Marine corrosion is a longstanding issue for underwater materials and structures, where the interlinked challenges of corrosion and biofouling require new approaches to source increasing needs of the marine resources. Herein we introduce environment-friendly chitosan coatings immobilized with corrosion inhibitor of 2-mercaptobenzothiazole (MBT) for active corrosion protection with antifouling properties against marine organisms. The molecular interaction between chitosan and MBT on corrosion resistance and antifouling performance was studied with the coatings where MBT was entrapped, physically associated, or chemically linked to chitosan. The physical association is achieved by the non-covalent π-π stacking between MBT and chitosan-benzophenone-3 (CS-BP-3) copolymer, which improved loading efficiency of MBT and formed a smoother coating. For the first time, MBT was chemically linked to chitosan confirmed by infrared spectroscopy. Electrochemical measurements revealed that both physical association and chemical linkage strategies can enhance the corrosion inhibition dramatically, where the chemical linked coating has a significantly higher corrosion resistance. The corrosion current of the physically associated coatings is a magnitude lower than that of MBT-entrapped coatings, while the coatings formed by chemical linking is even better, about one fifth compared to physically associated coatings. Antifouling activity of these coatings were evaluated against marine mussels (Mytilus coruscus), where chemically linked CS-MBT coating exhibits 10 % settlement after 48 h, compared to 20 % settlement on coatings prepared by physical association. The findings in this work provide a new route to construct coatings that are effective in corrosion inhibition and have long-term antifouling properties.

Salt removal from seawater and brackish water by Capacitive deionization (CDI) is an emerging technology that has a potential to contribute to solving global shortages of freshwater. Upon the application of an external voltage to a pair of nanostructured carbon electrodes, ions are removed by electrosorption in the electrical double layer (EDL) of the capacitor. The physical limitation due to repulsion of co-ions can be reduced using intercalation materials that are less sensitive to ion concentration variations. Herein, we report a hollow-concave high-entropy Prussian blue analogue (HEPBA) enhanced electrodes for superior electrochemical and capacitor performances. The half-cell of hollow-concave HEPBA has a high cycling stability of 1000 cycles at a current density of 1 A g−1. Lower energy consumption for desalination estimated over 90 cycles is due to an enhancement of salt adsorption capacity of HEPBA (∼ 26.2 mg g−1). The observed improvement in the electrochemical property is due to synergistic effects from multi-elemental composition that lead to the high entropy and specific surface area. Hollow-concave HEPBA are structurally stable with negligible changes in the lattice parameters during extensive charging and discharging cycles. This simple method offers an opportunity to modify the structure and morphology of PBAs for real-life applications.

PEGylation is regarded as a common antifouling strategy and the effect is normally linked with surface hydrophilicity of the coatings. Herein, the biopolymer chitosan (CS) was grafted by polyethylene glycol (PEG) of different chain lengths (molecular weight 200, 4 k and 100 k Da) to verify if the hydrophilicity of CS-PEG coatings is crucial in determining antifouling activities and if PEG chain length influences biofouling in marine environment. Properties of copolymers such as melting points and crystallinity are affected by grafting PEG. The water contact angle (WCA) of CS-PEG coatings increases with the chain length of grafted PEG, from 27° to 58°. Photocatalyst of zinc oxide-silver (ZnO/Ag) was also studied and its embedment (2 % to CS-PEG) renders the surface of CS-PEG coatings more hydrophobic with WCA increased from 52° to 86°. Antibacterial, anti-diatom, and anti-biofilm activities of the coatings were evaluated in natural sea water. The bacterial density on CS-PEG coatings was dramatically reduced to 4 × 104 compared to the control of 7 × 104 ind/mm2, and further to 2 × 104 for CS-PEG-ZnO/Ag coatings. CS-PEG coatings also strongly inhibit diatoms (120–200 ind/mm2), but the inclusion of ZnO/Ag did not obviously enhance such effect (50–150 ind/mm2). The findings provide useful insights for designing polymer-based antifouling coatings.

Chitosan (CS), an edible and non-toxic natural biopolymer, has been widely used in food preservation attributed to its intrinsic antimicrobial, biodegradable, and excellent film-forming properties. In this work, we report photocatalyst-loaded chitosan coating on commercial polyethylene (PE) film with enhanced antimicrobial properties for food packaging application. To improve the chemical stability of zinc oxide (ZnO) photocatalyst in acidic chitosan matrix, a thin layer (1–5 nm) of amorphous tin oxide (SnOx) was coated on ZnO nanoparticles. Consequently, the charge transfer efficiency of ZnO is improved and most of the surface defects are retained according to the studies of UV–Vis and fluorescence spectroscopy. The thin SnOx coating on ZnO was observed by high-resolution transmission electron microscopy (HRTEM) and its effects on crystallinity and particle size of ZnO were examined using X-ray diffraction (XRD) and particle sizer, respectively. The addition of ZnO@SnOx particles in chitosan coating increases water contact angle (WCA) and enhances thermal stability of chitosan coating. The antimicrobial activity of chitosan, ZnO-SnOx nanoparticles, and CS-ZnO@SnOx coated PE films were examined against both Gram-negative (E. coli, A. faecalis) and Gram-positive (S. aureus, B. subtilis) bacteria. Compared to the limited antimicrobial effects of chitosan, ZnO-SnOx demonstrates an improved inhibition effect on bacterial growth over 48 h period under light. For the CS-ZnO@SnOx nanocomposite coated PE films, no inhibition zone was observed due to the limitation of disc diffusion method. Meanwhile, there were no bacterial colonies found to develop on the film, rendering this CS nanocomposite coating a good candidate for food packaging applications.

Green hydrogen production from water is one attractive route to non-fossil fuel and a potential source of clean energy. Hydrogen is not only a zero-carbon energy source but can also be utilized as an efficient storage of electrical energy generated through various other sources, such as wind and solar. Cost-effective and environmentally benign direct hydrogen production through neutral water (similar to pH 7) reduction is particularly challenging due to the low concentration of protons. There is currently a major need for easy-to-prepare, robust, as well as active electrode materials. Herein we report three new molecular electrodes that were prepared by anchoring commercially available, and environmentally benign cobalt-containing electrocatalysts with three different ligand frameworks (porphyrin, phthalocyanine, and corrin) on a structurally modified graphite foil surface. Under the studied reaction conditions (over 7 h at 22 degrees C), the electrode with Co-porphyrin is the most efficient for the water reduction with starting similar to 740 mV onset potential (OP) (vs. RHE, current density 2.5 mA/cm(2)) and a Tafel slope (TS) of 103 mV/dec. It is followed by the molecular electrodes having Co-phthalocyanine [825 mV (OP), 138 mV/dec (TS)] and Vitamin-B-12 (Co-corrin moiety) [830 mV (OP), 194 mv/dec (TS)]. A clear time-dependent improvement (>200 mV over 3 h) in the H-2 production overpotential with the Co-porphyrin-containing cathode was observed. This is attributed to the activation due to water coordination to the Co-center. A long-term chronopotentiometric stability test shows a steady production of hydrogen from all three cathode surfaces throughout seven hours, confirmed using an H(2 )needle sensor. At a current density of 10 mA/cm(2), the Co-porphyrin-containing electrode showed a TOF value of 0.45 s(-1) at 870 mV vs. RHE, whereas the Co-phthalocyanine and Vitamin-B-12-containing electrodes showed 0.37 and 0.4 s(-1) at 1.22 V and 1.15 V (vs. RHE), respectively.

Ammonia (NH3) is globally one of the most produced chemicals. Despite being known for its use as a fuel and as a precursor of multiple chemicals, during its production, it is responsible for more than 1.2 % of the total global CO2 emission and consumes a large amount of energy. In this work, we studied a flow-through membrane-free electrocatalytic device (CMED) to produce continuous stream of NH3 from a common water contaminant, nitrate (NO3−). Indium-palladium (In−Pd) nanoparticles were impregnated in activated carbon cloth (ACC) and used as a cathode in the electrochemical device. It is found that in the counter electrode, adding oxygen evolution reaction (OER) active catalysts like platinum (Pt) for the regeneration of hydrogen ions enhances the rate of ammonia conversion to 7.28 μmol min−1 cm−2, eliminate the production of toxic nitrite by-products, as well as provide a platform for a stable energy consumption over long periods of time. This method for the conversion of NO3− into NH3 promises a way forward for sustainable resource utilization while generating fuel from waste and contributing to future circular economies, and managing the nitrogen cycle in water that is a major challenge of the 21st century society.

Transition metal phosphides (TMPs) have emerged as an alternative to precious metals as efficient and low-cost catalysts for water electrolysis. Elemental doping and morphology control are effective approaches to further improve the performance of TMPs. Herein, Fe-doped CoP nanoframes (Fe-CoP NFs) with specific open cage configuration were designed and synthesized. The unique nano-framework structured Fe-CoP material shows overpotentials of only 255 and 122 mV at 10 mA cm⁻² for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively, overwhelming most transition metal phosphides. For overall water splitting, the cell voltage is 1.65 V for Fe-CoP NFs at a current density of 10 mA cm⁻², much superior to what is observed for the classical nanocubic structures. Fe-CoP NFs show no activity degradation up to 100 h which contrasts sharply with the rapidly decaying performance of noble metal catalyst reference. The superior electrocatalytic performance of Fe-CoP NFs due to abundant accessible active sites, reduced kinetic energy barrier, and preferable *O-containing intermediate adsorption is demonstrated through experimental observations and theoretical calculations. Our findings could provide a potential method for the preparation of multifunctional material with hollow structures and offer more hopeful prospects for obtaining efficient earth-abundant catalysts for water splitting.

Background: Discharge of large amounts of untreated industrial effluent into water bodies pose significant environmental challenges worldwide. This is due to the limitations of traditional wastewater treatment methods in the treatment of recalcitrant organic pollutants. Fenton processes involves the generation of hydroxyl radicals that are well suited to degrade organics in effluent water. This study focuses on reducing slag generation during Fenton processes and enhancing the reuse of nano-zero-valent iron (NZVI) through the immobilization of NZVI on activated carbon cloth (ACC) through a chitosan (CH) linker with phenol as a model pollutant. Results: Microstructural and spectroscopic techniques were employed to study the materials prepared and 37.5 wt% iron loading was achieved. Phenol degradation of 96.3% at 40 °C at pH of 3.0 with 50 mM H2O2 was achieved using ACC-CH-NZVI. Adsorption and degradation studies carried out using ACC-CH-NZVI catalyst revealed that phenol adsorption onto ACC-CH-NZVI fits the Langmuir isotherm model, following the pseudo-second-order kinetic model and first-order reaction kinetics. Thermodynamic studies indicate the non-spontaneous, endothermic and irreversible nature of the removal process. Comparing ACC-CH-NZVI with ACC and ACC-CH, phenol removal using ACC drops from 87.8 to 39%, while using ACC-CH, the removal efficiency drops from 73 to 20.9% and using ACC-CH-NZVI, phenol removal drops from 96.3 to about 70% and total organic carbon removal drops from 79 to about 60% with minimal iron leaching, highlighting the superior performance of ACC-CH-ZVI and the role of NZVI in enhancing phenol removal. Conclusions: The catalyst demonstrated good stability for phenol degradation to about 70% phenol removal from simulated wastewater and 60% TOC removal from industrial wastewater after five treatment cycles with minimal Fe leaching. Graphical abstract: (Figure presented.)

The instability of molecular electrodes under oxidative/reductive conditions and insufficient understanding of the metal oxide-based systems have slowed down the progress of H2-based fuels. Efficient regeneration of the electrode's performance after prolonged use is another bottleneck of this research. This work represents the first example of a bifunctional and electrochemically regenerable molecular electrode which can be used for the unperturbed production of H2 from water. Pyridyl linkers with flexible arms (-CH2-CH2-) on modified fluorine-doped carbon cloth (FCC) were used to anchor a highly active ruthenium electrocatalyst [RuII(mcbp)(H2O)2] (1) [mcbp2− = 2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine]. The pyridine unit of the linker replaces one of the water molecules of 1, which resulted in RuPFCC (ruthenium electrocatalyst anchored on -CH2-CH2-pyridine modified FCC), a high-performing electrode for oxygen evolution reaction [OER, overpotential of ∼215 mV] as well as hydrogen evolution reaction (HER, overpotential of ∼330 mV) at pH 7. A current density of ∼8 mA cm−2 at 2.06 V (vs. RHE) and ∼−6 mA cm−2 at −0.84 V (vs. RHE) with only 0.04 wt% loading of ruthenium was obtained. OER turnover of >7.4 × 103 at 1.81 V in 48 h and HER turnover of >3.6 × 103 at −0.79 V in 3 h were calculated. The activity of the OER anode after 48 h use could be electrochemically regenerated to ∼98% of its original activity while it serves as a HE cathode (evolving hydrogen) for 8 h. This electrode design can also be used for developing ultra-stable molecular electrodes with exciting electrochemical regeneration features, for other proton-dependent electrochemical processes.

The search for new energy sources together with the need to control greenhouse gas emissions has led to continued interest in low-emitting renewable energy technologies. In this context, water splitting for hydrogen production is a reasonable alternative to replace fossil fuels due to its high energy density producing only water during combustion. Cellulose is abundant in nature and as residuals from human activity, and therefore a natural, ecological, and carbon-neutral source for hydrogen production. In the present work, we propose a sustainable method for hydrogen production using sunlight and cellulose as sacrificial agents during the photocatalytic water splitting process. Platinum (Pt) catalyst activates hydrogen production, and parameters such as pH of the system, cellulose concentration, and Pt loading were studied. Using different biomasses, we found that the presence of hemicellulose and xyloglucan as part of the molecular composition considerably increased the H-2 production rate from 36 mu mol L-1 in one hour for rapeseed cellulose to 167.44 mu mol L-1 for acid-treated cellulose isolated from Ulva fenestrata algae. Carboxymethylation and TEMPO-oxidation of cellulosic biomass both led to more stable suspensions with higher rates of H-2 production close to 225 mu mol L-1, which was associated with their water solubility properties. The results suggest that cellulosic biomass can be an attractive alternative as a sacrificial agent for the photocatalytic splitting of water for H-2 production.