Self‐Sacrificial Template‐Directed Vapor‐Phase Growth of MOF Assemblies and Surface Vulcanization for Efficient Water Splitting

Direct use of metal–organic frameworks (MOFs) with robust pore structures, large surface areas, and high density of coordinatively unsaturated metal sites as electrochemical active materials is highly desirable (rather than using as templates and/or precursors for high‐temperature calcination), but this is practically hindered by the poor conductivity and low accessibility of active sites in the bulk form. Herein, a universal vapor‐phase method is reported to grow well‐aligned MOFs on conductive carbon cloth (CC) by using metal hydroxyl fluorides with diverse morphologies as self‐sacrificial templates. Specifically, by further partially on‐site generating active Co₃S₄ species from Co ions in the echinops‐like Co‐based MOF (EC‐MOF) through a controlled vulcanization approach, the resulting Co₃S₄/EC‐MOF hybrid exhibits much enhanced electrocatalytic performance toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with overpotentials of 84 and 226 mV required to reach a current density of 10 mA cm^?2, respectively. Density functional theory (DFT) calculations and experimental results reveal that the electron transfer between Co₃S₄ species and EC‐MOF can decrease the electron density of the Co d‐orbital, resulting in more electrocatalytically optimized adsorption properties for Co. This study will open up a new avenue for designing highly ordered MOF‐based surface active materials for various electrochemical energy applications.     

Metal‐Layer Assisted Growth of Ultralong Quasi‐2D MOF Nanoarrays on Arbitrary Substrates for Accelerated Oxygen Evolution

Controlled growth of metal–organic frameworks (MOFs) nanocrystals on requisite surfaces is highly desired for myriad applications related to catalysis, energy, and electronics. Here, this challenge is addressed by overlaying arbitrary surfaces with a thermally evaporated metal layer to enable the well‐aligned growth of ultralong quasi‐2D MOF nanoarrays comprising cobalt ions and thiophenedicarboxylate acids. This interfacial engineering approach allows preferred chelation of carboxyl groups in the ligands with the metal interlayers, thereby making possible the fabrication and patterning of MOF nanoarrays on substrates of any materials or morphologies. The MOF nanoarrays grown on porous metal scaffolds demonstrate high electrocatalytic capability for water oxidation, exhibiting a small overpotential of 270 mV at 10 mA cm^?2, or 317 mV at 50 mA cm^?2 as well as negligible decay of performance within 30 h. The enhanced performance stems from the improved electron and ion transport in the hierarchical porous nanoarrays consisting of in situ formed oxyhydroxide nanosheets in the electrochemical processes. This approach for mediating the growth of MOF nanoarrays can serve as a promising platform for diverse applications.     

A DNA‐Threaded ZIF‐8 Membrane with High Proton Conductivity and Low Methanol Permeability

Natural biomolecules have potential as proton‐conducting materials, in which the hydrogen‐bond networks can facilitate proton transportation. Herein, a biomolecule/metal–organic framework (MOF) approach to develop hybrid proton‐conductive membranes is reported. Single‐strand DNA molecules are introduced into DNA@ZIF‐8 membranes through a solid‐confined conversion process. The DNA‐threaded ZIF‐8 membrane exhibits high proton conductivity of 3.40 × 10^?4 S cm^?1 at 25 °C and the highest one ever reported of 0.17 S cm^?1 at 75 °C, under 97% relatively humidity, attributed to the formed hydrogen‐bond networks between the DNA molecules and the water molecules inside the cavities of the ZIF‐8, but very low methanol permeability of 1.25 × 10^?8 cm² s^?1 due to the small pore entrance of the DNA@ZIF‐8 membranes. The selectivity of the DNA@ZIF‐8 membrane is thus significantly higher than that of developed proton‐exchange membranes for fuel cells. After assembling the DNA@ZIF‐8 hybrid membrane into direct methanol fuel cells, it exhibits a power density of 9.87 mW cm^?2 . This is the first MOF‐based proton‐conductivity membrane used for direct methanol fuel cells, providing bright promise for such hybrid membranes in this application.     

Formation of N‐Doped Carbon‐Coated ZnO/ZnCo2O4/CuCo2O4 Derived from a Polymetallic Metal–Organic Framework: Toward High‐Rate and Long‐Cycle‐Life Lithium Storage

Metal–organic frameworks (MOFs) are very promising self‐sacrificing templates for the large‐scale fabrication of new functional materials owing to their versatile functionalities and tunable porosities. Most conventional metal oxide electrodes derived from MOFs are limited by the low abundance of incorporated metal elements. This study reports a new strategy for the synthesis of multicomponent active metal oxides by the pyrolysis of polymetallic MOF precursors. A hollow N‐doped carbon‐coated ZnO/ZnCo₂O₄/CuCo₂O₄ nanohybrid is prepared by the thermal annealing of a polymetallic MOF with ammonium bicarbonate as a pore‐forming agent. This is the first report on the rational design and preparation of a hybrid composed of three active metal oxide components originating from MOF precursors. Interestingly, as a lithium‐ion battery anode, the developed electrode delivers a reversible capacity of 1742 mAh g^?1 after 500 cycles at a current density of 0.3 mA g^?1. Furthermore, the material shows large storage capacities (1009 and 667 mAh g^?1), even at high current flow (3 and 10 A g^?1). The remarkable high‐rate capability and outstanding long‐life cycling stability of the multidoped metal oxide benefits from the carbon‐coated integrated nanostructure with a hollow interior and the three active metal oxide components.     

Casting Nanoporous Platinum in Metal–Organic Frameworks

Nanocasting based on porous templates is a powerful strategy in accessing materials and structures that are difficult to form by bottom‐up syntheses in a controlled fashion. A facile synthetic strategy for casting ordered, nanoporous platinum (NP‐Pt) networks with a high degree of control by using metal–organic frameworks (MOFs) as templates is reported here. The Pt precursor is first infiltrated into zirconium‐based MOFs and subsequently transformed to 3D metallic networks via a chemical reduction process. It is demonstrated that the dimensions and topologies of the cast NP‐Pt networks can be accurately controlled by using different MOFs as templates. The Brunauer–Emmett–Teller surface areas of the NP‐Pt networks are estimated to be >100 m² g^?1 and they exhibit excellent catalytic activities in the methanol electrooxidation reaction (MEOR). This new methodology presents an attractive route to prepare well‐defined nanoporous materials for diverse applications ranging from energy to sensing and biotechnology.     

A Highly Conductive MOF of Graphene Analogue Ni3(HITP)2 as a Sulfur Host for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have been considered as one of the most promising energy storage systems owing to their high theoretical capacity and energy density. However, their commercial applications are obstructed by sluggish reaction kinetics and rapid capacity degradation mainly caused by polysulfide shuttling. Herein, the first attempt to utilize a highly conductive metal–organic framework (MOF) of Ni₃(HITP)₂ graphene analogue as the sulfur host material to trap and transform polysulfides for high‐performance Li–S batteries is made. Besides, the traditional conductive additive acetylene black is replaced by carbon nanotubes to construct matrix conduction networks for triggering the rate and cycling performance of the active cathode. As a result, the S@Ni₃(HITP)₂ with sulfur content of 65.5 wt% shows excellent sulfur utilization, rate performance, and cyclic durability. It delivers a high initial capacity of 1302.9 mAh g^?1 and good capacity retention of 848.9 mAh g^?1 after 100 cycles at 0.2 C. Highly reversible discharge capacities of 807.4 and 629.6 mAh g^?1 are obtained at 0.5 and 1 C for 150 and 300 cycles, respectively. Such kinds of pristine MOFs with high conductivity and abundant polar sites reveal broad promising prospect for application in the field of high‐performance Li–S batteries.     

Flexible Metal–Organic Framework‐Based Mixed‐Matrix Membranes: A New Platform for H2S Sensors

Metal–organic framework (MOF)–polymer mixed‐matrix membranes (MMMs) have shown great potential and superior performance in gas separations. However, their sensing application has not been fully established yet. Herein, a rare example of using flexible MOF‐based MMMs as a fluorescent turn‐on sensor for the detection of hydrogen sulfide (H₂S) is reported. These MOF‐based MMMs are readily prepared by mixing a highly stable aluminum‐based nano‐MOF (Al‐MIL‐53‐NO₂) into poly(vinylidene fluoride) with high loadings up to 70%. Unlike the intrinsic fragility and poor processability of pure‐MOF membranes, these MMMs exhibit desirable flexibility and processability that are more suitable for practical sensing applications. The uniform distribution of Al‐MIL‐53‐NO₂ particles combined with the permanent pores of MOFs enable these MMMs to show good water permeation flux and consequently have a full contact between the analyte and MOFs. The developed MMM sensor (70% MOF loading) thus shows a highly remarkable detection selectivity and sensitivity for H₂S with an exceptionally low detection limit around 92.31 × 10^?9m , three orders of magnitude lower than the reported powder‐form MOFs. This work demonstrates that it is feasible to develop flexible luminescent MOF‐based MMMs as a novel platform for chemical sensing applications.     

Carbon Necklace Incorporated Electroactive Reservoir Constructing Flexible Papers for Advanced Lithium–Ion Batteries

Metal–organic frameworks (MOFs) and their derivatives with well‐defined structures and compositions show great potential for wide applications such as sensors, catalysis, energy storage, and conversion, etc. However, poor electric conductivity and large volume expansion are main obstacles for their utilization in energy storage, e.g., lithium–ion batteries and supercapacitors. Herein, a facile strategy is proposed for embedding the MOFs, e.g., ZIF‐67 and MIL‐88 into polyacrylonitrile fibers, which is further used as a template to build a 3D interconnected conductive carbon necklace paper. Owing to the unique structure features of good electric conductivity, interconnected frameworks, electroactive reservoir, and dual dopants, the obtained flexible electrodes with no additives exhibit high specific capacities, good rate capability, and prolonged cycling stability. The hollow dodecahedral ZIF‐67 derived carbon necklace paper delivers a high specific capacity of 1200 mAh g^?1 and superior stability of more than 400 cycles without capacity decay. Moreover, the spindle‐like MIL‐88 derived carbon necklace paper shows a high reversible capacity of 980 mAh g^?1. Their unique 3D interconnected structure and outstanding electrochemical performance pave the way for extending the MOF‐based interweaving materials toward potential applications in portable and wearable electronic devices.     

Two‐Dimensional Arrays of Transition Metal Nitride Nanocrystals

The synthesis of low‐dimensional transition metal nitride (TMN) nanomaterials is developing rapidly, as their fundamental properties, such as high electrical conductivity, lead to many important applications. However, TMN nanostructures synthesized by traditional strategies do not allow for maximum conductivity and accessibility of active sites simultaneously, which is a crucial factor for many applications in plasmonics, energy storage, sensing, and so on. Unique interconnected two‐dimensional (2D) arrays of few‐nanometer TMN nanocrystals not only having electronic conductivity in‐plane, but also allowing transport of ions and electrolyte through the porous nanosheets, which are obtained by topochemical synthesis on the surface of a salt template, are reported. As a demonstration of their application in a lithium–sulfur battery, it is shown that 2D arrays of several nitrides can achieve a high initial capacity of >1000 mAh g^?1 at 0.2 C and only about 13% degradation over 1000 cycles at 1 C under a high areal sulfur loading (>5 mg cm^?2).     

Acid and Base Resistant Zirconium Polyphenolate‐Metalloporphyrin Scaffolds for Efficient CO2 Photoreduction

A series of zirconium polyphenolate‐decorated‐(metallo)porphyrin metal–organic frameworks (MOFs), ZrPP‐n (n = 1, 2), featuring infinite Zr^IV‐oxo chains linked via polyphenolate groups on four peripheries of eclipse‐arranged porphyrin macrocycles, are successfully constructed through a top–down process from simulation to synthesis. These are the unusual examples of Zr‐MOFs (or MOFs in general) based on phenolic porphyrins, instead of commonly known carboxylate‐based types. Representative ZrPP‐1 not only exhibits strong acid resistance (pH = 1, HCl) but also remains intact even when immersed in saturated NaOH solution (≈20 m ), an exceptionally large range of pH resistance among MOFs. The metallation at the porphyrin core gives rise to materials with enhanced sorption and catalytic properties. In particular, ZrPP‐1‐Co, with precise and uniform distribution of active centers, exhibits not only high CO₂ trapping capability (≈90 cm³ g^?1 at 1 atm, 273 K, among the highest in Zr‐MOFs) but also high photocatalytic activity for reduction of CO₂ into CO (≈14 mmol g^?1 h^?1) and high selectivity over CH₄ (>96.4%) without any cocatalyst under visible‐light irradiation (λ > 420 nm). Given the strong chemical resistance under extreme alkali conditions, these catalysts can be recycled without appreciable loss of activity. The possible mechanism for photocatalytic reduction of CO₂‐to‐CO over ZrPP‐1‐Co is also proposed.     

Novel MOF‐Derived Co@N‐C Bifunctional Catalysts for Highly Efficient Zn–Air Batteries and Water Splitting

Metal–organic frameworks (MOFs) and MOF‐derived materials have recently attracted considerable interest as alternatives to noble‐metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N‐C materials (C‐MOF‐C2‐T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C‐MOF‐C2‐900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N‐doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO₂, respectively. Primary Zn–air batteries based on C‐MOF‐900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h g_Zn^–1 under 10 mA cm^–2. Rechargeable Zn–air batteries based on C‐MOF‐C2‐900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm^–2), along with an excellent cycling stability with no increase in polarization even after 120 h – outperform their counterparts based on noble‐metal‐based air electrodes. The resultant rechargeable Zn–air batteries are used to efficiently power electrochemical water‐splitting systems, demonstrating promising potential as integrated green energy systems for practical applications.     

Metal–Organic Frameworks and Their Derived Materials: Emerging Catalysts for a Sulfate Radicals‐Based Advanced Oxidation Process in Water Purification

With the ever‐growing environmental issues, sulfate radical (SO₄^??)‐based advanced oxidation processes (SR‐AOPs) have been attracting widespread attention due to their high selectivity and oxidative potential in water purification. Among various methods generating SO₄^??, employing heterogeneous catalysts for activation of peroxymonosulfate or persulfate has been demonstrated as an effective strategy. Therefore, the future advances of SR‐AOPs depend on the development of adequate catalysts with high activity and stability. Metal–organic frameworks (MOFs) with large surface area, ultrahigh porosity, and diversity of material design have been extensively used in heterogeneous catalysts, and more recently, enormous effort has been made to utilize MOFs‐based materials for SR‐AOPs applications. In this work, the state‐of‐the‐art research on pristine MOFs, MOFs composites, and their derivatives, such as oxides, metal/carbon hybrids, and carbon materials for SR‐AOPs, is summarized. The mechanisms, including radical and nonradical pathways, are also detailed in the discussion. This work will hopefully promote the future development of MOFs‐based materials toward SR‐AOPs applications.     

Self‐Healing Proton‐Exchange Membranes Composed of Nafion–Poly(vinyl alcohol) Complexes for Durable Direct Methanol Fuel Cells

Proton‐exchange membranes (PEMs) that can heal mechanical damage to restore original functions are important for the fabrication of durable and reliable direct methanol fuel cells (DMFCs). The fabrication of healable PEMs that exhibit satisfactory mechanical stability, enhanced proton conductivity, and suppressed methanol permeability via hydrogen‐bonding complexation between Nafion and poly(vinyl alcohol) (PVA) followed by postmodification with 4‐carboxybenzaldehyde (CBA) molecules is presented. Compared with pure Nafion, the CBA/Nafion–PVA membranes exhibit enhanced mechanical properties with an ultimate tensile strength of ≈20.3 MPa and strain of ≈380%. The CBA/Nafion–PVA membrane shows a proton conductivity of 0.11 S cm^?1 at 80 °C, which is 1.2‐fold higher than that of a Nafion membrane. The incorporated PVA gives the CBA/Nafion–PVA membranes excellent proton conductivity and methanol resistance. The resulting CBA/Nafion–PVA membranes are capable of healing mechanical damage of several tens of micrometers in size and restoring their original proton conductivity and methanol resistance under the working conditions of DMFCs. The healing property originates from the reversibility of hydrogen‐bonding interactions between Nafion and CBA‐modified PVA and the high chain mobility of Nafion and CBA‐modified PVA.     

Nanoparticles of Mesoporous SO3H‐Functionalized Si‐MCM‐41 with Superior Proton Conductivity

Nanometer‐sized mesoporous silica particles of around 100‐nm diameter functionalized with a large amount of sulfonic acid groups are prepared using a simple and fast in situ co‐condensation procedure. A highly ordered hexagonal pore structure is established by applying a pre‐hydrolysis step in a high‐dilution synthesis approach, followed by adding the functionalization agent to the reaction mixture. The high‐dilution approach is advantageous for the in situ functionalization since no secondary reagents for an effective particle and framework formation are needed. Structural data are determined via electron microscopy, nitrogen adsorption, and X‐ray diffraction, proton conductivity values of the functionalized samples are measured via impedance spectroscopy. The obtained mesoporous SO₃H‐MCM‐41 nanoparticles demonstrate superior proton conductivity than their equally loaded micrometer‐sized counterparts, up to 5 × 10^?2 S cm^?1. The mesoporosity of the particles turns out to be very important for effective proton transport since non‐porous silica nanoparticles exhibit worse efficient proton transport, and the obtained particle size dependence might open up a new route in rational design of highly proton conductive materials.     

Ambient Fast Synthesis and Active Sites Deciphering of Hierarchical Foam‐Like Trimetal–Organic Framework Nanostructures as a Platform for Highly Efficient Oxygen Evolution Electrocatalysis

Metal–organic frameworks (MOFs) have attracted tremendous interest due to their promising applications including electrocatalysis originating from their unique structural features. However, it remains a challenge to directly use MOFs for oxygen electrocatalysis because it is quite difficult to manipulate their dimension, composition, and morphology of the MOFs with abundant active sites. Here, a facile ambient temperature synthesis of unique NiCoFe‐based trimetallic MOF nanostructures with foam‐like architecture is reported, which exhibit extraordinary oxygen evolution reaction (OER) activity as directly used catalyst in alkaline condition. Specifically, the (Ni₂Co₁)_0.925Fe_0.075‐MOF‐NF delivers a minimum overpotential of 257 mV to reach the current density of 10 mA cm^?2 with a small Tafel slope of 41.3 mV dec^?1 and exhibits high durability after long‐term testing. More importantly, the deciphering of the possible origination of the high activity is performed through the characterization of the intermediates during the OER process, where the electrochemically transformed metal hydroxides and oxyhydroxides are confirmed as the active species.     

Nanostructured Metal–Organic Framework (MOF)‐Derived Solid Electrolytes Realizing Fast Lithium Ion Transportation Kinetics in Solid‐State Batteries

Solid‐state batteries are hindered from practical applications, largely due to the retardant ionic transportation kinetics in solid electrolytes (SEs) and across electrode/electrolyte interfaces. Taking advantage of nanostructured UIO/Li‐IL SEs, fast lithium ion transportation is achieved in the bulk and across the electrode/electrolyte interfaces; in UIO/Li‐IL SEs, Li‐containing ionic liquid (Li‐IL) is absorbed in Uio‐66 metal–organic frameworks (MOFs). The ionic conductivity of the UIO/Li‐IL (15/16) SE reaches 3.2 × 10^?4 S cm^?1 at 25 °C. Owing to the high surface tension of nanostructured UIO/Li‐IL SEs, the contact between electrodes and the SE is excellent; consequently, the interfacial resistances of Li/SE and LiFePO₄/SE at 60 °C are about 44 and 206 Ω cm², respectively. Moreover, a stable solid conductive layer is formed at the Li/SE interface, making the Li plating/stripping stable. Solid‐state batteries from the UIO/Li‐IL SEs show high discharge capacities and excellent retentions (≈130 mA h g^?1 with a retention of 100% after 100 cycles at 0.2 C; 119 mA h g^?1 with a retention of 94% after 380 cycles at 1 C). This new type of nanostructured UIO/Li‐IL SEs is very promising for solid‐state batteries, and will open up an avenue toward safe and long lifespan energy storage systems.     

Kinetic‐Controlled Formation of Bimetallic Metal–Organic Framework Hybrid Structures

Heterometallic metal–organic frameworks (MOFs) are constructed from two or more kinds of metal ions, while still remaining their original topologies. Due to distinct reaction kinetics during MOF formation, partial distribution of different metals within a single MOF crystal can lead to sophisticated heterogeneous nanostructures. Here, this study reports an investigation of reaction kinetics for different metal ions in a bimetallic MOF system, the ZIF‐8/67 (M(2‐mIM)₂, M = Zn for ZIF‐8, and Co for ZIF‐67, 2‐mIM = 2‐methylimidazole), by in situ optical method. Distinct kinetics of the two metals forming single‐component MOFs are revealed, and when both Co and Zn ions are present in the starting solution, homogeneous distributions of the two metals are only achieved at high Co/Zn ratio, while at low Co/Zn ratio concentration gradient from Co‐rich cores to Zn‐rich shells is observed. Further, by adding the two metals in sequence, more sophisticated structures are achieved. Specifically, when Co²⁺ is added first, ZIF‐67@ZIF‐8/67 core–shell nanocrystals are achieved with tunable core/shell thickness ratio depending on the time intervals; while when Zn²⁺ is added first, only agglomerates of irregular shape form due to the weak nucleation ability of Zn²⁺.     

Coordination Polymers Derived General Synthesis of Multishelled Mixed Metal‐Oxide Particles for Hybrid Supercapacitors

Metal–organic frameworks (MOFs) or coordination polymers (CPs) have been used as precursors for synthesis of materials. Unlike crystalline MOF, amorphous CP is nonspecific to metal cation species, therefore its composition can be tuned easily. Here, it is shown that amorphous CP can be used as general synthesis precursors of highly complex mixed metal oxide shells. As a proof of concept, Ni? Co coordination polymer spheres are first synthesized and subsequently transformed into seven‐layered Ni? Co oxide onions by rapid thermal oxidation. This approach is very versatile and can be applied to produce ternary and quaternary metal oxide onions with tunable size and composition. The Ni? Co oxide onions exhibit exceptional charge storage capability in aqueous electrolyte with high specific capacitance (≈1900 F g^?1 at 2 A g^?1), good rate capability, and ultrahigh cycling stability (93.6% retention over 20 000 cycles). A hybrid supercapacitor against graphene/multishelled mesoporous carbon sphere shows a high energy density of 52.6 Wh kg^?1 at a power density of 1604 W kg^?1 (based on active materials weight), as well as remarkable cycling stability.     

Recent Progress in Time‐Resolved Biosensing and Bioimaging Based on Lanthanide‐Doped Nanoparticles

Luminescent nanomaterials have attracted great attention in luminescence‐based bioanalysis due to their abundant optical and tunable surface physicochemical properties. However, luminescent nanomaterials often suffer from serious autofluorescence and light scattering interference when applied to complex biological samples. Time‐resolved luminescence methodology can efficiently eliminate autofluorescence and light scattering interference by collecting the luminescence signal of a long‐lived probe after the background signals decays completely. Lanthanides have a unique [Xe]4f^N electronic configuration and ladder‐like energy states, which endow lanthanide‐doped nanoparticles with many desirable optical properties, such as long luminescence lifetimes, large Stokes/anti‐Stokes shifts, and sharp emission bands. Due to their long luminescence lifetimes, lanthanide‐doped nanoparticles are widely used for high‐sensitive biosensing and high‐contrast bioimaging via time‐resolved luminescence methodology. In this review, recent progress in the development of lanthanide‐doped nanoparticles and their application in time‐resolved biosensing and bioimaging are summarized. At the end of this review, the current challenges and perspectives of lanthanide‐doped nanoparticles for time‐resolved bioapplications are discussed.     

Anticorrosive,Ultralight, and Flexible Carbon‐Wrapped Metallic Nanowire Hybrid Sponges for Highly Efficient Electromagnetic Interference Shielding

Metal‐based materials with exceptional intrinsic conductivity own excellent electromagnetic interference (EMI) shielding performance. However, high density, corrosion susceptibility, and poor flexibility of the metal severely restrict their further applications in the areas of aircraft/aerospace, portable and wearable smart electronics. Herein, a lightweight, flexible, and anticorrosive silver nanowire wrapped carbon hybrid sponge (Ag@C) is fabricated and employed as ultrahigh efficiency EMI shielding material. The interconnected Ag@C hybrid sponges provide an effective way for electron transport, leading to a remarkable conductivity of 363.1 S m^?1 and superb EMI shielding effectiveness of around 70.1 dB in the frequency range of 8.2–18 GHz, while the density is as low as 0.00382 g cm^?3, which are among the best performances for electrically conductive sponges/aerogels/foams by far. More importantly, the Ag@C sponge surprisingly exhibits super‐hydrophobicity and strong corrosion resistance. In addition, the hybrid sponges possess excellent mechanical resilience even with a large strain (90% reversible compressibility) and an outstanding cycling stability, which is far better than the bare metallic aerogels, such as silver nanowire aerogels and copper nanowire foams. This strategy provides a facile methodology to fabricate lightweight, flexible, and anticorrosive metal‐based sponge for highly efficient EMI shielding applications.