A novel bimetallic RuFe nanocluster to enable highly efficient oxygen reduction in zinc-air batteries

Zinc-air batteries (ZABs) have the advantages of high energy density and safety but their large-scale application is hindered by sluggish kinetics of four-electron aqueous O₂ redox reactions. Widely used Ruthenium (Ru)-based catalysts possess intrinsic oxygen evolution catalytic activity but suffer from insufficient oxygen reduction reaction (ORR) performance. Herein, to optimize the ORR activity of Ru-based catalyst, an iron (Fe)-coordinated, bimetallic RuFe cluster is constructed and homogeneously dispersed within nitrogen (N)-doped carbon layers (denoted as RuFe@NC). Benefitting from the optimized ORR activity and more active site exposure, the RuFe@NC exhibits superior ORR activity with a half wave potential (E_1/2) of 0.88 ?V higher than that of Pt/C (0.82 ?V). Accordingly, the RuFe@NC-based ZAB outperforms the Pt/C ?+ ?IrO₂-based device, presenting a reduced polarization of 0.7 ?V and an enhanced cycling lifetime of 50 ?h at 10 ?mA ?cm^?2. Moreover, the optimized structural design ultralow Ru loading (0.013 mg_Ru cm^?2) overcomes the cost barriers and demonstrates its high practicality. This bimetallic RuFe nanocluster opens a new way for future design of more efficient and stable catalytic systems.     

Electrocatalytic oxidation of ethanol and ethylene glycol on bimetallic Ni and Ti nanoparticle-modified indium tin oxide electrode in alkaline solution

Bimetallic Ni and Ti nanoparticle-modified indium tin oxide electrode(Ni–TiNPs/ITO) were prepared by a twostep ion implantation method, and their electrocatalytic activity toward the oxidation of ethanol and glycol was evaluated. The ion-implantation method is simple, low-cost and environmental friendly without the use of any binder. The Ni–TiNPs/ITO electrode were characterized by scanning electron microscopy(SEM), atomic force microscopy(AFM) and X-ray photoelectron spectroscopy(XPS). SEM and AFM showed that the nanoparticles on the Ni–TiNPs/ITO electrode had a small range of dispersion(10–20 nm) and high dispersion. Electrochemical performances were measured by cyclic voltammetry(CV) and chronoamperometrics. The Ni–TiNPs/ITO electrode exhibited much higher electrocatalytic activity and stability for ethanol and ethylene glycol oxidation than NiNPs/ITO.     

NiPt hollow nanocatalyst: Green synthesis,size control and electrocatalysis

Nearly monodispersed hollow nanospheres of bimetallic NiPt have been synthesized by a one-pot wet chemical method at room temperature with a precursor Ni nanocompound as a sacrificial template. The size control is carried out via the sacrificial template, from about 35 nm to nearly100 nm in diameter. The shell thickness of the NiPt hollow sphere reaches down to as thin as 2–3 nm slightly larger than a single layer of alloyed NiPt nanocrystallites. The product with the citric acid as surfactant exhibits enhanced oxygen reduction activities compared to a commercial Pt/C catalyst and the hollow nanospheres coated with PVP. It has potential applications in fuel cells, biotechnology and environmental chemistry with the facile synthesis, low cost and excellent electrocatalytic activity.     

理论与计算化学研究进展

化学是一门有坚实理论体系的基础学科,作为其中一个分支,理论与计算化学的飞速发展使得化学成为实验与理论并重的科学.结合价键理论方法、生物体系理论模拟和激发态光化学、固体表面与纳米结构体系、复杂体系分子量子动力学和密度泛函理论方法发展和核磁共振理论研究等,简要回顾了近期本研究团队和国内外本学科的发展情况,重点介绍了厦门大学在量子化学理论计算方法发展、计算程序研发、复杂体系的动力学以及酶催化反应的计算模拟等方面的研究.     

Laser synthesized nanoparticle alloys of metals with bulk miscibility gaps

The nanoscale alloying of metals with bulk miscibility gaps, Ag-Pt and Ag-Rh, has been investigated using pulsed laser ablation of solids in solution(PLASiS). The procedure was in two steps. In the first step, the suspensions of monometallic nanoparticles were prepared by ablation of a metal rod submerged in water. In the second step,the monometallic suspensions were mixed and alloying was induced by re-irradiation. For the Ag-Pt system, a surface plasmon resonance was observed in the monometallic silver suspension. The surface plasmon resonance vanished in re-irradiated Ag-Pt suspensions, indicating alloying. Selected Area Electron Diffraction(SAED)analysis showed that the nanoparticles had a fcc structure with a lattice constant intermediate between that of monometallic Ag and Pt nanoparticles. First principles theoretical investigations of the mixing energy of Ag-Pt clusters confirm that mixing is favored at around ～1 nm. The same procedure used for Ag-Pt was followed for Ag-Rh. In this system where the two metals present miscibility gaps even in the liquid phase, no evidence of alloying was observed. Correspondingly, theoretical investigations found that the mixing energy of Ag-Rh clusters did not favor alloying.     

Influence of composition and size on the thermodynamic stability and structural evolution of CuAlNi nanoclusters

The heating process for CuAlNi nanoclusters with cuboctahedral structure was studied by molecular dynamics simulation with the embedded atom method. A diffusionless martensitic transformation from the cuboctahedral (CO) to the icosahedral (ICO) structure before the melting point was found in some CuAlNi nanoclusters. The effects of element composition and cluster size on the thermodynamic stability and structural transformation of trimetallic nanoclusters were investigated. The results show that the CO–ICO transformation temperature was size-dependent and occurred only for small clusters. It was also observed that the CO–ICO transformation temperature firstly dropped and then raised as Al concentration increased, which may be strongly related to the release of excess energy. Furthermore, the surface segregation phenomenon was also observed that the lower surface energy components, such as Al and Cu atoms, segregated to the surface of CuAlNi nanoclusters. The changes in the melting points of CuAlNi nanoclusters with different alloy compositions and cluster sizes were also studied. And furthermore, the physical basis of structural transition of CuAlNi nanoclusters was discussed.     

纳米团簇晶体的制备和结构研究

利用表面调制“幻数团簇”的方法制备出Al、Ga和In的纳米团簇人造晶体。这种方法是用Si(111) 7× 7表面作为“模板”生长尺寸相同和分布有序的纳米团簇。通过扫描隧道显微镜 (STM )原位分析结合第一性原理计算确定了金属纳米团簇的原子结构以及这些结构的形成机理。我们的研究表明对生长动力学的精确控制是制备团簇晶体的关键所在。此外 ,这种方法并不局限于制备某一种金属团簇。人造纳米团簇具有高的热稳定性和独特的结构使它们有希望在实际中得到广泛的应用。     

纳米团簇淀积过程的分形聚集特征

采用惰性气体凝聚法获得非金属团簇淀积体。透射电子显微分析及动力学模拟结果表明：纳米团簇淀积体的生长、聚集过程对构成团簇的原子的热力学性质、团簇制备中的蒸发率和惰性气体气压及淀积温度等参数极为敏感。在团簇的淀积体中，随生长条件不同，将会出现不同的聚集结构。因此可在一定程度上定量控制团簇淀积体的聚集状态，获得特定的纳米结构图案。     

钯团簇掺杂钇原子的密度泛函研究

在相对论有效原子实势近似下,用密度泛函方法(B3LYP/LANL2DZ)计算了二元合金团簇PdnY(n=1-5)可能的几何构型和对应的电子态,得到一系列稳定异构体的结构参数、电子态、能量和谐振频率.用最高占据轨道(HOMO)与最低空轨道(HOMO)之间的能级间隙描述团簇的稳定性,Pd2Y团簇的能级间隙最大,PdY团簇的能级间隙最小.Pd-Y相互作用改变了纯钯团簇的几何构形和稳定性.计算结果对系统研究Pd-Y体系的物理化学性质具有意义.