构畸变,改变了戈尔德施密特容限因子和包晶八面体倾斜,导致了相变。此外,用于稳定纳米晶体的油酸/胺配体被优先蚀刻掉,与 Cu1+ 形成络合物,使纳米立方体开始定向生长为纳米棒。通过对纳米棒演变的机理研究,我们深入了解了如何通过室温改性和过氧化物中的阳离子交换来调整耐受因子,从而实现各向异性和形态调整。这种不费吹灰之力就能获得的含 Cu1+ 的包晶纳米棒可有效地应用于光电子学和新型光催化剂。
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引用次数: 0
Stability and Surface Functionalization of Plasmonic Group 4 Transition Metal Nitrides 等离子体第 4 族过渡金属氮化物的稳定性和表面功能化
IF 2.6 4区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-08 DOI: 10.1002/cnma.202400236
Dreenan Shea, Reem A. Karaballi, Samantha Jee, Mita Dasog

Plasmonic transition metal nitrides (TMNs) have emerged as a low-cost and thermally and chemically robust alternatives to noble metals. While their superior thermal properties have been established, their chemical properties on the nanoscale haven't been as well investigated. Herein, the oxidative stability over time under ambient conditions and colloidal stability as function of pH was explored for plasmonic TiN, ZrN, and HfN nanoparticles. It was discovered that the TMN nanoparticles made via solid-state method had a narrow pH stability range between 2–3. Under highly acidic conditions, the particles underwent dissolution and at pH ≥4, they aggregate and precipitate from the solution. Additionally, TiN nanoparticles had poor oxidative stability and oxidized to TiO2 after ~40 days. 3-Aminopropyltriethoxysilane (APTES) and dimethylsilane coated TMNs were synthesized to yield water and organic solvent dispersible particles, respectively. These functionalized colloidal suspensions showed enhanced oxidative stability over 60 days and the APTES coating widened the pH stability window of TMNs to include physiological pH. This study shows that surface functionalization using M−O−Si linkages (where M=Ti, Zr, or Hf) can greatly enhance the stability, dispersibility and therefore applicability of plasmonic TMN nanoparticles.

等离子体过渡金属氮化物(TMNs)已成为贵金属的低成本、热稳定性和化学稳定性的替代品。虽然其优越的热性能已经得到证实,但对其纳米级化学性质的研究还不够深入。在此,研究人员探讨了等离子体 TiN、ZrN 和 HfN 纳米粒子在环境条件下的氧化稳定性以及胶体稳定性与 pH 值的关系。研究发现,固态法制备的 TMN 纳米粒子的 pH 稳定性范围较窄,在 2 - 3 之间。在高酸性条件下,颗粒会发生溶解,而在 pH 值≥ 4 时,颗粒会聚集并从溶液中析出。此外,TiN 纳米粒子的氧化稳定性较差,约 40 天后就会氧化成 TiO2。3-Aminopropyltriethoxysilane (APTES) 和二甲基硅烷包覆的 TMNs 被合成出来,分别产生可在水和有机溶剂中分散的颗粒。这些功能化胶体悬浮液在 60 天内显示出更强的氧化稳定性,而 APTES 涂层则将 TMN 的 pH 稳定窗口扩大到生理 pH 值。这项研究表明,使用 M-O-Si 链接(其中 M = Ti、Zr 或 Hf)进行表面功能化可大大提高等离子 TMN 纳米粒子的稳定性、分散性和适用性。
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引用次数: 0
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ChemNanoMat
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