Biochemical synthesis of palladium nanoparticles: The influence of chemical fixatives used in electron microscopy on nanoparticle formation and catalytic performance.

Palladium nanoparticles (PdNPs) can catalyse a range of reductive chemical reactions transforming both organic and inorganic environmental pollutants. PdNPs that ranged from <2 to 2-40 nm were synthesized using chemical methods, and bacterial biomass with/without chemical fixatives. PdNP formation was enhanced by adsorption of Pd(II) to bacterial biomass, followed by fixation with formate or glutaraldehyde. TEM-SAED analyses confirmed that the cell associated PdNPs were polycrystalline with a face-centered cubic structure. Chemically formed PdNPs possessed a higher Pd(0):Pd(II) ratio and produced structurally similar nanoparticles as the biotic systems. These PdNPs were employed to catalyze two, reductive chemical reactions, transforming 4-nitrophenol (4-NP) and hexavalent chromium [Cr(VI)], into 4-aminophenol and Cr(IV), respectively. In the reduction of 4-NP, the catalytic performance was directly proportional to PdNP surface area, i.e., the smallest PdNPs in formate-PdCH34 cells had the fastest rate of reaction. The mass of Pd(0) as PdNPs was the main contributor to Cr(VI) reduction; the chemically synthesized PdNPs showed the highest removal efficiency with 96% at 20 min. The use of glutaraldehyde enhanced the reduction of Pd(II) and promoted PdNPs formation, i.e., creating an artefact of fixation; however, this treatment also enhanced the catalytic performance of these PdNPs.