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Porous structure of reduced graphene oxide (rGO) plays an important role in developing flexible graphene-based devices. In this work, we report a novel methodology for reduction of freestanding graphite oxide (GO) sheet by picosecond pulse laser direct writing in liquid nitrogen. Non-agglomerate and porous structure of rGO is fabricated successfully due to frozen effect during laser processing. Compared with laser-irradiated rGO developed in N2 gas at ambient environment, the frozen rGO developed in liquid N2 shows better ordered structure with less defects, crack-free morphology as well as better electron supercapacitor performance including 50–60 Ω/sq in sheet electrical resistance. Mechanism of cryotemperature photoreduction GO is also discussed.

Cellulosic ethanol production from lignocellulosic biomass offers a sustainable solution for transition from fossil based fuels to renewable alternatives. However, a few long-standing technical challenges remain to be addressed in the development of an economically viable fermentation process from lignocellulose. Such challenges include the needs to improve yeast tolerance to toxic inhibitory compounds and to achieve high fermentation efficiency with minimum detoxification steps after a simple biomass pretreatment. Here we report an in-situ detoxification strategy by PEG exo-protection of an industrial dry yeast (starch-base). The exo-protected yeast cells displayed remarkably boosted vitality with high tolerance to toxic inhibitory compounds and with largely improved ethanol productivity from crude hydrolysate derived from a pretreated lignocellulose. The PEG chemical exo-protection makes the industrial S. cerevisiae yeast directly applicable for the production of cellulosic ethanol with substantially improved productivity and yield, without of the need to use genetically modified microorganisms.

A heat-initiated chemical reaction was developed to functionalize CVD-grown graphene at wafer scale and the reaction was universally extended to carbon nanotubes and other precursors that could be thermally converted to active radicals. The chemical reaction can occur in absence of oxygen and water vapor when the temperature is above the decomposition temperature of the reactants. The chemical reaction was also found to be substrate-dependent due to surface doping and inhomogeneity. A large-scale graphene pattern was demonstrated by combing with microfluidic technique. This heat-initiated solid-phase chemical reaction provides a facile and environmentally friendly approach to functionalize carbon nanomaterials with various functional groups.

A continuous stirred microbial electrochemical reactor (CSMER), comprising of a complete mixing zone (CMZ) and microbial electrochemical zone (MEZ), was used for brewery wastewater treatment. The system realized 75.4 ± 5.7% of TCOD and 64.9 ± 4.9% of TSS when fed with brewery wastewater concomitantly achieving an average maximum power density of 304 ± 31 m W m−2. Cascade utilization of organic matters made the CSMER remove a wider range of substrates compared with a continuous stirred tank reactor (CSTR), in which process 79.1 ± 5.6% of soluble protein and 86.6 ± 2.2% of soluble carbohydrates were degraded by anaerobic digestion in the CMZ and short-chain volatile fatty acids were further decomposed and generated current in the MEZ. Co-existence of fermentative bacteria (Clostridium and Bacteroides, 19.7% and 5.0%), acetogenic bacteria (Syntrophobacter, 20.8%), methanogenic archaea (Methanosaeta and Methanobacterium, 40.3% and 38.4%) and exoelectrogens (Geobacter, 12.4%) as well as a clear spatial distribution and syntrophic interaction among them contributed to the cascade degradation process in CSMER. The CSMER shows great promise for practical wastewater treatment application due to high pre-hydrolysis and acidification rate, high energy recovery and low capital cost.

Energy self-sufficiency is a highly desirable goal of sustainable wastewater treatment. Herein, a combined system of a microbial fuel cell and an intermittently aerated biological filter (MFC-IABF) was designed and operated in an energy self-sufficient manner. The system was fed with synthetic wastewater (COD = 1000 mg L−1) in continuous mode for more than 3 months at room temperature (~25 °C). Voltage output was increased to 5 ± 0.4 V using a capacitor-based circuit. The MFC produced electricity to power the pumping and aeration systems in IABF, concomitantly removing COD. The IABF operating under an intermittent aeration mode (aeration rate 1000 ± 80 mL h−1) removed the residual nutrients and improved the water quality at HRT = 7.2 h. This two-stage combined system obtained 93.9% SCOD removal and 91.7% TCOD removal (effluent SCOD = 61 mg L−1, TCOD = 82.8 mg L−1). Energy analysis indicated that the MFC unit produced sufficient energy (0.27 kWh m−3) to support the pumping system (0.014 kWh m−3) and aeration system (0.22 kWh m−3). These results demonstrated that the combined MFC-IABF system could be operated in an energy self-sufficient manner, resulting to high-quality effluent.

This study presents a simple and sustainable Microbial Fuel Cell as a standalone, self-powered reactor for in situ wastewater electrolysis, recovering nitrogen from wastewater. A process is proposed whereby the MFC electrical performance drives the electrolysis of wastewater towards the self-generation of catholyte within the same reactor. The MFCs were designed to harvest the generated catholyte in the internal chamber, which showed that liquid production rates are largely proportional to electrical current generation. The catholyte demonstrated bactericidal properties, compared to the control (open-circuit) diffusate and reduced observable biofilm formation on the cathode electrode. Killing effects were confirmed using bacterial kill curves constructed by exposing a bioluminescent Escherichia coli target, as a surrogate coliform, to catholyte where a rapid kill rate was observed. Therefore, MFCs could serve as a water recovery system, a disinfectant/cleaner generator that limits undesired biofilm formation and as a washing agent in waterless urinals to improve sanitation. This simple and ready to implement MFC system can convert organic waste directly into electricity and self-driven nitrogen along with water recovery. This could lead to the development of energy positive bioprocesses for sustainable wastewater treatment.

We developed a simple, scalable and high-throughput method for fabrication of large-area three-dimensional rose-like microflowers with controlled size, shape and density on graphene films by femtosecond laser micromachining. The novel biomimetic microflower that composed of numerous turnup graphene nanoflakes can be fabricated by only a single femtosecond laser pulse, which is efficient enough for large-area patterning. The graphene films were composed of layer-by-layer graphene nanosheets separated by nanogaps (~10–50 nm) and graphene monolayers with an interlayer spacing of ~0.37 nm constituted each of the graphene nanosheets. This unique hierarchical layering structure of graphene films provides great possibilities for generation of tensile stress during femtosecond laser ablation to roll up the nanoflakes, which contributes to the formation of microflowers. By a simple scanning technique, patterned surfaces with controllable densities of flower patterns were obtained, which can exhibit adhesive superhydrophobicity. More importantly, this technique enables fabrication of the large-area patterned surfaces at centimeter scales in a simple and efficient way. This study not only presents new insights of ultrafast laser processing of novel graphene-based materials but also shows great promise of designing new materials combined with ultrafast laser surface patterning for future applications in functional coatings, sensors, actuators and microfluidics.

Composting is a widely-used method to recycle the nutrients in livestock manure for agriculture. The spatial stratifications of microbial processes inside the manure particle that determine organic and nitrogen transformation are virtually unclear. Here, we show the evolution of the interior microenvironment of swine, cow and chicken manure by using microelectrodes during forced-aeration composting. Composting has generally been regarded as an aerobic bioprocess, however, the long-existing of a large anoxic zone inside these manures was confirmed during the active phase in this study. The profile of the oxidation–reduction potential dramatically decreased first and then gradually increased. The spatial difference in the ammonia concentration was not significant, but nitrate concentration continuously decreased with depth. The anoxic condition within the manure particle was demonstrated to be a primary cause of the severe ammonia emission and the long composting period. These founding provided a new insight toward “aerobic” composting process and a sound foundation for the development of efficient composting technology.

Graphene/Cu composites were fabricated through a graphene in-situ grown approach, which involved ball-milling of Cu powders with PMMA as solid carbon source, in-situ growth of graphene on flaky Cu powders and vacuum hot-press sintering. SEM and TEM characterization results indicated that graphene in-situ grown on Cu powders guaranteed a homogeneous dispersion and a good combination between graphene and Cu matrix, as well as the intact structure of graphene, which was beneficial to its strengthening effect. The yield strength of 244 MPa and tensile strength of 274 MPa were achieved in the composite with 0.95 wt.% graphene, which were separately 177% and 27.4% enhancement over pure Cu. Strengthening effect of in-situ grown graphene in the matrix was contributed to load transfer and dislocation strengthening.

Modification of titanium dioxide (TiO2) for H2 generation is a grand challenge due to its high chemical inertness, large bandgap, narrow light-response range and rapid recombination of electrons and holes. Herein, we report a simple process to prepare nanospherical like reduced graphene oxide (NS-rGO) decorated TiO2 nanoparticles (NS-rGO/TiO2) as photocatalysts. This modified TiO2 sample exhibits remarkably significant improvement on visible light absorption, narrow band gap and efficient charge collection and separation. The photocatalytic H2 production rate of NS-rGO/TiO2 is high as 13996 μmol g−1 h−1, which exceeds that obtained on TiO2 alone and TiO2 with parallel graphene sheets by 3.45 and 3.05 times, respectively. This improvement is due to the presence of NS-rGO as an electron collector and transporter. The geometry of NS-rGO should be effective in the design of a graphene/TiO2 composite for photocatalytic applications.

Conventional wastewater purification technologies consume large amounts of energy, while the abundant chemical energy and nutrient resources contained in sewage are wasted in such treatment processes. A microbial nutrient recovery cell (MNRC) has been developed to take advantage of the energy contained in wastewater, in order to simultaneously purify wastewater and recover nutrient ions. When wastewater was circulated between the anode and cathode chambers of the MNRC, the organics (COD) were removed by bacteria while ammonium and phosphate (NH4+-N and PO43−-P) were recovered by the electrical field that was produced using in situ energy in the wastewater without additional energy input. The removal efficiencies from wastewater were >82% for COD, >96% for NH4+-N and >64% for PO43−-P in all the operational cycles. Simultaneously, the concentrations of NH4+ and PO43− in the recovery chamber increased to more than 1.5 and 2.2 times, respectively, compared with the initial concentrations in wastewater. The MNRC provides proof-of-concept as a sustainable, self-driven approach to efficient wastewater purification and nutrient recovery in a comprehensive bioelectrochemical system.

During the anaerobic digestion of dewatered sludge, polyacrylamide (PAM), a chemical conditioner, can usually be consumed as a carbon and nitrogen source along with other organic matter (e.g., proteins and carbohydrates in the sludge). However, a significant accumulation of acrylamide monomers (AMs) was observed during the PAM biodegradation process. To improve the anaerobic hydrolysis of PAM, especially the amide hydrolysis process and to avoid the generation of the intermediate product AM, a new strategy is reported herein that uses an initial pH of 9, 200 mg COD/L of PAM and a fermentation time of 17 d. First, response surface methodology (RSM) was applied to optimize PAM removal in the anaerobic digestion of the sludge. The biological hydrolysis of PAM reached 86.64% under the optimal conditions obtained from the RSM. Then, the mechanisms for the optimized parameters that significantly improved the biological hydrolysis of PAM were investigated by the synergistic effect of the main organic compounds in the sludge, the floc size distribution and the enzymatic activities. Finally, semi-continuous-flow experiments for a microbial community study were investigated based on the determination of key microorganisms involved in the biological hydrolysis of PAM.

Recovering nutrients, especially phosphate resource, from wastewater have attracted increasing interest recently. Herein, an intermittently aerated membrane bioreactor (MBR) with a mesh filter was developed for simultaneous chemical oxygen demand (COD), total nitrogen (TN) and phosphorous removal, followed by phosphorus recovery from the phosphorus-rich sludge. This integrated system showed enhanced performances in nitrification and denitrification and phosphorous removal without excess sludge discharged. The removal of COD, TN and total phosphorus (TP) in a modified MBR were averaged at 94.4 ± 2.5%, 94.2 ± 5.7% and 53.3 ± 29.7%, respectively. The removed TP was stored in biomass and 68.7% of the stored phosphorous in the sludge could be recovered as concentrated phosphate solution with a concentration of phosphate above 350 mg/L. The sludge after phosphorus release could be returned back to the MBR for phosphorus uptake and 83.8% of its capacity could be recovered.

Growth of graphene by chemical vapor deposition on metal supports has become a promising approach for the large-scale synthesis of high quality graphene. Decoupling of the graphene from the metal has been achieved by either mechanical transfer or intercalation of elements/molecules in between the metal and graphene. Here we show that metal stabilized two-dimensional (2D)-oxide monolayers can be grown in between graphene and the metal substrate thus forming 2D-heterostructures that enable tuning of the materials properties of graphene. Specifically, we demonstrate the intercalation-growth of a 2D-FeO layer in between graphene and Pt(111), which can decouple the graphene from the metal substrate. It is known that the 2D-FeO/Pt(111) system exhibits a moiré-structure with locally strongly varying surface potential. This variation in the substrate surface potential modifies the interface charge doping to graphene locally, causing nanometer-scale variation in its work function and Fermi-level shifts relative to its Dirac point.

We introduce a high-performance molecular sensor using self-corrugated chemically modified graphene as a three dimensional (3D) structure that indicates anisotropic charge distribution. This is capable of room-temperature operation, and, in particular, exhibiting high sensitivity and reversible fast response with equilibrium region. The morphology consists of periodic, “cratered” arrays that can be formed by condensation and evaporation of graphene oxide (GO) solution on interdigitated electrodes. Subsequent hydrazine reduction, the corrugated edge area of the graphene layers have a high electric potential compared with flat graphene films. This local accumulation of electrons interacts with a large number of gas molecules. The sensitivity of 3D-graphene sensors significantly increases in the atmosphere of NO2 gas. The intriguing structures have several advantages for straightforward fabrication on patterned substrates, high-performance graphene sensors without post-annealing process.

Structural inhomogeneities, such as the wrinkles and ripples within a graphene film after transferring the free-standing graphene layer to a functional substrate, degrade the physical and electrical properties of the corresponding electronic devices. Here, we introduced titanium as a superior adhesion layer for fabricating wrinkle-free graphene films that is highly applicable to flexible and transparent electronic devices. The Ti layer does not influence the electronic performance of the functional substrates. Experimental and theoretical investigations confirm that the strong chemical interactions between Ti and any oxygen atoms unintentionally introduced on/within the graphene are responsible for forming the clean, defect-free graphene layer. Our results accelerate the practical application of graphene-related electronic devices with enhanced functionality. The large-area monolayer graphenes were prepared by a simple attachment of the Ti layer with the multi-layer wrinkle-free graphene films. For the first time, the graphene films were addressed for applications of superior bottom electrode for flexible capacitors instead of the novel metals.

It is estimated that approximately 1.1 billion people globally drink unsafe water. We previously reported both a novel copper-alginate bead, which quickly reduces pathogen loading in waste streams and the incorporation of these beads into a novel swirl flow bioreactor (SFB), of low capital and running costs and of simple construction from commercially available plumbing pipes and fittings. The purpose of the present study was to trial this system for pathogen reduction in waste streams from an operating Dewats system in Hinjewadi, Pune, India and in both simulated and real waste streams in Seattle, Washington, USA. The trials in India, showed a complete inactivation of coliforms in the discharged effluent (Mean Log removal Value (MLRV) = 3.51), accompanied by a total inactivation of E. coli with a MLRV of 1.95. The secondary clarifier effluent also showed a 4.38 MLRV in viable coliforms during treatment. However, the system was slightly less effective in reducing E. coli viability, with a MLRV of 1.80. The trials in Seattle also demonstrated the efficacy of the system in the reduction of viable bacteria, with a LRV of 5.67 observed of viable Raoultella terrigena cells (100%).

In the present study, struvite decomposition was performed by air stripping for ammonia release and a novel integrated reactor was designed for the simultaneous removal and recovery of total ammonia-nitrogen (TAN) and total orthophosphate (PT) from swine wastewater by internal struvite recycling. Decomposition of struvite by air stripping was found to be feasible. Without supplementation with additional magnesium and phosphate sources, the removal ratio of TAN from synthetic wastewater was maintained at >80% by recycling of the struvite decomposition product formed under optimal conditions, six times. Continuous operation of the integrated reactor indicated that approximately 91% TAN and 97% PT in the swine wastewater could be removed and recovered by the proposed recycling process with the supplementation of bittern. Economic evaluation of the proposed system showed that struvite precipitation cost can be saved by approximately 54% by adopting the proposed recycling process in comparison with no recycling method.

Hydrogen recovery through solar-driven biomass conversion by photo-fermentative bacteria (PFB) has been regarded as a promising way for sustainable energy production. However, a considerable fraction of organic substrate was consumed for the growth of PFB as biocatalysts, furthermore, these PFB were continuously washed out from the photobioreactor in continuous operation because of their poor flocculation. In this work, PFB bioaggregate induced by L-cysteine was applied in a sequencing batch photobioreactor to enhance continuous hydrogen production and reduce biomass washout. The effects of the hydraulic retention time (HRT), influent concentration and light intensity on hydrogen production of the photobioreactor were investigated. The maximum hydrogen yield (3.35 mol H2/mol acetate) and production rate (1044 ml/l/d) were obtained at the HRT of 96 h, influent concentration of 3.84 g COD/l and light intensity of 200 W/m2. With excellent settling ability, biomass accumulated in the photobioreactor and reached 2.15 g/l under the optimum conditions. Structural analysis of bioaggregate showed that bacterial cells were covered and tightly linked together by extracellular polymeric substances and formed a stable structure. Therefore, PFB bioaggregate induced by L-cysteine is an efficient strategy to improve biomass retention capacity of the photobioreactor and enhance hydrogen recovery efficiency from organic wastes.

Iron oxides/reduced graphene oxide composites were synthesized by facile thermochemical reactions of graphite oxide and FeSO4·7H2O. By adjusting reaction temperature, α-Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites can be obtained conveniently. Graphene oxide and reduced graphene oxide sheets were demonstrated to regulate the phase transition from α-Fe2O3 to Fe3O4 via γ-Fe2O3, which was reported for the first time. The hydroxyl groups attached on the graphene oxide sheets and H2 gas generated during the annealing of graphene oxide are believed to play an important role during these phase transformations. These samples showed good electromagnetic wave absorption performance due to their electromagnetic complementary effect. These samples possess much better electromagnetic wave absorption properties than the mixture of separately prepared Fe3O4 with rGO, suggesting the crucial role of synthetic method in determining the product properties. Also, these samples perform much better than commercial absorbers. Most importantly, the great stability of these composites is highly advantageous for applications as electromagnetic wave absorption materials at high temperatures.

The drying process of graphene-polymer composites fabricated by solution-processingfor excellent dispersion is time consuming and suffers from a restacking problem.Here, we have developed an innovative method to fabricate polymer compositeswith well dispersed graphene particles in the matrix resin by using solventfree powder mixing and in-situ polymerization of a low viscosity oligomerresin. We also prepared composites filled with up to 20 wt% of grapheneparticles by the solvent free process while maintaining a high degree of dispersion.The electrical conductivity of the composite, one of the most significantproperties affected by the dispersion, was consistent with the theoreticallyobtained effective electrical conductivity based on the mean field micromechanicalanalysis with the Mori-Tanaka model assuming ideal dispersion. It can be confirmedby looking at the statistical results of the filler-to-filler distance obtainedfrom the digital processing of the fracture surface images that the variousoxygenated functional groups of graphene oxide can help improve the dispersionof the filler and that the introduction of large phenyl groups to the graphenebasal plane has a positive effect on the dispersion.

A new graphene-based composite structure, monolayer-ordered macroporous film composed of a layer of orderly arranged macropores, was reported. As an example, SnO2-reduced graphite oxide monolayer-ordered macroporous film was fabricated on a ceramic tube substrate under the irradiation of ultra-violet light (UV), by taking the latex microsphere two-dimensional colloid crystal as a template. Graphite oxide sheets dispersed in SnSO4 aqueous solution exhibited excellent affinity with template microspheres and were in situ incorporated into the pore walls during UV-induced growth of SnO2. The growing and the as-formed SnO2, just like other photocatalytic semiconductor, could be excited to produce electrons and holes under UV irradiation. Electrons reduced GO and holes adsorbed corresponding negative ions, which changed the properties of the composite film. This film was directly used as gas-sensor and was able to display high sensitivity in detecting ethanol gas. More interestingly, on the basis of SnO2-induced photochemical behaviours, this sensor demonstrated tunable sensitivity when UV irradiation time was controlled during the fabrication process and post in water, respectively. This study provides efficient ways of conducting the in situ fabrication of a semiconductor-reduced graphite oxide film device with uniform surface structure and controllable properties.

Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system.

Denitrifying capability of glycogen accumulating organisms (GAOs) has received great attention in environmental science and microbial ecology. Combining this ability with granule processes would be an interesting attempt. Here, a laboratory-scale sequencing batch reactor (SBR) was operated to enrich GAOs and enable sludge granulation. The results showed that the GAO granules were cultivated successfully and the granules had denitrifying capability. The batch experiments demonstrated that all NO3−-N could be removed or reduced, some amount of NO2−-N were accumulated in the reactor and N2 was the main gaseous product. SEM analysis suggested that the granules were tightly packed with a large amount of tetrad-forming organisms (TFOs); filamentous bacteria served as the supporting structures for the granules. The microbial community structure of GAO granules was differed substantially from the inoculant conventional activated sludge. Most of the bacteria in the seed sludge grouped with members of Proteobacterium. FISH analysis confirmed that GAOs were the predominant members in the granules and were distributed evenly throughout the granular space. In contrast, PAOs were severely inhibited. Overall, cultivation of the GAO granules and utilizing their denitrifying capability can provide us with a new approach of nitrogen removal and saving more energy.

Improvement of sludge dewaterability is important for reducing the total costs for the treatment and disposal of sludge in wastewater treatment plants. In this study, we investigate the use of hydrogen peroxide as an oxidizing reagent for the conditioning of waste activated sludge. Significant improvement to sludge dewaterability was attained after the addition of hydrogen peroxide at 30 mg/g TS and 28 mg/g TS under acidic conditions (pH = 3.0), with the highest reduction of capillary suction time being 68% and 56%, respectively, for sludge containing an iron concentration of 56 mg Fe/g TS and 25 mg Fe/g TS, respectively. The observations were due to Fenton reactions between the iron contained in sludge (indigenous iron) and hydrogen peroxide. For the sludge with an insufficient level of indigenous iron, the addition of ferrous chloride was found to be able to improve the sludge dewaterability. The results firstly indicated that indigenous iron can be utilized similarly as the externally supplied iron salt to improve sludge dewaterability through catalyzing the Fenton reactions.

In this work, the piezoresistive effects of defective graphene used on a flexible pressure sensor are demonstrated. The graphene used was deposited at substrate temperatures of 750, 850 and 1000 °C using the hot-filament thermal chemical vapor deposition method in which the resultant graphene had different defect densities. Incorporation of the graphene as the sensing materials in sensor device showed that a linear variation in the resistance change with the applied gas pressure was obtained in the range of 0 to 50 kPa. The deposition temperature of the graphene deposited on copper foil using this technique was shown to be capable of tuning the sensitivity of the flexible graphene-based pressure sensor. We found that the sensor performance is strongly dominated by the defect density in the graphene, where graphene with the highest defect density deposited at 750 °C exhibited an almost four-fold sensitivity as compared to that deposited at 1000 °C. This effect is believed to have been contributed by the scattering of charge carriers in the graphene networks through various forms such as from the defects in the graphene lattice itself, tunneling between graphene islands and tunneling between defect-like structures.

A coupling process of anaerobic methanogenesis and electromethanogenesis was proposed to treat high organic load rate (OLR) wastewater. During the start-up stage, acetate removal efficiency of the electric-biological reactor (R1) reached the maximization about 19 percentage points higher than that of the control anaerobic reactor without electrodes (R2), and CH4 production rate of R1 also increased about 24.9% at the same time, while additional electric input was 1/1.17 of the extra obtained energy from methane. Coulombic efficiency and current recorded showed that anodic oxidation contributed a dominant part in degrading acetate when the metabolism of methanogens was low during the start-up stage. Along with prolonging operating time, aceticlastic methanogenesis gradually replaced anodic oxidation to become the main pathway of degrading acetate. When the methanogens were inhibited under the acidic conditions, anodic oxidation began to become the main pathway of acetate decomposition again, which ensured the reactor to maintain a stable performance. FISH analysis confirmed that the electric field imposed could enrich the H2/H(+)-utilizing methanogens around the cathode to help for reducing the acidity. This study demonstrated that an anaerobic digester with a pair of electrodes inserted to form a coupling system could enhance methanogenesis and reduce adverse impacts.

Grain boundaries (GBs) in graphene prepared by chemical vapor deposition (CVD) greatly degrade the electrical and mechanical properties of graphene and thus hinder the applications of graphene in electronic devices. The seamless stitching of graphene flakes can avoid GBs, wherein the identical orientation of graphene domain is required. In this letter, the graphene orientation on one of the most used catalyst surface — Cu(100) surface, is explored by density functional theory (DFT) calculations. Our calculation demonstrates that a zigzag edged hexagonal graphene domain on a Cu(100) surface has two equivalent energetically preferred orientations, which are 30 degree away from each other. Therefore, the fusion of graphene domains on Cu(100) surface during CVD growth will inevitably lead to densely distributed GBs in the synthesized graphene. Aiming to solve this problem, a simple route, that applies external strain to break the symmetry of the Cu(100) surface, was proposed and proved efficient.

Lithium vanadium phosphate (Li3V2(PO4)3, LVP)/reduced graphene oxide (rGO) composite is prepared with a rheological method followed by heat treatment. The size and interface of LVP particles, two important merits for a cathode material, can be effectively tuned by the rGO in the composite, which plays as surfactant to assist sol-gelation and simultaneously as conductive carbon coating. As a consequence, the composite with 7.0 ± 0.4 wt.% rGO shows a capacity of 141.6 mAh g(-1) at 0.075 C, and a rate capacity of 119.0 mAh g(-1) at 15 C with respect to the mass of LVP/rGO composite, and an excellent cycling stability that retains 98.7% of the initial discharge capacity after 50 cycles. The improved electrochemical performance is attributed to the well-controlled rGO content that yields synergic effects between LVP and rGO. Not only do the rGO sheets reduce the size of LVP particles that favor the Li(+) ion migration and the electron transfer during charging and discharging, but also contribute to the reversible lithium ions storage.

Microwave-assisted heating method is used to treat graphite oxide (GO), pyrolytic graphene oxide (PGO) and hydrogen-reduced pyrolytic graphene oxide (HPGO). Pure or doped graphene are prepared in the time of minutes and a thermal deoxygenization reduction mechanism is proposed to understand their microwave adsorption behaviors. These carbon materials are excellent catalysts in the reduction of nitrobenzene. The defects are believed to play an important role in the catalytic performance.

The interface structure of graphene with thermally evaporated metal oxide layers, in particular molybdenum trioxide (MoO3), is studied combining photoemission spectroscopy, sheet resistance measurements and organic light emitting diode (OLED) characterization. Thin (

A novel nano-porous 3D architecture of N-doped carbon nanorods arrays grown on the surface of graphene has been prepared by carbonizing polyaniline/graphene oxide (PANI-GO) composite with PANI nanorod arrays on both sides of GO nanosheets. The obtained carbon materials are entirely composed of regularly grown carbon nanorods on graphene with height of about 100 nm and width about 30 nm, showing porous property due to the decomposition of PANI chains. The morphology of PANI grown on GO at the different growth stages was investigated to demonstrate the mechanism of the finally hierarchical architecture formation. Due to its large specific surface area and incorporation of the nitrogen groups into the carbon matrix, the obtained 3D carbon material enhances the ionic transport and the super-capacitance by synergetic effect of both double-layer and faradaic capacitances. This study provides a controllable approach to fabricate hierarchical carbon material based on conducting polymers and graphene oxide with promising applications in the high-rate electrode material of supercapacitors.

We demonstrate direct production of graphene on SiO2 by CVD growth of graphene at the interface between a Ni film and the SiO2 substrate, followed by dry mechanical delamination of the Ni using adhesive tape. This result is enabled by understanding of the competition between stress evolution and microstructure development upon annealing of the Ni prior to the graphene growth step. When the Ni film remains adherent after graphene growth, the balance between residual stress and adhesion governs the ability to mechanically remove the Ni after the CVD process. In this study the graphene on SiO2 comprises micron-scale domains, ranging from monolayer to multilayer. The graphene has >90% coverage across centimeter-scale dimensions, limited by the size of our CVD chamber. Further engineering of the Ni film microstructure and stress state could enable manufacturing of highly uniform interfacial graphene followed by clean mechanical delamination over practically indefinite dimensions. Moreover, our findings suggest that preferential adhesion can enable production of 2-D materials directly on application-relevant substrates. This is attractive compared to transfer methods, which can cause mechanical damage and leave residues behind.

Graphene fibres are continuously prepared from universal graphene oxide precursors by a novel hydrogel-assisted spinning method. With assistance of a rolling process, meters of ribbon-like GFs, or GRs with improved conductivity, tensile strength, and a long-range ordered compact layer structure are successfully obtained. Furthermore, we refined our spinning process to obtained elastic GRs with a mixing microstructure and exceptional elasticity, which may provide a platform for electronic skins and wearable electronics, sensors, and energy devices.

Utilizing cyanobacteria as a bioenergy resource is difficult due to the cost and energy consuming harvests of microalgal biomass. In this study, an auto-floating system was developed by increasing the photobiological H2 production in the heterocysts of filamentous cyanobacteria. An amount of 1.0 μM of diuron, which inhibited O2 production in cyanobacteria, resulted in a high rate of H2 production in heterocysts. The auto-floating process recovered 91.71% ± 1.22 of the accumulated microalgal biomass from the liquid media. Quantification analysis revealed that 0.72-1.10 μmol H2 per mg dry weight microalgal biomass was necessary to create this auto-floating system. Further bio-conversion by using anaerobic digestion converted the harvested microalgal biomass into biogas. Through this novel coupled system of photobiological H2 production and anaerobic digestion, a high level of light energy conversion efficiency from solar energy to bioenergy was attained with the values of 3.79% ± 0.76.

Revealing the graphene growth mechanism at the atomic-scale is of great importance for achieving high quality graphene. However, the lack of direct experimental observation and density functional theory (DFT) verification hinders a comprehensive understanding of the structure of the carbon clusters and evolution of the graphene growth on surface. Here, we report an in-situ low-temperature scanning tunneling microscopy (LT-STM) study of the elementary process of chemical vapor deposition (CVD) graphene growth via thermal decomposition of methane on Cu(110), including the formation of monodispersed carbon clusters at the initial stage, the graphene nucleation and the ripening of graphene islands to form continuous graphene film. STM measurement, supported by DFT calculations, suggests that the carbon clusters on the surface are C2H5. It is found that graphene layers can be joined by different domains, with a relative misorientation of 30°. These graphene layers can be decoupled from Cu(110) through low temperature thermal cycling.

The rolling up of a graphene sheet into a tube is a standard visualization tool for illustrating carbon nanotube (CNT) formation. However, the actual processes of rolling up graphene sheets into CNTs in laboratory syntheses have never been demonstrated. Here we report conformal growth of graphene by carbon self-assembly on single-wall and multi-wall CNTs using chemical vapor deposition (CVD) of methane without the presence of metal catalysts. The new graphene layers roll up into seamless coaxial cylinders encapsulating the existing CNTs, but their adhesion to the primary CNTs is weak due to the existence of lattice misorientation. Our study shows that graphene nucleation and growth by self-assembly of carbon on the inactive carbon basal plane of CNTs occurs by a new mechanism that is markedly different from epitaxial growth on metal surfaces, opening up the possibility of graphene growth on many other non-metal substrates by simple methane CVD.

Graphene has a unique atom-thick two-dimensional structure and excellent properties, making it attractive for a variety of electrochemical applications, including electrosynthesis, electrochemical sensors or electrocatalysis, and energy conversion and storage. However, the electrochemistry of single-layer graphene has not yet been well understood, possibly due to the technical difficulties in handling individual graphene sheet. Here, we report the electrochemical behavior at single-layer graphene-based electrodes, comparing the basal plane of graphene to its edge. The graphene edge showed 4 orders of magnitude higher specific capacitance, much faster electron transfer rate and stronger electrocatalytic activity than those of graphene basal plane. A convergent diffusion effect was observed at the sub-nanometer thick graphene edge-electrode to accelerate the electrochemical reactions. Coupling with the high conductivity of a high-quality graphene basal plane, graphene edge is an ideal electrode for electrocatalysis and for the storage of capacitive charges.

Conventional leaching (extraction) methods for gold recovery from electronic waste involve the use of strong acids and pose considerable threat to the environment. The alternative use of bioleaching microbes for gold recovery is non-pollutive and relies on the secretion of a lixiviant or (bio)chemical such as cyanide for extraction of gold from electronic waste. However, widespread industrial use of bioleaching microbes has been constrained by the limited cyanogenic capabilities of lixiviant-producing microorganisms such as Chromobacterium violaceum. Here we show the construction of a metabolically-engineered strain of Chromobacterium violaceum that produces more (70%) cyanide lixiviant and recovers more than twice as much gold from electronic waste compared to wild-type bacteria. Comparative proteome analyses suggested the possibility of further enhancement in cyanogenesis through subsequent metabolic engineering. Our results demonstrated the utility of lixiviant metabolic engineering in the construction of enhanced bioleaching microbes for the bioleaching of precious metals from electronic waste.

A new chemical dual-functional reducing agent, thiophene, was used to produce high-quality reduced graphene oxide (rGO) as a result of a chemical reduction of graphene oxide (GO) and the healing of rGO. Thiophene reduced GO by donation of electrons with acceptance of oxygen while it was converted into an intermediate oxidised polymerised thiophene that was eventually transformed into polyhydrocarbon by loss of sulphur atoms. Surprisingly, the polyhydrocarbon template helped to produce good-quality rGOC (chemically reduced) and high-quality rGOCT after thermal treatment. The resulting rGOCT nanosheets did not contain any nitrogen or sulphur impurities, were highly deoxygenated and showed a healing effect. Thus the electrical properties of the as-prepared rGOCT were superior to those of conventional hydrazine-produced rGO that require harsh reaction conditions. Our novel dual reduction and healing method with thiophene could potentially save energy and facilitate the commercial mass production of high-quality graphene.

Chemical reduction of graphene oxide (GO) is the main route to produce the mass graphene-based materials with tailored surface chemistry and functions. However, the toxic reducing circumstances, multiple steps, and even incomplete removal of the oxygen-containing groups were involved, and the produced graphenes existed usually as the assembly-absent precipitates. Herein, a substrate-assisted reduction and assembly of GO (SARA-GO) method was developed for spontaneous formation of 3D graphene network on arbitrary conductive substrates including active and inert metals, semiconducting Si, nonmetallic carbon, and even indium-tin oxide glass without any additional reducing agents. The SARA-GO process offers a facile, efficient approach for constructing unique graphene assemblies such as microtubes, multi-channel networks, micropatterns, and allows the fabrication of high-performance binder-free rechargeable lithium-ion batteries. The versatile SARD-GO method significantly improves the processablity of graphenes, which could thus benefit many important applications in sensors and energy-related devices.

Graphene has been predicted to play a role in post-silicon electronics due to the extraordinary carrier mobility. Chemical vapor deposition of graphene on transition metals has been considered as a major step towards commercial realization of graphene. However, fabrication based on transition metals involves an inevitable transfer step which can be as complicated as the deposition of graphene itself. By ambient-pressure chemical vapor deposition, we demonstrate large-scale and uniform depositon of high-quality graphene directly on a Ge substrate which is wafer scale and has been considered to replace conventional Si for the next generation of high-performance metal-oxide-semiconductor field-effect transistors (MOSFETs). The immiscible Ge-C system under equilibrium conditions dictates graphene depositon on Ge via a self-limiting and surface-mediated process rather than a precipitation process as observed from other metals with high carbon solubility. Our technique is compatible with modern microelectronics technology thus allowing integration with high-volume production of complementary metal-oxide-semiconductors (CMOS).

Growth of vertically aligned carbon nanotube (CNT) forests is highly sensitive to the nature of the substrate. This constraint narrows the range of available materials to just a few oxide-based dielectrics and presents a major obstacle for applications. Using a suspended monolayer, we show here that graphene is an excellent conductive substrate for CNT forest growth. Furthermore, graphene is shown to intermediate growth on key substrates, such as Cu, Pt, and diamond, which had not previously been compatible with nanotube forest growth. We find that growth depends on the degree of crystallinity of graphene and is best on mono- or few-layer graphene. The synergistic effects of graphene are revealed by its endurance after CNT growth and low contact resistances between the nanotubes and Cu. Our results establish graphene as a unique interface that extends the class of substrate materials for CNT growth and opens up important new prospects for applications.

Production of renewable commodity chemicals from bio-oil derived from fast pyrolysis of biomass has received considerable interests, but hindered by the presence of innumerable components in bio-oil. In present work, we proposed and experimentally demonstrated an innovative approach combining atmospheric distillation of bio-oil with co-pyrolysis for mass production of renewable chemicals from biomass, in which no waste was produced. It was estimated that 51.86 wt.% of distillate just containing dozens of separable organic components could be recovered using this approach. Ten protogenetic and three epigenetic compounds in distillate were qualitatively identified by gas chromatography/mass spectrometry and quantified by gas chromatography. Among them, the recovery efficiencies of acetic acid, propanoic acid, and furfural were all higher than 80 wt.%. Formation pathways of the distillate components in this process were explored. This work opens up a fascinating prospect for mass production of chemical feedstock from waste biomass.

In myopia the eye grows too long, generating poorly focused retinal images when people try to look at a distance. Myopia is tightly linked to the educational status and is on the rise worldwide. It is still not clear which kind of visual experience stimulates eye growth in children and students when they study. We propose a new and perhaps unexpected reason. Work in animal models has shown that selective activation of ON or OFF pathways has also selective effects on eye growth. This is likely to be true also in humans. Using custom-developed software to process video frames of the visual environment in realtime we quantified relative ON and OFF stimulus strengths. We found that ON and OFF inputs were largely balanced in natural environments. However, black text on white paper heavily overstimulated retinal OFF pathways. Conversely, white text on black paper overstimulated ON pathways. Using optical coherence tomography (OCT) in young human subjects, we found that the choroid, the heavily perfused layer behind the retina in the eye, becomes about 16 µm thinner in only one hour when subjects read black text on white background but about 10 µm thicker when they read white text from black background. Studies both in animal models and in humans have shown that thinner choroids are associated with myopia development and thicker choroids with myopia inhibition. Therefore, reading white text from a black screen or tablet may be a way to inhibit myopia, while conventional black text on white background may stimulate myopia.

Current technologies for bioethanol production rely on the use of freshwater for preparing the fermentation media and use yeasts of a terrestrial origin. Life cycle assessment has suggested that between 1,388 to 9,812 litres of freshwater are consumed for every litre of bioethanol produced. Hence, bioethanol is considered a product with a high-water footprint. This paper investigated the use of seawater-based media and a novel marine yeast strain ‘Saccharomyces cerevisiae AZ65’ to reduce the water footprint of bioethanol. Results revealed that S. cerevisiae AZ65 had a significantly higher osmotic tolerance when compared with the terrestrial reference strain. Using 15-L bioreactors, S. cerevisiae AZ65 produced 93.50 g/L ethanol with a yield of 83.33% (of the theoretical yield) and a maximum productivity of 2.49 g/L/h when using seawater-YPD media. This approach was successfully applied using an industrial fermentation substrate (sugarcane molasses). S. cerevisiae AZ65 produced 52.23 g/L ethanol using molasses media prepared in seawater with a yield of 73.80% (of the theoretical yield) and a maximum productivity of 1.43 g/L/h. These results demonstrated that seawater can substitute freshwater for bioethanol production without compromising production efficiency. Results also revealed that marine yeast is a potential candidate for use in the bioethanol industry especially when using seawater or high salt based fermentation media.

Thirty-one samples of essential oils used both in perfumery and aromatherapy were purchased to business-to-consumers suppliers and submitted to standard gas chromatography-based analysis of their chemical composition. Their compliance with ISO AFNOR standards was checked and revealed, although ISO AFNOR ranges are relatively loose, that more than 45% of the samples analyzed failed to pass the test and more than 19% were diluted with solvents such as propylene and dipropylene glycol, triethyl citrate, or vegetal oil. Cases of non-compliance could be due to substitution or dilution with a cheaper essential oil, such as sweet orange oil, blending with selected compounds (linalool and linalyl acetate, maybe of synthetic origin), or issues of aging, harvest, or manufacturing that should be either deliberate or accidental. In some cases, natural variability could be invoked. These products are made available to the market without control and liability by resellers and could expose the public to safety issues, in addition to commercial prejudice, in sharp contrast with the ever-increasing regulations applying to the sector and the high demand of consumers for safe, controlled and traceable products in fragrances and cosmetic products.

The efficiency of anaerobic biofilters (AnBF) as low-cost wastewater treatment systems was investigated. Miscanthus-biochar was used as filtration media and compared with sand as a common reference material. Raw sewage from a municipal wastewater treatment plant was stored in a sedimentation tank for two days to allow pre-settlement of wastewater particles. Subsequently, wastewater was treated by AnBFs at 22 °C room temperature at a hydraulic loading rate of 0.05 m∙h−1 with an empty bed contact time of 14.4 h and a mean organic loading rate of 509 ± 173 gCOD∙m−3∙d−1. Mean removal of chemical oxygen demand (COD) of biochar filters was with 74 ± 18% significantly higher than of sand filters (61 ± 12%). In contrast to sand filters with a mean reduction of 1.18 ± 0.31 log-units, E. coli removal through biochar was with 1.35 ± 0.27 log-units significantly higher and increased with experimental time. Main removal took place within the schmutzdecke, a biologically active dirt layer that develops simultaneously on the surface of filter beds. Since the E. coli contamination of both filter materials was equal, the higher removal efficiency of biochar filters is probably a result of an improved biodegradation within deeper zones of the filter bed. Overall, performance of biochar filters was better or equal compared to sand and have thus demonstrated the suitability of Miscanthus-biochar as filter media for wastewater treatment.

Numerous researchers have expressed concern over the emerging water scarcity issues around the globe. Economic water scarcity is severe in the developing countries; thus, the use of inexpensive wastewater treatment strategies can help minimize this issue. An abundant amount of laundry wastewater (LWW) is generated daily and various wastewater treatment researches have been performed to achieve suitable techniques. This study addressed this issue by considering the economic perspective of the treatment technique through the selection of easily available materials. The proposed technique is a combination of locally available absorbent materials such as sand, biochar, and teff straw in a media. Biochar was prepared from eucalyptus wood, teff straw was derived from teff stem, and sand was obtained from indigenous crushed stones. In this study, the range of laundry wastewater flow rate was calculated as 6.23–17.58 m3/day; also studied were the efficiency of the media in terms of the removal percentage of contamination and the flux rate. The performances of biochar and teff straw were assessed based on the operation parameters and the percentage removal efficiency at different flux rates; the assessment showed 0.4 L/min flux rate to exhibit the maximum removal efficiency. Chemical oxygen demand, biological oxygen demand, and total alkalinity removal rate varied from 79% to ≥83%; total solids and total suspended solids showed 92% to ≥99% removal efficiency, while dissolved oxygen, total dissolved solids, pH, and electrical conductivity showed 22% to ≥62% removal efficiency. The optimum range of pH was evaluated between 5.8–7.1. The statistical analysis for finding the correlated matrix of laundry wastewater parameters showed the following correlations: COD (r = −0.84), TS (r = −0.83), and BOD (r = −0.81), while DO exhibited highest negative correlation. This study demonstrated the prospective of LWW treatment using inexpensive materials. The proposed treatment process involved low-cost materials and exhibited efficiency in the removal of contaminants; its operation is simple and can be reproduced in different scenarios.

The transfer process of graphene onto the surface of oxide substrates is well known. However, for many devices, we require high quality oxide thin films on the surface of graphene. This step is not understood. It is not clear why the oxide should adopt the epitaxy of the underlying oxide layer when it is deposited on graphene where there is no lattice match. To date there has been no explanation or suggestion of mechanisms which clarify this step. Here we show a mechanism, supported by first principles simulation and structural characterisation results, for the growth of oxide thin films on graphene. We describe the growth of epitaxial SrTiO3 (STO) thin films on a graphene and show that local defects in the graphene layer (e.g. grain boundaries) act as bridge-pillar spots that enable the epitaxial growth of STO thin films on the surface of the graphene layer. This study and in particular the suggestion of a mechanism for epitaxial growth of oxides on graphene, offers new directions to exploit the development of oxide/graphene multilayer structures and devices.