Thermal Shock Synthesis for Loading Sub-2 nm Ru nanoclusters on Titanium Nitride as a Remarkable Electrocatalyst towards Hydrogen Evolution Reaction.

Heterogeneous catalysts embracing metal entities on suitable supports are profound in catalyzing various chemical reactions, and substantial synthetic endeavors in metal-support interaction modulation have been made to enhance catalytic performance. Here, it is reported the loading of sub-2 nm Ru nanocrystals (NCs) on titanium nitride support (HTS-Ru-NCs/TiN) via a special Ru-Ti interaction using high temperature shock (HTS) method. Direct dechlorination of the adsorbed RuCl3, ultrafast nucleation process and short coalescence duration at ultrahigh temperatures contribute to the immobilization of Ru NCs on TiN support via producing the Ru-Ti interfacial perimeter. HTS-Ru-NCs/TiN shows remarkable activity towards hydrogen evolution reaction (HER) in alkaline solution, yielding ultralow overpotentials of 16.3 and 86.6 mV to achieve 10 and 100 mA cm-2, respectively. The alkaline and anion exchange membrane water electrolyzers assembled using HTS-Ru-NCs/TiN yield 1.0 A cm-2 at 1.65 and 1.67 V, respectively, which validate its applicability in hydrogen production industry. Theoretical simulations reveal the favorable formation of Ru-O and Ti-H bond at the interfacial perimeters between Ru NCs and TiN, which accelerates the prerequisite water dissociation kinetics for the enhanced HER activity. This exemplified work motivates the design of specific interfacial perimeters via the HTS strategy to improve the performance of diverse catalysis. This article is protected by copyright. All rights reserved.

Novel insights into the kinetics and mechanism of arsenopyrite bio-dissolution enhanced by pyrite.

Arsenopyrite and pyrite often coexist in metal deposits and tailings, thus simultaneous bioleaching of both sulfides has economic (as well as environmental) significance. Important targets in bio-oxidation operations are high solubilization rates and minimized accumulation of Fe(III)/As-bearing secondary products. This study investigated the role of pyrite bioleaching in the enhancement of arsenopyrite dissolution. At a pyrite to arsenopyrite mass ratio of 1:1, 93.6% of As and 93.0% of Fe were solubilized. The results show that pyrite bio-oxidation can promote arsenopyrite dissolution, enhance S0 bio-oxidation, and inhibit the formation of jarosites, tooeleite, and amorphous ferric arsenate. The dry weight of the pyrite & arsenopyrite residue was reduced by 95.1% after bioleaching, compared to the initial load, while only 5% weight loss was observed when pyrite was absent. A biofilm was formed on the arsenopyrite surface in the presence of pyrite, while a dense passivation layer was observed in the absence of pyrite. As(III) (as As2O3) was a dominant As species in the pyrite & arsenopyrite residue. Novel and detailed findings are presented on arsenopyrite bio-dissolution in the presence of pyrite, and the presented approach could contribute to the development of novel cost-effective extractive bioprocesses. ENVIRONMENTAL IMPLICATION: The oxidation of arsenopyrite presents significant environmental hazards, as it can contribute to acid mine drainage generation and arsenic mobilization from sulfidic mine wastes. Bioleaching is a proven cost-effective and environmentally friendly extractive technology, which has been applied for decades in metal recovery from minerals or tailings. In this work, efficient extraction of arsenic from arsenopyrite bioleaching was presented through coupling the process with bio-oxidation of pyrite, resulting in lowered accumulation of hazardous and metastable Fe(III)/As-bearing secondary phases. The results could help improve current biomining operations and/or contribute to the development of novel cost-effective bioprocesses for metal extraction.

Effect of yeast extract on microbiologically influenced corrosion of X70 pipeline steel by Desulfovibrio bizertensis SY-1.

Microbiologically influenced corrosion (MIC) is a complicated process that happens ubiquitously and quietly in many fields. As a useful nutritional ingredient in microbial culture media, yeast extract (YE) is a routinely added in the MIC field. However, how the YE participated in MIC is not fully clarified. In the present work, the effect of YE on the growth of sulfate reducing prokaryotes (SRP) Desulfovibrio bizertensis SY-1 and corrosion behavior of X70 pipeline steel were studied. It was found that the weight loss of steel coupons in sterile media was doubled when YE was removed from culture media. However, in the SRP assays without YE the number of planktonic cells decreased, but the attachment of bacteria on steel surfaces was enhanced significantly. Besides, the corrosion rate of steel in SRP assays increased fourfold after removing YE from culture media. MIC was not determined for assays with planktonic SRP but only for biofilm assays. The results confirm the effect of YE on D. bizertensis SY-1 growth and also the inhibitory role of YE on MIC.

Application of Response Surface Methodology (RSM) in the statistical evaluation of biodiesel production from the neutral lipids of the Coelastrella-Nannochloropsis consortium.

The paramount challenge in economically workable microalgal biodiesel production is the selection of a competent catalyst to improve the fatty acid methyl ester yield with desirable fatty acid composition. Though countless researchers have explored different homogeneous and heterogeneous catalysts to improve the transesterification efficacy, achieving greater biodiesel production from the neutral lipids of the microalgal consortium using a statistical tool, response surface methodology is scarce. Thus, the present study applied Response surface methodology to statistically analyze the biodiesel production from the neutral lipids of the indigenous Coelastrella-Nannochloropsis consortium (CNC) on the way to commercial feasibility. Onset of the study, the neutral lipids and acid value of the CNC were determined to be 18.74% and 2.73%, respectively. The transesterification of the neutral lipids of CNC was optimized through the coded factors in the RSM for various reaction parameters as combined influence viz., (i) Catalyst dose: methanol volume, (ii) Catalyst dose: reaction time; (iii) Catalyst dose: reaction temperature, (iv) Time: temperature, (v) time: methanol volume, (vi) temperature: methanol volume. Based on the ANOVA, coefficient determination, 2% KOH, 2 h time, 70 °C temperature, and 9 mL methanol volume were ascertained to be optimal values to accomplish 92% biodiesel production. Further, the biodiesel has desirable palmitic, palmitoleic, stearic, oleic, linoleic, and linolenic acids, with palmitic acid as the prevalent fatty acid contributing 16-18%. In addition, the tested fuel properties of CNC biodiesel satisfy international biodiesel standards.

Bubble column photobioreactor (BCPR) for cultivating microalgae and microalgal consortium (Co-CC) with additional CO2 supply for enhancing biomass, lipid, and preferable fatty acids production.

The present study has designed and developed a 5 L bubble column photobioreactor (BCPR) to investigate two microalgal strains Chlorella sp. S-01, Chlorella sp. S-02 and their consortium Co-CC (Chlorella sp. S-01 + Chlorella sp. S-02) at 0.03, 5, and 10% CO2 supply for biomass and lipid production. The dry cell weight of Chlorella sp. S-01, Chlorella sp. S-02 and Co-CC were, respectively about 1.41, 1.32, and 1.39 g/L on the 20th day without CO2 supply, while it was 1.76, 1.61, and 1.87 g/L, respectively at 10% CO2 supply and similarly, chlorophyll-a content was higher in 10% CO2 supplied condition over control. Interestingly, Co-CC grown at all the CO2 concentrations showed similar lipid content between 19.30 and 1F9.41%. As an integrated refinery approach, de-oiled biomass of Co-CC was subjected to carbohydrates and protein estimation and found that 46.2% and 30.80% in 10% CO2 supply condition in BCPR. Lipid extracted from the Co-CC grown under 0.03, 5, and 10% CO2 supply in 5L BCPR was converted to biodiesel, and the biodiesel yield was estimated to be 62.78%. Further, the fatty acid profile of Co-CC grown at 10% CO2 showed higher levels of C16:0, C16:1, C18:1, and monounsaturated fatty acids contents over other CO2 supplied conditions. Biodiesel of Co-CC showed favourable fuel properties such as density, higher heating value, oxidative stability, CFPP, viscosity, degree of unsaturation, saponification value, and cetane number, which were also in accordance with ASTM, and EN, biodiesel standards.

Comprehensive Review on the Use of Biocides in Microbiologically Influenced Corrosion.

A microbiologically influenced corrosion (MIC) causes huge economic losses and serious environmental damage every year. The prevention and control measures for MIC mainly include physical, chemical, and biological methods. Among them, biocide application is the most cost-effective method. Although various biocides have their own advantages in preventing and treating MIC, most biocides have the problem of polluting the environment and increasing microorganism resistance. Therefore, it has stimulated the exploration of continuously developing new environmentally friendly and efficient biocides. In this review, the application advantages and research progress of various biocides used to prevent and control MIC are discussed. Also, this review provides a resource for the research and rational use of biocides regarding MIC mitigation and prevention.

Regulating N Species in N-Doped Carbon Electro-Catalysts for High-Efficiency Synthesis of Hydrogen Peroxide in Simulated Seawater.

Electrochemical oxygen reduction reaction (ORR) is an attractive and alternative route for the on-site production of hydrogen peroxide (H2 O2 ). The electrochemical synthesis of H2 O2 in neutral electrolyte is in early studying stage and promising in ocean-energy application. Herein, N-doped carbon materials (N-Cx ) with different N types are prepared through the pyrolysis of zeolitic imidazolate frameworks. The N-Cx catalysts, especially N-C800 , exhibit an attracting 2e- ORR catalytic activity, corresponding to a high H2 O2 selectivity (≈95%) and preferable stability in 0.5 m NaCl solution. Additionally, the N-C800 possesses an attractive H2 O2 production amount up to 631.2 mmol g-1  h-1 and high Faraday efficiency (79.8%) in H-type cell. The remarkable 2e- ORR electrocatalytic performance of N-Cx catalysts is associated with the N species and N content in the materials. Density functional theory calculations suggest carbon atoms adjacent to graphitic N are the main catalytic sites and exhibit a smaller activation energy, which are more responsible than those in pyridinic N and pyrrolic N doped carbon materials. Furthermore, the N-C800 catalyst demonstrates an effective antibacterial performance for marine bacteria in simulated seawater. This work provides a new insight for electro-generation of H2 O2 in neutral electrolyte and triggers a great promise in ocean-energy application.

Review on Microbially Influenced Concrete Corrosion.

Microbially influenced concrete corrosion (MICC) causes substantial financial losses to modern societies. Concrete corrosion with various environmental factors has been studied extensively over several decades. With the enhancement of public awareness on the environmental and economic impacts of microbial corrosion, MICC draws increasingly public attention. In this review, the roles of various microbial communities on MICC and corresponding protective measures against MICC are described. Also, the current status and research methodology of MICC are discussed. Thus, this review aims at providing insight into MICC and its mechanisms as well as the development of protection possibilities.

Distribution of corrosive microbial communities in rust layers of steel immersed in seawater.

In this paper, high-throughput sequencing technology was adopted to visualize the microbial communities on the surfaces of two types of carbon steel immersed in Sea Area Ⅰ. The results showed that different microbial communities were formed on different carbon steel surfaces, in which the genus with the highest abundance on the surface of Q235 was Escherichia-Shigella, while anaerobic Desulfovibrio on the surface of 921a was the most abundant, and the dominant genus varied with the depth of the rust layer. In addition, the distribution of sulfate-reducing bacteria (SRB) on the surface of Q235 submerged in Sea Area Ⅱ was compared with the sulfate-reducing bacteria's distribution in Sea Area Ⅰ, using the environmental factors correlation analysis. The results showed that the concentrations of Ca2+, Na+, K+, Mg2+, and Al3+ were positively correlated with the distribution of SRB, while the concentrations of Cu2+, Zn2+, SO4 2-, Cl-, NO3 -, and organic carbon were negatively correlated with it. Furthermore, there was a highly significant correlation between each geochemical factor and Desulfotomaculum (p < 0.01).

Exopolymeric substances production by Bacillus cereus KMS3-1 enhanced its biosorption efficiency in removing Cd2+ and Pb2+ in single and binary metal mixtures.

The present study investigated the growth, exopolymeric substance (EPS) production, and biosorption efficiency of strain Bacillus cereus KMS3-1 in the Cd2+ and Pb2+ ions containing single and binary metal-treated broth (50 mg/L). In addition, the interaction of the KMS3-1 strain with Cd2+ and Pb2+ ions in single and binary metal-treated broths was investigated using SEM-EDS, FTIR, and XRD analyses. The results showed that the biosorption efficiency (%) and EPS production of KMS3-1 biomass in both single and binary metal-treated broths had increased with increasing incubation time and were higher for Pb2+ ions than for Cd2+ ions. In the single and binary metal-treated broths, the maximum biosorption efficiency of KMS3-1 for Pb2+ ions were 70.8% and 46.3%, respectively, while for Cd2+ ions, they were 29.3% and 16.8%, respectively, after 72 h. Moreover, the biosorption efficiency of strain KMS3-1 for both metal ions was dependent on its EPS production and peaked at the maximum EPS production. The copious EPS production by KMS3-1 was observed in metal-treated media (50 mg/L), in the following order: Pb2+ ions (1925.7 µg/mL) > binary metal mixtures (1286.8 µg/mL) > Cd2+ ions (1185.5 µg/mL), > control (1099 µg/mL) after 72 h of incubation. This result indicates that the metal biosorption efficiency of the KMS3-1 strain was enhanced by the increased EPS production in the surrounding metal-treated broth. SEM-EDS and FTIR characterization studies revealed that the KMS3-1 biomass effectively adsorbed Cd2+ and Pb2+ ions from the medium by interacting with their surface functional groups (hydroxyl, carbonyl, carboxyl, amide, and phosphate). Moreover, the biosorbed Cd2+ and Pb2+ ions were transformed into CdS and PbS, respectively, by the KMS3-1 biomass. This study suggests that the Bacillus cereus KMS3-1 strain may be a promising candidate for the treatment of metal contamination.

Sulfur enhancement effects for uranium bioleaching in column reactors from a refractory uranium ore.

The feasibility of sulfur enhancement for uranium bioleaching in column reactors was assessed with a designed mixed Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans and Leptospirillum ferriphilum from a refractory uranium ore. The uranium extraction reached 86.2% with the sulfur enhancement (1 g/kg) in 77 days leaching process, increased by 12.6% vs. the control without sulfur addition. The kinetic analysis showed that uranium bioleaching with sulfur enhancement in columns followed an internal diffusion through the product layer-controlled model. Ore residue characteristics indicated that sulfur enhancement could strengthen the porosity of passivation layer, improving the ore permeability. Notably, bacterial community analysis showed that sulfur enhancement at 1 g/kg could make the iron-oxidizing and sulfur-oxidizing bacteria on the ore surface maintain a good balance (approx. 1:1), and thus decomposing ore more effectively. Lastly, a possible mechanism model for uranium bioleaching with sulfur enhancement was proposed.

N-Doped Carbon/CeO2 Composite as a Biomimetic Catalyst for Antibacterial Application.

Exploring new and high efficiency mimic enzymes is a vital and novel strategy for antibacterial application. Haloperoxidase-like enzymes have attracted wide attention thanks to their amazing catalytic property for hypohalous acid generation from hydrogen peroxide and halides. However, few materials have displayed halogenating catalytic performance until now. Herein, we synthesized N-doped C/CeO2 (N-C/CeO2) composite materials by a combination of the liquid and solid-state method. N-C/CeO2 can possess haloperoxidase-like catalytic activity by catalyzing the bromination of organic signaling compounds (phenol red) with H2O2 at a wide range of temperatures (20 °C to 55 °C), with a solution color changing from yellow to blue. Meanwhile, it exhibits high catalytic stability/recyclability in the catalytic reaction. The synthesized N-C/CeO2 composite can effectively catalyze the oxidation of Br- with H2O2 to produce HBrO without the presence of phenol red. The produced HBrO can resist typical marine bacteria like Pseudomonas aeruginosa. This study provides an efficient biomimetic haloperoxidase and a novel sustainable method for antibacterial application.

Efficient dealkalization of red mud and recovery of valuable metals by a sulfur-oxidizing bacterium.

Red mud (RM) is a highly alkaline polymetallic waste generated via the Bayer process during alumina production. It contains metals that are critical for a sustainable development of modern society. Due to a shortage of global resources of many metals, efficient large-scale processing of RM has been receiving increasing attention from both researchers and industry. This study investigated the solubilization of metals from RM, together with RM dealkalization, via sulfur (S0) oxidation catalyzed by the moderately thermophilic bacterium Sulfobacillus thermosulfidooxidans. Optimization of the bioleaching process was conducted in shake flasks and 5-L bioreactors, with varying S0:RM mass ratios and aeration rates. The ICP analysis was used to monitor the concentrations of dissolved elements from RM, and solid residues were analyzed for surface morphology, phase composition, and Na distribution using the SEM, XRD, and STXM techniques, respectively. The results show that highest metal recoveries (89% of Al, 84% of Ce, and 91% of Y) were achieved with the S0:RM mass ratio of 2:1 and aeration rate of 1 L/min. Additionally, effective dealkalization of RM was achieved under the above conditions, based on the high rates (>95%) of Na, K, and Ca dissolution. This study proves the feasibility of using bacterially catalyzed S0 oxidation to simultaneously dealkalize RM and efficiently extract valuable metals from the amassing industrial waste.

Extracellular Polymeric Substances and Biocorrosion/Biofouling: Recent Advances and Future Perspectives.

Microbial cells secrete extracellular polymeric substances (EPS) to adhere to material surfaces, if they get in contact with solid materials such as metals. After phase equilibrium, microorganisms can adhere firmly to the metal surfaces causing metal dissolution and corrosion. Attachment and adhesion of microorganisms via EPS increase the possibility and the rate of metal corrosion. Many components of EPS are electrochemical and redox active, making them closely related to metal corrosion. Functional groups in EPS have specific adsorption ability, causing them to play a key role in biocorrosion. This review emphasizes EPS properties related to metal corrosion and protection and the underlying microbially influenced corrosion (MIC) mechanisms. Future perspectives regarding a comprehensive study of MIC mechanisms and green methodologies for corrosion protection are provided.

Corrosion of an AZ31B Magnesium Alloy by Sulfate-Reducing Prokaryotes in a Mudflat Environment.

To study the abnormal failure of magnesium anodes for buried pipelines in marine engineering in the unique environment of mudflats, a strain of a sulfate-reducing prokaryote (SRP) was isolated from pipe-laying soil, and identified as Desulfovibrio sp. HQM3. Weight-loss test, electrochemical measurements, SEM, EDS, XRD, and CLSM techniques were used to study the effect of corrosion on the AZ31B magnesium alloy. Under the influence of SRP, the magnesium alloy corroded severely at rates up to 1.31 mm/year in the mudflat environment. SRP accelerated corrosion by 0.3mm/year. Pitting occurred on the samples in both abiotic and biotic systems. The pitting depth reached 163.47 µm in the biotic system after 14 days. The main composition of a petal-like corrosion product was Mg(OH)2. The results show that a mudflat environment can lead to an accelerated corrosion of magnesium alloys.

Bioleaching of Chalcopyrite Waste Rock in the Presence of the Copper Solvent Extractant LIX984N.

Heap bioleaching, the solubilization of metal ions from metal sulfides by microbial oxidation, is often combined with solvent extraction (SX) and electrowinning to recover, e.g., copper from low-grade ores. After extraction, the leaching solution is recycled, but the entrained organic solvents may be toxic to the microorganisms. Here Acidithiobacillus ferrooxidans, Leptospirillum ferrooxidans, and Sulfobacillus thermosulfidooxidans were selected to perform bioleaching of chalcopyrite waste rock in the presence of the SX reagent (2.5% v/v LIX984N in kerosene). Possibly inhibitory effects have been evaluated by copper extraction, bacterial activity, number of actively Fe(II)-oxidizing cells, and biofilm formation. Microcalorimetry, most probable number determination, and atomic force microscopy combined with epifluorescence microscopy were applied. The results show that 100 and 300 mg/L SX reagent could hardly inhibit At. ferrooxidans from oxidizing Fe2+, but they seriously interfered with the biofilm formation and the oxidization of sulfur, thereby hindering bioleaching. L. ferrooxidans was sensitive to 50 mg/L SX reagent, which inhibited its bioleaching completely. Sb. thermosulfidooxidans showed different metabolic preferences, if the concentration of the SX reagent differed. With 10 mg/L LIX984N Sb. thermosulfidooxidans preferred to oxidize Fe2+ and extracted the same amount of copper as the assay without LIX984N. With 50 mg/L extractant the bioleaching stopped, since Sb. thermosulfidooxidans preferred to oxidize reduced inorganic sulfur compounds.

Effects of Inorganic Metabolites of Sulphate-Reducing Bacteria on the Corrosion of AZ31B and AZ63B Magnesium Alloy in 3.5 wt.% NaCl Solution.

This study seeks prevent and alleviate the failure of magnesium alloy anodes in pipelines, which we suspect is a problem related to SRB. The electrochemical corrosion behaviour of two kinds of magnesium alloys, AZ31B and AZ63B, in 3.5 wt.% NaCl solution with sulphide or phosphide-the two main inorganic metabolites of sulphate-reducing bacteria-were studied by electrochemical tests combined with other characterisation methods such as scanning electron microscopy and X-ray diffraction. The results show that the corrosion film formed by inorganic metabolites of SRB's initial stage of corrosion (1-3 d) can lead to the corrosion of magnesium alloys. However, the loose and porous corrosion product film cannot protect the substrate effectively. The inorganic metabolites in the solution can accelerate the corrosion of the surface of magnesium alloy after the corrosion products have fallen off. This study provides a theoretical basis for alleviating the premature failure of magnesium alloy anodes and for corrosion protection in the future.

Inadequate dosing of THPS treatment increases microbially influenced corrosion of pipeline steel by inducing biofilm growth of Desulfovibrio hontreensis SY-21.

Biocides are often used to mitigate the microbially influenced corrosion (MIC) of construction materials in many fields. To study the effect of inadequate dosing of non-oxidizing biocide tetrakis (hydroxymethyl) phosphonium sulfate (THPS) on corrosion of pipeline steel caused by microorganisms, a novel marine isolate Desulfovibrio hontreensis SY-21 was selected as a test microorganism. Weight loss rate determination, morphological analyses, and corrosion product analyses combined with electrochemical measurements were performed to investigate the influence of THPS on the MIC of X70 pipeline steel. The responses of sessile and planktonic cells of D. hontreensis to THPS were also studied. Results showed that D. hontreensis cells could significantly promote steel corrosion and induce local corrosion pits. With a THPS addition within the tolerance range of D. hontreensis for the biocide, MIC of the steel was further promoted by 65%. The growth of planktonic cells was inhibited by the biocide, but the number of biofilm cells was significantly increased. This study revealed that THPS concentrations within a specific range increased the corrosive effect of the presence of D. hontreensis by promoting the growth of sessile cells and biofilm formation. Therefore, the use of the biocide in practical applications needs to be properly considered and managed.