Mechanistic insights into aggregation process of graphene oxide and bacterial cells in microbial reduction of ferrihydrite.

Microbial reduction of ferrihydrite is prevalent in natural environments and plays an important role in reductive dissolution of Fe(III) minerals. With consistent release of anthropogenic graphene oxide (GO) into water bodies, new changes in the Fe(III)-reducing microorganisms/ferrihydrite binary system demand attention. Herein, we focused on the interaction of GO and bacterial cells in view of colloidal stability and interfacial forces, and on the consequences for microbial ferrihydrite reduction. The results showed that the addition of GO decreased the bioreduction efficiency of ferrihydrite down to 1/15 of the control. Meanwhile, the GO nanosheets were found not depositing on ferrihydrite but spontaneously aggregating with Shewanella spp., the representative dissimilatory Fe(III) reduction bacterial species. Using the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and atomic force microscopy (AFM), the aggregation process can be interpreted in three steps according to the interaction energy calculation, namely, colloidal instability, reversible aggregation and irreversible aggregation. The motility of living cells seems the reason inducing the colloidal instability between GO and bacteria. While, the aggregation remains reversible even the secondary minimum achieved at the separation distance of 8.74-9.24 nm from XDLVO. When the separation distance <5.74-6.01 nm, the adhesion work predominates and causes irreversible aggregation, validated by AFM. Additionally, the probable ecological risks raised by this aggregation behavior for the imbalance of iron biogeochemical cycle were demonstrated.

Metal-organic aerogel derived hierarchical porous metal-carbon nanocomposites as efficient bifunctional electrocatalysts for overall water splitting.

An efficient strategy to construct non-noble metal-base electrocatalysts for water splitting is the direct carbonization of metal-organic aerogel composites. Herein for the first time, a novel tube-like metal-carbon nanocomposite with encapsulated small-size individual Fe, Cr and Ni nanoparticles, is prepared by the carbonization of a FeCr-doped Ni-benzenetricarboxylate aerogel. The slender skeleton of the aerogel, supercritical drying and Cr doping alleviates metal aggregation and facilitates the in-situ growth of carbon tubes. This nanocomposite exhibits remarkably low overpotential of the hydrogen evolution reaction (137 mV) and oxygen evolution reaction (220 mV). Further, the cell voltage could be as low as 1.54 V with the current density of 10 mA cm-2 and illustrates excellent stability under a continuous operation for 50 h. This non-noble metal-base electrocatalyst is comparable to noble metal-based electrocatalysts and the impressive performance is ascribed to the abundant active catalytic sites and short reactant diffusion pathways. This work demonstrates great capability of aerogel derivation in the highly active electrocatalyst design for promising electrochemical applications.

Efficient adsorption removal of anionic dyes by an imidazolium-based mesoporous poly(ionic liquid) including the continuous column adsorption-desorption process.

The mesoporous poly(N,N'-methylene-bis(1-(3-vinylimidazolium)) chloride), labeled as PDVIm-Cl, with double anions (Cl-) and low monomer molecular weight was synthesized and applied in the adsorption of anionic dyes (acid orange 7 (AO7), sunset yellow (SY), reactive blue 19 (RB19), congo red (CR)). Due to the mesoporous structure, abundant Cl- and positively charged imidazole rings, the poly(ionic liquid) (PIL) exhibited superior adsorption ability towards anionic dyes. What is more, the RB19 adsorption by PDVIm-Cl could achieve the highest capacity (2605 ± 254 mg g-1) which was nearly twice higher than the maximum adsorption capacity of the previously reported materials. All the adsorption kinetic data and isotherms fitted well with the pseudo second-order model and Langmuir-Freundlich model. To better explore the practical potential of the PIL for dye adsorption, the adsorption under different pH values and column adsorption performances were also evaluated. Results showed that PDVIm-Cl exhibited high removal efficiencies for anionic dyes over a wide pH range (2-10). Also, the great reusability could be well demonstrated by the achievable continuous column adsorption-desorption process. It is worth mentioning that the regeneration could be realized with very little desorbent which was far less than the adsorption volume flowing through the column and the desorption efficiency was well maintained after three consecutive cycles. At last, the adsorption mechanism was explored by experiments combined with quantum chemical calculations and showed anionic dyes adsorption by PDVIm-Cl was a joint process dominated by the ion exchange, electrostatic interaction, hydrogen bond and π-π stacking.

Formation of nanoscale networks: selectively swelling amphiphilic block copolymers with CO2-expanded liquids.

Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO(2)-expanded liquid (CXL), CO(2)-methanol. The phase behavior of the CO(2)-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO(2), forming homogeneous CXL under the experimental conditions. When treated with the CO(2)-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows "thermodynamically restricted" character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia.