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Atomically dispersed Fe-N-C catalysts emerged as promising alternatives to commercial Pt/C for the oxygen reduction reaction. However, the majority of Fe-N-C catalysts showed unsatisfactory activity and durability due to their inferior O-O bond-breaking capability and rapid Fe demetallization. Herein, we create a pseudo-phthalocyanine environment coordinated diatomic iron (Fe2-pPc) catalyst by grafting the core domain of iron phthalocyanine (Fe-Nα-Cα-Nß) onto defective carbon. In situ characterizations and theoretical calculation confirm that Fe2-pPc follows the fast-kinetic dissociative pathway, whereby Fe2-pPc triggers bridge-mode oxygen adsorption and catalyzes direct O-O radical cleavage. Compared to traditional Fe-N-C and FePc-based catalysts exhibiting superoxo-like oxygen adsorption and an *OOH-involved pathway, Fe2-pPc delivers a superior half-wave potential of 0.92 V. Furthermore, the ultrastrong Nα-Cα bonds in the pPc environment endow the diatomic iron active center with high tolerance for reaction-induced geometric stress, leading to significantly promoted resistance to demetallization. Upon an unprecedented harsh accelerated degradation test of 150,000 cycles, Fe2-pPc experiences negligible Fe loss and an extremely small activity decay of 17 mV, being the most robust candidate among previously reported Fe-N-C catalysts. Zinc-air batteries employing Fe2-pPc exhibit a power density of 255 mW cm-2 and excellent operation stability beyond 440 h. This work brings new insights into the design of atomically precise metallic catalysts.
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Metal-organic frameworks have garnered attention as highly efficient pre-electrocatalysts for the oxygen evolution reaction (OER). Current structure-activity relationships primarily rely on the assumption that the complete dissolution of organic ligands occurs during electrocatalysis. Herein, modeling based on NiFe Prussian blue analogs (NiFe-PBAs) show that cyanide ligands leach from the matrix and subsequently oxidize to corresponding inorganic ions (ammonium and carbonate) that re-adsorb onto the surface of NiFe OOH during the OER process. Interestingly, the surface-adsorbed inorganic ions induce the OER reaction of NiFe OOH to switch from the adsorbate evolution to the lattice-oxygen-mediated mechanism, thus contributing to the high activity. In addition, this reconstructed inorganic ion layer acting as a versatile protective layer can prevent the dissolution of metal sites to maintain contact between catalytic sites and reactive ions, thus breaking the activity-stability trade-off. Consequently, our constructed NiFe-PBAs exhibit excellent durability for 1250 h with an ultralow overpotential of 253 mV at 100 mA cm-2. The scale-up NiFe-PBAs operated with a low energy consumption of â¼4.18 kWh m-3 H2 in industrial water electrolysis equipment. The economic analysis of the entire life cycle demonstrates that this green hydrogen production is priced at US$2.59/ [Formula: see text] , meeting global targets (
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Single-molecule localization methods have been popularly exploited to obtain super-resolved images of biological structures. However, the low blinking frequency of randomly switching emission states of individual fluorophores greatly limits the imaging speed of single-molecule localization microscopy (SMLM). Here we present an ultrafast SMLM technique exploiting spontaneous fluorescence blinking of cyanine dye aggregates confined to DNA framework nanostructures. The DNA template guides the formation of static excimer aggregates as a "light-harvesting nanoantenna", whereas intermolecular excitation energy transfer (EET) between static excimers causes collective ultrafast fluorescence blinking of fluorophore aggregates. This DNA framework-based strategy enables the imaging of DNA nanostructures with 12.5-fold improvement in speed compared to conventional SMLM. Further, we demonstrate the use of this strategy to track the movement of super-resolved DNA nanostructures for over 20 min in a microfluidic system. Thus, this ultrafast SMLM holds great potential for revealing the dynamic processes of biomacromolecules in living cells.
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ADN , Colorantes Fluorescentes , Nanoestructuras , ADN/química , Colorantes Fluorescentes/química , Nanoestructuras/química , Imagen Individual de Molécula/métodos , Carbocianinas/química , Microscopía Fluorescente/métodosRESUMEN
As a novel electrochemical energy conversion device, direct ethanol fuel cells are currently encountering two significant challenges: CO poisoning and the difficulty of C-C bond cleavage in ethanol. In this work, an amorphous PdS nanowires/ultrafine IrMnOx bimetallic oxides (denoted as a-PdS/IrMnOx NWs) catalyst with abundant oxide/metal (crystalline/amorphous) inverse heterogeneous interfaces was synthesized via a hydrothermal process succeeded by a nonthermal air-plasma treatment. This unique interfacial electronic structure along with the incorporation of oxyphilic metal has resulted in a significant enhancement in the electrocatalytic performance of a-PdS/IrMnOx NWs toward the ethanol oxidation reaction, achieving current densities of 12.45 mA·cm-2 and 3.68 A·mgPd-1. Moreover, the C1 pathway selectivity for ethanol oxidation has been elevated to 47%, exceeding that of other as-prepared Pd-based counterparts and commercial Pd/C catalysts. Density functional theory calculations have validated the findings that the decoration of IrMn species onto the amorphous PdS surface has induced a charge redistribution in the interface region. The redistribution of surface charges on the a-PdS/IrMnOx NWs catalyst results in a significant decrease in the activation energy required for C-C bond cleavage and a notable weakening of the CO binding strength at the Pd active sites. Consequently, it enhanced both the EOR C1 pathway selectivity and CO poisoning resistance to the a-PdS/IrMnOx NWs catalyst.
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The development of a highly efficient, stable, and low-cost bifunctional catalyst is imperative for facilitating the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). However, significant challenges are involved in extending its applications to rechargeable zinc-air batteries. This study presents a bifunctional catalyst, Zr2ON2@NiFe layered double hydroxide (LDH), that was developed by utilizing a urea-glass route for synthesizing the Zr2ON2 precursor, followed by riveting NiFe LDH nanosheets using a hydrothermal method. Specifically, the vertical distribution of NiFe LDH on the Zr2ON2 surface ensures the maximization of the number of accessible active sites and interfacial catalysis of NiFe LDH. Notably, Zr2ON2@NiFe LDH demonstrates ORR and OER bifunctional electrocatalytic behavior and high stability owing to its heterostructure and composition. Furthermore, a rechargeable zinc-air battery using a Zr2ON2@NiFe LDH electrocatalyst as the air cathode demonstrated a high peak power density (172 mW cm-2) and galvanostatic charge-discharge cycle stability (5 mA cm-2 over 443 h). Thus, this study presents an efficient and cost-effective strategy for the design of bifunctional electrocatalysts.
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The creation of frustrated Lewis pairs on catalyst surface is an effective strategy for tuning CO2 activation. The critical step in the formation of frustrated Lewis pairs is the spatial effect of proximal Lewis acid-Lewis base pairs. Here, we demonstrate a facile surface functionalization methodology that enables hydrogen bonding between N and H atoms to mediate the construction of frustrated Lewis pairs in poly(heptazine imide), thereby increasing the propensity to activate CO2 molecules. Experimental and theoretical results show that the construction of active hydrogen bonding regions can facilitate the bending of CO2 molecules. Furthermore, the delocalization of electron clouds induced by the hydrogen bonding-mediated frustrated Lewis pairs can promote the heterolytic cleavage and photocatalytic conversion of CO2. This work highlights the potential of utilizing hydrogen bonding-mediated strategy in heterogeneously photocatalytic activation of CO2 over polymer materials.
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Cu-based catalysts have been shown to selectively catalyze CO2 photoreduction to C2+ solar fuels. However, they still suffer from poor activity and low selectivity. Herein, we report a high-performance carbon nitride supported Cu single-atom catalyst featuring defected low-coordination Cu-N2 motif (Cu-N2-V). Lead many recently reported photocatalysts and its Cu-N3 and Cu-N4 counterparts, Cu-N2-V exhibits superior photocatalytic activity for CO2 reduction to ethanol and delivers 69.8â µmol g-1 h-1 ethanol production rate, 97.8 % electron-based ethanol selectivity, and a yield of ~10 times higher than Cu-N3 and Cu-N4. Revealed by the extensive experimental investigation combined with DFT calculations, the superior photoactivity of Cu-N2-V stems from its defected Cu-N2 configuration, in which the Cu sites are electron enriched and enhance electron delocalization. Importantly, Cu in Cu-N2-V exist in both Cu+ and Cu2+ valence states, although predominantly as Cu+. The Cu+ sites support the CO2 activation, while the co-existence of Cu+/Cu2+ sites are highly conducive for strong *CO adsorption and subsequent *CO-*CO dimerization enabling C-C coupling. Furthermore, the hollow microstructure of the catalyst also promotes light adsorption and charge separation efficiency. Collectively, these make Cu-N2-V an effective and high-performance catalyst for the solar-driven CO2 conversion to ethanol. This study also elucidates the C-C coupling reaction path via *CO-*CO to *COCOH and rate-determining step, and reveals the valence state change of partial Cu species from Cu+ to Cu2+ in Cu-N2-V during CO2 photoreduction reaction.
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High-fidelity patterning of DNA origami nanostructures on various interfaces holds great potential for nanoelectronics and nanophotonics. However, distortion of a DNA origami often occurs due to the strong interface interactions, e.g., on two-dimensional (2D) materials. In this study, we discovered that the adsorption of silica precursors in rapid silicification can prevent the distortion caused by graphene and generates a high shape-fidelity DNA origami-silica composite on a graphene interface. We found that an incubation time of 1 min and silicification time of 16 h resulted in the formation of DNA origami-silica composites with the highest shape fidelity of 99%. By comparing the distortion of the DNA origami on the graphene interface with and without silicification, we observed that rapid silicification effectively preserved the integrity of the DNA origami. Statistical analysis of scanning electron microscopy data indicates that compared to bare DNA origami, the DNA origami-silica composite has an increased shape fidelity by more than two folds. Furthermore, molecular dynamics simulations revealed that rapid silicification effectively suppresses the distortion of the DNA origami through the interhelical insertion of silica precursors. Our strategy provides a simple yet effective solution to maintain the shape-fidelity DNA origami on interfaces that have strong interaction with DNA molecules, expanding the applicable interfaces for patterning 2D DNA origamis.
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Grafito , Nanoestructuras , Microscopía de Fuerza Atómica , Grafito/química , Nanoestructuras/química , ADN/química , Dióxido de Silicio/químicaRESUMEN
DNA monolayers with inherent chirality play a pivotal role across various domains including biosensors, DNA chips, and bioelectronics. Nonetheless, conventional DNA chiral monolayers, typically constructed from single-stranded DNA (ssDNA) or double-stranded DNA (dsDNA), often lack structural orderliness and design flexibility at the interface. Structural DNA nanotechnology has emerged as a promising solution to tackle these challenges. In this study, we present a strategy for crafting highly adaptable twisted DNA origami-based chiral monolayers. These structures exhibit distinct interfacial assembly characteristics and effectively mitigate the structural disorder of dsDNA monolayers, which is constrained by a limited persistence length of â¼50 nm of dsDNA. We highlight the spin-filtering capabilities of seven representative DNA origami-based chiral monolayers, demonstrating a maximal one-order-of-magnitude increase in spin-filtering efficiency per unit area compared with conventional dsDNA chiral monolayers. Intriguingly, our findings reveal that the higher-order tertiary chiral structure of twisted DNA origami further enhances the spin-filtering efficiency. This work paves the way for the rational design of DNA chiral monolayers.
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ADN de Cadena Simple , ADN , ADN/química , Nanotecnología , Conformación de Ácido NucleicoRESUMEN
Potassium-sulfur batteries attract tremendous attention as high-energy and low-cost energy storage system, but achieving high utilization and long-term cycling of sulfur remains challenging. Here we show a strategy of optimizing potassium polysulfides for building high-performance potassium-sulfur batteries. We design the composite of tungsten single atom and tungsten carbide possessing potassium polysulfide migration/conversion bi-functionality by theoretical screening. We create two ligand environments for tungsten in the metal-organic framework, which respectively transmute into tungsten single atom and tungsten carbide nanocrystals during pyrolysis. Tungsten carbide provide catalytic sites for potassium polysulfides conversion, while tungsten single atoms facilitate sulfides migration thereby significantly alleviating the insulating sulfides accumulation and the associated catalytic poisoning. Resultantly, highly efficient potassium-sulfur electrochemistry is achieved under high-rate and long-cycling conditions. The batteries deliver 89.8% sulfur utilization (1504 mAh g-1), superior rate capability (1059 mAh g-1 at 1675 mA g-1) and long lifespan of 200 cycles at 25 °C. These advances enlighten direction for future KSBs development.
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A ratiometric fluorometry based on silicon quantum dots (SiQDs) and gold nanoclusters (AuNCs) is constructed for detecting activity of butyrylcholinesterase (BChE) in human serum. By using thiobutyrylcholine iodide (BTCh) as the substrate of BChE-catalyzed hydrolysis reaction, variation of fluorescence emission from AuNCs is employed as an indicator of BChE activity since one of the hydrolysis products, thiocholine (TCh), would influence the aggregation state of AuNCs and consequently led to the change of fluorescence quantum efficiency of AuNCs. It is interesting that there are two mechanisms working for the fluorescence emission of aggregated AuNCs: aggregation-induced emission enhancement (AIEE) and aggregation-caused quenching (ACQ) with the presence of TCh at very low and higher concentration levels, respectively. Although both of these mechanisms can be utilized for sensing BChE, their opposite influence on the fluorescence emission of aggregated AuNCs should be worthy of attention, especially in the process of developing fluorescence methods for detecting trace targets by using AuNCs. In order to eliminate the fluctuation of fluorophotometer, SiQDs is chosen as the fluorophore to develop by ratiometric fluorescence methods in this work. Additionally, obvious aggregation of AuNCs induces significant decrease of inner filter effect (IFE) on the fluorescence emitted from SiQDs, while mild aggregation of AuNCs demonstrates little IFE. The linear ranges for detecting activity of BChE are 0.004 - 0.05 U/L and 0.5 - 20 U/L by ratiometric fluorometry based on the AIEE and ACQ, respectively. The very different responses originated from AIEE and ACQ of AuNCs would respectively make their own contributions to the determination of BChE activities at very low or high levels, which facilitate the developments of enhanced or quenched fluorescence methods. However, the detection of BChE activities at medium levels might suffer from the combination of AIEE and ACQ with ambiguous fractions. Therefore, it must be careful during the processes of developing and applying fluorescence methods based on the AIEE and ACQ of AuNCs, as well as the process of evaluating their analytical performance.
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Nanopartículas del Metal , Puntos Cuánticos , Humanos , Silicio , Oro , Butirilcolinesterasa , Fluorometría , Espectrometría de Fluorescencia/métodosRESUMEN
Developing highly active oxygen evolution reaction (OER) catalysts in acidic conditions is a pressing demand for proton-exchange membrane water electrolysis. Manipulating proton character at the electrified interface, as the crux of all proton-coupled electrochemical reactions, is highly desirable but elusive. Herein we present a promising protocol, which reconstructs a connected hydrogen-bond network between the catalyst-electrolyte interface by coupling hydrophilic units to boost acidic OER activity. Modelling on N-doped-carbon-layer clothed Mn-doped-Co3O4 (Mn-Co3O4@CN), we unravel that the hydrogen-bond interaction between CN units and H2O molecule not only drags the free water to enrich the surface of Mn-Co3O4 but also serves as a channel to promote the dehydrogenation process. Meanwhile, the modulated local charge of the Co sites from CN units/Mn dopant lowers the OER barrier. Therefore, Mn-Co3O4@CN surpasses RuO2 at high current density (100â mA cm-2 @ ~538â mV).
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Aqueous zinc ion batteries (ZIBs), especially those with self-charging properties, have been promisingly developed in recent years. Yet, most inorganic materials feature high redox potential, which limit their development in the self-charging field. To achieve this target, by pre-embedding potassium ions into δ-MnO2 to reduce the energy barrier in oxygen adsorption, the first application of MnO2 in self-charging ZIBs is realized. The design features a facile two-electrode configuration with no excessively complex component to allow for energy storage and conversion. Due to the voltage difference between the oxygen in the air and the discharge products, a redox reaction can be carried out spontaneously to realize the self-charging process. After the chemical self-charging process, the Zn-K0.37 MnO2 ·0.54H2 O/C cell achieves an open circuit voltage of around 1.42 V and a discharge capacity of 201 mAh g-1 , reflecting the promising self-charging capability. Besides, the chemically self-charging ZIBs operate well in multiple modes of constant current charge/discharge/chemical charging. And decent cycling capability can also be achieved at extreme temperatures and high mass loading. This work promotes the development of ZIBs and further broadens the application of inorganic metal oxides in the self-charging systems.
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A general and adaptable method is proposed to reliably extract quantitative information from smartphone images of microfluidic sensors. By analyzing and processing the color information of selected standard substances, the influence of light conditions, device differences, and human factors could be significantly reduced. Machine learning and multivariate fitting methods were proved to be effective for chroma correction, and a key element was the training of sample size and the fitting form, respectively. A custom APP was developed and validated using a high-sensitivity chromium ion quantification paper chip. The average chroma deviations under different conditions were reduced by more than 75% in RGB color space, and the concentration test error was reduced by more than half compared with the commonly used method. The proposed approach could be a beneficial supplement to existing and potential colorimetry-based detection methods.
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The sluggish kinetics and mutual interference of oxygen evolution and reduction reactions in the air electrode resulted in large charge/discharge overpotential and low energy efficiency of Zn-air batteries. In this work, we designed a breathing air-electrode configuration in the battery using P-type Ca3 Co4 O9 and N-type CaMnO3 as charge and discharge thermoelectrocatalysts, respectively. The Seebeck voltages generated from thermoelectric effect of Ca3 Co4 O9 and CaMnO3 synergistically compensated the charge and discharge overpotentials. The carrier migration and accumulation on the cold surface of Ca3 Co4 O9 and CaMnO3 optimized the electronic structure of metallic sites and thus enhanced their intrinsic catalytic activity. The oxygen evolution and reduction overpotentials were enhanced by 101 and 90â mV, respectively, at temperature gradient of 200 °C. The breathing Zn-air battery displayed a remarkable energy efficiency of 68.1 %. This work provides an efficient avenue towards utilizing waste heat for improving the energy efficiency of Zn-air battery.
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The recent development of some special oxygen evolution reaction (OER) electrocatalysts shows that the lattice oxygen could participate in the catalysis process via the lattice oxygen oxidation mechanism (LOM), which the provides good possibility of exploring advanced electrocatalysts that could overcome the scaling relationship in conventional catalysis processes through a traditional adsorbate evolution mechanism. In this work, we theoretically predict that, benefiting from the unhybridized O-Li orbitals and the resulting metastable Li-O-Li ligands, the lattice oxygen could be easily activated and oxidized at relatively high oxidation voltages. Thus, lithium-excess disordered rocksalts (DRX) should possess the potential for acting as active OER electrocatalysts, which catalyze through the LOM pathway. The isotope labelling experimental results show that the lattice oxygen in the DRX was activated and participated in the OER process through the LOM pathway. The typical DRX of Li1.2Fe0.4Ti0.5O2 displays obviously pH-dependent OER activity under the LOM process and shows a low overpotential of 263 mV to reach 10 mA cm-2 with long-term stability for 100 hours. The turnover frequency of Li1.2Fe0.4Ti0.5O2 is nearly 9 times that of LiFePO4 at the overpotential of 300 mV. This work opens a new chemical space for exploring efficient electrocatalysts to enhance the OER performance through the LOM pathway.
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The state-of-the-art active hydrogen evolution reaction (HER) catalysts in acid electrolytes generally lose considerable catalytic performance in alkaline electrolytes mainly due to the additional water dissociation step. Designing composite materials is an effective strategy to accelerate alkaline water electrolysis by optimizing the electronic structure of materials. Here, different phases of Co(OH)2 -supported Ru clusters (α/ß-Co(OH)2 @Ru) are prepared for enabling a highly efficient electrocatalytic HER performance in alkaline solution. The prepared α-Co(OH)2 nanosheets facilitate the loading of uniform and high-density Ru clusters and the formed highly active RuOCo bonds at the interface. The synergistic interaction endows the hybrid catalyst with low overpotential of 33 mV at 10 mA cm-2 . Moreover, the homemade anion exchange membrane water electrolysis cell based on α-Co(OH)2 @Ru affords a cell voltage of 2 V to drive a current density of 270 mA cm-2 and performs stably during continuous operation for over 100 h. Density functional theory calculations demonstrate that active RuOCo bonds in α-Co(OH)2 @Ru optimize the energy barriers for H2 O dissociation and OH- desorption to facilitate the Volmer reaction step. This work offers a strategy for designing interfacial chemical bonds for high electrocatalytic activity.
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It is vitally important to develop highly active, robust and low-cost transition metal-based electrocatalysts for overall water splitting in neutral solution especially at large current density. In this work, amorphous Mo-doped NiS0.5 Se0.5 nanosheets@crystalline NiS0.5 Se0.5 nanorods (Am-Mo-NiS0.5 Se0.5 ) was synthesized using a facil one-step strategy. In phosphate buffer saline solution, the Am-Mo-NiS0.5 Se0.5 shows tiny overpotentials of 48 and 209â mV for hydrogen evolution reaction (HER), 238 and 514â mV for oxygen evolution reaction (OER) at 10 and 1000â mA cm-2 , respectively. Moreover, Am-Mo-NiS0.5 Se0.5 delivers excellent stability for at least 300â h without obvious degradation. Theoretical calculations revealed that the Ni sites in the defect-rich amorphous structure of Am-Mo-NiS0.5 Se0.5 owns higher electron state density and strengthened the binding energy of H2 O, which will optimize H adsorption/desorption energy barriers and reduce the adsorption energy of OER determining step.
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Increasing pursuit of next-generation wearable electronics has put forward the demand of reliable energy devices with high flexibility, durability, and enhanced electrochemical performances. Flexible aqueous zinc-air batteries (FAZABs) have attracted great interests owing to the high energy density, safety, and environmental benignity, for which quasi-solid-state gel polymer electrolytes (QSGPEs) are state-of-the-art electrolytes with high ionic conductivity, flexibility, and resistance to leakage problems of traditional liquid electrolytes. Compared to commonly used PVA-KOH electrolyte with poor electrolyte retention capability and cycling stability, a new type of sulfonate functionalized nanocomposite QSGPE is applied in FAZABs with high ionic conductivity, strong alkaline tolerance, and high zinc anode stability. Notably, the existence of (1) strong anionic sulfonate groups of QSGPEs, contributing to the exposure of preferred Zn (002) plane that is more resistant to zinc dendrite formation, and (2) nano-attapulgite electrolyte additives, beneficial for the enhancement of ionic conductivity, electrolyte uptake, and retention capability, endows a ultralong cycling life of 450 h for the fabricated FAZAB. Furthermore, flexible energy belts and knittable energy wires fabricated with a series/parallel unit of several FAZABs can be used to power various wearable electronics.
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Atmospheric water harvesting is an emerging strategy for decentralized and potable water supplies. However, water nucleation and microdroplet coalescence on condensing surfaces often result in surface flooding owing to the lack of a sufficient directional driving force for shedding. Herein, inspired by the fascinating properties of lizards and catfish, we present a condensing surface with engineered hydrogel patterns that enable rapid and sustainable water harvesting through the directional pumping and drag-reduced sliding of water droplets. The movement of microscale condensed droplets is synergistically driven by the surface energy gradient and difference in Laplace pressure induced by the arch hydrogel patterns. Meanwhile, the superhydrophilic hydrogel surface can strongly bond inner-layer water molecules to form a lubricant film that reduces drag and facilitates the sliding of droplets off the condensing surface. Thus, this strategy is promising for various water purification techniques based on liquid-vapor phase-change processes.