Fe-doped g-C3N4 with duel active sites for ultrafast degradation of organic pollutants via visible-light-driven photo-Fenton reaction: Insight into the performance, kinetics, and mechanism.

The photo-Fenton process provides a sustainable and cost-effective strategy for removing refractory organic contaminants in wastewater. Herein, a high-efficient Fe-doped g-C3N4 photocatalyst (Fe@CN10) with a unique 3D porous mesh structure was prepared by one-pot thermal polymerization for ultrafast degradation of azo dyes, antibiotics, and phenolic acids in heterogeneous photo-Fenton systems under visible light irradiation. Fe@CN10 exhibited a synergy between adsorption-degradation processes due to the co-existence of Fe3C and Fe3N active sites. Specifically, Fe3C acted as an adsorption site for pollutant and H2O2 molecules, while Fe3N acted as a photocatalytic active site for the high-efficient degradation of MO. Resultingly, Fe@CN10 showed a photocatalytic degradation rate of MO up to 140.32 mg/L min-1. The dominant ROS contributed to the removal of MO in the photo-Fenton pathway was hydroxyl radical (•OH). Surprisingly, as the key reactive species, singlet oxygen (1O2) generated from superoxide radical (•O2-) also efficiently attacked MO in a photo-self-Fenton pathway. Additionally, sponge/Fe@CN10 was prepared and filled in the continuous flow reactors for nearly 100% degradation of MO over 150 h when treating artificial organic wastewater. This work provided a facile route to prepare highly-active Fe-doped photocatalysts and develop a green photocatalytic system for wastewater treatment in the future.

Enhancing extracellular electron transfer through selective enrichment of Geobacter with Fe@CN-modified carbon-based anode in microbial fuel cells.

Microbial fuel cells (MFCs) have been demonstrated as a renewable energy strategy to efficiently recover chemical energy stored in wastewater into clean electricity, yet the limited power density limits their practical application. Here, Fe-doped carbon and nitrogen (Fe@CN) nanoparticles were synthesized by a direct pyrolysis process, which was further decorated to fabricate Fe@CN carbon paper anode. The modified Fe@CN anode with a higher electrochemically active surface area was not only benefit for the adhesion of electrochemically active microorganisms (EAMs) and extracellular electron transfer (EET) between the anode and EAMs but also selectively enriched Geobacter, a typical EAMs species. Accordingly, the MFCs with Fe@CN anode successfully achieved a highest voltage output of 792.76 mV and a prolonged stable voltage output of 300 h based on the mixed culture feeding with acetate. Most importantly, the electroactive biofilms on Fe@CN anode achieved more content ratio of proteins to polysaccharides (1.40) in extracellular polymeric substances for the balance between EET and cell protection under a harsh environment. This work demonstrated the feasibility of development on anode catalysts for the elaboration of the catalytic principle about interface modification, which may contribute to the practical application of MFC in energy generation and wastewater treatment.

Quorum sensing signals improve the power performance and chlortetracycline degradation efficiency of mixed-culture electroactive biofilms.

Electroactive biofilms (EABs) play an important role in bioelectrochemical systems due to their abilities to generate electrons and perform extracellular electron transfer (EET). Here, we investigated the effects of quorum sensing (QS) signals on power output, chlortetracycline degradation, and structure of EABs in MFCs treating antibiotic wastewater. The voltage output of MFCs with C4-HSL and PQS increased by 21.57% and 13.73%, respectively, compared with that without QS signals. The chlortetracycline degradation efficiency in closed-circuit MFCs with C4-HSL and PQS increased by 56.53% and 50.04%, respectively, which resulted from the thicker biofilms, higher biomass, and stronger activities. Additionally, QS signals induced the heterogeneous distribution of EPS for a balance between self-protection and EET under environmental pressure. Geobacter prevailed by the addition of QS signals to resist high chlortetracycline concentration. Our results provided a broader understanding on regulating EABs within electrode interface to improve their performance for environmental remediation and clean energy development.

Production of poly-γ-glutamic acid (γ-PGA) from xylose-glucose mixtures by Bacillus amyloliquefaciens C1.

Due to the promising applications, the demand to enhance poly-γ-glutamic acid (γ-PGA) production while decreasing the cost has increased in the past decade. Here, xylose/glucose mixture and corncob hydrolysate (CCH) was evaluated as alternatives for γ-PGA production by Bacillus amyloliquefaciens C1. Although both have been validated to support cell growth, glucose and xylose were not simutaneously consumed and exhibited a diauxic growth pattern due to carbon catabolite repression (CCR) in B. amyloliquefaciens C1, while the enhanced transcription of araE alleviated the xylose transport bottleneck across a cellular membrane. Additionally, the xyl operon (xylA and xylB), which was responsible for xylose metabolism, was strongly induced by xylose at the transcriptional level. When cultured in a mixed medium, xylR was sharply induced to 3.39-folds during the first 8-h while reduced to the base level similar to that in xylose medium. Finally, pre-treated CCH mainly contained a mixture of glucose and xylose was employed for γ-PGA fermentation, which obtained a final concentration of 6.56 ± 0.27 g/L. Although the glucose utilization rate (84.91 ± 1.81%) was lower than that with chemical substrates, the xylose utilization rate (43.41 ± 2.14%) and the sodium glutamate conversion rate (77.22%) of CCH were acceptable. Our study provided a promising approach for the green production of γ-PGA from lignocellulosic biomass and circumvent excessive non-food usage of glucose.

A novel core-shell Fe@Co nanoparticles uniformly modified graphite felt cathode (Fe@Co/GF) for efficient bio-electro-Fenton degradation of phenolic compounds.

In this study, a core-shell Fe@Co nanoparticles uniformly modified graphite felt (Fe@Co/GF) was fabricated as the cathode by one-pot self-assembly strategy for the degradation of vanillic acid (VA), syringic acid (SA), and 4-hydroxybenzoic acid (HBA) in the Bio-Electro-Fenton (BEF) system. The Fe@Co/GF cathode showed dual advantages with excellent electrochemical performance and catalytic reactivity not only due to the high electron transfer efficiency but also the synergistic redox cycles between Fe and Co species, both of which significantly enhanced the in situ generation of H2O2 and hydroxyl radicals (OH) to 152.40 µmol/L and 138.48 µmol/L, respectively. In this case, the degradation rates of VA, SA, and HBA reached 100, 94.32, and 100%, respectively, within 22 h. Representatively, VA was degraded and ultimately mineralized via demethylation, decarboxylation and ring-opening reactions. This work provided a promising approach for eliminating typical recalcitrant organic pollutants generated by the pre-treatment of lignocellulose resources.

Coordinated response of Au-NPs/rGO modified electroactive biofilms under phenolic compounds shock: Comprehensive analysis from architecture, composition, and activity.

Electroactive biofilms (EABs) can be integrated with conductive nanomaterials to boost extracellular electron transfer (EET) for achieving efficient waste treatment and energy conversion in bioelectrochemical systems. However, the in situ nanomaterial-modified EABs of mixed-culture, and their response under environmental stress are rarely revealed. Here, two nanocatalyst-decorated EABs were established by self-assembled Au nanoparticles-reduced graphene oxide (Au-NPs/rGO) in mixed-biofilms with different maturities, then their multi-property were analyzed under long-term phenolic shock. Results showed that the power density of Au-NPs/rGO decorated EABs was significantly enhanced by 28.66-42.82% due to the intensified EET pathways inside biofilms. Meanwhile, the electrochemical and catalytic performance of EABs were controllably regulated by 0.3-3.0 g/L phenolic compounds, which, however, resulted in differential alterations in their architecture, composition, and viability. EABs originated with higher maturity displayed more compact structure, lower thickness (110 µm), higher biomass (8.67 mg/cm2) and viability (0.85-0.91), endowing it better antishock ability to phenolic compounds. Phenolic-shock also induced the heterogeneous distribution of extracellular polymeric substances in terms of both spatial and bonding degrees of the decorated EABs, which could be regarded as an active response to strike a balance between self-protection and EET under environmental pressure. Our findings provide a broader understanding of microbe-electrode interactions in the micro-ecology interface and improve their performance in the removal of complex contaminants for sustainable remediation and new-energy development.

Degradation of phenolic compounds with simultaneous bioelectricity generation in microbial fuel cells: Influence of the dynamic shift in anode microbial community.

This study evaluated the feasibility of microbial fuel cells (MFCs) for simultaneous electricity generation and degradation of phenolic compounds. The voltage generation was inhibited by 36.18-63.90%, but the degradation rate increased by 146.15-392.31% when the initial concentration of syringic acid (SA), vanillic acid (VA), and 4-hydroxybenzoic acid (HBA) increased from 0.3 to 3.0 g/L. The collaboration among the functional microbes significantly enhanced the degradation rate of parent compounds and their intermediates in MFCs systems, while the accumulated intermediates severely inhibited their complete mineralization in fermentative systems. High-throughput sequencing showed that the growth of fermentative bacteria prevailed, but electrogenic bacteria were inhibited in the anode microbial community (AMC) under high concentrations of phenolic compounds (3.0 g/L). These findings provide a better understanding of the dynamic shift and synergy effects of the AMC to evaluate its potential for the treatment of phenolic-containing wastewater.

Enhanced Bio-Electro-Fenton degradation of phenolic compounds based on a novel Fe-Mn/Graphite felt composite cathode.

Phenolic compounds are problematic byproducts generated from lignocellulose pretreatment. In this study, the feasibility degradation of syringic acid (SA), vanillic acid (VA), and 4-hydroxybenzoic acid (HBA) by Bio-Electro-Fenton (BEF) system with a novel Fe-Mn/graphite felt (Fe-Mn/GF) composite cathode were investigated. The nano-scale Fe-Mn multivalent composite catalyst with core shell structure distributed more evenly on GF surface to form a catalyst layer with higher oxygen reduction reaction performance. Accordingly, the maximum power density generated with Fe-Mn/GF cathode was 48.1% and 238.9% higher than Fe/GF and GF respectively, which further enhanced the in situ generation of H2O2 due to the superiority of nano-scale core shell structure and synergistic effect of Fe and Mn species. The degradation efficiency of the three phenolic compounds in the BEF system could reached 100% after optimization of influencing parameters. Furthermore, a possible SA degradation pathway by BEF process in the present system was proposed based on the detected intermediates. These results demonstrated an efficient approach for the degradation of phenolic compounds derived from lignocellulose hydrolysates.

Increased fermentative adenosine production by gene-targeted Bacillus subtilis mutation.

Adenosine, which is produced mainly by microbial fermentation, plays an important role in the therapy of cardiovascular disease and has been widely used as an antiarrhythmic agent. In this study, guanosine 5'-monophosphate (GMP) synthetase gene (guaA) was inactivated by gene-target manipulation to increase the metabolic flux from inosine 5'-monophosphate (IMP) to adenosine in B. subtilis A509. The resulted mutant M3-3 showed an increased adenosine production from 7.40 to 10.45 g/L, which was further enhanced to a maximum of 14.39 g/L by central composite design. As the synthesis of succinyladenosine monophosphate (sAMP) from IMP catalysed by adenylosuccinate synthetase (encoded by purA gene) is the rate-limiting step in adenosine synthesis, the up-regulated transcription level of purA was the potential underlying mechanism for the increased adenosine production. This work demonstrated a practical strategy for breeding B. subtilis strains for industrial nucleoside production.

[Degradation Characteristics and Metabolic Pathway of a Pyrene-Degrading Pseudomonas aeruginosa Strain].

Polycyclic aromatic hydrocarbons (PAHs) pose a potential threat to ecosystems due to their mutagenic, carcinogenic, and teratogenic effects. Microbial degradation has been suggested as the best way to remove PAHs from contaminated environments. Screening of bacterial strains capable of efficiently degrading PAHs is the key to the bio-remediation technique. With the method of enrichment culture, the bacterial strain LX2, which can use pyrene as the sole carbon source, was isolated from sludge contaminated with PAHs. The strain was identified as Pseudomonas aeruginosa (Pseudomonas sp. LX2) according to the results of the analyses of its morphology, physiology, and phylogeny of its 16S rDNA sequence. The degradation rate of pyrene by Pseudomonas sp. LX2 was 32.1% after 21 days of cultivation at an initial pyrene concentration of 50 mg·L-1. Pyrene, 4,5-dihydro-, 2'-Hydroxypropiophenone, Phenol, and Protocatechuate were identified as the major metabolites by GC/MS analysis. Based on the identified metabolites, it was concluded that pyrene was degraded via two different routes by Pseudomonas aeruginosa, namely the 'naphthalene' and the 'phthalic acid' routes.

An integrated aerobic-anaerobic strategy for performance enhancement of Pseudomonas aeruginosa-inoculated microbial fuel cell.

Microbial fuel cell (MFC) is a promising device for energy generation and organic waste treatment simultaneously by electrochemically active bacteria (EAB). In this study, an integrated aerobic-anaerobic strategy was developed to improve the performance of P. aeruginosa-inoculated MFC. With an aerobic start-up and following an anaerobic discharge process, the current density of MFC reached a maximum of 99.80µA/cm2, which was 91.6% higher than the MFC with conventional constant-anaerobic operation. Cyclic voltammetry and HPLC analysis showed that aerobic start-up significantly increased electron shuttle (pyocyanin) production (76% higher than the constant-anaerobic MFC). Additionally, enhanced anode biofilm formation was also observed in the integrated aerobic-anaerobic MFC. The increased pyocyanin production and biofilm formation promoted extracellular electron transfer from EAB to the anode and were the underlying mechanism for the MFC performance enhancement. This work demonstrated the integrated aerobic-anaerobic strategy would be a practical strategy to enhance the electricity generation of MFC.

Bio-Electron-Fenton (BEF) process driven by microbial fuel cells for triphenyltin chloride (TPTC) degradation.

The intensive use of triphenyltin chloride (TPTC) has caused serious environmental pollution. In this study, an effective method for TPTC degradation was proposed based on the Bio-Electron-Fenton process in microbial fuel cells (MFCs). The maximum voltage of the MFC with graphite felt as electrode was 278.47% higher than that of carbon cloth. The electricity generated by MFC can be used for in situ generation of H2O2 to a maximum of 135.96µmolL-1 at the Fe@Fe2O3(*)/graphite felt composite cathode, which further reacted with leached Fe2+ to produce hydroxyl radicals. While 100µmolL-1 TPTC was added to the cathodic chamber, the degradation efficiency of TPTC reached 78.32±2.07%, with a rate of 0.775±0.021µmolL-1h-1. This Bio-Electron-Fenton driving TPTC degradation might involve in SnC bonds breaking and the main process is probably a stepwise dephenylation until the formation of inorganic tin and CO2. This study provides an energy saving and efficient approach for TPTC degradation.

[Utilization of Copper (â ¡) Wastewater for Enhancing the Treatment of Chromium (â ¥) Wastewater in Microbial Fuel Cells].

The effect of copper (Ⅱ) wastewater addition on the treatment of chromium (Ⅵ) wastewater in dual-chamber microbial fuel cells (MFCs) was investigated for different Cr(Ⅵ)/Cu(Ⅱ) concentration ratios (2:1, 1:1, 1:2, 1:4) and external resistances (10, 500, 1000, 2000 Ω). The results demonstrated that the addition of Cu(Ⅱ) and Cr(Ⅵ) into the cathode chamber of MFCs could enhance the Cr(Ⅵ) removal efficiency. The Cr(Ⅵ) removal efficiency increased with the increase in the Cr(Ⅵ)/Cu(Ⅱ) concentration ratio. The Cu(Ⅱ) on the Cr(Ⅵ) removal efficiencies increased with the decrease of external resistance. The highest Cr(Ⅵ) removal efficiency achieved was 91.00% in MFC at the Cr(Ⅵ)/Cu(Ⅱ) concentration ratio of 1:4 and external resistance of 10 Ω, which was 132.57% higher than the MFC with Cr(Ⅵ) only (39.13%). The scanning electron microscopy with coupled energy dispersive spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS) analyses of the cathode electrode at the end of the experiments indicated that Cr(Ⅵ) reduced to non-conductive Cr(Ⅲ) deposits (Cr2O3) on the cathode electrode, resulting in cathode deactivation which blocked the electron transfer. However, the addition of Cu(Ⅱ) could improve the electrical conductivity of the cathode due to its conductive reduzates (copper and Cu2O) on the cathode which could reduce the cathode deactivation and subsequently enhance the Cr(Ⅵ) removal efficiency.

[Effect of Activated Carbon Addition on the Anaerobic Fermentation of Corn Straw in Mesophilic and Thermophilic Conditions].

In order to improve the methane production and concentration, effect of activated carbon addition on the anaerobic fermentation of corn straw under the conditions of mesophilic temperature (38℃) and thermophilic temperature(50℃) was investigated in this study. The results showed that the addition of activated carbon could significantly promote methane production. Compared with the control group in mesophilic and thermophilic conditions, cumulative methane production could be increased by 63% and 96% in test groups. By DGGE analysis, the bacterium enriched by addition of activated carbon was mainly Clostridiales bacterium, compared to Bacillus (without adding activated carbon) in the thermophilic system, while the differences in fermentation with adding activated carbon and without adding activated carbon was not significant in the mesophilic system. With addition of activated carbon, the archaea enriched in the fermentation liquid was mainly Methanosaeta concilii in the mesophilic system, whereas the archaea enriched in the fermentation liquid was mainly Methanosarcina acetivorans in the thermophilic system. The archaea enriched on activated carbon was mainly Methanosaeta concilii at mesophilic temperature, while the archaea enriched on activated carbon was mainly Methanosarcina thermophila at thermophilic temperature.

Trace heavy metal ions promoted extracellular electron transfer and power generation by Shewanella in microbial fuel cells.

Although microbial fuel cells (MFCs) is considered as one of the most promising technology for renewable energy harvesting, low power output still accounts one of the bottlenecks and limits its further development. In this work, it is found that Cu(2+) (0.1µgL(-1)-0.1mgL(-1)) or Cd(2+) (0.1µgL(-1)-1mgL(-1)) significantly improve the electricity generation in MFCs. The maximum power output achieved with trace level of Cu(2+) (∼6nM) or Cd(2+) (∼5nM) is 1.3 times and 1.6 times higher than that of the control, respectively. Further analysis verifies that addition of Cu(2+) or Cd(2+) effectively improves riboflavin production and bacteria attachment on the electrode, which enhances bacterial extracellular electron transfer (EET) in MFCs. These results unveil the mechanism for power output enhancement by Cu(2+) or Cd(2+) addition, and suggest that metal ion addition should be a promising strategy to enhance EET as well as power generation of MFCs.

Endogenously enhanced biosurfactant production promotes electricity generation from microbial fuel cells.

Microbial fuel cell (MFC) is considered as a promising green energy source and energy-saving pollutants treatment technology as it integrates pollutant biodegradation with energy extraction. In this work, a facile approach to enhance endogenous biosurfactant production was developed to improve the electron transfer rate and power output of MFC. By overexpression of rhlA, the key gene responsible for rhamnolipids synthesis, over-production of self-synthesized rhamnolipids from Pseudomonas aeruginosa PAO1 was achieved. Strikingly, the increased rhamnolipids production by rhlA overexpression significantly promoted the extracellular electron transfer of P. aeruginosa by enhancing electron shuttle (pyocyanin) production and increasing bacteria attachment on the anode. As a result, the strain with endogenously enhanced rhamnolipids production delivered 2.5 times higher power density output than that of the parent strain. This work substantiated that the enhancement on endogenous biosurfactant production could be a promising approach for improvement on the electricity output of MFC.

Enhanced bioelectricity generation by improving pyocyanin production and membrane permeability through sophorolipid addition in Pseudomonas aeruginosa-inoculated microbial fuel cells.

Improvement on electron shuttle-mediated extracellular electron transfer (EET) is of great potential to enhance the power output of MFCs. In this study, sophorolipid was added to enhance the performance of Pseudomonas aeruginosa-inoculated MFC by improving the electron shuttle-mediated EET. Upon sophorolipid addition, the current density and power density increased ∼ 1.7 times and ∼ 2.6 times, respectively. In accordance, significant enhancement on pyocyanin production (the electron shuttle) and membrane permeability were observed. Furthermore, the conditions for sophorolipid addition were optimized to achieve maximum pyocyanin production (14.47 ± 0.23 µg/mL), and 4 times higher power output was obtained compared to the control. The results substantiated that enhanced membrane permeability and pyocyanin production by sophorolipid, which promoted the electron shuttle-mediated EET, underlies the improvement of the energy output in the P. aeruginosa-inoculated MFC. It suggested that addition of biosurfactant could be a promising way to enhance the energy generation in MFCs.

Enhancement of bioelectricity generation by cofactor manipulation in microbial fuel cell.

Microbial fuel cells (MFCs) are promising for harnessing bioenergy from various organic wastes. However, low electricity power output (EPT) is one of the major bottlenecks in the practical application of MFCs. In this study, EPT improvement by cofactor manipulation was explored in the Pseudomonas aeruginosa-inoculated MFCs. By overexpression of nadE (NAD synthetase gene), the availability of the intracellular cofactor pool (NAD(H/(+))) significantly increased, and delivered approximately three times higher power output than the original strain (increased from 10.86 µW/cm(2) to 40.13 µW/cm(2)). The nadE overexpression strain showed about a onefold decrease in charge transfer resistance and higher electrochemical activity than the original strain, which should underlie the power output improvement. Furthermore, cyclic voltammetry, HPLC, and LC-MS analysis showed that the concentration of the electron shuttle (pyocyanin) increased approximately 1.5 fold upon nadE overexpression, which was responsible for the enhanced electrochemical activity. Thus, the results substantiated that the manipulation of intracellular cofactor could be an efficient approach to improve the EPT of MFCs, and implied metabolic engineering is of great potential for EPT improvement.

Enhancement of bioelectricity generation by manipulation of the electron shuttles synthesis pathway in microbial fuel cells.

Microbial fuel cells (MFCs) are promising for generating bioenergy and treating organic waste simultaneously. However, low extracellular electron transfer (EET) efficiency between electrogens and anodes remains one of the major bottlenecks in practical applications of MFCs. In this paper, pyocyanin (PYO) synthesis pathway was manipulated to improve the EET efficiency in Pseudomonas aeruginosa-inoculated MFCs. By overexpression of phzM (methyltransferase encoding gene), the maximum power density of P. aeruginosa-phzM-inoculated MFC was enhanced to 166.68 µW/cm(2), which was four folds of the original strain. In addition, the phzM overexpression strain exhibited an increase of 1.6 folds in PYO production and about a onefold decrease in the total internal resistance than the original strain, which should underlie the enhancement of the EET efficiency and the electricity power output (EPT). On the basis of these results, the manipulation of electron shuttles synthesis pathways could be an efficient approach to improve the EPT of MFCs.