Hydrogel is an ideal material for oily sewage treatment due to its strong hydration ability, low-adhesive and antifouling properties. Advanced hydrogel separation membranes with harsh-environment-tolerant (such as strong acidic environments) superoleophobicity are of significance but rarely reported. Herein, a supramolecular nanofibrous hydrogel membrane was designed via one-step coaxial electrospinning method with polyvinylidene fluoride (PVDF) as the reinforced core material. Dimethyl sulfoxide (DMSO) regulates hydrogen bond crosslinking between tannic acid (TA) and polyvinylpyrrolidone (PVP). With the evaporation of DMSO, the water-insoluble supramolecular shell was formed between PVP and TA, which was tightly wrapped around the PVDF core. The pore size and wettability of the resulting membrane could be tuned by the core/shell velocity ratio. The stable superwetting properties and interspatial connectivity endow the fibrous hydrogel membranes with high separation performance for various oil-in-water emulsions and even for strong acidic oil-water emulsion. The separation permeance can reach 22,293 L m⁻² h⁻¹ bar⁻¹ for SDS stabilized acidic oil-water emulsion (pH = 1) and maintain at approximately 17,834 L m⁻² h⁻¹ bar⁻¹ after 3 h continuous separation, exhibiting significant applicability for large-scale filtration.

水凝胶具有很强的水化能力、低粘附性和防污性，是处理含油污水的理想材料。具有耐恶劣环境（如强酸性环境）超疏油性的先进水凝胶分离膜具有重要意义，但鲜有报道。在此，以聚偏二氟乙烯（PVDF）为增强芯材料，通过一步同轴静电纺丝法设计了一种超分子纳米纤维水凝胶膜。二甲基亚砜(DMSO) 调节单宁酸 (TA) 和聚乙烯吡咯烷酮 (PVP) 之间的氢键交联。随着 DMSO 的挥发，PVP 和 TA 之间形成了水不溶性超分子壳，紧紧包裹在 PVDF 核周围。所得膜的孔径和润湿性可以通过核/壳速度比来调节。稳定的超润湿性和空间连通性赋予纤维水凝胶膜对各种水包油乳液甚至强酸性油水乳液的高分离性能。SDS 稳定的酸性油水乳液（pH = 1）的分离渗透率可达 22,293 L m ^-2 h^-1bar^-1-2 h⁻¹ bar ⁻¹连续分离3小时后，表现出对大规模过滤的显着适用性。