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Poly(vinylidene fluoride) (PVDF) membranes have been widely applied to treat wastewater, however, the removal of toxic aromatic phenolic compounds remains a technical challenge due to the serious adsorption fouling and difficult degradation. Herein, we aimed to design a superhydrophilic PVDF membrane decorated with Au nanoparticles, which enhanced the rapid degradation of p-nitrophenol (4-NP). The superhydrophilic PVDF membrane with a micro/nano structured surface was decorated with Au nanoparticles via poly(dopamine) (PDA) as a spacer. The influences of membrane affinity (e.g.Hydrophilic Membrane (HM), micro/nano structured superhydrophilic membrane (MSiM), and micro/ nano structured superhydrophobic membrane (MSoM)) on PDA deposition and the subsequent Au decoration were comprehensively investigated. The synthesized Au nanoparticles were characterized using transmission electron microscopy (TEM) and UV-vis absorption spectra. The morphology and composition was evaluated using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Static catalytic experiments demonstrated that MSiM degraded over 90% of 4-NP in 5 minutes with a kinetic reaction rate constant of 47.84 Â 10 À2 min À1 and high stability over 6 cycles. A membrane catalytic reactor (MCR) was designed to realize the continuous catalytic degradation of 4-NP with a kinetic reaction rate constant of 7 Â 10 À2 min À1 .

Instability of superwetting surface is the stumbling block of flexible polymeric membranes for continuous separation of water-in-oil or oil-in-water emulsions. Manipulation of rigid superwetting nano-TiO2 on hierarchical poly(vinylidene fluoride) (PVDF) membrane by mimicking the plant roots holding soil behaviour enabled the generation of robust superwetting surface withstanding the harshly physical and chemical torture. The unique interface combination, which fabricated by a compacted nano-layer with the thickness of ~20 μm, was disclosed by systematic structure characterization. As demonstrated by SEM, LSCM and nano-CT, the pristine PVDF membrane with large quantities of cilia-like micro/nano-fibrils can function as the plant roots to capture, cage and confine the nanoparticles to form a robustly rigid nano-coating. The as-prepared membranes showed excellent durable separation performance both in varieties of stabilized water-in-oil and oil-in-water emulsion separation for a long term with few nanoparticles loss in a continuous crossflow mode. The strategy of assembling rigid inorganic nano-particles on flexible surface offers a window of opportunity for preparation of robust organic-inorganic hybrid membranes not only for continuous oil/water emulsion separation, but also for other functional application, such as electric conduction, heat conduction, ion exchange, and in membrane catalytic reactors etc.

Oxygen vacancies (Vo) in electrocatalysts are closely correlated with the hydrogen evolution reaction (HER) activity. The role of vacancy defects and the effect of their concentration, however, yet remains unclear. Herein, Bi2O3, an unfavorable electrocatalyst for the HER due to a less than ideal hydrogen adsorption Gibbs free energy (ΔGH*), is utilized as a perfect model to explore the function of Vo on HER performance. Through a facile plasma irradiation strategy, Bi2O3 nanosheets with different Vo concentrations are fabricated to evaluate the influence of defects on the HER process. Unexpectedly, while the generated oxygen vacancies contribute to the enhanced HER performance, higher Vo concentrations beyond a saturation value result in a significant drop in HER activity. By tunning the Vo concentration in the Bi2O3 nanosheets via adjusting the treatment time, the Bi2O3 catalyst with an optimized oxygen vacancy concentration and detectable charge carrier concentration of 1.52 × 1024 cm−3 demonstrates enhanced HER performance with an overpotential of 174.2 mV to reach 10 mA cm−2, a Tafel slope of 80 mV dec−1, and an exchange current density of 316 mA cm−2 in an alkaline solution, which approaches the top-tier activity among Bi-based HER electrocatalysts. Density-functional theory calculations confirm the preferred adsorption of H* onto Bi2O3 as a function of oxygen chemical potential (∆μO) and oxygen partial potential (PO2) and reveal that high Vo concentrations result in excessive stability of adsorbed hydrogen and hence the inferior HER activity. This study reveals the oxygen vacancy concentration-HER catalytic activity relationship and provides insights into activating catalytically inert materials into highly efficient electrocatalysts.