Natural-inspired hierarchic double-Janus solar evaporator for stable clean water production from high-salinity emulsions.

Interfacial solar evaporation shows great potential in clean water production, emulsions separation, and high-salinity brine treatment. However, it remains challenging for the evaporators to maintain a high evaporation rate in the high-salinity emulsions due to the co-pollution of salt and oil. Herein, we first proposed a hierarchic double-Janus solar evaporator (HDJE) with a hydrophobic salt-rejecting top layer and oil-rejecting bottom layer. Compared to the traditional one, HDJE could treat industrial high-salinity oil-in-water emulsions stably for over 70 h, with a stable average evaporation rate of 1.73 kg m-2 h-1 and a high purification efficiency of up to 99.8 % for oil and ions. It was also verified that HDJE could be used for high-efficiency purification of oily concentrated seawater outdoor. An average water production rate of 3.59 kg m-2 d-1 and a TOC removal ratio of over 98 % was obtained. In conclusion, this study provides a novel way to effectively dispose of high-salinity oily wastewater.

Enhancing Extracellular Electron Transfer of a 3D-Printed Shewanella Bioanode with Riboflavin-Modified Carbon Black Bioink.

3D printing of a living bioanode holds the potential for the rapid and efficient production of bioelectrochemistry systems. However, the ink (such as sodium alginate, SA) that formed the matrix of the 3D-printed bioanode may hinder extracellular electron transfer (EET) between the microorganism and conductive materials. Here, we proposed a biomimetic design of a 3D-printed Shewanella bioanode, wherein riboflavin (RF) was modified on carbon black (CB) to serve as a redox substance for microbial EET. By introducing the medicated EET pathways, the 3D-printed bioanode obtained a maximum power density of 252 ± 12 mW/m2, which was 1.7 and 60.5 times higher than those of SA-CB (92 ± 10 mW/m2) and a bare carbon cloth anode (3.8 ± 0.4 mW/m2). Adding RF reduced the charge-transfer resistance of a 3D-printed bioanode by 75% (189.5 ± 18.7 vs 47.3 ± 7.8 Ω), indicating a significant acceleration in the EET efficiency within the bioanode. This work provided a fundamental and instrumental concept for constructing a 3D-printed bioanode.

Synthesis of P-(NiCo)CO3 /TiO2 /Ti Self-Supported Electrode with High Catalytic Activity and Stability for Hydrogen Evolution.

Hydrogen is considered an ideal clean energy due to its high mass-energy density, and only water is generated after combustion. Water electrolysis is a sustainable method of obtaining a usable amount of pure hydrogen among the various hydrogen production methods. However, its development is still limited by applying expensive noble metal catalysts. Here, the dissolution-recrystallization process of TiO2 nanotube arrays in water with the hydrothermal reaction of a typical nickel-cobalt hydroxide synthesis process followed by phosphating to prepare a self-supported electrode with (NiCo)CO3 /TiO2 heterostructure named P-(NiCo)CO3 /TiO2 /Ti electrode is combined. The electrode exhibits an ultra-low overpotential of 31 mV at 10 mA  cm-2 with a Tafel slope of 46.2 mV dec-1 in 1 m KOH and maintained its stability after running for 500 h in 1 m KOH. The excellent catalytic activity can be attributed to the structure of nanotube arrays with high specific surface area, superhydrophilicity, and super aerophobicity on the electrode surface. In addition, the uniform (NiCo)CO3 /TiO2 heterostructure also accelerates the electron transfer on the electrode surface. Finally, DFT calculations demonstrate that phosphating also improves the ΔGH* and ΔGH2O of the electrode. The synthesis strategy also promotes the exploration of catalysts for other necessary electrocatalytic fields.

Improving anammox activity and reactor start-up speed by using CO2/NaHCO3 buffer.

Anammox bacteria grow slowly and can be affected by large pH fluctuations. Using suitable buffers could make the start-up of anammox reactors easy and rapid. In this study, the effects of three kinds of buffers on the nitrogen removal and growth characteristics of anammox sludge were investigated. Reactors with CO2/NaHCO3 buffer solution (CCBS) performed the best in nitrogen removal, while 4-(2-hydroxyerhyl)piperazine-1-ethanesulfonic acid (HEPES) and phosphate buffer solution (PBS) inhibited the anammox activity. Reactors with 50 mmol/L CCBS could start up in 20 days, showing the specific anammox activity and anammox activity of 1.01±0.10 gN/(gVSS·day) and 0.83±0.06 kgN/(m3·day), respectively. Candidatus Kuenenia was the dominant anammox bacteria, with a relative abundance of 71.8%. Notably, anammox reactors could also start quickly by using 50 mmol/L CCBS under non-strict anaerobic conditions. These findings are meaningful for the quick start-up of engineered anammox reactors and prompt enrichment of anammox bacteria.

Micro-Nano Water Film Enabled High-Performance Interfacial Solar Evaporation.

Interfacial solar evaporation holds great promise to address the freshwater shortage. However, most interfacial solar evaporators are always filled with water throughout the evaporation process, thus bringing unavoidable heat loss. Herein, we propose a novel interfacial evaporation structure based on the micro-nano water film, which demonstrates significantly improved evaporation performance, as experimentally verified by polypyrrole- and polydopamine-coated polydimethylsiloxane sponge. The 2D evaporator based on the as-prepared sponge realizes an enhanced evaporation rate of 2.18 kg m-2 h-1 under 1 sun by fine-tuning the interfacial micro-nano water film. Then, a homemade device with an enhanced condensation function is engineered for outdoor clean water production. Throughout a continuous test for 40 days, this device demonstrates a high water production rate (WPR) of 15.9-19.4 kg kW-1 h-1 m-2. Based on the outdoor outcomes, we further establish a multi-objective model to assess the global WPR. It is predicted that a 1 m2 device can produce at most 7.8 kg of clean water per day, which could meet the daily drinking water needs of 3 people. Finally, this technology could greatly alleviate the current water and energy crisis through further large-scale applications.

Insights into the Origin of High Activity of Ni5P4(0001) for Hydrogen Evolution Reaction.

Hydrogen evolution reaction (HER) is directly relevant to green hydrogen production from water splitting. Recently, a low-cost Ni5P4 material has been demonstrated experimentally and theoretically to exhibit excellent electrocatalytic activity toward HER. However, a fundamental understanding of the origin of Ni5P4(0001) activity is still lacking. In this work, density functional theory (DFT) calculations were employed for a comprehensive investigation. The calculation results indicate that the Ni5P4(0001) surface exposing Ni3P4 termination gains the highest stability, on which a nearly thermoneutral hydrogen adsorption was found at the P3-hollow sites, providing a high activity for HER. The activity was also observed to be maintained over a wide H-coverage. HER occurs via the Volmer-Heyrovsky mechanism as evidenced from the optimal hydrogen adsorption free energy, but unlikely through the Tafel reaction due to its large energy barrier. Furthermore, the P3-hollow sites also exhibit a low kinetic barrier for water dissociation, promoting HER in alkaline media. A series of electronic structure analyses were performed in gaining insights into the origin of the HER activity. First, the density of states (DOS) and crystal orbital Hamilton population (COHP) analyses revealed a favorable interaction of electronic states between P and H atoms, leading to stable H adsorption at P3-hollow sites. In addition, the Bader charge analysis demonstrates that the strength of H adsorption at P3-hollow sites linearly increases with the electrons carried by the latter. The optimal net charge on the P3-hollow sites leads to a desired ΔG H that is close-to-zero. Finally, a highly efficient electron transfer was observed between the P3-hollow sites and their neighboring atoms, facilitating the HER.

Self-Sustained Programmable Hygroelectronic Interfaces for Humidity-Regulated Hierarchical Information Encryption and Display.

The emerging moisture-driven energy generation (MEG) technology opens up new possibilities for humidity-responsive materials, devices, and interdisciplinary opportunities in fields like information security. However, such potential remains untapped. Here, an original MEG structure with a hygroionic energy-conversion route by selective coating of ionic hygroscopic hydrogels on a carbon black surface is reported. The hygroionic route features a process in which the scavenged energy is stored in the electrical double layers formed at the interfaces between the ionic hydrogel and the carbon nanoparticles. The resultant electrical field developed across the hydrogel-coated wet carbon and the rest of the dry carbon area is thus durably lasted. Based on this unique structure, hygroelectronic information interfaces (HEII) for humidity-regulated information encryption and display are put forward by devising hydrogel patterns on a carbon platform. Further by tuning the hygroscopicity of the ionic hydrogels and incorporating encoding methods (e.g., Morse code), it is demonstrated that the HEII platform is programmable to carry different information in certain humidity ranges. Unlike those conventional anti-counterfeiting methods that optically reveal the hidden information once the required stimulus is provided, the new HEII serves as a hierarchical solution for high-security encryption and display.

Hydroxyl-modified zirconia/porous carbon nanocomposite used as a highly efficient and renewable adsorbent for removal of carbamazepine from water.

Metal-organic frameworks (MOFs) derived metal oxides/porous carbon nanocomposites were used as adsorbents to remove pollutants from wastewater. The adsorption performance of the metal oxides/porous carbon nanocomposites could be improved by introducing functional groups. In this study, hydroxyl-modified zirconia/porous carbon nanocomposite (C-UiO-66-OH) was prepared and tested, choosing carbamazepine as a typical pollutant. The results showed that the adsorption capacity (186.21 mg g-1) of C-UiO-66-OH was 6.96 times to that of normal UiO-66. The Langmuir isotherm model and pseudo-first-order kinetic model was well fit the adsorption process. The thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic. The adsorbent regeneration could be accomplished by washing C-UiO-66-OH with ethanol and DI water. The good adsorption/desorption performance comes from the synergistic effect of (EDA) interaction and hydrogen bond between C-UiO-66-OH and CBZ molecule. A membrane prepared by immobilizing C-UiO-66-OH into melamine foam (MF) with sodium alginate (SA) was also investigated for CBZ adsorption. The results indicated the excellent removal efficiency (86.0%) and good regeneration of the prepared membrane. Therefore, this paper provides an efficient and applicable way to remove CBZ from water.

Highly selective and sensitive nitrite biocathode biosensor prepared by polarity inversion method coupled with selective removal of interfering electroactive bacteria.

Nitrite is a multipurpose marker that needs to be detected quickly and accurately, including for water pollution and human urinary tract infections. In this study, we reported a novel nitrite-reducing bacteria electrochemical biosensor based on the metronidazole-treated biocathode (MT-NBEB). The biocathode with high nitrite response sensitivity used was first prepared by polarity inversion method and then treated with metronidazole to selectively remove the interfering electroactive bacteria for selectivity improvement. MT-NBEB could detect nitrite in the range of 0.0001 mg NO2--N L-1-8 mg NO2--N L-1 within 1.7 min and maintain stable detection performance for over 50 continuous cycles with relative standard deviations < 2.4%. Besides, the response signals of MT-NBEB were not affected by the common inorganic salts (such as nitrate and ammonia) and organic matter (such as acetate). MT-NBEB successfully detected nitrite in five types of wastewaters with relative errors < 14.3%. Our study provided a feasible way to prepare highly selective and sensitive electrochemical biosensors to quickly and accurately detect nitrite in real wastewaters.

Enhanced adsorption performance of UiO-66 via modification with functional groups and integration into hydrogels.

University of Oslo-66 (UiO-66) was a potential adsorbent for removing various pollutants from wastewater. Modifying the UiO-66 surface with different functional groups could enhance the adsorption performance. In this study, the UiO-66 modified with a functional group of -NH2 or -NO2 was prepared and tested to adsorb different pollutants. The results showed that -NO2 modified UiO-66 increased the adsorption capacity of tetracycline by 17 times to 94.08 mg g-1 compared with unmodified UiO-66. The adsorption process of UiO-66-NO2 followed the pseudo-second-order adsorption kinetic model and Langmuir isotherm model with a maximum isotherm adsorption capacity of 127.32 mg g-1. The adsorption interaction was hydrogen bonding and electrostatic attraction. The UiO-66-NO2 also showed good adsorption performance to Co2+, Methylene blue, Congo red. Fixing UiO-66-NO2 into hydrogel performed a stable absorption performance with a high absorption capacity (71.56 mg g-1) to TC and a good regeneration rate (85%) after five cycles, providing a novel applicable way to remove pollutants from wastewater.

Fast and simultaneous detection of dissolved BOD and nitrite in wastewater by using bioelectrode with bidirectional extracellular electron transport.

Timely and simultaneously detecting BOD and nitrite concentrations is of great significance for curbing of water pollution and adjusting wastewater treatment strategies. However, existing BOD and nitrite biosensors cannot perform synchronous detection due to their single electroactivity and differences in detection time. This study reported a novel dual-function electrochemical biosensor (DFEB) that could perform fast, simultaneous detection of nitrite and dissolved BOD. DFEB conducted a potential-step chronoamperometry on the mixed-bacteria bioelectrode with bidirectional electron transfer ability to obtain response signals. DFEB accurately measured dissolved BOD in the range of 5 ∼ 100 mg BOD L-1 and nitrite in the range of 0.05 ∼ 16 mg NO2--N L-1 within 20 min and maintain stable performance over 200 tests. DFEB performed well in artificial wastewater, aquatic wastewater, anaerobic tank effluent and anammox effluent, with relative errors < 15.7% and 16.8% in detecting nitrite and dissolved BOD, respectively. Our study provided a feasible way to develop multifunctional biosensors for detecting pollutants with different redox properties in wastewater.

External resistance acclimation regulates bio-anode: new perspective from biofilm structure and its correlation with anode performance.

External resistance is important for the anode and cell performance. However, little attentions were paid on the effect of external resistance on the variation of biofilm structure. Here, we used external resistance ranged from 4000 to 500 Ω for anodic acclimation to investigate the correlation between anode performance and biofilm structure. With the reduce of external resistance, the maximum current density of anode increased from 1.0 to 3.4 A/m2, which was resulted from a comprehensive effect of reduced charge transfer resistance and increased diffusion resistance. Biological analysis showed that with the reduce of external resistance, biomass and extracellular polymeric substances content increased by 109 and 286%, cell viability increased by 22.7%, which contributed to the reduced charge transfer resistance. But the porosity of anodic biofilm decreased by 27.8%, which led to an increased diffusion resistance of H+. This work provided a clear correlation between the electrochemical performance and biofilm structure.

Modifying Ti3C2 MXene with NH4+ as an excellent anode material for improving the performance of microbial fuel cells.

Poor anode performance is one of the main bottlenecks in the development of microbial fuel cells (MFCs) for practical applications. Multilayered Ti3C2 MXene (m-MXene) is an alternative anode modification material because of its high specific surface area and electrical conductivity. However, the multilayered structure, negatively charged surface, and electropositivity of m-MXene could limit its modification effects. In this work, we used a solution-phase flocculation method (ammonium ion method) to restack and aggregate MXene nanosheets as an anode modification material (n-MXene). The n-MXene-modified anode had a higher specific surface area, surface hydrophilicity and surface electropositivity than the m-MXene-modified anode. The n-MXene-modified anode obtained a maximum current density of 2.1 A m-2, which was 31.2% and 61.5% higher than that of the m-MXene-modified anode (1.6 A m-2) and bare carbon fiber cloth anode (1.3 A m-2). This improved anode performance was attributed to both the decrease in the charge transfer resistance and diffusion resistance, which were related to the increased quantity of biomass and microbial nanowire (or pili)-shaped filaments on the electrode surface. This work provides a simple and cost-effective approach to prepare MXene nanosheets for the modification of MFC anodes.

A novel, rapidly preparable and easily maintainable biocathode electrochemical biosensor for the continuous and stable detection of nitrite in water.

Nitrite is a highly toxic and pathogenic pollutant that is widely distributed in various nitrogenous wastewaters. Therefore, there is an urgent need for fast and stable nitrite detection to avoid water pollution and protect human health. In this study, we developed a novel rapidly preparable and easily maintainable biocathode electrochemical biosensor (BEB) using nitrite-reducing bacteria as the detectors to realize continuous nitrite monitoring in wastewater. The preparation of the biocathode was shortened by the polarity inversion method to less than 6 d. The BEB could detect nitrite solution samples in the range of 0.1- 16.0 mg NO2--N L-1 within 1.7 min. The BEB was also successfully used to detect nitrite in real wastewater with a relative error < 4.0% and a relative standard deviation < 5.8%. In addition, the BEB could be easily maintained by an operation mode of microbial fuel cells and stably detected nitrite for at least 150 tests. Our study provided a feasible and convenient way to develop electrochemical biosensors based on the biocathode for continuous and stable monitoring of pollutants in wastewater.

Promoting Extracellular Electron Transfer of Shewanella oneidensis MR-1 by Optimizing the Periplasmic Cytochrome c Network.

The low efficiency of extracellular electron transfer (EET) is a major bottleneck for Shewanella oneidensis MR-1 acting as an electroactive biocatalyst in bioelectrochemical systems. Although it is well established that a periplasmic c-type cytochrome (c-Cyt) network plays a critical role in regulating EET efficiency, the understanding of the network in terms of structure and electron transfer activity is obscure and partial. In this work, we attempted to systematically investigate the impacts of the network components on EET in their absence and overproduction individually in microbial fuel cell (MFC). We found that overexpression of c-Cyt CctA leads to accelerated electron transfer between CymA and the Mtr system, which function as the primary quinol oxidase and the outer-membrane (OM) electron hub in EET. In contrast, NapB, FccA, and TsdB in excess severely impaired EET, reducing EET capacity in MFC by more than 50%. Based on the results from both strategies, a series of engineered strains lacking FccA, NapB, and TsdB in combination while overproducing CctA were tested for a maximally optimized c-Cyt network. A strain depleted of all NapB, FccA, and TsdB with CctA overproduction achieved the highest maximum power density in MFCs (436.5 mW/m2), ∼3.62-fold higher than that of wild type (WT). By revealing that optimization of periplasmic c-Cyt composition is a practical strategy for improving EET efficiency, our work underscores the importance in understanding physiological and electrochemical characteristics of c-Cyts involved in EET.

Efficient degradation of polyacrylamide using a 3-dimensional ultra-thin SnO2-Sb coated electrode.

Polyacrylamide (PAM) is widely used in polymer flooding processes to increase oil recovery while the byproduct of PAM-containing wastewater is a serious environmental issue. In this study, electrochemical oxidation process (EAOP) was applied for treating PAM wastewater using a new type of 3-dimensional ultra-thin SnO2-Sb electrode. Nano-sized catalysts were evenly dispersed both on the surface and inside of a porous Ti filter forming nano-thickness catalytic layer that enhances the utilization and bonding of catalysts. This porous Ti electrode showed 20% improved OH· production and 16.3 times increased accelerated service life than the planar Ti electrode. Using this electrode to treat 100 mg L-1 PAM, the TOC removal efficiency reached over 99% within 3 h under current density of 20 mA cm-2. The EAOP could fastly break the long-chain PAM molecules into small molecular intermediates. With the porous electrode treating 5 g L-1 PAM under current density of 30 mA cm-2, EAOP reduced 94.2% of average molecular weight in 1 h and 92.0% of solution viscosity in 0.5 h. Moreover, the biodegradability of PAM solution was significantly improved as the solution BOD5/COD ratio raised from 0.05 to 0.41 after 4 h treatment. The degradation pathway of PAM was also investigated.

Deciphering Single-Bacterium Adhesion Behavior Modulated by Extracellular Electron Transfer.

For bacterial adhesion and biofilm formation, a thorough understanding of the mechanism and effective modulating is lacking due to the complex extracellular electron transfer (EET) at bacteria-surface interfaces. Here, we explore the adhesion behavior of a model electroactive bacteria under various metabolic conditions by an integrated electrochemical single-cell force microscopy system. A nonlinear model between bacterial adhesion force and electric field intensity is established, which provides a theoretical foundation for precise tuning of bacterial adhesion strength by the surface potential and the direction and flux of electron flow. In particular, based on quantitative analyses with equivalent charge distribution modeling and wormlike chain numerical simulations, it is demonstrated that the chain conformation and unfolding events of outer membrane appendages are dominantly impacted by the dynamic bacterial EET processes. This reveals how the anisotropy of bacterial conductive structure can translate into the desired adhesion behavior in different scenarios.

Enhancing stability and resilience of electromethanogenesis system by acclimating biocathode with intermittent step-up voltage.

Electromethanogenesis (EMG) system could efficiently convert CO2 to CH4 by using excess renewable electricity. However, the fluctuation and interruption of renewable electricity will adversely affect the biocathode and therefore the CH4 production of the EMG system. In this work, a novel biocathode acclimation strategy with intermittent step-up voltage (ISUV) was proposed to improve the stability and resilience of the EMG system against the unstable input of renewable power. Compared with the intermittent application of constant voltage (IACV), the ISUV increased the rate of CH4 production by 11.7 times with the improvement of the stability and resilience by 56% and 500%, respectively. Morphology and microflora structure analysis revealed that the biofilm enriched with ISUV exhibited a compact microflora structure with high-density cells and nanowires interconnected. This study provided a novel effective strategy to regulate the biofilm structure and enhance the performance of the EMG system.

A novel electrochemical oxidation-methanogenesis system for simultaneously degrading antibiotics and reducing CO2 to CH4 with low energy costs.

A novel electrochemical oxidation-methanogenesis (EO-M) system was proposed for the first time to simultaneously achieve antibiotic degradation and a bioelectrochemical conversion of CO2 to CH4 with low energy costs. A dual-chamber system was installed with an antimony-doped tin oxide anode (Ti/SnO2-Sb) for the electrocatalytic generation of hydroxyl radicals to degrade ciprofloxacin (CIP), and a CO2-reducing methanogenic biocathode was enriched based on a three-dimensional (3D) graphitized granular activated carbon (GGAC) for microbial electromethanogenesis. The anode achieved removal efficiencies as high as 99.99% and 90.53% for CIP (14 mL, 50 mg L-1) and the chemical oxygen demand (COD, 89 mg L-1), respectively. The biocathode was rapidly enriched within 15 days and exhibited a methane production rate that stabilized at 15.12 ± 1.82 m3 m-3 d-1; additionally, the cathodic coulombic efficiency reached 71.76 ± 17.24%. The energy consumption of CIP degradation was reduced by 3.03 Wh L-1 compared to that of a single electrochemical oxidation system due to the lower cathodic overpotential of CO2 bioelectrochemical reduction in the EO-M system. A detailed analysis of the biofilm evolution in the 3D biocathode during the start-up process demonstrated that the enhanced absorption of extracellular polymeric substances by the GGAC cathode accelerated the enrichment of methanogens and induced the formation of methanogens with a large number of flagella. An analysis of the microbial community showed that a high relative abundance of Methanobacterium movens could promote a flagella-mediated direct electron transfer of the biocathode, eventually reducing the cathodic overpotential and energy costs of the EO-M system.

Enhancing bio-cathodic nitrate removal through anode-cathode polarity inversion together with regulating the anode electroactivity.

Bio-cathodic nitrate removal uses autotrophic nitrate-reducing bacteria as catalysts to realize the nitrate removal process and has been considered as a cost-effective way to remove nitrate contamination. However, the present bio-cathodic nitrate removal process has problems with long start-up time and low performance, which are urgently required to improve for its application. In this study, we investigated an anode-cathode polarity inversion method for rapidly cultivating high-performance nitrate-reducing bio-cathode by regulating bio-anodic bio-oxidation electroactivities under different external resistances and explored at the first time the correlation between the oxidation performance and the reduction performance of one mixed-bacteria bioelectrode. A high bio-electrochemical nitrate removal rate of 2.74 ± 0.03 gNO3--N m-2 d-1 was obtained at the bioelectrode with high bio-anodic bio-oxidation electroactivity, which was 4.0 times that of 0.69 ± 0.03 gNO3--N m-2 d-1 at the bioelectrode with low bio-oxidation electroactivity, and which was 1.3-7.9 times that of reported (0.35-2.04 gNO3--N m-2 d-1). 16S rRNA gene sequences and bacterial biomass analysis showed higher bio-cathodic nitrate removal came from higher bacterial biomass of electrogenic bacteria and nitrate-reducing bacteria. A good linear correlation between the bio-cathodic nitrate removal performance and the reversed bio-anodic bio-oxidation electroactivity was presented and likely implied that electrogenic biofilm had either action as autotrophic nitrate reduction or promotion to the development of autotrophic nitrate removal system. This study provided a novel strategy not only to rapidly cultivate high-performance bio-cathode but also to possibly develop the bio-cathode with specific functions for substance synthesis and pollutant detection.