三角形Au@TiO2介孔催化剂可见光降解亚甲蓝

利用溶胶凝胶法制备出一种三角形Au@TiO₂核壳材料。经过水热晶化,该材料膨胀至300 nm,壳层TiO₂晶化为介孔锐钛矿相,但核心三角形Au颗粒的形貌保持不变。采用粉末X射线衍射(PXRD)、ζ电位、高分辨透射电子显微镜(HRTEM)、热重分析(TGA)、光致发光(PL)光谱、光电流(i-t)以及光催化降解技术,对样品的结构和性能进行了系统、详细的检测与分析。经过晶化处理的Au@TiO₂在可见光波段的光降解亚甲蓝性能比未晶化时有了显著的提升, 1 mg·mL^-1 Au@c-TiO₂可以在可见光照射1 h后实现对60 mg·L^-1亚甲蓝全降解。电子顺磁共振(EPR)测试表明·O₂^-和·OH两种自由基对光降解起到了很大作用。通过综合分析实验结果和时域有限差分(FDTD)分析,探究了催化反应的机理。     

Highly Robust but Surface‐Active: An N‐Heterocyclic Carbene‐Stabilized Au25 Nanocluster

Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface‐active for liquid‐phase catalysis without any pre‐treatment. Now, an N‐heterocyclic carbene‐stabilized Au₂₅ nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au₂₅(ⁱPr₂‐bimy)₁₀Br₇]²⁺ (ⁱPr₂‐bimy=1,3‐diisopropylbenzimidazolin‐2‐ylidene) ( 1 ), was synthesized by direct reduction of AuSMe₂Cl and ⁱPr₂‐bimyAuBr with NaBH₄ in one pot. X‐ray crystallization analysis revealed that the cluster comprises two centered Au₁₃ icosahedra sharing a vertex. Cluster 1 is highly stable and can survive in solution at 80 °C for 12 h, which is superior to Au₂₅ nanoclusters passivated with phosphines or thiols. DFT computations reveal the origins of both electronic and thermal stability of 1 and point to the probable catalytic sites. This work provides new insights into the bonding capability of N‐heterocyclic carbene to Au in a cluster, and offers an opportunity to probe the catalytic mechanism at the atomic level.     

The Structure–Property Correlations in the Isomerism of Au21(SR)15 Nanoclusters by Density Functional Theory Study

Isomerism of atomically precise noble metal nanoclusters provides an excellent platform to investigate the structure–property correlations of metal nanomaterials. In this study, we performed density functional theory (DFT) and time‐dependent (TD‐DFT) calculations on two Au₂₁(SR)₁₅ nanoclusters, one with a hexagonal closed packed core (denoted as Au₂₁ ^hcp ), and the other one with a face‐centered cubic core (denoted as Au₂₁ ^fcc ). The structural and electronic analysis on the typical Au–Au and Au–S bond distances, bond orders, composition of the frontier orbitals and the origin of optical absorptions shed light on the inherent correlations between these two clusters.     

Preparation and Characterization of Polymer‐Protected Pt@Pt/Au Core‐Shell Nanoparticles

Poly(N‐vinyl‐2‐pyrolidone) protected Pt‐core bimetallic Pt/Au‐shell (Pt@Pt/Au) nanoparticles were prepared by multi‐step reduction of HAuCl₄ and H₂PtCl₆ alternately by hydrogen adsorbed on platinum atom. Transmission electronic microscopy (TEM) and x‐ray diffraction (XRD) were used to characterize Pt@Pt/Au nanoparticles. The structure of the shell of the nanoparticles seems to be the Au‐Pt solid solution.     

Boosting the Efficiency of Dye-Sensitized Solar Cells by a Multifunctional Composite Photoanode to 14.13 %

We report a new strategy to fabricate a multifunctional composite photoanode containing TiO₂ hollow spheres (TiO₂-HSs), Au nanoparticles (AuNPs) and novel NaYF₄ : Yb,Er@NaLuF₄ : Eu@SiO₂ upconversion nanoparticles (UCNPs). The AuNPs are grown on the photoanode film including TiO₂-HSs and UCNPs by a simple in situ plasmonic treatment. As a result, an impressive power conversion efficiency of 14.13 % is obtained, which is a record for N719 dye-based dye-sensitized solar cells, demonstrating great potential for the solar cells toward commercialization. This obvious enhancement is ascribed to a collaborative mechanism of the TiO₂-HSs exhibiting excellent light-scattering ability, of the UCNPs converting near-infrared photons into visible photons and of the AuNPs presenting outstanding surface plasmon resonance effect. Notably, a steady-state experiment further reveals that the champion cell exhibits 95.33 % retainment in efficiency even after 180 h of measurements, showing good device stability.     

作为表面增强拉曼光谱基底的高度均匀Au纳米棒的构筑及对福美双的检测

采用种子生长法制备Au纳米棒(GNRs),随后进行组装和煅烧得到单层致密堆积的GNRs薄膜.在煅烧过程中,组装所需有机物在煅烧过程中分解,从而使得GNRs表面具有较高的清洁度.研究中发现,煅烧前后金纳米棒表面的间隙进一步提高,增强了其SERS(表面增强拉曼光谱)活性.为了研究其SERS活性,选择了2种探针分子以研究其灵...     

PDMS-Au复合基底上多环芳烃分子的表面增强拉曼光谱

利用聚二甲基硅氧烷(PDMS)对有机物的富集功能,通过在金纳米粒子单层膜(Au MLF)表面旋涂薄层PDMS膜制备PDMS-Au MLF复合表面增强拉曼光谱(SERS)基底.研究了SERS增强性能与旋涂液浓度及稀释溶剂间的关系,考察了复合基底增强活性的均匀性.研究发现,采用叔丁醇为稀释溶剂,浓度为2%(质量分数)的旋涂液时所得复合基底表面多环芳烃(PAHs)的SERS信号强度最高,且此基底SERS信号强度偏差小于10%.分别以PDMS-Au MLF复合材料和Au MLF作为基底,对比研究了对萘、蒽、菲和芘4种多环芳烃的SERS检测能力.结果表明,PDMS-Au MLF复合基底对以上4种有机物的检出限分别为10~(-6),10~(-7),10~(-8)及10~(-7)mol/L,相比于单一Au MLF基底,其检测限至少降低了1个数量级,这主要源自于PDMS对PAHs的富集作用,且此类复合基底可用于多种多环芳烃混合物的特征识别.