Table of contents

Volume 34

Number 24, 11 June 2023

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Topical Review

242001

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Carbon nanotubes (CNTs) are nominated to be the successor of several semiconductors and metals due to their unique physical and chemical properties. It has been concerning that the anisotropic and low controllability of CNTs impedes their adoption in commercial applications. Dielectrophoresis (DEP) is known as the electrokinetics motion of polarizable nanoparticles under the influence of nonuniform electric fields. The uniqueness of this phenomenon allows DEP to be employed as a novel method to align, assemble, separate, and manipulate CNTs suspended in liquid mediums. This article begins with a brief overview of CNT structure and production, with the emphasize on their electrical properties and response to electric fields. The DEP phenomenon as a CNT alignment method is demonstrated and graphically discussed, along with its theory, procedure, and parameters. We also discussed the side forces that arise in DEP systems and how they negatively or positively affect the CNT alignment. The article concludes with a brief review of CNT-based devices fabricated using DEP, as well as the method's limitations and future prospects.

Papers

Biology and medicine

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In order to prevent drugs from being captured and degraded by the acidic environment of organelles, such as lysosomes, after entering cells, this study designed and synthesized a novel carrier amphiphilic polypeptide (DGRHHHLLLAAAA), designated P13, for use as a tumor-targeting drug delivery vehicle. The P13 peptide was synthesized by the solid phase synthesis method, and its self-assembly behavior and drug-loading capacity in aqueous solution were studied and characterized in vitro. Doxorubicin (DOX) was loaded by dialysis method, and P13 and DOX were mixed at a mass ratio of 6:1 to form regular rounded globules. The acid–base buffering capacity of P13 was investigated determined by acid–base titration. The results revealed that P13 had excellent acid–base buffering capacity, a critical micelle concentration value of about 0.000 21 g l−1, and the particle size of P13-Dox nanospheres was 167 nm. The drug encapsulation efficiency and drug loading capacity of micelles were 20.40 ± 1.21% and 21.25 ± 2.79%, respectively. At the concentration of 50 μg ml−1 of P13-DOX , the inhibition rate was 73.35%. The results of the in vivo antitumor activity assay in mice showed that P13-DOX also exhibited excellent inhibitory effect on tumor growth, compared with the tumor weight of 1.1 g in the control group, the tumor weight in the P13-DOX-treated group was only 0.26 g. Additionally, the results of hematoxylin and eosin staining of the organs showed that P13-DOX had no damaging effect on normal tissues. The novel amphiphilic peptide P13 with proton sponge effect designed and prepared in this study is expected to be a promising tumor-targeting drug carrier with excellent application potential.

Electronics and photonics

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Efficient manipulation of the emission direction of a chiral nanoscale light source is significant for information transmission and on-chip information processing. Here, we propose a scheme to control the directionality of nanoscale chiral light sources based on gap plasmons. The gap plasmon mode formed by a gold nanorod and a silver nanowire realizes the highly directional emission of chiral light sources. Based on the optical spin-locked light propagation, the hybrid structure enables the directional coupling of chiral emission to achieve a contrast ratio of 99.5%. The emission direction can be manipulated by tailoring the configuration of the structure, such as the positions, aspect ratios, and orientation of the nanorod. Besides, a great local field enhancement exists for highly enhanced emission rates within the nanogap. This chiral nanoscale light source manipulation scheme provides a way for chiral valleytronics and integrated photonics.

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Focus on Amorphous and Nano-Crystalline Semiconductors

Low-dimensional tin selenide nanoribbons (SnSe NRs) show a wide range of applications in optoelectronics fields such as optical switches, photodetectors, and photovoltaic devices due to the suitable band gap, strong light–matter interaction, and high carrier mobility. However, it is still challenging to grow high-quality SnSe NRs for high-performance photodetectors so far. In this work, we successfully synthesized high-quality p-type SnSe NRs by chemical vapor deposition and then fabricated near-infrared photodetectors. The SnSe NR photodetectors show a high responsivity of 376.71 A W−1, external quantum efficiency of 5.65 × 104%, and detectivity of 8.66 × 1011 Jones. In addition, the devices show a fast response time with rise and fall time of up to 43 μs and 57 μs, respectively. Furthermore, the spatially resolved scanning photocurrent mapping shows very strong photocurrent at the metal-semiconductor contact regions, as well as fast generation-recombination photocurrent signals. This work demonstrated that p-type SnSe NRs are promising material candidates for broad-spectrum and fast-response optoelectronic devices.

245203
The following article is Open access

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Conductive bridge random access memory devices such as Cu/SiO2/W are promising candidates for applications in neuromorphic computing due to their fast, low-voltage switching, multiple-conductance states, scalability, low off-current, and full compatibility with advanced Si CMOS technologies. The conductance states, which can be quantized, originate from the formation of a Cu filament in the SiO2 electrolyte due to cation-migration-based electrochemical processes. A major challenge related to the filamentary nature is the strong variability of the voltage required to switch the device to its conducting state. Here, based on a statistical analysis of more than hundred fifty Cu/SiO2/W devices, we point to the key role of the activation energy distribution for copper ion diffusion in the amorphous SiO2. The cycle-to-cycle variability is modeled well when considering the theoretical energy landscape for Cu diffusion paths to grow the filament. Perspectives of this work point to developing strategies to narrow the distribution of activation energies in amorphous SiO2.

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Gallium nitride (GaN) is one of the most promising materials for high-frequency devices owing to its prominent material properties. We report on the fabrication and study of a series of Schottky diodes in the ground-signal-ground topology based on individual GaN nanowires. The electrical characterization of IV curves demonstrated relatively high ideality factor value (about 6–9) in comparison to the planar Au/GaN diodes that can be attributed to the nanowire geometry. The effective barrier height in the studied structures was defined in the range of 0.25–0.4 eV. The small-signal frequency analysis was employed to study the dependency of the scattering parameters in the broad range from 0.1 to 40 GHz. The approximation fitting of the experimental data indicated the record high cutoff frequency of about 165.8 GHz.

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Various spectral bands provide different types of information, and information enhancement could be achieved by selective fusion of different spectral bands. The fused solar-blind Ultraviolet (UV)/Visible (VIS) bi-spectral sensing and imaging can provide the precise location of UV targets in virtue of VIS background, which has been increasingly promoted. However, most reported UV/VIS bi-spectral photodetectors (PDs) only have one single channel towards a broadband spectrum of both UV and VIS light, which cannot distinguish two kinds of signals, hindering the image fusion of bi-spectral signals. This work demonstrates the solar-blind UV/VIS bi-spectral PD based on vertically stacking perovskite of MAPbI3 and ternary oxide of ZnGa2O4 with independent and distinct response toward solar-blind UV and VIS light in a single pixel. The PD exhibits excellent sensing properties with an Ion/Ioff ratio of >107 and 102, detectivity of >1010 and 108 Jones, and response decay time of 90 μs and 16 ms for VIS and UV channels, respectively. The successful fusion of VIS and UV images suggests that our bi-spectral PD can be applied in the accurate identification of corona discharge and fire detection.

Energy at the nanoscale

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A particular bird's nest-like pseudo-boehmite (PB) composed of cohesive nanostrips was prepared by a novel and facile approach based on the reaction of Al–Ga–In–Sn alloy and water, together with ammonium carbonate. The PB possesses a large specific surface area (465.2 m2 g−1), pore volume (1.0 cm3 g−1), and pore diameter (8.7 nm). Subsequently, it was utilized as a precursor to form the TiO2/γ-Al2O3 nanocomposite for tetracycline hydrochloride removal. The removal efficiency can reach above 90% at TiO2:PB = 1:1.5 under the Sunlight irradiation simulated by a LED lamp. Our results indicate that the nest-like PB is a promising carrier precursor for efficient nanocomposite catalysts.

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As an alternative anode to graphene, molybdenum disulfide (MoS2) has attracted much attention due to its layered structure and high specific capacity. Moreover, MoS2 can be synthesized by hydrothermal method with low cost and the size of its layer spacing can be controlled. In this work, the results of experiment and calculation proved that the presence of intercalated Mo atoms, leading to the expansion of MoS2 layer spacing and weakening of Mo–S bonding. For the electrochemical properties, the presence of intercalated Mo atoms causes the lower reduction potentials for the Li+ intercalation and Li2S formation. In addition, the effective reduction of diffusion resistance and charge transfer resistance in Mo1+xS2 leads to the acquisition of high specific capacity for battery applications.

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Multi-walled carbon nanotubes (MWCNTs) with one-dimensional nanostructure are an ideal support for oxygen reduction reaction (ORR) catalysts thanks to their intrinsic outstanding electrical conductivity and high specific surface area. Iron and nitrogen doping could alter the local electronic structure and therefore enhance the ORR activity of MWCNTs, but the preparation process always includes complicated growth conditions and post-treatment. Herein, an iron and nitrogen co-modified multi-walled carbon nanotubes (Fe–N-MWCNTs) with hierarchical nanostructure is engineered and synthesized via a simple two-step pyrolysis approach. Large specific surface area, low resistivity, and intensified charge density near the Fermi level synergistically endow the Fe–N-MWCNTs with outstanding ORR activity. The optimal Fe–N-MWCNTs exhibit a higher onset potential value of 0.92 V (versus RHE) and half-wave potential (E1/2) of 0.85 V (versus RHE) in 0.1 M KOH medium, which exceeds the benchmark Pt/C electrocatalyst (E1/2 = 0.84 V). This strategy of modifying MWCNTs support by a simple calcination process provides a feasible method to prepare cost-efficient ORR electrocatalysts.

Materials: synthesis or self-assembly

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Metal halide perovskite quantum dots (QDs) have excellent optoelectronic properties; however, their poor stability under water or thermal conditions remains an obstacle to commercialization. Here, we used a carboxyl functional group (−COOH) to enhance the ability of a covalent organic framework (COF) to adsorb lead ions and grow CH3NH3PbBr3 (MAPbBr3) QDs in situ into a mesoporous carboxyl-functionalized COF to construct MAPbBr3 QDs@COF core–shell-like composites to improve the stability of perovskites. Owing to the protection of the COF, the as-prepared composites exhibited enhanced water stability, and the characteristic fluorescence was maintained for more than 15 d. These MAPbBr3 QDs@COF composites can be used to fabricate white light-emitting diodes with a color comparable to natural white emission. This work demonstrates the importance of functional groups for the in situ growth of perovskite QDs, and coating with a porous structure is an effective way to improve the stability of metal halide perovskites.

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Nanoporous GaN layers were fabricated using selective area sublimation through a self-organized AlN nanomask in a molecular beam epitaxy reactor. The obtained pore morphology, density and size were measured using plan-view and cross-section scanning electron microscopy experiments. It was found that the porosity of the GaN layers could be adjusted from 0.04 to 0.9 by changing the AlN nanomask thickness and sublimation conditions. The room temperature photoluminescence properties as a function of the porosity were analysed. In particular, a strong improvement (>100) of the room temperature photoluminescence intensity was observed for porous GaN layers with a porosity in the 0.4–0.65 range. The characteristics of these porous layers were compared to those obtained with a SixNy nanomask. Furthermore, the regrowth of p-type GaN on light emitting diode structures made porous by using either an AlN or a SixNy nanomask were compared.

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Construction of various nanostructures with nanometre-scale precision through various DNA building blocks depends upon self-assembly, base-pair complementarity and sequence programmability. During annealing, unit tiles are formed by the complementarity of base pairs in each strand. Enhancement of growth of target lattices is expected if seed lattices (i.e. boundaries for growth of target lattices) are initially present in a test tube during annealing. Although most processes for annealing DNA nanostructures adopt a one-step high temperature method, multi-step annealing provides certain advantages such as reusability of unit tiles and tuneability of lattice formation. We can construct target lattices effectively (through multi-step annealing) and efficiently (via boundaries) by multi-step annealing and combining boundaries. Here, we construct efficient boundaries made of single, double, and triple double-crossover DNA tiles for growth of DNA lattices. Two unit double-crossover DNA tile-based lattices and copy-logic implemented algorithmic lattices were introduced to test the growth of target lattices on boundaries. We used multi-step annealing to tune the formation of DNA crystals during fabrication of DNA crystals comprised of boundaries and target lattices. The formation of target DNA lattices was visualized using atomic force microscopy (AFM). The borders between boundaries and lattices in a single crystal were clearly differentiable from AFM images. Our method provides way to construct various types of lattices in a single crystal, which might generate various patterns and enhance the information capacity in a given crystal.

Materials: properties, characterization or tools

245701
The following article is Open access

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Graphene oxide (GO) and reduced graphene oxide have outstanding qualities that could be exploited as reinforcement and antibacterial agents in a plethora of biomedical applications. In this contribution, it is reported the deployment of a polyacrylamide GO-hydrogel composite (GO@pAAm) which was photo-converted and structured by ultra-short laser irradiation using a direct laser writing (DLW) approach. The materials were characterized by Fourier Transform Infrared spectroscopy, scanning electron microscopy and confocal microscopy. The laser structure generates a multi-photo-induced effect: surface foaming and patterning, microdomains with enhanced selective water-swelling and effective GO photo-reduction. A first laser scan seems likely to induce the photo-reduction of GO and subsequent laser pulses trigger the structure/foaming. The photo-reduction of GO is evidenced by Raman spectroscopy by the relatively changing intensities of the D to G signals. Macroscopically by an increase in conductivity (decrease in sheet resistance from RS-GO@pAAm = 304 ± 20 kΩ sq−1 to RS-rGO@pAAm-DLW = 27 ± 8 kΩ sq−1) suggesting a reduction of the material measured by 4-Point-Probe.

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A cardiomyocyte is the basic structural and functional unit of the heart, which is the actual executor of the systolic function. The study of the contraction and relaxation characteristics of cardiomyocyte is of great significance to the physiological behavior and pathology of the heart. How to dynamically express its contraction and relaxation behaviors in 3D has become a challenging issue. Although the video analysis method under the optical microscope can observe the changes in the horizontal direction, it is difficult to describe the changes in the vertical direction. The atomic force microscope (AFM) can accurately express the mechanical and morphological characteristics of the changes in the vertical direction, but it cannot be fully expressed in real time because it is acquired by scanning with a single probe. In order to express the contraction and relaxation characteristics of cardiomyocyte accurately and three dimensionally, a dynamic imaging method in this study is proposed using the periodicity of AFM acquisition and the periodicity of cardiomyocyte contraction. Compared with the optical experiment, it is proven that this method can dynamically represent the contraction and relaxation processes of cardiomyocyte and solve the problem of how to express it in 3D. It brings a new way for the study of physiological characteristics of cardiomyocytes and dynamic imaging by AFM.

245703
The following article is Open access

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The mechanical properties of polymer nanocomposites can be improved by incorporating various types of nanofillers. The hybridization of nanofillers through covalent linkages between nanofillers with different dimensions and morphology can further increase the properties of nanocomposites. In this work, aramid nanofibers (ANFs) are modified using chlorinated cellulose nanocrystals (CNCs) and functionalized with 3-glycidoxypropyltrimethoxysilane to improve the chemical and mechanical interaction in an epoxy matrix. The integration of CNC functionalized ANFs (fACs) in the epoxy matrix simultaneously improves Young's modulus, tensile strength, fracture properties, and viscoelastic properties. The test results show that 1.5 wt% fAC reinforced epoxy nanocomposites improve Young's modulus and tensile strength by 15.1% and 10.1%, respectively, and also exhibit 2.5 times higher fracture toughness compared to the reference epoxy resin. Moreover, the glass transition temperature and storage modulus are found to increase when fACs are incorporated. Thus, this study demonstrates that the enhanced chemical and mechanical interaction by the CNC functionalization on the ANFs can further improve the static and dynamic mechanical properties of polymer nanocomposites.

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SnSe based compounds have attracted much attention due to the ultra-low lattice thermal conductivity and excellent thermoelectric properties. The origin of the low thermal conductivity has been ascribed to the strong phonon anharmonicity. Generally, the microstructures are also effective in scattering the phonons and further reducing the lattice thermal conductivity. In this work, the microstructures of undoped SnSe and Bi-doped Sn0.97SeBi0.03 have been investigated by transmission electron microscopy. A characteristic microstructure of lath-like grains has been observed in SnSe based compounds from perpendicular to the pressure direction. In addition, there exist a large quantity of low-angle grain boundaries and a high concentration of edge dislocations and stacking faults in the grains. All these microstructures result in lattice mismatch and distortion and can act as the phonon scattering centers, which broaden the understanding of the low thermal conductivity of SnSe based compounds.

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Focus on Amorphous and Nano-Crystalline Semiconductors

Two-dimensional (2D) MoSi2N4 is a newly created material that has superstability and ultrahigh carrier mobility. Besides, the hydrogen evolution reaction activity was proved excellent by doping transition metal (TM) atoms and introducing N vacancies. But, the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) of 2D MoSi2N4 is unclear even. We have explored the electrocatalytic properties (OER/ORR) of MoSi2N4 by introducing Si vacancies and attaching various TM atoms. The structure and optoelectronic characteristics of MoSi2N4 have been researched in detail using density functional theory calculations. By analyzing the density of states, the free energy change diagram and contour maps of TM@VSi-MoSiN, the results show that Co@VSi-MoSiN has the lowest OER overpotential (0.53 V) among all samples. Additionally, the d-band center is used to explain the electrocatalytic origin of the OER and ORR of TM@VSi-MoSiN. Our discoveries expand the 2D TM@VSi-MoSiN applicability in the realm of catalysis.

245706

The optical Stark effect is a universal response of the electronic structure to incident light. In semiconductors, particularly nanomaterials, the optical Stark effect achieved with sub-band gap photons can drive large, narrowband, and potentially ultrafast changes in the absorption or reflection at the band gap through excitation of virtual excitons. Rapid optical modulation using the optical Stark effect is ultimately constrained, however, by the generation of long-lived excitons through multiphoton absorption. This work compares the modulation achievable using the optical Stark effect on CdSe nanoplatelets with several different pump photon energies, from the visible to mid-infrared. Despite expected lower efficiencies for spectrally-remote pump energies, infrared pump pulses can ultimately drive larger sub-picosecond optical Stark shifts of virtual excitons without creation of real excitons. The CdSe nanoplatelets show subpicosecond shifts of the lowest excitonic resonance of up to 22 meV, resulting in change in absorption as large as 0.32 OD (49% increase in transmission), with a long-lived offset from real excitons less than 1% of the peak signal.

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This article addresses the synthesis of Fe3+ doped TiO2 nanoparticles with variations of molar concentrations of Fe3+ and their adequate use as potential photocatalysts for Photocatalysis applications. Synthesized photocatalysts were characterized thoroughly by different analytical techniques in terms of morphological, chemical, structural, crystalline, optical, electronic structure, surface area etc properties. The occurrence of red shift phenomenon of the energy band gap attributes to the transfer of charges and transition between the d electrons of dopant and conduction band (CB) or valence band (VB) of TiO2. The doping of Fe3+ ions generates more trap sites for charge carriers with the surface trap sites. Thorough experimental conclusions revealed that the Fe3+ ions necessarily regulate the catalytic property of TiO2 nanomaterial. The obtained total degradation efficiency rate of Methylene Blue (MB) was 93.3% in the presence of 0.1 M Fe3+ in the host material and for Malachite Green Oxalate the efficiency was 100% in the presence of 0.05 M and 0.1 M Fe3+in the host material. In both the cases the total visible light irradiation time was 90 min. The adsorption properties of the photocatalysts have been also performed in a dark for 90 min in the presence of MB dye. However, till now there are hardly reported photocatalysts which shows complete degradation of these toxic organic dyes by visible light driven photocatalysis. of potential values of valence and conduction band shows the production of active oxidizing species for hydrogen yield and the possible mechanism of the Schottky barrier has been proposed. A schematic diagram of visible light driven Photocatalysis has been pictured showing degradation activity of Fe3+-TiO2 catalysts sample.

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Atomic layer deposition (ALD) has become an essential technology in many areas. To better develop and use this technology, it is of the pivot to understand the surface chemistry during the ALD film growth. The growth of an ALD oxide film may also induce an electric dipole at the interface, which may be further tuned to modulate the flat band voltage for electronic device applications. To understand the associated surface chemistry and interface dipole formation process, we herein employ an in situ x-ray photoelectron spectroscopy technique to study the ALD growth of Al2O3, from trimethylaluminum and H2O, on the SiOx/Si surface. We find that an electric dipole is formed at the Al2O3/SiOx interface immediately after the first Al2O3 layer is deposited. We also observe persistent surface methyl groups in the H2O half-cycle during ALD, and the amount of the persistent methyls is particularly higher during the initial Al2O3 ALD growth, which suggests the formation of Si−CH3 on the surface. These findings can provide useful routes and insights toward interface engineering by ALD.

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While synthesizing quasi-one-dimensional nanoribbons, there is a finite probability that edges have cove-edge defects. This paper focuses on the structural, electronic, and transport properties of cove-edge aluminum nitride nanoribbons (AlNNR) using density functional theory and the non-equilibrium Green's function (NEGF) method. The cove-edge AlNNRs are thermodynamically stable and exhibit metallic behavior. Interestingly, the calculated current–voltage characteristics of the cove-edge AlNNR-based nanodevices show negative differential resistance (NDR). The H-AlN-Cove nanodevice exhibits high peak-to-valley current ratio (PVCR) of the order of 107. The calculated PVCR of the H-AlN-Cove nanodevice is 106 times higher than that of the silicene nanoribbon (SiNR) and graphene nanoribbon (GNR), and 104 times higher than that of the phosphorene nanoribbon (PNR) and arsenene nanoribbons (ANR)-based devices respectively. The NDR feature with high PVCR provides a prospect for the cove-edge AlNNR in nanodevice applications.

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Znic-based metal–organic framework materials (ZIF-8) show great potential and excellent performance in the fields of sensing and catalysis. However, powdered metal–organic framework makes it easy to lose in the process of application. Herein, we use a simple blending electrostatic spinning method to combine ZIF-8 particles with polyacrylonitrile (PAN) nanofibers. ZIF-8/PAN composite nanofiber membrane. The ZIF-8/PAN nanofiber membrane is characterized by scanning electron microscope (SEM), x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and N2 adsorption–desorption. The results show that the ZIF-8/PAN nanofiber membrane has the characteristic peaks of XRD and FTIR, which are consistent with those of simulated ZIF-8. The specific surface area of ZIF-8/PAN nanofiber membrane increases from 13.5371 to 711.4171 m2 g−1 due to the introduction of ZIF-8 particles. The sensor using the nanofiber membrane as the gas sensing layer shows good response and linear correlation to different concentrations of acetone gas. The minimum detection limit of the sensor for acetone is 51.9 ppm. The blank control shows that the response of the sensor to acetone is mainly due to the introduction of ZIF-8 particles. In addition, the sensor also shows a good cyclic response to acetone.

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