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Covalent bonding interactions determine the energy-momentum (E-k) dispersion (band structure) of solid-state materials. Here, we show that noncovalent interactions can modulate the E-k dispersion near the Fermi level of a low-dimensional nanoscale conductor. We demonstrate that low energy band gaps may be opened in metallic carbon nanotubes through polymer wrapping of the nanotube surface at fixed helical periodicity. Electronic spectral, chiro-optic, potentiometric, electronic device, and work function data corroborate that the magnitude of band gap opening depends on the nature of the polymer electronic structure. Polymer dewrapping reverses the conducting-to-semiconducting phase transition, restoring the native metallic carbon nanotube electronic structure. These results address a long-standing challenge to develop carbon nanotube electronic structures that are not realized through disruption of π conjugation, and establish a roadmap for designing and tuning specialized semiconductors that feature band gaps on the order of a few hundred meV.
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Current un-sustainable plastic management is exacerbating plastic pollution, an urgent shift is thus needed to create a recycling society. Such recovering carbon (C) and hydrogen (H) from waste plastic has been considered as one practical route to achieve a circular economy. Here, we performed a simple pyrolysis-catalysis deconstruction of waste plastic via a monolithic multilayer stainless-steel mesh catalyst to produce multiwalled carbon nanotubes (MWCNTs) and H2, which are important carbon material and energy carrier to achieve sustainable development. Results revealed that the C and H recovery efficiencies were as high as 86% and 70%, respectively. The unique oxidation-reduction process and improvement of surface roughness led to efficient exposure of active sites, which increased MWCNTs by suppressing macromolecule hydrocarbons. The C recovery efficiency declined by only 5% after 10 cycles, proving the long-term employment of the catalyst. This catalyst can efficiently convert aromatics to MWCNTs by the vapor-solid-solid mechanism and demonstrate good universality in processing different kinds of waste plastics. The produced MWCNTs showed potential in applications of lithium-ion batteries and telecommunication. Owing to the economic profits and environmental benefits of the developed route, we highlighted its potential as a promising alternative to conventional incineration, simultaneously achieving the waste-to-resource strategy and circular economy.
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Lung diseases characterized by type 2 inflammation are reported to occur with a female bias in prevalence/severity in both humans and mice. This includes previous work examining multi-walled carbon nanotube (MWCNT)-induced eosinophilic inflammation, in which a more exaggerated M2a phenotype was observed in female alveolar macrophages (AMs) compared to males. The mechanisms responsible for this sex difference in AM phenotype are still unclear, but estrogen receptor (ER) signaling is a likely contributor. Accordingly, male AMs downregulated ERα expression after MWCNT exposure while female AMs did not. Thus, ER antagonist Fulvestrant was administered prior to MWCNT instillation. In females, Fulvestrant significantly attenuated MWCNT-induced M2a gene expression and eosinophilia without affecting IL-33. In males, Fulvestrant did not affect eosinophil recruitment but reduced IL-33 and M2a genes compared to controls. Regulation of cholesterol efflux and oxysterol synthesis is a potential mechanism through which estrogen promotes the M2a phenotype. Levels of oxysterols 25-OHC and 7α,25-OHC were higher in the airways of MWCNT-exposed males compared to MWCNT-females, which corresponds with the lower IL-1ß production and greater macrophage recruitment previously observed in males. Sex-based changes in cholesterol efflux transporters Abca1 and Abcg1 were also observed after MWCNT exposure with or without Fulvestrant. In vitro culture with estrogen decreased cellular cholesterol and increased the M2a response in female AMs, but did not affect cholesterol content in male AMs and reduced M2a polarization. These results reveal the modulation of (oxy)sterols as a potential mechanism through which estrogen signaling may regulate AM phenotype resulting in sex differences in downstream respiratory inflammation.
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Pulmão , Nanotubos de Carbono , Feminino , Masculino , Humanos , Animais , Camundongos , Pulmão/metabolismo , Interleucina-33/metabolismo , Nanotubos de Carbono/toxicidade , Caracteres Sexuais , Fulvestranto , Inflamação/induzido quimicamente , Inflamação/metabolismo , Macrófagos/metabolismo , Colesterol/metabolismo , Camundongos Endogâmicos C57BLRESUMO
A carbon nanotube (CNT) may facilitate near-frictionless water transport within it. In this work, we elucidate the slip flow characteristics for a CNT embedded in a silicon nitride matrix using the molecular dynamics (MD) method. We reveal that the wetting transparency of a CNT, the transmission of the membrane matrix wetting property over a CNT, cannot be ignored. Due to the effect of CNT wetting transparency, the orientation flip behavior of water molecules should be the primary cause of the entrance and exit losses, which is a dominant factor influencing the interfacial friction coefficient for the thin CNT membrane. The relationship between the friction coefficient and pore size follows a logarithmic function, which agrees well with the reported experimental data. Our findings bridge the gap between the MD prediction and experimental observation for water transport in a CNT membrane and provide a clear understanding of the mechanism behind its ultrafast flow performance.
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Dielectric screening plays a vital role in determining physical properties at the nanoscale and affects our ability to detect and characterize nanomaterials using optical techniques. We study how dielectric screening changes electromagnetic fields and many-body effects in nanostructures encapsulated inside carbon nanotubes. First, we show that metallic outer walls reduce the scattering intensity of the inner tube by 2 orders of magnitude compared to that of air-suspended inner tubes, in line with our local field calculations. Second, we find that the dielectric shift of the optical transition energies in the inner walls is greater when the outer tube is metallic than when it is semiconducting. The magnitude of the shift suggests that the excitons in small-diameter inner metallic tubes are thermally dissociated at room temperature if the outer tube is also metallic, and in essence, we observe band-to-band transitions in thin metallic double-walled nanotubes.
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Photoelectrochemical (PEC) H2O2 production via two-electron O2 reduction is promising for H2O2 production without emitting CO2. For PEC H2O2 production, α-Fe2O3 is an ideal semiconductor owing to its earth abundance, superior stability in water, and an appropriate band gap for efficient solar light utilization. Moreover, its conduction band is suitable for O2 reduction to produce H2O2. However, a significant overpotential for water oxidation is required due to the poor surface properties of α-Fe2O3. Thus, unassisted solar H2O2 production is not yet possible. Herein, we demonstrate unassisted PEC H2O2 production using α-Fe2O3 for the first time by applying glycerol oxidation, which requires less bias compared with water oxidation. We obtain maximum Faradaic efficiencies of 96.89 ± 0.6% and 100% for glycerol oxidation and H2O2 production, respectively, with high stability for 25 h. Our results indicate that unassisted and stable PEC H2O2 production is feasible with in situ glycerol valorization using the α-Fe2O3 photoanode.
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Neurotransmitters are important signaling molecules in the brain and are relevant in many diseases. Measuring them with high spatial and temporal resolutions in biological systems is challenging. Here, we develop a ratiometric fluorescent sensor/probe for catecholamine neurotransmitters on the basis of near-infrared (NIR) semiconducting single wall carbon nanotubes (SWCNTs). Phenylboronic acid (PBA)-based quantum defects are incorporated into them to interact selectively with catechol moieties. These PBA-SWCNTs are further modified with poly(ethylene glycol) phospholipids (PEG-PL) for biocompatibility. Catecholamines, including dopamine, do not affect the intrinsic E11 fluorescence (990 nm) of these (PEG-PL-PBA-SWCNT) sensors. In contrast, the defect-related E11* emission (1130 nm) decreases by up to 35%. Furthermore, this dual functionalization allows tuning selectivity by changing the charge of the PEG polymer. These sensors are not taken up by cells, which is beneficial for extracellular imaging, and they are functional in brain slices. In summary, we use dual functionalization of SWCNTs to create a ratiometric biosensor for dopamine.
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Catecolaminas , Nanotubos de Carbono , Dopamina , Fluorescência , NeurotransmissoresRESUMO
We present a first-principles many-body perturbation theory study of nitrophenyl-doped (6,5) single-walled nanotubes (SWCNTs) to understand how sp3 doping impacts the excitonic properties. sp3-doped SWCNTs are promising as a class of optoelectronic materials with bright tunable photoluminescence, long spin coherence, and single-photon emission (SPE), motivating the study of spin excitations. We predict that the dopant results in a single unpaired spin localized around the defect site, which induces multiple low-energy excitonic peaks. By comparing optical absorption and photoluminescence from experiment and theory, we identify the transitions responsible for the red-shifted, defect-induced E11* peak, which has demonstrated SPE for some dopants; the presence of this state is due to both the symmetry-breaking associated with the defect and the presence of the defect-induced in-gap state. Furthermore, we find an asymmetry between the contribution of the two spin channels, suggesting that this system has potential for spin-selective optical transitions.
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The postharvest life of cut flowers is limited, which is a major challenge and varies greatly depending on plant varieties, cut flower stage, flower length of the harvested shoots, and storage conditions including postharvest treatments. As a result, improving the vase life and quality of cut flowers in regulating postharvest characteristics and overcoming these challenges is critical to the horticulture business. Novel engineered nanocomposites were created and tested for possible impacts on flower bud opening, postharvest life extension, longevity regulation, and preservation and enhancement of the strength and appearance of cut flowers. The experiment was conducted as a factorial experiment using a completely randomized design (CRD) with two factors. The first factor was two holding solutions (without or with sucrose at 20 gL-1). The second factor was 12 pulsing treatments for 24 h; distilled water as a control, 75 ppm GA3, multi-walled carbon nanotubes MWCNTs at 10, 20, 30, 40, and 50 ppm, and MWCNTs (10, 20, 30, 40, and 50 ppm)/GA3 (75 ppm) composites; each treatment had 3 replicates, for a total of 72 experimental units. In the present study, gibberellic acid (GA3) was synthesized in functionalized (MWCNT/GA3 composites) as a novel antisenescence agent, and their effect on the vase life quality of cut rose flowers Rosa hybrida cv. 'Moonstone' was compared by assaying several parameters critical for vase life. The adsorption of GA3 on MWCNTs was proven by performing FTIR spectroscopy which ensures that the formation of the MWCNTs/GA3 composite preserves the nanostructure and was examined by high-resolution transmission electron microscopy (HR-TEM). The results revealed that sucrose in the holding solution showed a significant increase in fresh weight, flower diameter, and vase life by 10.5, 10.6, and 3.3% respectively. Applying sucrose with MWCNTs 20 ppm/GA3 75 ppm composites or MWCNTs 20 ppm alone, was critical for the significant increase in flower opening by 39.7 and 28.7%, and longevity by 34.4 and 23.2%, respectively, and significantly increased chlorophyll a, b, total chlorophyll, anthocyanin, total phenolic content, and 2,2-Diphenyl-1-picrylhydrazyl scavenging activity as compared to the control.
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Giberelinas , Nanotubos de Carbono , Rosa , Clorofila A , SacaroseRESUMO
Salvia verticillata L. is a well-known herb rich in rosmarinic acid (RA) and with therapeutic values. To better understand the possible roles of phytohormones in the production of phenolic acids in S. verticillata, in this work, we investigated some physiological and biochemical responses of the species to methyl jasmonate (MJ) and multi-walled carbon nanotubes (MWCNTs) as two effective elicitors. The leaves were sprayed with aqueous solutions containing 100 mg L-1 MWCNTs and 100 µM MJ and then harvested during interval times of exposure up to 96 h. The level of abscisic acid, as the first effective phytohormone, was altered in the leaves in response to MJ and MWCNTs elicitation (2.26- and 3.06-fold more than the control, respectively), followed by significant increases (P Ë 0.05) detected in jasmonic acid and salicylic acid contents up to 8 h after exposure. Obtained data revealed that simultaneously with changes in phytohormone profiles, significant (P Ë 0.05) rises were observed in the content of H2O2 (8.85- and 9.74-folds of control), and the amount of lipid peroxidation (10.18- and 17.01-folds of control) during the initial times after exposure to MJ and MWCNTs, respectively. Later, the content of phenolic acids increased in the elicited leaves due to changes in the transcription levels of key enzymes involved in their biosynthesis pathways, so 2.71- and 11.52-fold enhances observed in the RA content of the leaves after exposure to MJ and MWCNTs, respectively. It is reasonable to conclude that putative linkages between changes in some phytohormone pools lead to the accumulation of phenolic acids in the leaves of S. verticillata under elicitation. Overall, the current findings help us improve our understanding of the signal transduction pathways of the applied stimuli that led to enhanced secondary metabolite production in medicinal plants.
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Acetatos , Nanotubos de Carbono , Salvia , Reguladores de Crescimento de Plantas/farmacologia , Peróxido de Hidrogênio/farmacologia , Ciclopentanos/farmacologia , Ciclopentanos/metabolismo , Oxilipinas/farmacologia , Oxilipinas/metabolismoRESUMO
Poor dispersibility of carbon nanotubes greatly hinders their practical applications. Herein, a long-term stable dispersion of multiwalled carbon nanotubes (MWCNTs) in peroxydisulfate (PDS) is achieved. MWCNTs at 40 mg L-1 are completely dispersed by PDS upon ultrasonication (US/PDS) within 64 min and a stable dispersion is maintained at least 20 days. Mechanistically, US created defects on the nanomaterial and PDS-origin free radicals attacked these defects to introduce O-containing moieties (âOH and âCOOH). Interestingly, dispersion efficiency of MWCNTs by US/PDS initially at pH 7 and 3.8 is comparable, but lower than that initially at pH 12. Both â¢OH and SO4 â¢- are produced under alkaline condition, while SO4 â¢- is the dominant free radicals initially at pH 7 and 3.8 during the whole dispersion period. Stronger dispersion of MWCNTs initially at pH 12 resulted from greater amounts of O-containing moieties mainly in âOH (46.32%) rather than âCOOH (24.19%) form. This differential more strongly promotes MWCNTs-water interaction via hydrogen bonding, thereby enhancing the dispersion. Notably, no significant mass loss of MWCNTs occurred during dispersion. Overall, the developed method achieves long-term stable dispersion of MWCNTs in a manner that can significantly extend their applications.
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Constructing a semi-permanent base on the moon or Mars will require maximal use of materials found in situ and minimization of materials and equipment transported from Earth. This will mean a heavy reliance on regolith (Lunar or Marian soil) and water, supplemented by small quantities of additives fabricated on Earth. Here it is shown that SiO2-based powders, as well as Lunar and Martian regolith simulants, can be fabricated into building materials at near-ambient temperatures using only a few weight-percent of carbon nanotubes as a binder. These composites have compressive strength and toughness up to 100 MPa and 3 MPa respectively, higher than the best terrestrial concretes. They are electrically conductive (>20 S m-1) and display an extremely large piezoresistive response (gauge factor >600), allowing these composites to be used as internal sensors to monitor the structural health of extra-terrestrial buildings.
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A novel and sustainable carbon-based material, referred to as hollow porous carbon particles encapsulating multi-wall carbon nanotubes (MWCNTs) (CNTs@HPC), is synthesized for use in supercapacitors. The synthesis process involves utilizing LTA zeolite as a rigid template and dopamine hydrochloride (DA) as the carbon source, along with catalytic decomposition of methane (CDM) to simultaneously produce MWCNTs and COx -free H2 . The findings reveal a distinctive hierarchical porous structure, comprising macropores, mesopores, and micropores, resulting in a total specific surface area (SSA) of 913 m2 g-1 . The optimal CNTs@HPC demonstrates a specific capacitance of 306 F g-1 at a current density of 1 A g-1 . Moreover, this material demonstrates an electric double-layer capacitor (EDLC) that surpasses conventional capabilities by exhibiting additional pseudocapacitance characteristics. These properties are attributed to redox reactions facilitated by the increased charge density resulting from the attraction of ions to nickel oxides, which is made possible by the material's enhanced hydrophilicity. The heightened hydrophilicity can be attributed to the presence of residual silicon-aluminum elements in CNTs@HPC, a direct outcome of the unique synthesis approach involving nickel phyllosilicate in CDM. As a result of this synthesis strategy, the material possesses excellent conductivity, enabling rapid transportation of electrolyte ions and delivering outstanding capacitive performance.
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Fullertubes, that is, fullerenes consisting of a carbon nanotube moiety capped by hemifullerene ends, are emerging carbon nanomaterials whose properties show both fullerene and carbon nanotube (CNT) traits. Albeit it may be expected that their electronic states show a certain resemblance to those of the extended nanotube, such a correlation has not yet been found or described. Here it shows a scanning tunneling microscopy (STM) and spectroscopy (STS) characterization of the adsorption, self-assembly, and electronic structure of 2D arrays of [5,5]-C90 fullertube molecules on two different noble metal surfaces, Ag(111) and Au(111). The results demonstrate that the shape of the molecular orbitals of the adsorbed fullertubes corresponds closely to those expected for isolated species on the grounds of density functional theory calculations. Moreover, a comparison between the electronic density profiles in the bands of the extended [5,5]-CNT and in the molecules reveals that some of the frontier orbitals of the fullertube molecules can be described as the result of the quantum confinement imposed by the hemifullerene caps to the delocalized band states in the extended CNT. The results thus provide a conceptual framework for the rational design of custom fullertube molecules and can potentially become a cornerstone in the understanding of these new carbon nanoforms.
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This study focuses on the fabrication of nanocomposite thermoelectric devices by blending either a naphthalene-diimide (NDI)-based conjugated polymer (NDI-T1 or NDI-T2), or an isoindigo (IID)-based conjugated polymer (IID-T2), with single-walled carbon nanotubes (SWCNTs). This is followed by sequential process doping method with the small molecule 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI) to provide the nanocomposite with n-type thermoelectric properties. Experiments in which the concentrations of the N-DMBI dopant are varied demonstrate the successful conversion of all three polymer/SWCNT nanocomposites from p-type to n-type behavior. Comprehensive spectroscopic, microstructural, and morphological analyses of the pristine polymers and the various N-DMBI-doped polymer/SWCNT nanocomposites are performed in order to gain insights into the effects of various interactions between the polymers and SWCNTs on the doping outcomes. Among the obtained nanocomposites, the NDI-T1/SWCNT exhibits the highest n-type Seebeck coefficient and power factor of -57.7 µV K-1 and 240.6 µW m-1 K-2 , respectively. However, because the undoped NDI-T2/SWCNT exhibits a slightly higher p-type performance, an integral p-n thermoelectric generator is fabricated using the doped and undoped NDI-T2/SWCNT nanocomposite. This device is shown to provide an output power of 27.2 nW at a temperature difference of 20 K.
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The high-performance and sustainable electrocatalysts toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for rechargeable Zn-air batteries (ZABs). In this paper, a natural all-components bamboo is provided as the carbon source, and melamine and cobalt chloride are provided as the nitrogen and cobalt sources, respectively. As a result, the unique helical carbon nanotubes (HCNTs) encapsulated cobalt nanoparticles are prepared, which are acted as ORR/OER electrocatalysts to improve ZABs performance. The resultant HCNTs contribute to high ORR/OER activities via exposing more CoâN sites, providing excellent electron conductivity, and facilitating mass transfer of the reactant. The HCNTs assembled rechargeable liquid ZABs showed a maximum output power density of 226 mW cm-2 and a low voltage gap of 0.85 V for 330 h cycles. The flexible all-solid-state ZABs achieved the maximum power density with 59.4 mW cm-2 and charge-discharge cycles over 25 h. The density functional theory (DFT) calculations reveal that the increase of CoâN at HCNTs effectively regulates the electronic structure of Co, optimizing the binding affinity of oxygen intermediates and resulting in the low ORR/OER overpotentials. This work paves the way for transforming renewable bamboo biomass into versatile electrocatalysts, which boosts the development of next-generation energy storage and conversion devices.
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Inert inorganic nano-building blocks, such as carbon nanotubes (CNTs) and boron nitride (BN) nanosheets, possess excellent physicochemical properties. However, it remains challenging to build aerogels with these inert nanomaterials unless they are chemically modified or compounded with petrochemical polymers, which affects their intrinsic properties and is usually not environmentally friendly. Here, a universal biomacromolecule-enabled assembly strategy is proposed to construct aerogels with 90 wt% ultrahigh inorganic loading. The super-high inorganic content is beneficial for exploiting the inherent properties of inert nanomaterials in multifunctional applications. Taking chitosan-CNTs aerogel as a proof-of-concept demonstration, it delivers sensitive pressure response as a pressure sensor, an ultrahigh sunlight absorption (94.5%) raising temperature under light (from 25 to 71 °C within 1 min) for clean-up of crude oil spills, and superior electromagnetic interference shielding performance of up to 68.9 dB. This strategy paves the way for the multifunctional application of inert nanomaterials by constructing aerogels with ultrahigh inorganic loading.
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In this study, lightweight, flexible, and environmentally robust dual-nanofibrous membranes made of carbon nanotube (CNT) and polytetrafluoroethylene (PTFE) are fabricated using a novel shear-induced in situ fibrillation method for electromagnetic interference (EMI) shielding. The unique spiderweb-like network, constructed from fine CNTs and PTFE fibrils, integrates the inherent characteristics of these two materials to achieve high conductivity, superhydrophobicity, and extraordinary chemical resistance. The dual-nanofibrous membranes demonstrate a high EMI shielding effectiveness (SE) of 25.7-42.2 dB at a thickness range of 100-520 µm and the normalized surface-specific SE can reach up to 9931.1 dB·cm2·g-1, while maintaining reliability even under extremely harsh conditions. In addition, distinct electrothermal and photothermal conversion properties can be achieved easily. Under the stimulation of a modest electrical voltage (5 V) and light power density (400 mW·cm-2), the surface temperatures of the CNT/PTFE membranes can reach up to 135.1 and 147.8 °C, respectively. Moreover, the CNT/PTFE membranes exhibit swift, stable, and highly efficient thermal conversion capabilities, endowing them with self-heating and de-icing performance. These versatile, flexible, and breathable membranes, coupled with their efficient and facile fabrication process, showcase tremendous application potential in aerospace, the Internet of Things, and the fabrication of wearable electronic equipment for extreme environments.
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Graphene nanoribbons (GNRs) are promising in nanoelectronics for their quasi-1D structures with tunable bandgaps. The methods for controllable fabrication of high-quality GNRs are still limited. Here a way to generate sub-5-nm GNRs by annealing single-walled carbon nanotubes (SWCNTs) on Cu(111) is demonstrated. The structural evolution process is characterized by low-temperature scanning tunneling microscopy. Substrate-dependent measurements on Au(111) and Ru(0001) reveal that the intermediate strong SWCNT-surface interaction plays a pivotal role in the formation of GNRs.
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Covalent organic frameworks (COFs) with precisely controllable structures and highly ordered porosity possess great potential as electrocatalysts for hydrogen evolution reaction (HER). However, the catalytic performance of pristine COFs is limited by the poor active sites and low electron transfer. Herein, to address these issues, the conductive carbon nanotubes (CNTs) are coated by a defined structure RuBpy(H2 O)(OH)Cl2 in bipyridine-based COF (TpBpy). And this composite with single site Ru incorporated can be used as HER electrocatalyst in alkaline conditions. A series of crucial issues are carefully discussed through experiments and density functional theory (DFT) calculations, such as the coordination structure of the atomically dispersion Ru ions, the catalytic mechanism of the embedded catalytic site, and the effect of COF and CNTs on the electrocatalytic properties. According to DFT calculations, the embedded single sites Ru act as catalytic sites for H2 generation. Benefitting from increasing the catalyst conductivity and the charge transfer, the as-prepared c-CNT-0.68@TpBpy-Ru shows an excellent HER overpotential of 112 mV at 10 mA cm-2 under alkaline conditions as well as an excellent durability up to 12 h, which is superior to that of most of the reported COFs electrocatalysts in alkaline solution.