Search

The green biogenic PdAu nanoparticles (bio-PdAu NPs) exhibits remarkable catalytic performance in hydrogenation, which is highly desired. However, the catalytic principles and effectiveness of bio-PdxAuy NPs in response to various catalytic systems (electrocatalysis and suspension-catalysis) are unclear. Herein, a facile synthetic strategy for bio-PdxAuy NPs synthesis with controlled size and the catalytic principles for hydrogen evolution reaction (HER) and azo dye degradation is reported. In the biosynthetic process, the size and composition of the bio-PdxAuy NPs could be precisely controlled by predesigning the precursor mass ratio of Pd/Au, and the Au proportion showed a linear relationship with the size of NPs (R2 = 0.92). The obtained bio-PdxAuy NPs exhibit variable activity in electrocatalysis (HER) and suspension-catalysis (azo dye degradation). For electrocatalysis, the formation of conductive networks that facilitates the extracellular electron transfer is crucial. It was revealed that the bio-Pd2Au8 exhibited superior electrocatalytic performance in HER/toward hydrogen evolution, with a maximum current density of 1.65 mA cm−2, which was 1.54 times higher than that commercial Pd/C (1.07 mA cm−2). The high electrocatalytic activity was attributed to its appropriate size (81.38 ± 6.14 nm) and uniform distribution on the cell surface, which promoted the extracellular electron transfer by constructing a conductive network between catalyst and electrode. However, for suspension-catalysis, the size effect and synergistic effect of bimetallic NPs have a more prominent effect on the degradation of azo dyes. As the increase of Au proportion the particle size decreases, and the catalytic activity of bio-PdxAuy improved significantly. The response principles of bio-PdxAuy proposed in this study provide a reliable reference for the rational design of bio-based bimetallic catalysts with enhanced catalytic performance. [Display omitted] • Series of bio-PdxAuy NPs synthesize by S. oneidensis MR-1. • The mass ratio of Pd(II)/Au(III) is proportional to the particle size. • The conductive network constructed by bio-Pd2Au8 enhances electrocatalytic activity. • The increase of Au content in bio-PdAu improves the degradation activity of azo dyes. [ABSTRACT FROM AUTHOR]

Biologically synthesized palladium nanoparticles (bio-Pd) have attracted considerable interest as promising green catalysts for environmental remediation. However, the mechanisms by which microorganisms produce bio-Pd remain unclear. In the present study, we investigated the roles of Shewanella oneidensis MR-1 and its NADH dehydrogenases and hydrogenases (HydA and HyaB) in bio-Pd production using formate as the electron donor. The roles of NADH dehydrogenases and hydrogenases were studied by inhibiting NADH dehydrogenases and using hydrogenase mutants (Δ hydA , Δ hyaB , and Δ hydA Δ hyaB), respectively. The results showed ~97% reduction of palladium by S. oneidensis MR-1 after 24 h using 250 μM palladium and 500 μM formate. Electron microscopy images showed the presence of bio-Pd on both the outer and cytoplasmic membranes of S. oneidensis MR-1. However, the inhibition of NADH dehydrogenases in S. oneidensis MR-1 resulted in only ~61% reduction of palladium after 24 h, and bio-Pd were not found on the outer membrane. The mutants lacking one or two hydrogenases removed 91–96% of palladium ions after 24 h and showed more cytoplasmic bio-Pd but less periplasmic bio-Pd. To the best of our knowledge, this is the first study to demonstrate the role of NADH dehydrogenases of S. oneidensis MR-1 in the formation of bio-Pd on the outer membrane. It also demonstrates that the hydrogenases (especially HyaB) of S. oneidensis MR-1 contribute to the formation of bio-Pd in the periplasmic space. This study provides mechanistic insights into the production of biogenic metal nanoparticles towards their possible use in industrial and environmental applications. • S. oneidensis MR-1 deposited bio-Pd on both the outer and cytoplasmic membranes. • The inhibition of NADH dehydrogenases in S. oneidensis MR-1 significantly slowed down the Pd(II) reduction. • The NADH dehydrogenases in S. oneidensis MR-1 participated in the formation of bio-Pd on the outer membrane. • The hydrogenase mutants of S. oneidensis MR-1 produced less periplasmic bio-Pd and more cytoplasmic bio-Pd. • The hydrogenases in S. oneidensis MR-1 promoted the formation of bio-Pd in the periplasmic space. [ABSTRACT FROM AUTHOR]

Biosynthesized noble metal nanoparticles (NPs) as promising green catalysts for electrochemical application has invited a lot of attention. However, effective electron transfer between biosynthesized NPs and electrode remains a challenge due to the uncontrollable and poor conductive property of cell substrates. In this study, graphene oxide (GO) was introduced into a bio-Pd synthesis process governed by Shewanella oneidensis MR-1, which was demonstrated to be simultaneously reduced with Pd(II) and transformed to reduced GO (rGO), resulting in the formation of a Pd-cells-rGO composite. Compared to the control without rGO (Pd-cells), the electrochemical conductivity of Pd-cells-rGO composite increased from almost zero to 196 μS cm−1, indicating the rGO facilities the electron transport across the composite. Electrochemical characterizations revealed the electrochemical active surface area (ECSA) of Pd in Pd-cells-rGO was enlarged by increasing the amount of rGO in the composite, clearly indicating that the conductive network created by rGO enable the Pd NPs receive electrons from electrode and become electrochemical active. A considerable enhancement of electrocatalytic activity was further confirmed for Pd-cells-rGO as indicated by 36.7- and 17.2-fold increase (Pd-cells-rGO with Pd/GO ratio of 5/1 vs Pd-cells) of steady state current density toward hydrogen evolution and nitrobenzene reduction at −0.7 V and −0.55 V vs Ag/AgCl, respectively. We also compared the electrocatalytic performance with MWCNTs hybrids Pd-cells-CNTs. It was found that the association of Pd, cells and rGO creates an interactive and synergistic environment to allow higher conductivity and catalytic activity under the same amount of carbon nanomaterial. The strategy developed in this work activates a highly reactive NPs and proposed a designable protocol for enhancing electrocatalytic activity of biocatalysts. • MR-1 self-assembly of Pd-cells-rGO by one-step reduction of Pd(II) and GO • Hybrid rGO improves the stability of Pd NPs to against agglomeration • Pd-cells-rGO can be used as valid electrocatalyst for HER and NB reduction • Synergistic effect of Pd and rGO increases conductivity and quantity of active Pd [ABSTRACT FROM AUTHOR]

To characterize the impact of reactor configuration and influent loading on elemental sulphur (S0) recovery during denitrification desulfurization, a laboratory-scale expanded granular sludge bed (EGSB) reactor was established under two influent acetate/nitrate/sulphide loadings; the water flow velocity, microbial community, and functional genes at different heights were investigated. There was no S0 generated when acetate/nitrate/sulphide loadings were set to 0.95/0.60/1.05 kg/m3.d (low-loading). Furthermore, there were no typical denitrifying sulphide oxidizing bacteria under this condition, and Syntrophobacter , Anaerolineaceae genera were predominant in the reactor. As the influent loading was doubled (high-loading), S0 recovery increased to 87%; the bacterial distribution was relatively homogeneous with sulphide oxidation genera (Thauera) being predominant. Neither nirK nor sqr genes were detected in the low-loading sample at a height of 50 cm. The sqr / sox ratios of low-loading stage were 2.50 (10 cm), 0.94 (30 cm), and 0 (50 cm), and the ratios of the high-loading stage were 1.38 (10 cm), 1.33 (30 cm), and 1.08 (50 cm). A hydrodynamics analysis indicated that the water flow velocity was homogenous throughout the reactor. Appropriate reactor configuration and operation parameters play an important role in the efficient regulation of S0 recovery during denitrification desulfurization. • S0 recovery during denitrification desulfurization in an EGSB reactor investigated. • Low-loading: no S0 generation & no typical denitrifying sulfide oxidizing bacteria. • As influent loading doubled (high-loading), S0 recovery decreased. • High-loading: homogeneous bacteria distribution/sulfide oxidation genera dominate. • Reactor configuration & operation parameters critical for efficient S0 recovery. [ABSTRACT FROM AUTHOR]