RESUMO
Reverse electrodialysis (RED) systems employing charged nanochannels have gained prominence for harvesting salinity gradient energy. Nevertheless, fabricating nanochannel membranes with optimal ion selectivity and high energy conversion efficiency remains a significant challenge. In this study, we develop oppositely charged bacterial cellulose (BC)/polymer composite nano-channel membranes with precisely designed nanochannel architectures by integrating chemical modification with composite material technology. Initially, BC undergoes chemical modifications, including 2,2,6,6-Tetramethylpiperidine 1-oxy radical (TEMPO) oxidation and quaternisation. Subsequently, a polymer network is integrated into the modified BC network through a polymer synthesis technique. This approach successfully yields negatively charged BC/poly(sodium p-styrene sulfonate) (NBC/PSS) composite double-networked nanochannel membranes and positively charged BC/poly(dopamine) (PBC/PDA) composite double-networked nanochannel membranes. Notably, these membranes exhibit significantly enhanced ionic conductivities, with values of 0.0008 and 0.0014 S cm-1 for the NBC/PSS and PBC/PDA composites, respectively, while also demonstrating superior ion selectivity with cation transfer numbers of 0.9 and 0.1 respectively. Furthermore, a series connection of 30 BCE/charged polymer-based RED devices successfully powers an electronic calculator. This work offers novel insights into the design of BC-based RED devices by integrating chemical modification and polymeric composite strategies for efficient salinity gradient energy generation.
Assuntos
Celulose , Membranas Artificiais , Polímeros , Salinidade , Celulose/química , Polímeros/química , Bactérias , Óxidos N-Cíclicos/química , Nanoestruturas/químicaRESUMO
The development of advanced nanofluidic membranes with better ion selectivity, efficient energy conversion and high output power density remains challenging. Herein, we prepared nanofluidic hybrid membranes based on TEMPO oxidized cellulose nanofibers (T-CNF) and manganese-based metal organic framework (MOF) using a simple in situ synthesis method. Incorporated T-CNF endows the MOF/T-CNF hybrid membrane with a high cation selectivity up to 0.93. Nanoporous MOF in three-dimensional interconnected nanochannels provides massive ion transport pathways. High transmembrane ion flux and low ion permeation energy barrier are correlated with a superior energy conversion efficiency (36 %) in MOF/T-CNF hybrid membrane. When operating under 50-fold salinity gradient by mixing simulated seawater and river water, the MOF/T-CNF hybrid membrane achieves a maximum power density value of 1.87 W m-2. About 5-fold increase in output power density was achieved compared to pure T-CNF membrane. The integration of natural nanofibers with high charge density and nanoporous MOF materials is demonstrated an effective and novel strategy for the enhancement of output power density of nanofluidic membranes, showing the great potential of MOF/T-CNF hybrid membranes as efficient nanofluidic osmotic energy generators.
Assuntos
Celulose Oxidada , Estruturas Metalorgânicas , Nanofibras , Celulose , Transporte de ÍonsRESUMO
Reverse electrodialysis (RED) using nanofluidic ion-selective membrane may convert the salinity difference between seawater and river water into electricity. However, heterogeneous modification reactions of cellulose commonly leads to the inhomogeneous distribution of surface charges, thereby hampering the improvement of cellulose-based nanofluidic membranes for energy conversion. Herein, RED devices based on cellulose nanofibers (CNF) membranes with opposite charge characteristics were developed for the generation of salinity gradient power. Anion-CNF membrane (A-CNF) with varying negative charge densities was synthesized using 2,2,6,6-Tetramethylpiperidine 1-oxy radical (TEMPO) oxidation modification, whereas cation-CNF membrane (C-CNF) was prepared through etherification. By mixing artificial seawater and river water, the output power density of CNF RED device is up to 2.87 W m-2. The output voltage of 30 RED units connected in series may reach up to 3.11 V, which can be used to directly power tiny electronic devices viz. LED lamp, calculator, etc. The results of this work provide a feasible possibility for widespread application of ion exchange membranes for salinity gradient energy harvesting.
Assuntos
Celulose , Nanofibras , Salinidade , Membranas Artificiais , Diálise Renal , ÁguaRESUMO
Deformation processing of immiscible systems is observed to disrupt thermodynamic equilibrium, often resulting in nonequilibrium microstructures. The microstructural changes including nanostructuring, hierarchical distribution of phases, localized solute supersaturation, and oxygen ingress result from high-strain extended deformation, causing a significant change in mechanical properties. Because of the dynamic evolution of the material under large strain shear load, a detailed understanding of the transformation pathway has not been established. Additionally, the influence of these microstructural changes on mechanical properties is also not well characterized. Here, an immiscible Cu-4 at. % Nb alloy is subjected to a high-strain shear deformation (â¼200); the deformation-induced changes in the morphology, crystal structure, and composition of Cu and Nb phases as a function of total strain are characterized using transmission electron microscopy and atom probe tomography. Furthermore, a multimodal experiment-guided computational approach is used to depict the initiation of deformation by an increase in misorientation boundaries by crystal plasticity-based grain misorientation modeling (strain â¼0.6). Then, co-deformation and nanolamination of Cu and Nb are envisaged by a finite element method-based computational fluid dynamic model with strain ranging from 10 to 200. Finally, the experimentally observed amorphization of the severely sheared supersaturated Cu-Nb-O phase was validated using the first principle-based simulation using density functional theory while highlighting the influence of oxygen ingress during deformation. Furthermore, the nanocrystalline microstructure shows a >2-fold increase in hardness and compressive yield strength of the alloy, elucidating the potential of deformation processing to obtain high-strength low-alloyed metals. Our approach presents a step-by-step evolution of a microstructure in an immiscible alloy undergoing severe shear deformation, which is broadly applicable to materials processing based on friction stir, extrusion, rolling, and surface shear deformation under wear and can be directly applied to understanding material behavior during these processes.
RESUMO
OBJECTIVES: (i) To distinguish Neisseria gonorrhoeae isolates in Shanghai by porB typing; (ii) to ascertain the congruence of porB DNA sequence typing with cases linked epidemiologically; (iii) to determine the association of specific PorB mutations with antimicrobial resistance to penicillin or tetracycline. METHODS: porB DNA sequences of 174 N. gonorrhoeae isolates, collected from 143 male patients and 31 female sexual partners in Shanghai were determined. Phylogenetic analysis was used to determine sequence associations and concordance with epidemiologically linked cases. PorB protein sequences were compared with the wild-type sequence to identify mutations associated with antimicrobial resistance to penicillin and tetracycline. RESULTS: porB1a genotypes comprised 27.0% of the isolates and included 15 distinct DNA sequences, while 73.0% of the isolates carried porB1b genotypes with 63 distinct DNA sequences. porB DNA sequence typing was congruent with patient-reported sexual contacts. In addition, porB DNA sequence analysis revealed a number of strains with identical DNA sequences not identified through traditional epidemiological methods. The porB1b isolates had a significantly higher percentage of chromosomally mediated resistance to tetracycline and higher MIC50s to penicillin and ciprofloxacin. G120K/A121D mutations were observed in 71.1% of PIB isolates and were associated with resistance to penicillin and/or tetracycline. The majority of the PIA isolates (82.1%) also carried G120D/A121G double mutations. The index of discrimination for porB DNA sequence analysis was 95%. CONCLUSIONS: The porB1b genotype was found to be predominant in Shanghai. porB DNA sequence typing was sufficiently discriminatory for differentiating N. gonorrhoeae isolates and was congruent with epidemiological linkages. Novel porB sequences of N. gonorrhoeae and novel mutations of PorB proteins were identified.