Yong Ping, Rowson Neil A, Farr J Peter G, Harris I Rex, Macaskie Lynne E
School of Biosciences, The University of Birmingham, Edgbaston, Birmingham B15 2TT, United Kingdom.
Biotechnol Bioeng. 2002 Nov 20;80(4):369-79. doi: 10.1002/bit.10369.
The reduction of Pd(II) to Pd(0) was accelerated by using the sulfate-reducing bacterium Desulfovibrio desulfuricans NCIMB 8307 at the expense of formate or H(2) as electron donors at pH 2-7. With formate no reduction occurred at pH 2, but with H(2) 50% of the activity was retained at pH 2, with the maximum rate (1.3-1.4 micromol min(-1) mg dry cells(-1)) seen at pH 3-7, which was similar to the rate with formate at neutral pH. Excess nitrate was inhibitory to Pd(II) reduction using formate, but not H(2). Chloride ion was inhibitory as low as 100 mM using formate but with H(2) only ca. 25% inhibition was observed at 500 mM Cl(-) and H(2) was concluded to be the electron donor of choice for the potential remediation of industrial wastes. Deposited Pd was visible on the cells using transmission and scanning electron microscopy and analysis by energy dispersive X-ray microanalysis (EDAX) identified the deposit as Pd, confirmed as Pd(0) by X-ray powder diffraction analysis (XRD). The crystal size of the biodeposited Pd(0) was determined to be only 50% of the size of Pd(0) crystals manufactured chemically from Pd(II) at the expense of H(2) and, unlike the chemically manufactured material, the biocrystal size was independent of the pH. The "biological" Pd(0) functioned as a superior chemical catalyst in a test reaction which liberated hydrogen from hypophosphite. Pd, and also Pt and Rh, could be recovered by resting cell suspensions under H(2) from an industrial processing wastewater, suggesting a possible future application of bioprocessing technology for precious metals.
利用硫酸盐还原菌脱硫脱硫弧菌NCIMB 8307,以甲酸盐或H₂作为电子供体,在pH 2 - 7的条件下,Pd(II)还原为Pd(0)的过程得以加速。以甲酸盐为电子供体时,在pH 2条件下不发生还原反应,但以H₂为电子供体时,在pH 2条件下仍保留50%的活性,在pH 3 - 7时达到最大速率(1.3 - 1.4 μmol min⁻¹ mg干细胞⁻¹),这与中性pH条件下以甲酸盐为电子供体时的速率相似。过量硝酸盐对以甲酸盐为电子供体的Pd(II)还原有抑制作用,但对以H₂为电子供体的还原无抑制作用。氯离子浓度低至100 mM时对以甲酸盐为电子供体的还原有抑制作用,但以H₂为电子供体时,在500 mM Cl⁻条件下仅观察到约25%的抑制作用,因此得出结论,H₂是工业废水潜在修复的首选电子供体。使用透射电子显微镜和扫描电子显微镜观察到细胞上有沉积的Pd,通过能量色散X射线微分析(EDAX)分析确定沉积物为Pd,经X射线粉末衍射分析(XRD)确认为Pd(0)。生物沉积的Pd(0)晶体尺寸仅为以H₂为代价由Pd(II)化学制造的Pd(0)晶体尺寸的50%,并且与化学制造的材料不同,生物晶体尺寸与pH无关。在一个从次磷酸盐中释放氢气的测试反应中,“生物”Pd(0)作为一种优异的化学催化剂发挥作用。在H₂条件下,静止细胞悬液可从工业加工废水中回收Pd,以及Pt和Rh,这表明生物处理技术在贵金属方面可能具有未来应用前景。