Breaking Scaling Relations for Highly Efficient Electroreduction of CO2 to CO on Atomically Dispersed Heteronuclear Dual-Atom Catalyst.

Conversion of CO2 into value-added products by electrocatalysis provides a promising way to mitigate energy and environmental problems. However, it is greatly limited by the scaling relationship between the adsorption strength of intermediates. Herein, Mn and Ni single-atom catalysts, homonuclear dual-atom catalysts (DACs), and heteronuclear DACs are synthesized. Aberration-corrected annular dark-field scanning transmission electron microscopy (ADF-STEM) and X-ray absorption spectroscopy characterization uncovered the existence of the Mn─Ni pair in Mn─Ni DAC. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy reveal that Mn donated electrons to Ni atoms in Mn─Ni DAC. Consequently, Mn─Ni DAC displays the highest CO Faradaic efficiency of 98.7% at -0.7 V versus reversible hydrogen electrode (vs RHE) with CO partial current density of 16.8 mA cm-2. Density functional theory calculations disclose that the scaling relationship between the binding strength of intermediates is broken, resulting in superior performance for ECR to CO over Mn─Ni─NC catalyst.

Up-regulation of ribosomal and carbon metabolism proteins enhanced pyrene biodegradation in fulvic acid-induced biofilm system.

The polycyclic aromatic hydrocarbons (PAHs) that enter the aqueous phase usually coexist with fulvic acid (FA). Therefore, we initiated this investigation to explore the influences of FA on bacterial biofilm formation and its potential to biodegrade pyrene (PYR), using electron microscopic techniques and isobaric tags for relative and absolute quantification (iTRAQ). Our results revealed that FA stimulated biofilm formation and enhanced the biodegradation of PYR. First, FA favored the three-dimensional proliferation of bacteria, with an OD590/OD600 value of up to 14.78, and the extracellular surfaces covered by a layer of biomaterials. Distinctive intracellular morphologies of texture and organization were accompanied by reduced inter-bacterial distances of less than 0.31 µm. The biofilms formed displayed interactions between FA and surficial proteins, as noted by band shifts for the C-O and CO groups. Strikingly, FA triggered the upregulation of 130 proteins that were either operational in biofilm formation or in metabolic adjustments; with the changes supported by the increasing intensity of free amino acids and the newly generated N-O bonds. The results above revealed that the enhanced biodegradation was related to the up-regulation of the proteins functioned for ribosomal and carbon metabolism, and the ultra-structural changes in FA-induced biofilm system.

Sulfur-Decorated Ni-N-C Catalyst for Electrocatalytic CO2 Reduction with Near 100 % CO Selectivity.

Developing highly efficient electrocatalysts for electrochemical CO2 reduction (ECR) to value-added products is important for CO2 conversion and utilization technologies. In this work, a sulfur-doped Ni-N-C catalyst is fabricated through a facile ion-adsorption and pyrolysis treatment. The resulting Ni-NS-C catalyst exhibits higher activity in ECR to CO than S-free Ni-N-C, yielding a current density of 20.5 mA cm-2 under -0.80 V versus a reversible hydrogen electrode (vs. RHE) and a maximum CO faradaic efficiency of nearly 100 %. It also displays excellent stability with negligible activity decay after electrocatalysis for 19 h. A combination of experimental investigations and DFT calculations demonstrates that the high activity and selectivity of ECR to CO is due to a synergistic effect of the S and Ni-NX moieties. This work provides insights for the design and synthesis of nonmetal atom-decorated M-N-C-based ECR electrocatalysts.

Evaluation of bacterial biodegradation and accumulation of phenanthrene in the presence of humic acid.

This study evaluated the effect of humic acid (HA) on physicochemical properties of bacterial surfaces and on mass transfer of polycyclic aromatic hydrocarbons (PAHs) from aqueous phase into intracellular bacteria. Due to this process' potential for bacterial degradation, using Sphingobium sp. PHE3, degradation of phenanthrene (PHE) was compared in HA and non-HA sets. The results showed that approximately 51.1% of PHE at a concentration of 102.0 mg L-1 was biodegraded in the non-HA sets, whereas almost all PHE was biodegraded with HA after 72 h. Interestingly, PHE that accumulated in the intracellular bacteria reached 3.80 mg L-1 for the HA sets, which was significantly higher than that of non-HA. Lipid inclusion bodies appeared when Sphingobium sp. PHE3 was treated with HA. The results were further confirmed by the enhanced bacterial surface sorption capacity for the HA sets. Therefore, we concluded that added HA not only act as carriers and biosurfactants facilitating PHE uptake but also adjust bacteria cell wall properties for internalizing PHE, which ultimately overcame the PHE bioavailability resulting in enhanced biodegradation.

Mechanical and thermal property characterization of poly-l-lactide (PLLA) scaffold developed using pressure-controllable green foaming technology.

Poly-l-lactide (PLLA) is one of the most promising biological materials used for tissue engineering scaffolds (TES) because of their excellent biodegradability and tenability. Here, microcellular PLLA foams were fabricated by pressure-controllable green foaming technology. Scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), wide angle X-ray diffraction measurement (WAXRD), thermogravimetric (TG) analysis, reflection-Fourier transform infrared (FTIR) analysis, enzymatic degradation study and MTT assay were used to analyze the scaffolds' morphologies, structures and crystallinities, mechanical and biodegradation properties, as well as their cytotoxicity. The results showed that PLLA foams with pore sizes from 8 to 103µm diameters were produced when the saturation pressure decreased from 7.0 to 4.0MPa. Through a combination of StepScan DSC (SSDSC) and WAXRD approaches, it was observed in PLLA foams that the crystallinity, highly-oriented metastable state and rigid amorphous phase increased with the increasing foaming pressure. It was also found that both the glass transition temperature and apparent enthalpy of PLLA significantly increased after the foaming process, which suggested that the changes of microcellular structure could provide PLLA scaffolds better thermal stability and elasticity. Moreover, MTT assessments suggested that the smaller pore size should benefit cell attachment and growth in the scaffold. The results of current work will give us better understanding of the mechanisms involved in structure and property changes of PLLA at the molecular level, which enables more possibilities for the design of PLLA scaffold to satisfy various requirements in biomedical and green chemical applications.

A sulfated ZrO2 hollow nanostructure as an acid catalyst in the dehydration of fructose to 5-hydroxymethylfurfural.

Mesoporous hollow colloidal particles with well-defined characteristics have potential use in many applications. In liquid-phase catalysis, in particular, they can provide a large active surface area, reduced diffusion resistance, improved accessibility to reactants, and excellent dispersity in reaction media. Herein, we report the tailored synthesis of sulfated ZrO2 hollow nanostructures and their catalytic applications in the dehydration of fructose. ZrO2 hollow nanoshells with controllable thickness were first synthesized through a robust sol-gel process. Acidic functional groups were further introduced to the surface of hollow ZrO2 shells by sulfuric acid treatment followed by calcination. The resulting sulfated ZrO2 hollow particles showed advantageous properties for liquid-phase catalysis, such as well-maintained structural integrity, good dispersity, favorable mesoporosity, and a strongly acidic surface. By controlling the synthesis and calcination conditions and optimizing the properties of sulfated ZrO2 hollow shells, we have been able to design superacid catalysts with superior performance in the dehydration of fructose to 5-hydroxymethyfurfural than the solid sulfated ZrO2 nanocatalyst.