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In this work, ACs were originated from two different bio-waste sources of Date and Jujube seeds (DS and JS). The influence of the precursor type as well as KOH chemical activator ratio on the structural properties and CO2 adsorption performances of synthesized ACs were assessed. Impact of pre-treatment of raw material via functionalization with urea on the performance of prepared adsorbents was also evaluated. Functionalized DS-based AC possessed the highest surface area and largest micropore volume equal to 864 m2/g and 0.33 cm3/g, respectively. CO2 adsorption behavior of ACs was experimentally evaluated via TGA at different adsorption temperatures of 25 and 50 °C and CO2 concentrations of 10 and 90 vol% under atmospheric pressure. Based on the TGA results, functionalized and non-functionalized DS-prepared ACs with KOH: biochar weight ratio of 2:1, demonstrated great CO2 capture capacity up to 1.3 and 1.2 mmol/g, respectively under realistic condition of 10 vol% CO2 and 25 °C. The urea-nitrogenation and KOH-activation as economical and simple approaches sensitively assisted preparation of a novel and promising N-doped porous AC from bio-waste resources which can be exploited for superior CO2 capture applications.

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Catalytic performance decline is a general issue when shaping fine powder into macroscale catalysts (e.g., beads, fiber, pellets). To address this challenge, a phenolic resin-assisted strategy was proposed to prepare porous Co/N carbon beads (ZACBs) at millimeter scale via the phase inversion method followed by confined pyrolysis. Specially, p-aminophenol-formaldehyde (AF) resin-coated zeolitic imidazolate framework (ZIF-67) nanoparticles were introduced to polyacrylonitrile (PAN) solution before pyrolysis. The thermosetting of the coated AF improved the interface compatibility between the ZIF-67 and PAN matrix, inhibiting the shrinkage of ZIF-67 particles, thus significantly improving the void structure of ZIF-67 and the dispersion of active species. The obtained ZACBs exhibited a 99.9% removal rate of tetracycline (TC) within 120 min, with a rate constant of 0.069 min-1 (2.3 times of ZIF-67/PAN carbon beads). The quenching experiments and electron paramagnetic resonance (EPR) tests showed that radicals dominated the reaction. This work provides new insight into the fabrication of high-performance MOF catalysts with outstanding recycling properties, which may promote the use of MOF powder in more practical applications.

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It is crucial to employ an integrated catalyst to avoid the complications of the recovery process. This work reports the fabrication of porous carbon@ionic liquid (PC@IL) composites with readily accessible active ion sites, achieved by confining cross-linked ionic liquid (IL) within the channels of porous carbon (PC). The incorporation of porous carbon not only confines the IL within its framework, creating microsites for CO2 adsorption and conversion, but also simplifies catalyst recovery. The results indicate that PC@IL composites exhibit excellent cycloaddition activity towards CO2 in a co-catalyst- and solvent-free environment. Notably, PC@IL(C)-24 demonstrates remarkable catalytic performance across various epoxides under 1 bar of CO2, with yields above 90 % at 90 °C for 12 h, and achieving a remarkable styrene carbonate yield of up to 92.8 % under a CO2 pressure of 1 bar (at 100 °C for 12 h). Control experiments confirm that the confinement effect exerted by N,S co-doped carbon on cross-linked IL plays a pivotal role in enhancing both stability and activity of PC@IL composites, thereby providing novel insights for designing functionalized porous carbon catalysts for CO2 cycloaddition conversion.

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Designing and developing efficient, low-cost bi-functional oxygen electrocatalysts is essential for effective zinc-air batteries. In this study, we propose a copper dual-doping strategy, which involves doping both porous carbon nanofibers (PCNFs) and nickel fluoride nanoparticles with copper alone, successfully preparing copper-doped nickel fluoride (NiF2) nanorods and copper nanoparticles co-modified PCNFs (Cu@NiF2/Cu-PCNFs) as an efficient bi-functional oxygen electrocatalyst. When copper is doped into the PCNFs in the form of metallic nanoparticles, the doped elemental copper can improve the electronic conductivity of composite materials to accelerate electron conduction. Meanwhile, the copper doping for NiF2 can significantly promote the transformation of nickel fluoride nanoparticles into nanorod structures, thus increasing the electrochemical active surface area and enhancing mass diffusion. The Cu-doped NiF2 nanorods also possess an optimized electronic structure, including a more negative d-band center, smaller bandgap width and lower reaction energy barrier. Under the synergistic effect of these advantages, the obtained Cu@NiF2/Cu-PCNFs exhibit outstanding bi-functional catalytic performances, with a low overpotential of 0.68 V and a peak power density of 222 mW cm-2 in zinc-air batteries (ZABs) and stable cycling for 800 h. This work proposes a one-step way based on the dual-doping strategy, providing important guidance for designing and developing efficient catalysts with well-designed architectures for high-performance ZABs.

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Utilization of three-dimensional biomass-derived porous carbons can effectively address issues of easy leakage, low thermal conductivity, and weak photothermal conversion of phase change materials (PCMs). This enables the production of high-performance composites for solar-induced energy collection, conversion, and storage. In this study, hierarchical lignin-derived porous carbon (HLPC), microporous lignin-derived porous carbon (MILPC) and mesoporous lignin-derived porous carbon (MELPC) were prepared through high-temperature in-situ activation using lignosulphonate (LS) as a carbon precursor and CaCO3, KOH and ZnCO3 as activators. Carbon-based PCM composites with high performance were obtained by encapsulating paraffin wax (PW) in porous carbon supports. Results demonstrated that PW/HLPC exhibited comprehensive performance superior to other tested PW composites owing to its higher specific surface area (2,358 m2/g), larger pore volume (1.1 cm3/g) and well-interconnected framework structure. Additionally, PW/HLPC displayed relatively high latent heat (123.4 kJ/kg), photothermal conversion and storage efficiency (95 %), and photoelectric conversion performance (174.5 mV). Moreover, PW/HLPC also showed better leak-proof properties at 90 °C. The cycling stability and photothermal conversion performance of PW/HLPC were superior to those of the selected crude biochar-based PW composites. This study highlights the advantages of the prepared PW/HLPC for both the high-value utilization of lignin and its practical applications in solar-induced energy harvest, conversion, and storage.

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Manure biogas residue has attracted increasing attention in waste recycling but faces substantial challenges because of its low carbon content, high ash content, and high heavy metal content. A novel sequential carbonization approach was proposed for recycling biogas residue; this approach consisted of pre-pyrolysis, activation with Ca(OH)2, and then activation with KOH. Pig manure-derived biogas residue was upcycled into engineered biochar (EB) with a high yield (26 %) and showed excellent performance in removing a typical plasticizer, diethyl phthalate (DEP). The proportion of carbon content greatly increased from 18 % (biogas residue) to 67 % (EB); however, the ash content decreased from 50 % (biogas residue) to 24 % (EB). The concentration of heavy metals decreased, and Zn had the largest decrease from 713 mg kg-1 to 61 mg kg-1 (p < 0.001). The sorption of DEP onto EB was rapid and reached equilibrium within 20 h. The developed specific surface area of EB was 1247 m2/g and provided abundant sorption sites for DEP; additionally, the sorption quantity reached 309 mg/g. The sorption capacity was dominated by surface adsorption. The oxygen-containing functional groups, graphene structure, porous structure, and hydrophobicity of EB contributed to the pore filling, hydrogen bonding, π-π stacking, and partitioning processes. Furthermore, the EB showed excellent practical application potential and great cycling stability. A sequential carbonization strategy was proposed to upcycle manure biogas residue into the EB for DEP removal; moreover, this strategy can aid in the attainment of environmental sustainability, including sustainable waste management and environmental pollution mitigation.

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Introduction: In the fragrance and perfume industry, the controlled release of fragrances are crucial factors that contribute to consumer appeal and product quality enhancement. In this study, various aromatic active substances were extracted from dandelion root (DR), which was subsequently calcined to produce high-performance porous biochar material. Methods: The dandelion root biochar (DRB) material was identified as promising adsorbents for the controlled release of fragrances. Furfuryl alcohol was chosen as the model fragrance for inclusion and controlled release studies. Results and discussion: The DRB exhibited a substantial specific surface area of 991.89 m2/g, facilitating efficient storage and controlled release capabilities. Additionally, the DRB's high stability and porous nature facilitated rapid collection and efficient recyclability. This research significantly contributes to the development of a sustainable, zero-waste multistage utilization strategy for dandelion roots, indicating a potential applications in the food flavoring industry and environmental conservations.

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Due to excellent flexibility and dispersibility, 2D graphene oxide (GO) is regarded as one of the prospective materials for preparing self-supporting electrode material. Nevertheless, the self-stacking characteristic of GO significantly restricts the ion transmission and accessibility in GO-based electrodes, especially in the direction perpendicular to the electrode surface. Herein, a novel composite film was fabricated from GO and 3D porous carbon (PC) through vacuum filtration combined with thermal reduction strategy. The combination of GO and PC not only avoids the self-stacking of GO, but also exposes more active sites for ions in the inner. A massive released nitrogen and oxygen-containing gases during the thermal reduction endows the reduced graphene oxide (RGO) with abundant porous and CC, which contributes to the energy storage in the direction perpendicular to the electrode surface. Besides, the high specific surface area of the prepared composite film is favorable for the storage and release of charge on the electrode surface. Benefiting from the above characteristics, the electrode assembled by the as-prepared film exhibits ultrahigh areal/volumetric specific capacitance in supercapacitor and ZIHCs (Zinc ion hybrid capacitors). This work provides a promising approach for the development of advanced self-supported electrode materials with desirable electrochemical properties.

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Electrochemical CO2 conversion into formate by intermittent renewable electricity, presents a captivating prospect for both the storage of renewable electrical energy and the utilization of emitted CO2. Typically, Cu-based catalysts in CO2 reduction reactions favor the production of CO and other by-products. However, we have shifted this selectivity by incorporating B, N co-doped carbon (BNC) in the fabrication of Cu clusters. These Cu clusters are regulated with B, N atoms in a porous carbon matrix (Cu/BN-C), and Zn2+ ions were added to achieve Cu clusters with the diameter size of ∼1.0 nm. The obtained Cu/BN-C possesses a significantly improved catalytic performance in CO2 reduction to formate with a Faradaic efficiency (FE) of up to 70 % and partial current density (jformate) surpassing 20.8 mA cm-2 at -1.0 V vs RHE. The high FE and jformate are maintained over a 12-hour. The overall catalytic performance of Cu/BN-C outperforms those of the other investigated catalysts. Based on the density functional theory (DFT) calculation, the exceptional catalytic behavior is attributed to the synergistic effect between Cu clusters and N, B atoms by modulating the electronic structure and enhancing the charge transfer properties, which promoted a preferential adsorption of HCOO* over COOH*, favoring formate formation.

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Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are pervasive contaminants in aquatic environments. They are characterized by persistence, toxicity, bioaccumulation, and long-range transport, significantly threatening human health. The development of sensitive methods for nitro-PAH analysis in environmental samples is in great need. This study developed a novel carbonaceous SPME coating derived from metal-organic framework (MOF), namely a spherical assembly consisting of carbon nanorods with hierarchical porosity (HP-MOF-C), for the extraction and determination of nitro-PAHs in waters. The HP-MOF-C coated fiber demonstrated superior nitro-PAH extraction efficiencies, with enrichment factors 2∼70 times higher than commercial fibers. This enhancement was due to the strong hydrophobic, π-π electron coupling/stacking, and π-π electron donor-acceptor interactions between the carbonaceous framework of HP-MOF-C and the nitro-PAHs. Moreover, the unique hierarchical porous structure of HP-MOF-C accelerated the diffusion of nitro-PAHs, further facilitating their enrichment. The fiber also exhibited good thermal stability, remarkable chemical stabilities against common acid, base, and polar/non-polar solvents, and long service life (> 150 SPME cycles). The nitro-PAH determination method based on HP-MOF-C coating yielded wide linear ranges, low detection limits (0.4∼5.0 ng L-1), satisfactory repeatability and reproducibility, and good recoveries in real water samples. The proposed method was considered to be green according to the Analytical GREEnness assessment. The present study not only offers an efficient SPME coating for the enrichment of nitro-PAHs, but also provides insights into the design of porous coating materials.

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Nanoporous metals, fabricated via dealloying, offer versatile applications but are typically limited to unimodal porous structures, which hinders the integration of conflicting pore-size-dependent properties. A strategy is presented that exploits the homologous temperature (TH)-dependent scaling of feature sizes to generate hierarchical porous structures through multistep dealloying at varied TH levels, adjusted by altering dealloying temperatures or the material melting points. This technique facilitates the creation of monolithic architectures of bimodal porous nickel and trimodal porous carbon, each characterized by well-defined, self-similar bicontinuous porosities across distinct length scales. These materials merge extensive surface area with efficient mass transport, showing improved current delivery and rate capabilities as electrodes in electrocatalytic hydrogen production and electrochemical supercapacitors. These results highlight TH as a unifying parameter for precisely tailoring feature sizes of dealloyed nanoporous materials, opening avenues for developing materials with hierarchical structures that enable novel functionalities.

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"White pollution" is regarded as one of the most serious problems in the natural environment. Thus greener recycling of plastic waste has attracted significant efforts in recent research. In this study, to kill two birds with one stone, a series of porous carbon nanobulks (PCNs) were synthesized from the pyrolysis of plastic waste (polyethylene terephthalate, PET) and inorganic salt (including NaHCO3, Na2CO3, NaCl, and ZnCl2) for sulfadiazine (SDZ) degradation via peroxymonosulfate (PMS) activation. PCNs-1 (co-calcinated from PET and NaHCO3) with a large number of CO and COOH active sites, which were in favor of PMS activation and electron transfer during the catalytic process, had shown the best catalytic activity for SDZ degradation. Significantly, PCNs-1 exhibited excellent universality, adaptability, and stability. The degradation pathways of SDZ were identified by the total content of organic carbon (TOC), and high-resolution mass spectrometry (HR-MS). The possible mechanism was proposed according to the anion effect, quenching experiments, electron paramagnetic resonance (EPR), and electrochemical analysis, indicating that radical (OH, SO4-, O2-) and non-radical (1O2 and e) species were the catalytically active species for SDZ decomposition in the PCNs-1/PMS system. Moreover, Ecological Structure-Activity-Relationship Model (ECOSAR) program and wheat seed cultivation experiments clearly demonstrated that the biotoxicity of SDZ could be effectively reduced by the PCNs-1/PMS system. Here we successfully upcycled plastic waste into high-value materials for efficient water decontamination.

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The rational design of MoS2/carbon composites have been widely used to improve the lithium storage capability. However, their deep applications remain a big challenge due to the slow electrochemical reaction kinetics of MoS2 and weak bonding between MoS2 and carbon substrates. In this work, anthracite-derived porous carbon (APC) is sequential coated by TiO2 nanoparticles and MoS2 nanosheets via a chemical activation and two-step hydrothermal method, forming the unique APC@TiO2@MoS2 ternary composite. The dynamic analysis, in-situ electrochemical impedance spectroscopy as well as theoretical calculation together demonstrate that this innovative design effectively improves the ion/electron transport behavior and alleviates the large volume expansion during cycles. Furthermore, the introduction of middle TiO2 layer in the composite significantly strengthens the mechanical stability of the entire electrode. As expected, the as-prepared APC@TiO2@MoS2 anode displays a high lithium storage capacity with a reversible capacity of 655.8 mAh g-1 after 150 cycles at 200 mA g-1, and robust cycle stability. Impressively, even at a high current density of 2 A g-1, the electrode maintains a superior reversible capacity of 597.7 mAh g-1 after 1100 cycles. This design highlights a feasibility for the development of low-cost anthracite-derived porous carbon-based electrodes.

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Intensifying the synergy between confined carbon nanopores and ionic liquids (ILs) and a deep comprehension of the ion behavior is required for enhancing the capacitive storage performance. Despite many theoretical insights on the storage mechanism, experimental verification has remained lacking due to the intricate nature of pore texture. Here, a compressed micropore-rich carbon framework (CMCF) with tailored monolayer and bilayer confinement pores is synthesized, which exhibits a compatible ionophilic interface to accommodate the IL [EMIM][BF4]. By deploying in situ Raman spectroscopy, in situ Fourier-transform infrared spectroscopy, and solid-state nuclear magnetic resonance, the effect of the pore textures on ions storage behaviors is elucidated. A voltage-induced ion gradient filling process in these ionophilic pores is proposed, in which ion exchange and co-ion desorption dominate the charge storage process. Moreover, it is established that the monolayer confinement of ions enhances the capacity, and bilayer confinement facilitates the charging dynamics. This work may guide the design of nanoconfinement carbon for high-energy-density supercapacitors and deepen the understanding of the charge storage mechanism in ionophilic pores.

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Aqueous zinc-ion batteries (AZIBs) are expected to be a promising large-scale energy storage system owing to their intrinsic safety and low cost. Nevertheless, the development of AZIBs is still plagued by the design and fabrication of advanced cathode materials. Herein, the amorphous vanadium pentoxide and hollow porous carbon spheres (AVO-HPCS) hybrid is elaborately designed as AZIBs cathode material by integrating vacuum drying and annealing strategy. Amorphous vanadium pentoxide provides abundant active sites and isotropic ion diffusion channels. Meanwhile, the hollow porous carbon sphere not only provides a stable conductive network, but also enhances the stability during charging/discharging process. Consequently, the AVO-HPCS exhibits a capacity of 474 mAh/g at 0.5 A/g and long-term cycle stability. Moreover, the corresponding reversible insertion/extraction mechanism is elucidated by ex-situ X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Furthermore, the flexible pouch battery with AVO-HPCS cathode shows high comprehensive performance. Hence, this work provides insights into the development of advanced amorphous cathode materials for AZIBs.

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The unique design of the core-shell heterostructure is significant for obtaining electrode materials with excellent electrochemical properties. In this paper, porous carbon nanofibers (NPC@PPZ) embedded with N-doped porous carbon nanoparticles are used to construct flexible electrodes (NPC@PPZ@Bi2O3). Zeolite imidazole skeleton (ZIF)-8 and poly(methyl methacrylate) (PMMA) derived porous carbon fibers and Bi2O3 nanosheets, were utilized as the porous core and multilayer shell, respectively. The unique core and shell result in abundant pores and channels for fast ion transport and storage, high specific surface area, and additional electroactive sites. This perfect structural design enables the NPC@PPZ@Bi2O3 composite electrode to have excellent electrochemical performance. The results show that this electrode can obtain a high specific capacitance of 697 F g-1 at a current density of 1 A g-1 and a stable cycling performance at a high current density of 5 A g-1. The strategy developed in this study provides a new approach for the design and fabrication of flexible supercapacitors by electrostatic spinning combined with hierarchical porous structures.

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How to address the destruction of the porous structure caused by elemental doping in biochar derived from biomass is still challenging. In this work, the in-situ nitrogen-doped porous carbons (ABPCs) were synthesized for supercapacitor electrode applications through pre-carbonization and activation processes using nitrogen-rich pigskin and broccoli. Detailed characterization of ABPCs revealed that the best simple ABPC-4 exhibited a super high specific surface area (3030.2-3147.0 m2 g-1) and plentiful nitrogen (1.35-2.38 wt%) and oxygen content (10.08-15.35 wt%), which provided more active sites and improved the conductivity and electrochemical activity of the material. Remarkably, ABPC-4 showed an outstanding specific capacitance of 473.03 F g-1 at 1 A g-1. After 10,000 cycles, its capacitance retention decreased by only 4.92% at a current density of 10 A g-1 in 6 M KOH. The assembled symmetric supercapacitor ABPC-4//ABPC-4 achieved a power density of 161.85 W kg-1 at the maximum energy density of 17.51 Wh kg-1 and maintained an energy density of 6.71 Wh kg-1 when the power density increased to 3221.13 W kg-1. This study provides a mixed doping approach to achieve multi-element doping, offering a promising way to apply supercapacitors using mixed biomass.

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Layered double hydroxides (LDHs) have attracted significant attention due to their compositional and structural flexibility. However, it is challenging but meaningful to design and fabricate hierarchical mixed-dimensional LDHs with synergistic effects to increase the electrical conductivity of LDHs and promote the intrinsic activity. Herein, 3D hollow NiCo-LDH nanocages decorated porous biochar (3D NiCo-LDH/PBC) has been synthesized by using ZIF-67 as precursor, which was utilized for constructing electrochemical sensing platform to realize simultaneous determination of Cu2+ and Hg2+. The 3D NiCo-LDH/PBC possessed the characteristics of hollow material and three-dimensional porous material, revealing a larger surface area, more exposed active sites, and faster electron transfer, which is beneficial to enhancing its electrochemical performance. Consequently, the developed sensor displayed good performance for simultaneously detecting Cu2+ and Hg2+ with ultra-low limit of detection (LOD) of 0.03 µg L-1 and 0.03 µg L-1, respectively. The proposed sensor also demonstrated excellent stability, repeatability and reproducibility. Furthermore, the sensor can be successfully used for the electrochemical analysis of Cu2+ and Hg2+ in lake water sample with satisfactory recovery, which is of great feasibility for practical application.

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The utilization efficiency of palladium-based catalysts has sharply increased in many catalytic reactions. However, numerous studies have shown that preparing alloys of palladium with other metals has superior catalytic activity than pure palladium. Additionally, hierarchical porous carbon has gradually developed into an excellent carrier for loading bimetallic nanoparticles. In this study, we firstly pyrolyzed chitosan, sodium bicarbonate and nickel nitrate to create highly dispersed porous carbon materials doped with Ni NPs. The carbon materials were then grafted with silane coupling agent (APTMS) to afford them with amino groups on the surface. Taking advantage of the fact that Pd2+ can react with Ni in spontaneous reduction reaction, Pd was deposited on the surface of Ni to produce PdNi bimetallic-loaded carbon catalysts containing amino groups. The resulting catalysts were examined by a series of characterizations and were found to have a hierarchically porous structure and large specific surface area, which increased the number of active sites of the catalysts. In comparison to other Pd catalysts, the PdNi/HPCS-NH2 catalysts displayed remarkable activity for Suzuki coupling reaction and hydro reduction of nitroaromatics, which exhibited a high turnover frequency value (TOF) of 37,857 h-1 and 680.9 h-1, respectively. These were mainly due to the high dispersion of the PdNi NPs and the superior structure of the carriers. Moreover, the catalysts did not experience a significant decline in activity after ten cycles. All in all, this investigation has created a new approach for the fabrication of novel carriers for Pd catalysts, which is in line with the concept of green chemistry and recyclable.

Asunto(s)

RESUMEN

An electrochemical platform for signal amplification probing chloride ions (Cl-) is constructed by the composite integrating core-shell structured nitrogen-doped porous carbon@Ag-based metal-organic frameworks (NC@Ag-MOF) with polypyrrole (PPy). It is based on the signal of solid-state AgCl derived from Ag-MOF, since both NC and PPy have good electrical conductivity and promote the electron transport capacity of solid-state AgCl. NC@Ag-MOF was firstly synthesized with NC as the scaffold and then, PPy was anchored on NC@Ag-MOF by chemical polymerization. The composite NC@Ag-MOF-PPy was utilized to modify the electrode, which exhibited a higher peak current and lower peak potential during Ag oxidation compared with those of Ag-MOF and NC@Ag-MOF-modified electrodes. More importantly, in the coexistence of chloride (Cl-) ions in solution, the NC@Ag-MOF-PPy-modified electrode displayed a fairly stable and sharp peak of solid-state AgCl with the peak potentials gradually approaching zero, which might effectively overcome the background interference caused by electroactive substances. The oxidation peak currents of solid-state AgCl increased linearly with the concentration of  Cl- ions in a broad range of 0.15 µM-40 mM and 40-250 mM, with detection limits of 0.10 µM and 40 mM, respectively. The practical applicability for Cl- ions determination was demonstrated using human serum and urine samples. The results suggest that NC@Ag-MOF-PPy composite could be a promising candidate for the construction of the electrochemical sensor.