Enhanced electrocatalytic activity in MOFs-derived 3D hollow NiCo-LDH nanocages decorated porous biochar for simultaneously ultra-sensitive electrochemical sensing of Cu2+ and Hg2.

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.

Highly sensitive turn-on electrochemical sensing of organophosphorus pesticides by integration of homogeneous reaction and heterogeneous catalytic signal amplification.

Enzyme-inhibited electrochemical sensor is a promising strategy for detecting organophosphorus pesticides (OPs). However, the poor stability of enzymes and the high oxidation potential of thiocholine signal probe limit their potential applications. To address this issue, an indirect strategy was proposed for highly sensitive and reliable detection of chlorpyrifos by integrating homogeneous reaction and heterogeneous catalysis. In the homogeneous reaction, Hg2+ with low oxidation potential was employed as signal probe for chlorpyrifos detection since its electroactivity can be inhibited by thiocholine, which was the hydrolysate of acetylthiocholine catalyzed by acetylcholinesterase. Additionally, Co,N-doped hollow porous carbon nanocage@carbon nanotubes (Co,N-HPNC@CNT) derived from ZIF-8@ZIF-67 was utilized as high-performance electrode material to amplify the stripping voltammetry signal of Hg2+. Thanks to their synergistic effect, the sensor exhibited outstanding sensing performance, excellent stability and good anti-interference ability. This strategy paves the way for the development of high-performance OP sensors and their application in food safety.

Electroactive poly(thionine) as imprinted polymer and reference probe simultaneously for ratiometric ion imprinted electrochemical Pb2+sensor.

In this work, an electrochemical sensor based on ion-imprinted polymer/Au nanoparticles/porous biochar (IIP/AuNPs/PBC) composite was proposed for the highly selective and sensitive detection of Pb2+. In this work, poly (thionine) (pTHI) served simultaneously as imprinted polymer and reference probe. It could not only realize the specific detection of Pb2+, but also provide an internal reference signal to eliminate the influence of human and environmental factors on the detection signal and further improve the stability of the sensor. In addition, the AuNPs/PBC composite with large specific surface area, excellent electron transport and electrocatalytic performance could effectively enhance the detection signal as a carrier material. At the same time, the AuNPs on the PBC surface would promote the formation of uniform and stable IIP through Au-S bonds. The synergistic effect between IIP, AuNPs/PBC and ratiometric signal mode gave the Pb2+sensor excellent performance, including a wide linear range (0.1-1000µg l-1), low detection limit (0.03µg l-1, S/N = 3), excellent selectivity and stability. All these results indicate that the proposed sensor could provide a meaningful reference for highly selective detection of heavy metal ions (HMIs).

Modified Bamboo Charcoal as a Bifunctional Material for Methylene Blue Removal.

Biomass-derived raw bamboo charcoal (BC), NaOH-impregnated bamboo charcoal (BC-I), and magnetic bamboo charcoal (BC-IM) were fabricated and used as bio-adsorbents and Fenton-like catalysts for methylene blue removal. Compared to the raw biochar, a simple NaOH impregnation process significantly optimized the crystal structure, pore size distribution, and surface functional groups and increase the specific surface area from 1.4 to 63.0 m2/g. Further magnetization of the BC-I sample not only enhanced the surface area to 84.7 m2/g, but also improved the recycling convenience due to the superparamagnetism. The maximum adsorption capacity of BC, BC-I, and BC-IM for methylene blue at 328 K was 135.13, 220.26 and 497.51 mg/g, respectively. The pseudo-first-order rate constants k at 308 K for BC, BC-I, and BC-IM catalytic degradation in the presence of H2O2 were 0.198, 0.351, and 1.542 h-1, respectively. A synergistic mechanism between adsorption and radical processes was proposed.

Electrochemical determination of benomyl using MWCNTs interspersed graphdiyne as enhanced electrocatalyst.

Graphdiyne (GDY) has attracted a lot of interest in electrochemical sensing application with the advantages of a large conjugation system, porous structure, and high structure defects. Herein, to further improve the sensing effect of GDY, conductive MWCNTs were chosen as the signal accelerator. To get a stable composite material, polydopamine (PDA) was employed as connecting bridge between GDY and MWCNTs-NH2, where DA was firstly polymerized onto GDY, followed by covalently linking MWCNTs-NH2 with PDA through Michael-type reaction. The formed GDY@PDA/MWCNTs-NH2 composite was then explored as an electrochemical sensor for benomyl (Ben) determination. GDY assists the adsorption and accumulation of Ben molecules to the sensing surface, while MWCNTs-NH2 can enhance the electrical conductivity and electrocatalytic activity, all of which contributing to the significantly improved performance. The proposed sensor displays an obvious oxidation peak at 0.72 V (vs. Hg|Hg2Cl2) and reveals a wide linear range from 0.007 to 10.0 µM and a low limit of detection (LOD) of 1.8 nM (S/N = 3) toward Ben detection. In addition, the sensor shows high stability, repeatability, reproducibility, and selectivity. The feasibility of this sensor was demonstrated by detecting Ben in apple and cucumber samples with a recovery of 94-106% and relative standard deviations (RSDs) less than 2.3% (n = 5). A sensitive electrochemical sensing platform was reported for benomyl (Ben) determination based on a highly stable GDY@PDA/MWCNTs-NH2 composite.

Ultrasensitive indirect electrochemical sensing of thiabendazole in fruit and water by the anodic stripping voltammetry of Cu2+ with hierarchical Ti3C2Tx-TiO2 for signal amplification.

The development of effective electrochemical methods for the determination of pesticide residues is highly desirable for food safety requirements. Herein, a novel electrochemical sensing strategy for indirect detection of thiabendazole (TBZ) was achieved by monitoring the anodic stripping peak signal change of media Cu2+ induced by a significant activity difference between active Cu2+ and inactive Cu2+-TBZ complexes. In this sensing system, a heterostructured Ti3C2Tx-TiO2 composite synthesized via a simple in-situ-oxidization strategy is used as the electrode material to boost the anodic stripping peak signal. After optimizing various conditions, the developed sensor presents satisfactory analytical performance for TBZ assay with a linear range from 0.3 to 100.0 nM and a limit of detection as low as 0.1 nM (S/N = 3). Furthermore, the proposed sensing platform also exhibits outstanding anti-interference, repeatability, and stability, which is effective for the determination of TBZ in fruit and water samples.

Electrochemical Aptasensor Based on Au Nanoparticles Decorated Porous Carbon Derived from Metal-Organic Frameworks for Ultrasensitive Detection of Chloramphenicol.

A facile and sensitive electrochemical aptamer sensor (aptasensor) based on Au nanoparticles-decorated porous carbon (AuNPs/PC) composite was developed for the efficient determination of the antibiotic drug chloramphenicol (CAP). AuNPs modified metal-organic framework (AuNPs/ZIF-8) is applied as a precursor to synthesize the porous carbon with homogeneous AuNPs distribution through a direct carbonization step under nitrogen atmosphere. The as-synthesized AuNPs/PC exhibits high surface area and improved conductivity. Moreover, the loading AuNPs could enhance the attachment of the aptamers on the surface of electrode through the Au-S bond. When added to CAP, poorly conductive aptamer-CAP complexes are formed on the sensor surface, which increases the hindrance to electron transfer resulting in a decrease in electrochemical signal. Based on this mechanism, the developed CAP aptasensor represents a wide linear detection range of 0.1 pM to 100 nM with a low detection limit of 0.03 pM (S/N = 3). In addition, the proposed aptasensor was employed for the analysis of CAP in honey samples and provided satisfactory recovery.

2D Leaf-Like Structured ZIF-L Embedded Electrochemically Reduced Graphene Oxide Composite as an Electrochemical Sensing Platform for Sensitively Detecting Benomyl.

In this work, a two-dimensional leaf-like framework-L embedded electrochemically reduced graphene oxide (ERGO@ZIF-L) was proposed as an outstanding electrode material for the sensitive electrochemical sensing of benomyl (BM). ZIF-L is surrounded by ERGO, which could effectively ensure the stability and dispersion of ZIF-L. With this unique combination, the prepared ERGO@ZIF-L displayed excellent synergistic characteristics with a large surface area, excellent conductivity, plentiful active sites, and high electrocatalytic properties, thus endowing it with high sensitivity for BM determination. The experimental parameters, such as solution pH, material volume, and accumulation time, were optimized. Under optimal conditions, the BM sensor showed a wide linear range (0.009-10.0 µM) and low-limit detection (3.0 nM). Moreover, the sensor displayed excellent stability, repeatability, and reproducibility, and good anti-interference capability. The method was successfully applied to detect BM in real-world samples.

ß-Cyclodextrin/CMK-8-Based Electrochemical Sensor for Sensitive Detection of Cu2.

In this work, ß-cyclodextrin (ß-CD)/mesoporous carbon (CMK-8) nanocomposite was synthesized and used as an electrochemical sensing platform for highly sensitive and selective detection of Cu2+. The morphology and structure of ß-CD/CMK-8 were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). In addition, the dates from electrochemical impedance spectroscopy (EIS) and Cyclic voltammetry (CV) demonstrated that the ß-CD/CMK-8 possessed a fast electronic transfer rate and large effective surface area. Besides this, the ß-CD/CMK-8 composite displayed high enrichment ability toward Cu2+. As a result of these impressive features, the ß-CD/CMK-8 modified electrode provided a wide linear response ranging from 0.1 ng·L-1 to 1.0 mg·L-1 with a low detection limit of 0.3 ng·L-1. Furthermore, the repeatability, reproducibility and selectivity of ß-CD/CMK-8 towards Cu2+ were commendable. The sensor could be used to detect Cu2+ in real samples. All in all, this work proposes a simple and sensitive method for Cu2+ detection, which provides a reference for the subsequent detection of HMIs.

Facile Synthesis of Nitrogen Self-Doped Porous Carbon Derived from Cicada Shell via KOH Activation for Simultaneous Detection and Removal of Cu2.

Sensitive detection and efficient removal of heavy metal ions with high toxicity and mobility are of great importance for environmental monitoring and control. Although several kinds of functional materials have been reported for this purpose, their preparation processes are complicated. Herein, nitrogen self-doped activated porous biochar (NAC) was synthesized in a facile process via an activation-carbonization strategy from cicada shell rich in chitin, and subsequently employed as an effective functional material for the simultaneous determination and removal of Cu2+ from aqueous media. With its unique porous structure and abundant oxygen-containing functional groups, along with the presence of heteroatoms, NAC exhibits high sensitivity for the electrochemical sensing of Cu2+ in concentrations ranging from 0.001 to 1000 µg·L-1, with a low detection limit of 0.3 ng·L-1. Additionally, NAC presents an excellent removal efficiency of over 78%. The maximum adsorption capacity is estimated at 110.4 mg/g. These excellent performances demonstrate that NAC could serve as an efficient platform for the detection and removal of Cu2+ in real environmental areas.

Amplified electrochemical determination of niclosamide in food based on carbon nanohorn@MWCNT composite.

In this work, carbon nanohorn (CNH)-decorated multi-walled carbon nanotube (MWCNT) (CNH@MWCNT) composite was prepared and used to modify glass carbon electrode (GCE) as sensitive electrochemical sensor for niclosamide (NA) determination. Herein, the decoration of CNHs induces higher dispersibility for MWCNTs, and endows the composite with better conductivity, larger surface area, and higher catalytic activity, which leads to significantly enhanced electrochemical behavior toward NA oxidation. The parameters such as mass ratios of CNHs and MWCHTs, the amount of composite materials, the accumulation time, and the solution pH are systematically optimized. Under optimized conditions, the developed electrochemical sensor exhibits a low detection limit of 2.0 nM with a wide linear range of 7.0 nM-10.0 µM and high anti-interference ability. In addition, the sensor displays good stability, repeatability, and reproducibility. The feasibility of the assay was verified by testing NA in brown rice and rice field water samples.

MXene-AuNP-Based Electrochemical Aptasensor for Ultra-Sensitive Detection of Chloramphenicol in Honey.

A simple and label-free electrochemical aptasensor was developed for ultra-sensitive determination of chloramphenicol (CAP) based on a 2D transition of metal carbides (MXene) loaded with gold nanoparticles (AuNPs). The embedded AuNPs not only inhibit the aggregation of MXene sheets, but also improve the quantity of active sites and electronic conductivity. The aptamers (Apts) were able to immobilize on the MXene-AuNP modified electrode surface through Au-S interaction. Upon specifically binding with CAP with high affinity, the CAP-Apt complexes produced low conductivity on the aptasensor surface, leading to a decreased electrochemical signal. The resulting current change was quantitatively correlated with CAP concentration. Under optimized experimental conditions, the constructed aptasensor exhibited a good linear relationship within a wide range of 0.0001-10 nM and with a low detection limit of 0.03 pM for CAP. Moreover, the developed aptasensor has been applied to the determination of CAP concentration in honey samples with satisfactory results.

Bismuth Nanoclusters/Porous Carbon Composite: A Facile Ratiometric Electrochemical Sensing Platform for Pb2+ Detection with High Sensitivity and Selectivity.

In this work, a ratiometric electrochemical sensor was constructed for the detection of Pb2+ based on a bismuth nanocluster-anchored porous activated biochar (BiNCs@AB) composite. BiNCs with loose structure and AB with abundant oxygen-containing functional groups are favorable for Pb2+ adsorption and preconcentration; meanwhile, porous AB provides more mass transfer pathways and increases electronic and ion diffusion coefficients, realizing high sensitivity for Pb2+ detection. At the same time, BiNCs were proposed as an inner reference for ratiometric electrochemical detection, which could greatly enhance the determination accuracy. Under optimized experimental conditions, the anodic peak current ratio between Pb2+ and BiNCs exhibited a good linear relationship with the concentration from 3.0 ng/L to 1.0 mg/L. The detection limit can be detected down to 1.0 ng/L. Furthermore, the proposed sensor demonstrated good reproducibility, stability, and interference resistance, as well as satisfactory recoveries for the detection of Pb2+ in real samples.

Core-shell Cu@C@ZIF-8 composite: a high-performance electrode material for electrochemical sensing of nitrite with high selectivity and sensitivity.

Herein, an efficient electrochemical sensing platform is proposed for selective and sensitive detection of nitrite on the basis of Cu@C@Zeolitic imidazolate framework-8 (Cu@C@ZIF-8) heterostructure. core-shell Cu@C@ZIF-8 composite was synthesized by pyrolysis of Cu-metal-organic framework@ZIF-8 (Cu-MOF@ZIF-8) in Ar atmosphere on account of the difference of thermal stability between Cu-MOF and ZIF-8. For the sensing system of Cu@C@ZIF-8, ZIF-8 with proper pore size allows nitrite diffuse through the shell, while big molecules cannot, which ensures high selectivity of the sensor. On the other hand, Cu@C as electrocatalyst promotes the oxidation of nitrite, thereby resulting high sensitivity of the sensor. Accordingly, the Cu@C@ZIF-8 based sensor presents excellent performance for nitrite detection, which achieves a wide linear response range of 0.1-300.0µM, and a low limit of detection of 0.033µM. In addition, the Cu@C@ZIF-8 sensor possesses excellent stability and reproducibility, and was employed to quantify nitrite in sausage samples with recoveries of 95.45%-104.80%.

2D leaf-like ZIF-L decorated with multi-walled carbon nanotubes as electrochemical sensing platform for sensitively detecting thiabendazole pesticide residues in fruit samples.

Excessive use of pesticides in modern agriculture results in large amounts of pesticide residues in agricultural production, greatly threatening human health. Herein, novel two-dimensional leaf-like zeolitic imidazolate framework-L decorated with multi-walled carbon nanotubes (MWCNTs/ZIF-L) was prepared by a facile solvent way and exploited as electrode material for sensitive electrochemical sensing of thiabendazole (TBZ). Two-dimensional ZIF-L presents high surface area, large pore volume, and abundant active sites, which exhibits high enrichment ability towards TBZ molecules, while the MWCNTs interspersed on ZIF-L can prominently enhance the electron transport capability and improve the electrocatalytic activity for TBZ oxidation. Due to the intriguing synergy between the components, the MWCNTs/ZIF-L-based electrochemical sensor reveals a limit of detection (LOD) of 6.0 nmol·L-1, which is lower than that reported in most literatures. Additionally, satisfactory reproducibility and repeatability, long-term stability, and excellent selectivity are acquired. The proposed method was also applied for the detection of TBZ in apple and orange samples with acceptable recoveries.

MXene@Ag-based ratiometric electrochemical sensing strategy for effective detection of carbendazim in vegetable samples.

In this paper, a novel ratiometric electrochemical sensor for carbendazim (CBZ) detection was constructed by a composite of MXene@Ag nanoclusters and amino-functionalized multi-walled carbon nanotubes (MXene@AgNCs/NH2-MWCNTs). The Ag nanoclusters (AgNCs) embedded in the MXene not only could inhibit the aggregation of MXene flakes and enhance the electrocatalytic ability, but also serve as an internal reference probe for the ratiometric electrochemical detection. Moreover, the introduction of NH2-MWCNTs can further improve the electrochemical signals of CBZ and Ag, resulting in the enhanced signal amplification and higher sensitivity. Based on these characteristics of the MXene@AgNCs/NH2-MWCNTs composite, the proposed sensor exhibits a favorable linear relationship between ICBZ/IAgNCs and the concentration of CBZ ranging from 0.3 nM to 10 µM and a low limit of detection of 0.1 nM. Moreover, the proposed ratiometric electrochemical sensing platform also demonstrates high selectivity, good reproducibility, secular stability, and satisfactory applicability in vegetable samples.

Nitrogen, sulfur co-doped hierarchical carbon encapsulated in graphene with "sphere-in-layer" interconnection for high-performance supercapacitor.

Rational design of electrode with hierarchical charge-transfer structure and good electronic conductivity is important to achieve high specific capacitance and energy density for supercapacitor, but it still remains a challenge. Herein, a nitrogen, sulfur co-doped pollen-derived carbon/graphene (PCG) composite with interconnected "sphere-in-layer" structure was fabricated, in which hierarchically pollen-derived carbon microspheres can serve as "porous spacers" to prevent the agglomeration of graphene nanosheets. The optimized PCG composite prepared with 0.5 wt% of graphene oxide (PCG-0.5) exhibited high specific capacitance (420Fg-1 at 1Ag-1), rate performance (280Fg-1 at 20Ag-1), and excellent cycling stability with 94% of capacitance retention after 10,000 cycles. The symmetrical device delivered a remarkable energy density of 31.3Whkg-1 in neutral medium. Moreover, density functional theory calculation revealed that PCG electrode possessed the accelerated charge transfer and enhanced electronic conductivity, thus ensuring a remarkable electrochemical performance. This work may afford an effective strategy for the development of biomass-derived carbon electrodes with novel charge-transfer structure toward supercapacitor applications.

Flexible polypyrrolone-based microporous carbon nanofibers for high-performance supercapacitors.

Flexible materials have drawn considerable attention due to the demand for wearable and flexible electronic products. Seeking new kinds of precursors for preparing carbon nanofibers with good flexibility for high-performance supercapacitors is a hot issue. In this work, a flexible polypyrrolone (BBB)/polyimide (PI) composite-based carbon nanofiber membrane (PBPICF) is prepared by a facile electrospinning and carbonization process. The PBPICF membranes exhibit a three-dimensional (3D) porous, fluffy and self-standing structure with good mechanical performance and flexibility, and can be arbitrarily bent and folded. PBPICF-65-35 (consisting of BBB (65 wt%) and PI (35 wt%)) exhibits a high specific capacitance of 172.44 F g-1 in 6 M KOH aqueous solution, which is two-fold more than that of commercial polyacrylonitrile-based carbon nanofibers. In addition, PBPICF-65-35 also displays good power density (90 W kg-1) and energy density (19.4 W h kg-1), and the capacitance remains at 96% even after 10 000 cycles at 1.0 A g-1. Therefore, the simple preparation and good capacitance performance of PBPICFs make them a promising binder-free electrode for wearable supercapacitors.