Unit of Functional Bionanomaterials, School of Biosciences, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK.
J R Soc Interface. 2012 Jul 7;9(72):1705-12. doi: 10.1098/rsif.2012.0003. Epub 2012 Mar 7.
We report a novel biochemical method based on the sacrificial hydrogen strategy to synthesize bimetallic gold (Au)-palladium (Pd) nanoparticles (NPs) with a core/shell configuration. The ability of Escherichia coli cells supplied with H(2) as electron donor to rapidly precipitate Pd(II) ions from solution is used to promote the reduction of soluble Au(III). Pre-coating cells with Pd(0) (bioPd) dramatically accelerated Au(III) reduction, with the Au(III) reduction rate being dependent upon the initial Pd loading by mass on the cells. Following Au(III) addition, the bioPd-Au(III) mixture rapidly turned purple, indicating the formation of colloidal gold. Mapping of bio-NPs by energy dispersive X-ray microanalysis suggested Au-dense core regions and peripheral Pd but only Au was detected by X-ray diffraction (XRD) analysis. However, surface analysis of cleaned NPs by cyclic voltammetry revealed large Pd surface sites, suggesting, since XRD shows no crystalline Pd component, that layers of Pd atoms surround Au NPs. Characterization of the bimetallic particles using X-ray absorption spectroscopy confirmed the existence of Au-rich core and Pd-rich shell type bimetallic biogenic NPs. These showed comparable catalytic activity to chemical counterparts with respect to the oxidation of benzyl alcohol, in air, and at a low temperature (90°C).
我们报告了一种基于牺牲氢策略的新型生化方法,用于合成具有核/壳结构的双金属金(Au)-钯(Pd)纳米粒子(NPs)。利用提供 H(2)作为电子供体的大肠杆菌细胞从溶液中快速沉淀 Pd(II)离子的能力来促进可溶性 Au(III)的还原。用 Pd(0)(生物 Pd)预先涂覆细胞可显著加速 Au(III)的还原,Au(III)的还原速率取决于细胞上初始 Pd 负载的质量。Au(III)加入后,生物 Pd-Au(III)混合物迅速变成紫色,表明胶体金的形成。通过能量色散 X 射线微分析对生物 NPs 的映射表明 Au 密集的核心区域和外围 Pd,但 X 射线衍射 (XRD) 分析仅检测到 Au。然而,通过循环伏安法对清洁 NPs 的表面分析表明存在大量 Pd 表面位点,这表明,由于 XRD 显示没有结晶 Pd 成分,Pd 原子层包围着 Au NPs。使用 X 射线吸收光谱对双金属颗粒的表征证实了存在富 Au 核和富 Pd 壳型双金属生物衍生 NPs。这些在空气中和低温(90°C)下氧化苄醇的催化活性与化学对应物相当。