Metal Organic Frameworks as Polysulfide Reaction Modulators for Lithium Sulfur Batteries: Advances and Perspectives.

Currently, lithium sulfur (Li-S) battery with high theoretical energy density has attracted great research interest. However, the diffusion and loss process of intermediate lithium polysulfide during charge-discharge hindered the application of the Li-S battery in modern life. To overcome this issue, metal organic frameworks (MOFs) and their composites have been regarded as effective additions to restrain the LiPS diffusion process for Li-S battery. Benefiting from the unique structure with rich active sites to adsorb LiPS and accelerate the LiPS redox, the Li-S batteries with MOFs modified exhibit superior electrochemical performance. Considering the rapid development of MOFs in Li-S battery, this review summarizes the recent studies of MOFs and their composites as the sulfur host materials, functional interlayer, separator coating layer, and separator/solid electrolyte for Li-S batteries in detail. In addition, the promising design strategies of functional MOF materials are proposed to improve the electrochemical performance of Li-S battery.

Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long-Life All-Solid-State Li Batteries.

Here, we build a tunable multipolar conjugated polymer framework platform via pore wall chemistry to probe the role of electronic structure engineering in improving the Li+ conduction by theoretical studies. Guided by theoretical prediction, we develop a new cyano-vinylene-linked multipolar polymer framework namely CNF-COF, which can act as efficient ion sieves to modify solid polymer electrolytes to simultaneously tune Li+ migration and stable Li anodes for long-lifespan all-solid-state (ASS) Li metal batteries at high rate. The dual-decoration of cyano and fluorine groups in CNF-COF favorably regulates electronic structure via multipolar donor-acceptor electronic effects to afford proper energy band structure and abundant electron-rich sites for enhanced oxidative stability, facilitated ion-pair dissociation and suppressed anion movements. Thus, the CNF-COF incorporation into poly (ethylene oxide) (PEO) electrolytes not only renders fast selective Li+ transport but also facilitates the Li dendrite suppression. Specifically, the constructed PEO composite electrolyte with an ultra-low CNF-COF content of only 0.5 wt % is endowed with a wide electrochemical window, a high ionic conductivity of 0.634 mS cm-1 at 60 °C and a large Li+ transference number of 0.81-remarkably outperforming CNF-COF-free counterparts (0.183 mS cm-1 and 0.22). As such, the Li symmetric cell delivers stable Li plating/stripping over 1400 h at 0.1 mA cm-2. Impressively, by coupling with LiFePO4 (LFP) cathodes, the assembled ASS Li battery under 60 °C allows for stable cycling over 2000 cycles at 1 C and over 1000 cycles even at 2 C with a large capacity retention of ~75 %, surpassing most reported ASS Li batteries using PEO-based electrolytes.

Robust, Ultrafast and Reversible Photoswitching in Bulk Polymers Enabled by Octupolar Molecule Design.

Improving the photoswitching rate and robustness of photochromic molecules in bulk solids is paramount for practical applications but remains an on-going challenge. Here, we introduce an octupolar design paradigm to develop a new family of visible light organic photoswitches, namely multi-branched octupolar Stenhouse Adducts (MOPSAs) featuring a C3-symmetrical A3-(D-core) architecture with a dipolar donor-acceptor (D-A) photochrome in each branch. Our design couples multi-dimensional geometric and electronic effects of MOPSAs to enable robust ultrafast reversible photoswitching in bulk polymers. Specifically, the optimal MOPSA (4 wt %) in commercial polyurethane films accomplishes nearly 100 % discoloration in 6 s under visible light with ∼ 100 % thermal-recovery in 17.4 s at 60 °C, while the acquired kinetics constants are 3∼7 times that of dipolar DASA counterpart and 1∼2 orders of magnitude higher than those of reported DASAs in polymers. Importantly, the MOPSA-doped polymer films sustain 500 discoloration/recovery cycles with slow degradation, superior to the existing DASAs in polymers (≤30 cycles). We discover that multi-dipolar coupling in MOPSA enables enhanced polarization and electron delocalization, promoting the rate-determining thermal cyclization, while the branched and non-planar geometry of MOPSA induces large free volume to facilitate the isomerization. This design can be extended to develop spiropyran or azobenzene-based ultrafast photochromic films. The superior photoswitching performance of MOPSAs together with their high-yield and scalable synthesis and facile film processing inspires us to explore their versatile uses as smart inks or labels for time-temperature indicators, optical logic encryption and multi-levelled data encryption.

Photo-Assisted Metal-Air Batteries: Recent Progress, Challenges and Opportunities.

To meet the need of high energy density, long durability, safe and cost-efficient energy conversion and storage devices, metal-air batteries like Li-O2 and Zn-O2 batteries have received enormous attention and were subject to exciting development in the past decade. Photo-assisted strategies that enable the effective combination of photo/electric energy conversion/storage render a new dimension for the conventional metal-air batteries techniques with mere electric energy utilization. Therefore, tremendous research is ongoing in search of more efficient and durable devices with photo-assisted strategies. This review provides an overview of photo-assisted Li-O2 batteries, Zn-O2 batteries, and batteries with various metal/air components. The working mechanism, the basic device architecture and practical performances of various photo-assisted systems are summarized and discussed. Furthermore, certain technical challenges and future opportunities for the photo-assisted metal air batteries are emphasized and discussed in the hope of stimulating further research.

Unique Octupolar 2D-Polymer Frameworks as Mixed Conductors and Metal-Free Catalysts for Dual-Promoted Li and S Electrochemistry: Multi-regulation Role of Ethoxylation Chemistry.

Here, we for the first time introduce ethoxylation chemistry to develop a new octupolar cyano-vinylene-linked 2D polymer framework (Cyano-OCF-EO) capable of acting as efficient mixed electron/ion conductors and metal-free sulfur evolution catalysts for dual-promoted Li and S electrochemistry. Our strategy creates a unique interconnected network of strongly-coupled donor 3-(acceptor-core) octupoles in Cyano-OCF-EO, affording enhanced intramolecular charge transfer, substantial active sites and crowded open channels. This enables Cyano-OCF-EO as a new versatile separator modifier, which endows the modified separator with superior catalytic activity for sulfur conversion and rapid Li ion conduction with the high Li+ transference number up to 0.94. Thus, the incorporation of Cyano-OCF-EO can concurrently regulate sulfur redox reactions and Li-ion flux in Li-S cells, attaining boosted bidirectional redox kinetics, inhibited polysulfide shuttle and dendrite-free Li anodes. The Cyano-OCF-EO-involved Li-S cell is endowed with excellent overall electrochemical performance especially large areal capacity of 7.5 mAh cm-2 at high sulfur loading of 8.7 mg cm-2 . Mechanistic studies unveil the dominant multi-promoting effect of the triethoxylation on electron and ion conduction, polysulfide adsorption and catalytic conversion as well as previously-unexplored -CN/C-O dual-site synergistic effect for enhanced polysulfide adsorption and reduced energy barrier toward Li2 S conversion.

Cutting COF-like C4 N to Give Colloidal Quantum Dots: Towards Optical Encryption and Bidirectional Sulfur Chemistry via Functional Group and Edge Effects.

Herein, we report the first synthesis of colloidal C4 N quantum dots (QDs) and their functional composites and explore their optical activities and edge-selective polysulfide adsorption-catalysis. As-obtained C4 NQDs are rich in carbonyl groups and edges, allowing good solution processability and facile assembly with other moieties for creating functionalities. While C4 NQDs show normal fluorescence (FL), the QD/poly(vinyl alcohol) (PVA) composites give FL/room-temperature-phosphorescence (RTP) dual-mode emission, enabling the corresponding solution to be used as an encryption ink. The QDs anchored onto carbon nanotubes can be used as a barrier layer to decorate commercial separators, endowing a Li-S cell with excellent cycling stability, high rate capability, and large areal capacity. Computation and experiment studies show that edge sites in C4 N favor polysulfide adsorption and catalysis and the enriched edges and carbonyl groups in QDs synergically promotecatalytic conversion of sulfur species.

Engineering Support and Distribution of Palladium and Tin on MXene with Modulation of the d-Band Center for CO-resilient Methanol Oxidation.

The efficiency of direct methanol fuel cell (DMFC) is largely determined by the activity and durability of methanol oxidation reaction (MOR) catalysts. Herein, we present a CO-resilient MOR catalyst of palladium-tin nano-alloy anchored on Se-doped MXene (PdSn0.5 /Se-Ti3 C2 ) via a progressive one-step electrochemical deposition strategy. MOR mass activity resulting from Pd/Se-Ti3 C2 catalyst (1046.2 mA mg-1 ) is over 2-fold larger than that of Pd/Ti3 C2 , suggesting that the introduction of Se atoms on MXene might accelerate the reaction kinetics. PdSn0.5 /Se-Ti3 C2 with Se-doping progress of MXene and the cooperated Pd-Sn sites has a superior MOR mass activity (4762.8 mA mg-1 ), outperforming many other reported Pd-based catalysts. Both experimental results and theoretical calculation reveal that boosted electron interaction of metal crystals with Se-doped MXene and optimized distribution of Pd-Sn sites can modulate the d band center, reduce adsorption energies of CO* at Pd site and enhance OH* generation at Sn site, resulting in highly efficient removal of CO intermediates by reaction with neighboring OH species on adjacent Sn sites.

Octupolar Acrylonitrile-Bridged 2D-Conjugated Polymers Enable Bright Far-Red Emission with Intense Two-Photon Absorption via Alkoxylation Chemistry.

Herein, alkoxylation chemistry is introduced as a "one-stone-three-birds" solution for exploring a new family of highly-fluorescent octupolar 2D-conjugated organic polymers/frameworks (OCOPs/OCOFs) combining far-red emission, high fluorescence quantum yield (QY), and strong two-photon absorption (TPA). Both alkoxy-substituted OCOP and OCOF comprising acrylonitrile-bridged strongly-coupled donor3-(acceptor core) chromophores densely packed in either disordered or ordered forms, exhibit significantly redshifted emission. They produce high QY of 22.2% and 27.8% in tetrahydrofuran, large TPA cross section of 600 and 1124 GM, and 2-3 folds and 15-30 folds that of non-alkoxylate amorphous counterpart respectively. Combined theoretical and experimental studies reveal unique "one-stone-three-birds" role of the alkoxylation in realizing red-shifted-emission, improved QY and TPA enabled by inducing steric hindrance effect for weakened π-π stacking, and triggering p-π conjugation effect for electronically engineering octupolar chromophores, while the crystalline engineering enables enforced coplanarity conformation and improved π-electron delocalization for further improved QY and TPA. The robust and biocompatible pentoxy-substituted polymer can be used not only as metal-free red-emissive phosphor for efficient warm white light-emitting diodes, but also as efficient two-photon fluorescence probes for bio-imaging.

Redox Donor-Acceptor Conjugated Microporous Polymers as Ultralong-Lived Organic Anodes for Rechargeable Air Batteries.

Herein, we explore a new redox donor-acceptor conjugated microporous polymer (AQ-CMP) by utilizing anthraquinone and benzene as linkers via C-C linkages and demonstrate the first use of CMP as ultralong-lived anodes for rechargeable air batteries. AQ-CMP features an interconnected octupole network, which affords not only favorable electronic structure for enhanced electron transport and n-doping activity compared to linear counterpart, but also high density of active sites for maximizing the formula-weight-based redox capability. This coupled with highly cross-linked and porous structure endows AQ-CMP with a specific capacity of 202 mAh g-1 (96 % of theoretical capacity) at 2 Ag-1 and ≈100 % capacity retention over 60000 charge/discharge cycles. The assembled CMP-air full cell shows a stable and high capacity with full capacity recovery after only refreshing cathodes, while the decoupled electrolyte and cathode design boosts the discharge voltage and voltage efficiency to ≈1 V and 87.5 %.

Capturing Visible Light in Low-Band-Gap C4 N-Derived Responsive Bifunctional Air Electrodes for Solar Energy Conversion and Storage.

We report facile synthesis of low-band-gap mesoporous C4 N particles and their use as responsive bifunctional oxygen catalysts for visible-light-sensitive (VLS) rechargeable Zn-air battery (RZAB) and polymer-air battery (RPAB). Compared to widely studied g-C3 N4 , C4 N shows a smaller band gap of 1.99 eV, with a larger photocurrent response, and it can function as visible-light-harvesting antenna and bifunctional oxygen reduction/evolution (ORR/OER) catalysts, enabling effective photocoupling to tune oxygen catalysis. The C4 N-enabled VLS-RZAB displays a low charge voltage of 1.35 V under visible light, which is below the theoretical RZAB voltage of 1.65 V, corresponding to a high energy efficiency of 97.78 %. Pairing a C4 N cathode with a polymer anode also endows an VLS-RPAB with light-boosted charge performance. It is revealed that the ORR and OER active sites in C4 N are separate carbon sites near pyrazine-nitrogen atoms and photogenerated energetic holes can activate OER for improved reaction kinetics.

Versatile, Aqueous Soluble C2N Quantum Dots with Enriched Active Edges and Oxygenated Groups.

C2N has emerged as a new family of promising two-dimensional (2D) layered frameworks in both fundamental studies and potential applications. Transforming bulk C2N into zero-dimensional quantum dots (QDs) could induce unique quantum confinement and edge effects that produce improved or new properties. Despite their appealing potential, C2NQDs remain unexplored, and their intriguing properties and a fundamental understanding of their prominent edge effects are still not well understood. Here, we report the first synthesis of water-soluble C2NQDs via a top-down approach without any foreign stabilizer and exploit their linear/nonlinear optical properties and unique edge-preferential electrocatalytic activity toward polysulfides for versatile applications. The resultant dispersant-free C2NQDs with an average size of less than 5 nm feature rich oxygen-carrying groups and active edges, not only enabling excellent dispersion in water but also creating interesting multifunctionality. They can emit not only blue one-photon luminescence (OPL) under ultraviolet (UV) excitation but also green two-photon luminescence (TPL) with a wide near-infrared (NIR) excitation range of 750-900 nm, enabling their use as a new fluorescent ink. Interestingly, when C2NQDs are introduced to modify commercial separators, they can function as new metal-free catalysts to boost polysulfide redox kinetics and endow Li-S batteries with excellent cycling stability, high rate capability, and large areal capacity (7.0 mA h cm-2) at a high sulfur loading of 8.0 mg cm-2. Detailed theoretical and experimental results indicate that the edge of C2N is more favorable for trapping and catalyzing the polysulfide conversion than the terrace and that the synergy between the active edges and oxygenated groups enriched in C2NQDs remarkably improves polysulfide immobilization and catalytic conversion.

Ultrathin Black Phosphorus-on-Nitrogen Doped Graphene for Efficient Overall Water Splitting: Dual Modulation Roles of Directional Interfacial Charge Transfer.

Few-layered exfoliated black phosphorus (EBP) has attracted surging interest for electronics, optoelectronics, and catalysis. As compared to excellent progress in electronic and optoelectronic applications, very few reports are available for electrocatalysis by metal-free EBPs. Herein, we couple solution-processable ultrathin EBP nanosheets with higher Fermi level of N-doped graphene (NG) into a new metal-free 2D/2D heterostructure (EBP@NG) with well-designed interfaces and unique electronic configuration, as efficient and durable bifunctional catalysts toward hydrogen evolution and oxygen evolution reactions (HER/OER) for overall water splitting in alkaline media. By rational interface engineering, the synergy of EBP and NG is fully exploited, which not only improves the stability of EBP, but also effectively modulates electronic structures of each component to boost their intrinsic activities. Specifically, due to the lower Fermi level of EBP relative to NG, their electronic interaction induces directional interfacial electron transfer, which not only enriches the electron density over EBP and optimizes H adsorption/desorption to promote HER, but also introduces abundant positively charged carbon sites on NG and provides favorable formation of key OER intermediates (OOH*) to improve OER energetics. Thus, despite that pure EBP or NG alone has poor or negligible activity, EBP@NG achieves remarkably enhanced bifunctional HER/OER activities, along with an excellent durability. This endows an optimized electrolyzer using EBP@NG as anode and cathode with a low cell voltage of 1.54 V at 10 mA cm-2, which is smaller than that of the costly integrated Pt/C@RuO2 couple (1.60 V).

Tactile UV- and Solar-Light Multi-Sensing Rechargeable Batteries with Smart Self-Conditioned Charge and Discharge.

A tactile, UV- and solar-light multi-sensing smart rechargeable Zn-air battery (SRZAB) with excellent cell performance, self-conditioned charge/discharge, and reliable environmental responsivity is made by using multi-scale conjugated block-copolymer-carbon nanotube-polyurethane foam assemblies as both a self-standing air electrode and a sensing unit. Multiscale engineering fully exploits the multi-synergy among components to endow the newly designed metal-free multi-sensing air electrode (MSAE) with bifunctional oxygen reduction and evolution activities, pressure sensitivity, and photothermal and photoelectric conversion functions in a single electrode, enabling effective regulation of interface properties, electronic/ionic transport, or redox reactions in SRZAB upon various stimulations and establishing multiple working principles. MSAE-driven SRZAB can be used as compressible power sources, self-powered pressure and optical sensors and light-to-electrochemical energy systems.

Donor-Acceptor Nanocarbon Ensembles to Boost Metal-Free All-pH Hydrogen Evolution Catalysis by Combined Surface and Dual Electronic Modulation.

A combined surface and dual electronic modulation strategy is used to realize metal-free all-pH catalysis towards the hydrogen evolution reaction (HER) by coupling a N-doped carbon framework (MHCF, electron acceptors) derived from MOFs with higher-Fermi-level pure carbon nanotubes (CNTs, electron donors), followed by surface modification with carboxyl-group-rich polymers. Although the three constituents are inactive, as-assembled ternary membranes yield superior HER performance with low overpotentials and high durability (≤5 % activity loss over 100 h) at all pH values. The C adjacent to pyrrolic N in MHCF is the most active site and the induced directional interfacial electron transfer from CNTs to MHCF coupled with N-driven intramolecular electron transfer in MHCF optimizes Gibbs free energy for hydrogen adsorption (ΔGH* ) near zero, while the polymer modulation enables local H+ enrichment in acidic media and enhanced water adsorption and activation in neutral and basic media.

Isolated Square-Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO2 to CO.

Photocatalytic reduction of CO2 to value-added fuel has been considered to be a promising strategy to reduce global warming and shortage of energy. Rational design and synthesis of catalysts to maximumly expose the active sites is the key to activate CO2 molecules and determine the reaction selectivity. Herein, we synthesize a well-defined copper-based boron imidazolate cage (BIF-29) with six exposed mononuclear copper centers for the photocatalytic reduction of CO2 . Theoretical calculations show a single Cu site including weak coordinated water delivers a new state in the conduction band near the Fermi level and stabilizes the *COOH intermediate. Steady-state and time-resolved fluorescence spectra show these Cu sites promote the separation of electron-hole pairs and electron transfer. As a result, the cage achieves solar-driven reduction of CO2 to CO with an evolution rate of 3334 µmol g-1 h-1 and a high selectivity of 82.6 %.

Emergence of fiber supercapacitors.

Supercapacitors (SCs) are energy storage devices which have high power density and long cycle life. Conventional SCs have two-dimensional planar structures. As a new family of SCs, fiber SCs utilize one-dimensional cylindrically shaped fibers as electrodes. They have attracted significant interest since 2011 and have shown great application potential either as micro-scale devices to complement or even replace micro-batteries in miniaturized electronics and microelectromechanical systems or as macro-scale devices for wearable electronics or smart textiles. This tutorial review provides an essential introduction to this new field. We first introduce the basics of performance evaluation for fiber SCs as a foundation to understand different research approaches and the diverse performance metrics reported in the literature. Next, we summarize the current state-of-the-art progress in structure design and electrode fabrication of fiber SCs. This is followed by a discussion on the integration of multiple fiber SCs and the combination with other energy harvesting or storage devices. Last, we present our perspectives on the future development of fiber SCs and highlight key technical challenges with the hope of stimulating further research progress.

Nickel hydroxide-carbon nanotube nanocomposites as supercapacitor electrodes: crystallinity dependent performances.

Nickel hydroxide (Ni(OH)2) is a promising pseudocapacitive material to increase the energy storage capacity of supercapacitors. Ni(OH)2 has three common crystalline structures: amorphous (amor-), α-, and ß-Ni(OH)2. There is a lack of good understanding on their pros and cons as supercapacitor electrodes. In this work, we synthesized three nanocomposites with thin layers (10-15 nm) of amor-, α-, and ß-Ni(OH)2 deposited on conductive multi-walled carbon nanotubes (MWCNTs). The mass loading of Ni(OH)2 is analogous in these nanocomposites, ranging from 49.1-52.2 wt% with a comparable narrow-pore size distribution centered around 4-5 nm. They were fabricated into supercapacitor electrodes at a mass loading of 6 mg cm(-2) with a thickness of ∼250 µm, similar to the electrodes used in commercial supercapacitors. Our results show that MWCNT/amor-Ni(OH)2 has the highest specific capacitance (1495 or 2984 F g(-1), based on the mass of total active materials or Ni(OH)2 only at the scan rate of 5 mV s(-1) in 1 M KOH electrolyte). It also has the best rate capability among the three nanocomposites. Better performances can be attributed to its disordered structure, which increases its effective surface area and reduces diffusion resistance for redox reactions. However, superior performances gradually deteriorate to the same level as that of MWCNT/ß-Ni(OH)2 over 3000 charge/discharge cycles, because amor- and α-Ni(OH)2 transform slowly to more ordered ß-Ni(OH)2. Our results highlight that the electrochemical performances of MWCNT/Ni(OH)2 nanocomposites depend on the crystallinity of Ni(OH)2, and the performances of electrodes change upon the crystalline structure transformation of Ni(OH)2 under repeated redox reactions. Future research should focus on improving the structure stability of amor-Ni(OH)2.

Nitrogen-doped graphene/carbon nanotube hybrids: in situ formation on bifunctional catalysts and their superior electrocatalytic activity for oxygen evolution/reduction reaction.

There is a growing interest in oxygen electrode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), as they play a key role in a wide range of renewable energy technologies such as fuel cells, metal-air batteries, and water splitting. Nevertheless, the development of highly-active bifunctional catalysts at low cost for both ORR and OER still remains a huge challenge. Herein, we report a new N-doped graphene/single-walled carbon nanotube (SWCNT) hybrid (NGSH) material as an efficient noble-metal-free bifunctional electrocatalyst for both ORR and OER. NGSHs were fabricated by in situ doping during chemical vapor deposition growth on layered double hydroxide derived bifunctional catalysts. Our one-step approach not only provides simultaneous growth of graphene and SWCNTs, leading to the formation of three dimensional interconnected network, but also brings the intrinsic dispersion of graphene and carbon nanotubes and the dispersion of N-containing functional groups within a highly conductive scaffold. Thus, the NGSHs possess a large specific surface area of 812.9 m(2) g(-1) and high electrical conductivity of 53.8 S cm(-1) . Despite of relatively low nitrogen content (0.53 at%), the NGSHs demonstrate a high ORR activity, much superior to two constituent components and even comparable to the commercial 20 wt% Pt/C catalysts with much better durability and resistance to crossover effect. The same hybrid material also presents high catalytic activity towards OER, rendering them high-performance cheap catalysts for both ORR and OER. Our result opens up new avenues for energy conversion technologies based on earth-abundant, scalable, noble-metal-free catalysts.

Graphene-based nanowire supercapacitors.

We present a new type of electrochemical supercapacitors based on graphene nanowires. Graphene oxide (GO)/polypyrrole (PPy) nanowires are prepared via electrodepostion of GO/PPy composite into a micoroporous Al2O3 template, followed by the removal of template. PPy is electrochemically doped by oxygen-containing functional groups of the GO to enhance the charging/discharging rates of the supercapacitor. A high capacitance 960 F g(-1) of the GO/PPy nanowires is obtained due to the large surface area of the vertically aligned nanowires and the intimate contact between the nanowires and the substrate electrode. The capacitive performance remains stable after charging and discharging for 300 cycles. To improve the thermal stability and long-term charge storage, GO is further electrochemically reduced into graphene and PPy is subsequently thermally carbonized, leading to a high capacitance of 200 F g(-1) for the resultant pure reduced graphene oxide/carbon based nanowire supercapacitor. This value of capacitance (200 F g(-1)) is higher than that of conventional porous carbon materials while the reduced graphene oxide/carbon nanowires show a lower Faraday resistance and higher thermal stability than the GO/PPy nanowires.

Proton-Conductive COF Evenly Embedded Cellulose Aerogels toward Water Harvesting and Spontaneous Sustained Power Generation from Ambient Moisture and Human Respiration.

Herein, we develop a new intelligent moisture-sensitive hybrid aerogel by evenly embedding a proton-conductive covalent organic framework (COF-2SO3H) into a carboxylated cellulose nanofiber network (CNF-C) for water harvesting and spontaneous sustained electricity production from ambient humidity and human respiration. Our strategy first exploits the "suspending agent" role of CNF-C to stably disperse COF materials in water for forming uniform hierarchical hybrid structures. By utilizing the synergy of COF-2SO3H and CNF-C together with their inherent structure merits and surface group effects, the hybrid aerogel displays increased water uptake and ion conductivity. Upon asymmetric moisturization, it can create a self-maintained moisture gradient to engender a concentration difference for mobile Na+ and H+, resulting in efficient charge separation and diffusion. Thus, the hybrid aerogel-based coin-type generator achieves a continuous output voltage of ∼0.55 V for at least 5 h in ambient environments in contrast to that using pure CNF-C and carbon-based generators with transient voltage response. Intriguingly, the wearable generator with an aerogel in a mask is more sensitive to human respiration and achieves repeatable and reliable self-charge for persistent electricity along with an increased output voltage of up to 1.0 V and much faster self-charge (only 3 min), both of which surpass most reported moisture-enabled generators.