Ying Zhu

Interfacial water structure critically influences CO₂ electroreduction pathway and product selectivity, yet molecular-level strategies to precisely regulate interfacial solvation and quantitatively correlate it with C–C coupling remain limited. Here, we report a hydrogel-mediated, customizable interfacial solvation strategy by integrating an ultrathin, ion-cross-linked, water-retentive hydrogel layer on Cu (Cu-IWH), formed via coordination between chitosan and divalent metal cations. The resulting charged and hydrated interface enables controlled modulation of the interfacial electrostatics, ion hydration, and local chemical environment, thereby steering CO₂ electroreduction toward C₂₊ products. In situ Raman spectroscopy reveals that solvated K⁺(H₂O)_n species interact with adsorbed hydroxyl groups (OH_ad), leading to a reorganization of the interfacial hydration structure and the formation of Cu·OH_ad·K⁺(H₂O)_n* interfacial complexes. By tuning the hydrogel cross-linking density, an optimal balance between OH_ad coverage and cation accessibility is achieved, maximizing the population of these complexes, which shows a quantitative correlation with enhanced C₂₊ selectivity. Density functional theory calculations further show that these complexes induce interfacial charge redistribution, stabilize *CO adsorption in configurations favorable for C–C coupling, and lower the kinetic barrier for *CO-*CO dimerization. Meanwhile, the hydrogel matrix enriches interfacial OH^–, creating a locally alkaline microenvironment that promotes *CO_L/*CO_B coadsorption and facilitates C–C coupling. As a result, the optimized Cu-IWH_M catalyst delivers a C₂₊ Faradaic efficiency of 87.5% at −1.2 A cm^–2 and a single-pass carbon efficiency of 94.3% at −1.0 A cm^–2, while sustaining stable operation for over 800 h at 800 mA in a 4 cm² MEA electrolyzer. When scaling to a 100 cm² MEA, the system achieves 81.5% C₂₊ selectivity with a C₂₊ energy efficiency of 34.0% at 40 A and operates stably for 82 h at 20 A. This work establishes hydrogel-mediated interfacial solvation engineering as a tunable approach for regulating interfacial environments and promoting C–C coupling in CO₂ electrocatalysis.

Salt precipitation remains a bottleneck in scaling carbon dioxide (CO₂) electroreduction to ethylene (C₂H₄), as it blocks gas transport, induces electrode flooding, and causes rapid performance degradation. Identifying electric field-driven cation accumulation and the consequent hydrophobicity loss as key factors, here, we show a wettability-engineered Cu-based electrode that decouples hydrophobicity from electronic conductivity. The electrode incorporates in situ embedded Cu active sites within an insulating, hydrophobic polymer matrix, forming localized “hydrophobic trap”. This architecture preserves interfacial hydrophobicity under operation, suppresses cation accumulation, and confines locally generated OH⁻ ions to sustain an alkaline microenvironment for C-C coupling. The optimized electrode achieves a faradaic efficiency of 75.9% for C₂H₄ at 1.2 A cm⁻² in a flow cell, and operates for over 1000 h in a membrane electrode assembly electrolyzer. The electrode maintains high productivity under low CO₂ concentrations and in the presence of flue gas impurities. Techno-economic analysis confirms the feasibility of this strategy.

Ice accretion remains a major challenge to the safety and reliability of infrastructures and transportation systems, particularly under harsh environmental conditions where conventional deicing strategies are inefficient. Herein, we report a fracture-responsive deicing coating that leverages modulus mismatch-driven microphase separation within an ultraslippery (MSU) architecture. By tuning the grafting density of polydimethylsiloxane (PDMS) and incorporating silicone oil (SO), we constructed a bicontinuous network comprising soft PDMS/SO-rich and rigid SiO_x-rich domains. This interlocked structure introduces strong modulus contrast and mechanical heterogeneity, enabling interfacial slippage, stress localization, and fracture-assisted ice delamination. The optimized MSU-50 coating exhibits ultralow ice adhesion strength (τ_ice, ∼ 4.5 kPa) and maintains performance after 100 icing/deicing cycles, 30 day of water immersion, and 300 abrasion cycles. Under large-scale or dynamic conditions, its low interface toughness (∼0.022 J m^-2) enables complete, gravity-driven ice removal within 76 ms. Finite element analyses reveal that the interlocked microphase network significantly amplifies local stress intensity and microcrack formation compared with homogeneous controls, validating the proposed fracture-responsive mechanism. This study establishes a scalable and durable design framework for mechanically adaptive, energy-efficient anti-icing coatings, offering practical potential for aerospace, wind power, and cold-region applications.

Osmotic energy, an infinite, clean energy source, can be efficiently harnessed through reverse electrodialysis using ion‐selective membranes. While polymeric membranes are excellent candidates due to their solution‐processability and scalability, their non‐uniform pore architecture and high resistance limit their power density output. Here, an in situ space‐confined synthesis strategy is proposed to fabricate sulfonated covalent organic frameworks within a sulfonated polymeric network, resulting in interconnected, well‐defined ion channels. This allows a maximum power density reaching up to 40.33 W m ⁻² under a 500‐fold salinity gradient and a real‐world power density of 14.84 W m ⁻² when extracting osmotic energy from natural seawater and river water. This study underscores the potential of space‐confined synthesis strategies in creating flexible and scalable ion‐selective membranes for efficient salinity gradient energy harvesting, marking a significant step toward their practical applications.

The electroreduction of CO ₂ to multi‐carbon (C ₂₊ ) products offers a sustainable route for chemicals production. However, the competing hydrogen evolution reaction (HER), especially at high current densities where proton transport dominates, remains a major challenge to achieving high C ₂₊ selectivity. In this study, an interfacial water engineering strategy guided by hydrogen bonding is reported to construct a dual‐functional Cu‐based catalyst that simultaneously enhances C ₂₊ selectivity and suppresses HER. By co‐assembling cobalt tetraaminated phthalocyanine (CoTAPc) and perfluorosulfonic acid (PFSA) onto Cu surface, a hydrophobic, hydrogen‐bond‐rich microenvironment is formed. This interfacial network reorganizes water molecules into spatially confined clusters, enabling directional proton transport and accelerating water dissociation. Such dual modulation of CO ₂ availability and proton dynamic effectively decouples C─C coupling from HER, leading to selective C ₂₊ formation. The resulting CoTAPc/Cu catalyst exhibits a C ₂₊ Faraday efficiency (FE) of 90.7% with only 3.5% H ₂ FE at 1.1 A cm ⁻² . Moreover, it maintains 81% C ₂₊ selectivity at 30 A in a 100 cm ² membrane electrode assembly (MEA) electrolyzer. Operando spectroscopic analyses and density functional theory (DFT) calculations reveal that CoTAPc‐PFSA interface lowers the *CO dimerization barrier while facilitating water dissociation and increasing *H adsorption energy, thus suppressing HER and enabling efficient CO ₂ conversion.

Ice accumulation on industrial and operational surfaces presents formidable challenges, necessitating effective deicing solutions for diverse applications. In this study, we develop a self-replenishing slippery lubricant (SRLS) coating designed to enhance large-scale deicing efficiency and overcome the limitations of existing low-ice-adhesion surfaces. The SRLS coating is based on a polyorganosilazane (PSZ) matrix infused with silicone oil-loaded hollow mesoporous SiO₂ microspheres (SO@HMSs). These SiO₂ microspheres serve as reservoirs of silicone oil, mitigating premature exudation and enhancing the coating's deicing durability in complex environments. Silicone oil functions as a plasticizer within the PSZ matrix, reducing the interfacial toughness and ice adhesion strength. By optimizing the SO@HMSs content, the SRLS-20 coating achieves a remarkably low interfacial toughness of 0.028 J m^-2 and an ice adhesion strength of 8.51 ± 1.89 kPa, surpassing current state-of-the-art coatings. This reduction in interfacial toughness transitions the ice removal mechanism from strength-controlled to toughness-controlled fracture. The SRLS-20 coating maintains a constant deicing force of 15.43 ± 1.51 N cm^-1 for ice layers exceeding a critical length of 12.20 cm, proving its effectiveness for large-scale deicing applications. Finite element analysis further reveals that the inclusion of SO@HMSs lowers the shear stress required for ice interface crack initiation, enhancing deicing efficiency across an extensive surface. This approach enables the development of durable, large-scale ice-phobic surfaces with low ice adhesion strength and reduced interfacial toughness, offering a robust solution for mitigating ice accumulation in industrial applications.

Highly efficient proton transfer in biological processes has driven the pursuit of synthetic analogs; however, replicating high proton permeance in natural systems remains a significant challenge. Herein, inspired by the function of the ClC-ec1 protein, we report the design of Cl^--assisted proton transport channels within a hybrid membrane composed of covalent organic frameworks (COFs) integrated with aramid nanofibers (ANFs). By leveraging buffer layer-mediated interfacial polymerization and the flocculation behavior of ANF in aqueous environments, we establish robust hydrogen-bonding interactions between COFs and ANFs. The hydride material enables Cl^- binding, significantly accelerating proton transport in a manner similar to that of the ClC-ec1 protein channel. In the presence of a small concentration of Cl^- ions (0.1% of the proton concentration), the proton permeation rate is enhanced approximately by 3 times, reaching 9.8 mol m^-2 h^-2. Notably, the membrane facilitates sustainable osmotic power generation from acidic wastewater, delivering an output power density of 434.8 W m^-2. Theoretical calculations revealed that ANF preferentially binds Cl^-, promoting proton hopping and lowering the energy barrier for proton transport. This study establishes a new paradigm for bioinspired ion-assisted proton transport, presenting an approach for sustainable energy harvesting from acidic wastewater.

Electrosynthesis of multicarbon products, such as C₂H₄, from CO₂ reduction on copper (Cu) catalysts holds promise for achieving carbon neutrality. However, maintaining a steady high current-level C₂H₄ electrosynthesis still encounters challenges, arising from unstable alkalinity and carbonate precipitation caused by undesired ion migration at the cathode under a repulsive electric field. To address these issues, we propose a universal "charge release" concept by incorporating tiny amounts of an oppositely charged anionic ionomer (e.g., perfluorinated sulfonic acid, PFSA) into a cationic covalent organic framework on the Cu surface (cCOF/PFSA). This strategy effectively releases the hidden positive charge within the cCOF, enhancing surface immobilization of cations to impede both outward migration of generated OH^- and inward migration of cations, inhibiting carbonate precipitation and creating a strong alkaline microenvironment. Meanwhile, the ionomer's hydrophobic chains create a hydrophobic environment within the cCOF, facilitating efficient gas transport. In situ characterizations and theoretical calculations demonstrate that the cCOF/PFSA catalyst establishes a hydrophobic strong alkaline microenvironment, optimizing the adsorption strength and configuration of *CO intermediates to promote the C₂H₄ formation. The optimized catalyst achieves a 70.5% Faradaic efficiency for C₂H₄ with a partial current density over 470 mA cm^-2. Notably, it delivers a high single-pass carbon efficiency of 96.5% for CO₂RR and sustains an exceptional stability over 760 h. When implemented in a large-area MEA electrolyzer and a 5-cell MEA stack, the system achieves an industrial current of 15 A and continuous C₂H₄ production exceeding 19 mL min^-1, marking a significant step toward industrial feasibility in CO₂RR-to-C₂H₄ conversion.

Electrocatalytic CO ₂ reduction reaction (CO ₂ RR) to produce multicarbon (C ₂₊ ) products over Cu‐based catalysts represents an ideal approach for renewable energy storage and carbon emissions reduction. The Cu ⁰ /Cu ^{δ +} interfaces are widely recognized as crucial sites that promote C–C coupling and enhance the generation of C ₂₊ products. However, a major challenge arises from the tendency of Cu ^{δ +} active sites within Cu ⁰ /Cu ^{δ +} interfaces to undergo reduction to Cu ⁰ during the CO ₂ RR process, leading to a decline in catalytic performance. Hence, it is crucial to establish durable Cu ⁰ /Cu ^{δ +} interfaces to enhance the conversion of CO ₂ to C ₂₊ products. In this work, an iodine modification strategy is proposed to prepare a stable Cu@CuI composite catalyst with well‐maintained Cu ⁰ /Cu ^{δ +} interfaces through a one‐step redox reaction between iodine and copper. The optimized Cu@CuI‐3 composite catalyst demonstrates an excellent performance in CO ₂ RR, achieving a Faradaic efficiency of 75.7% for C ₂₊ products and a partial current density of 288 mA·cm ⁻² at − 1.57 V _RHE in a flow cell. Operando techniques reveal that a numerous persistent Cu ^{δ +} species exist on the surface of the Cu@CuI‐ X composite catalyst even after CO ₂ RR due to the presence of adsorbed iodine ions, which prevent complete reduction of Cu ^{δ +} species to Cu ⁰ owing to their high electronegativity. Density functional theory calculations further verify that adsorbed iodine ions on the surface of Cu@CuI‐ X serve as charge regulators by adjusting local charge density, thereby facilitating the formation of *CHO intermediates from CO ₂ and lowering the energy barriers associated with coupling the *CHO and *CO intermediates during CO ₂ RR. Consequently, this phenomenon enhances the selectivity toward C ₂₊ products during electrocatalytic CO ₂ reduction.