Functional study of two ER localized sterol C-14 reductases in Aspergillus oryzae.

Ergosterol is an important component of fungal cell membrane. Ergosterol biosynthesis involves sterol C-14 reductase, a key enzyme in ergosterol biosynthesis, which has been well studied in Saccharomyces cerevisiae. However, little studies about this important enzyme in Aspergillus oryzae. In this study, two sterol C-14 reductases named AoErg24A and AoErg24B were identified in A. oryzae using bioinformatics analysis. Through phylogenetic tree, expression pattern, subcellular localization, and yeast functional complementation analyses, we discovered that both AoErg24A and AoErg24B are conserved and localized to the endoplasmic reticulum (ER). Both enzymes can partially restore the temperature sensitivity phenotype of a S. cerevisiae erg24 weak mutant. Overexpression of AoErg24A in A. oryzae increased 1.6 times of ergosterol content, while overexpression of AoErg24B led to a slight decrease of ergosterol. Both genes affect the sporulation of A. oryzae. These results uncovered that the two genes function differently in ergosterol biosynthesis. Thus, this study further enhances our understanding of ergosterol biosynthesis in A. oryzae and lays a good foundation for A. oryzae to be used in industrial ergosterol production.

Surface Boron Modulation on Cobalt Oxide Nanocrystals for Electrochemical Oxygen Evolution Reaction.

Herein, we show that coupling boron with cobalt oxide tunes its structure and significantly boost its electrocatalytic performance for the oxygen evolution reaction (OER). Through a simple precipitation and thermal treatment process, a series of Co-B oxides with tunable morphologies and textural parameters were prepared. Detailed structural analysis supported first the formation of an disordered and partially amorphous material with nanosized Co3 BO5 and/or Co2 B2 O6 being present on the local atomic scale. The boron modulation resulted in a superior OER reactivity by delivering a large current and an overpotential of 338 mV to reach a current density of 10 mA cm-2 in 1 M KOH electrolyte. Identical location transmission electron microscopy and in situ electrochemical Raman spectroscopy studies revealed alteration and surface re-construction of materials, and formation of CoO2 and (oxy)hydroxide intermediate, which were found to be highly dependent on crystallinity of the samples.

Principles of Water Electrolysis and Recent Progress in Cobalt-, Nickel-, and Iron-Based Oxides for the Oxygen Evolution Reaction.

Water electrolysis that results in green hydrogen is the key process towards a circular economy. The supply of sustainable electricity and availability of oxygen evolution reaction (OER) electrocatalysts are the main bottlenecks of the process for large-scale production of green hydrogen. A broad range of OER electrocatalysts have been explored to decrease the overpotential and boost the kinetics of this sluggish half-reaction. Co-, Ni-, and Fe-based catalysts have been considered to be potential candidates to replace noble metals due to their tunable 3d electron configuration and spin state, versatility in terms of crystal and electronic structures, as well as abundance in nature. This Review provides some basic principles of water electrolysis, key aspects of OER, and significant criteria for the development of the catalysts. It provides also some insights on recent advances of Co-, Ni-, and Fe-based oxides and a brief perspective on green hydrogen production and the challenges of water electrolysis.

Highly Ordered Mesoporous Co3 O4 Electrocatalyst for Efficient, Selective, and Stable Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid.

Electrochemical oxidation of biomass substrates to valuable bio-chemicals is highly attractive. However, the design of efficient, selective, stable, and inexpensive electrocatalysts remains challenging. Here it is reported how a 3D highly ordered mesoporous Co3 O4 /nickel foam (om-Co3 O4 /NF) electrode fulfils those criteria in the electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to value-added 2,5-furandicarboxylic acid (FDCA). Full conversion of HMF and an FDCA yield of >99.8 % are achieved with a faradaic efficiency close to 100 % at a potential of 1.457 V vs. reversible hydrogen electrode. Such activity and selectivity to FDCA are attributed to the fast electron transfer, high electrochemical surface area, and reduced charge transfer resistance. More impressively, remarkable catalyst stability under long-term testing is obtained with 17 catalytic cycles. This work highlights the rational design of metal oxides with ordered meso-structures for electrochemical biomass conversion.

Tunable eg Orbital Occupancy in Heusler Compounds for Oxygen Evolution Reaction*.

Heusler compounds have potential in electrocatalysis because of their mechanical robustness, metallic conductivity, and wide tunability in the electronic structure and element compositions. This study reports the first application of Co2 YZ-type Heusler compounds as electrocatalysts for the oxygen evolution reaction (OER). A range of Co2 YZ crystals was synthesized through the arc-melting method and the eg orbital filling of Co was precisely regulated by varying Y and Z sites of the compound. A correlation between the eg orbital filling of reactive Co sites and OER activity was found for Co2 MnZ compounds (Z=Ti, Al, V, and Ga), whereby higher catalytic current was achieved for eg orbital filling approaching unity. A similar trend of eg orbital filling on the reactivity of cobalt sites was also observed for other Heusler compounds (Co2 VZ, Z=Sn and Ga). This work demonstrates proof of concept in the application of Heusler compounds as a new class of OER electrocatalysts, and the influence of the manipulation of the spin orbitals on their catalytic performance.

Dual Role of Silver Moieties Coupled with Ordered Mesoporous Cobalt Oxide towards Electrocatalytic Oxygen Evolution Reaction.

Herein, we show that the performance of mesostructured cobalt oxide electrocatalyst for oxygen evolution reaction (OER) can be significantly enhanced by coupling of silver species. Various analysis techniques including pair distribution function and Rietveld refinement, X-ray absorption spectroscopy at synchrotron as well as advanced electron microscopy revealed that silver exists as metallic Ag particles and well-dispersed Ag2 O nanoclusters within the mesostructure. The benefits of this synergy are twofold for OER: highly conductive metallic Ag improves the charge transfer ability of the electrocatalysts while ultra-small Ag2 O clusters provide the centers that can uptake Fe impurities from KOH electrolyte and boost the catalytic efficiency of Co-Ag oxides. The current density of mesostructured Co3 O4 at 1.7 VRHE is increased from 102 to 211 mA cm-2 with incorporation of silver spices. This work presents the dual role of silver moieties and demonstrates a simple method to increase the OER activity of Co3 O4 .

A hydrogen-dependent geochemical analogue of primordial carbon and energy metabolism.

Hydrogen gas, H2, is generated by alkaline hydrothermal vents through an ancient geochemical process called serpentinization, in which water reacts with iron-containing minerals deep within the Earth's crust. H2 is the electron donor for the most ancient and the only energy-releasing route of biological CO2 fixation, the acetyl-CoA pathway. At the origin of metabolism, CO2 fixation by hydrothermal H2 within serpentinizing systems could have preceded and patterned biotic pathways. Here we show that three hydrothermal minerals-greigite (Fe3S4), magnetite (Fe3O4) and awaruite (Ni3Fe)-catalyse the fixation of CO2 with H2 at 100 °C under alkaline aqueous conditions. The product spectrum includes formate (up to 200 mM), acetate (up to 100 µM), pyruvate (up to 10 µM), methanol (up to 100 µM) and methane. The results shed light on both the geochemical origin of microbial metabolism and the nature of abiotic formate and methane synthesis in modern hydrothermal vents.

Laser Fragmentation-Induced Defect-Rich Cobalt Oxide Nanoparticles for Electrochemical Oxygen Evolution Reaction.

Sub-5 nm cobalt oxide nanoparticles are produced in a flowing water system by pulsed laser fragmentation in liquid (PLFL). Particle fragmentation from 8 nm to 4 nm occurs and is attributed to the oxidation process in water where oxidative species are present and the local temperature is rapidly elevated under laser irradiation. Significantly higher surface area, crystal phase transformation, and formation of structural defects (Co2+ defects and oxygen vacancies) through the PLFL process are evidenced by detailed structural characterizations by nitrogen physisorption, electron microscopy, synchrotron X-ray diffraction, and X-ray photoelectron spectroscopy. When employed as electrocatalysts for the oxygen evolution reaction under alkaline conditions, the fragmented cobalt oxides exhibit superior catalytic activity over pristine and nanocast cobalt oxides, delivering a current density of 10 mA cm-2 at 369 mV and a Tafel slope of 46 mV dec-1 , which is attributed to a larger exposed active surface area, the formation of defects, and an increased charge transfer rate. The study provides an effective approach to engineering cobalt oxide nanostructures in a flowing water system, which shows great potential for sustainable production of active cobalt catalysts.

Surface states in bulk single crystal of topological semimetal Co3Sn2S2 toward water oxidation.

The band inversion in topological phase matters bring exotic physical properties such as the topologically protected surface states (TSS). They strongly influence the surface electronic structures of the materials and could serve as a good platform to gain insight into the surface reactions. Here we synthesized high-quality bulk single crystals of Co3Sn2S2 that naturally hosts the band structure of a topological semimetal. This guarantees the existence of robust TSS from the Co atoms. Co3Sn2S2 crystals expose their Kagome lattice that constructed by Co atoms and have high electrical conductivity. They serves as catalytic centers for oxygen evolution process (OER), making bonding and electron transfer more efficient due to the partially filled orbital. The bulk single crystal exhibits outstanding OER catalytic performance, although the surface area is much smaller than that of Co-based nanostructured catalysts. Our findings emphasize the importance of tailoring TSS for the rational design of high-activity electrocatalysts.

Highly Active Cobalt-Based Electrocatalysts with Facile Incorporation of Dopants for the Oxygen Evolution Reaction.

In situ formation of electroactive cobalt species for the oxygen evolution reaction is simply achieved by applying an anodic bias to a commercially available cobalt precursor and Nafion binder mixture coated on a glassy carbon electrode. This preparation does not require energy-intensive materials preparation steps or noble metals, yet a low overpotential of 322 mV at 10.2 mA cm-2 and a high current density of more than 300 mA cm-2 at 1.7 VNHE were obtained in 1 m KOH. An operando electrochemical Raman spectroscopy study confirmed the formation of cobalt oxyhydroxide species and the iron stimulated the equilibrium state between Co3+ and Co4+ . The iron present in the alkali electrolyte or ink solution effectively activated the cobalt species, and most of the first row transition metals could also enhance the catalytic performance. The concept presented here is one of the simplest strategies for preparing highly active electrocatalysts and is very flexible for the replacement of cobalt by other transition metals.

Coffee-Waste Templating of Metal Ion-Substituted Cobalt Oxides for the Oxygen Evolution Reaction.

A facile and scalable method using coffee waste grounds as a hard template has been developed to fabricate nanostructured Co3 O4 for the oxygen evolution reaction (OER). Co3 O4 incorporating metals with different valences (M/Co=1:4; M=Cu, Ni, Fe, Cr, and W) were also prepared with similar sheet-like structures comprising nanosized crystallites. After detailed characterization by X-ray diffraction, electron microscopy, and nitrogen sorption, the oxides were employed as OER electrocatalysts. Substitution of octahedral and tetrahedral sites of the spinel structure with divalent and trivalent transition metals (Cu, Ni, Fe, and Cr) increased the activity of Co3 O4 for the OER, whereas incorporation of hexavalent W led to formation of a second crystal phase and significantly higher electrocatalytic performance. Furthermore, this method is easily scaled up for mass production of Co3 O4 with the same nanostructure, which is highly desirable for large-scale application.

[Effects of urbanization on soil nitrogen supply in Pinus elliottii plantations].

With the Pinus elliottii plantations along an urban-rural gradient in Nanchang City as test objectives, and by using ion-exchange resin (IER) bag, this paper studied the seasonal dynamics of soil available nitrogen in the plantations, and analyzed the effects of urbanization on soil nitrogen supply. The results showed that the soil nitrogen supply in the plantations had an obvious seasonal fluctuation. Soil NH4+ -N concentration was significantly higher in autumn and winter than in spring and summer, while soil NO3- -N concentration, mineral N concentration, and relative nitrification rate were in adverse (P < 0.05). The seasonal dynamics of soil available nitrogen was basically consistent with the growth rhythm of P. elliottii. The soil nitrogen availability and relative nitrification ratio along the gradient differed greatly, being significantly higher in urban than in rural area (P < 0.05). Urbanization accelerated soil N mineralization and nitrification, enhanced soil nitrogen supply capacity, and increased soil NO3- -N content. It was suggested that in the construction of urban forest, the plants with high N demand, especially with high NO3- -N absorption capacity, should be introduced to mitigate the soil available N loss and its induced environmental pollution.