Signal Modulation Induced by a Hole Transfer Layer Participant Photoactive Gate: A Highly Sensitive Organic Photoelectrochemical Transistor Sensing Platform.

It is urgent to pursue appropriate gate photoactive materials for gate-to-channel signal modulation to achieve superior transconductance performances of organic photoelectrochemical transistor (OPECT) sensors. Notably, a hole transfer layer (HTL) participant CdZnS/sulfur-doped Ti3C2 MXene (S-MXene) gate was designed and developed in this work, which exhibited a remarkable signal modulation performance by up to 3 orders of magnitude. Because of the incorporation of S-MXene with an enhanced electrical conductivity as the effective HTL, the signal modulation capabilities of the CdZnS/S-MXene photoactive gate were superior to those of CdZnS and CdZnS/MXene. This incorporation inhibited the recombination of the interfacial charge and facilitated the transfer of photogenerated holes, thus enhancing the photoelectric conversion performance. This enhancement facilitated fast electron transfer with a larger effective photovoltage to augment the dedoping ability of channel ions. Based on these findings, an aptasensing platform that exhibited good performance was constructed using the proposed OPECT device, with ofloxacin as a model target and an aptamer for specific recognition. The developed OPECT aptasensor had various advantages, including a high sensitivity, good linear range (1.0 × 10-13 to 1.0 × 10-6 M), and low limit of detection (3.3 × 10-15 M). This study provided a proof-of-concept for the generalized development of HTL participant gates for OPECT sensors and other related applications.

Metal-organic-framework-confined quantum dots enhance photocurrent signals: A molecularly imprinted photoelectrochemical cathodic sensor for rapid and sensitive tetracycline detection.

BACKGROUND: Tetracycline (TC), a cost-effective broad-spectrum antibacterial drug, has been excessively utilized in the livestock and poultry industry, leading to a serious overabundance of TC in livestock wastewater. However, conventional analytical methods such as liquid chromatography and gas chromatography face challenges in achieving sensitive detection of trace amounts of TC in complex substrates. Therefore, it is imperative to develop a highly sensitive and anti-interference analytical method for the detection of tetracycline in livestock wastewater. RESULTS: A porphyrin-based MOF (PCN-224)-confined carbon dots (CDs) material (CDs@PCN-224) was synthesized by a "bottle-around-ship" strategy. The reduced carrier migration distance is conducive to the separation of electron-hole pairs and enhanced the photocurrent signal due to the tight coupling of CDs and PCN-224. Further, molecularly imprinted polymer (MIP) was synthesized by rapid in-situ UV-polymerization and employed as a recognition element. The specific recognition of the target by imprinted cavities blocks electron transfer, resulting in a "turn off" response signal, thus realizing the selective detection of TC. Under optimal conditions, the constructed MIP-PEC cathodic sensor detected 1.00 × 10-12 M to 1.00 × 10-7 M of TC sensitively, with a limit of detection of 3.72 × 10-13 M. In addition, the proposed MIP-PEC sensor demonstrated good TC detection performance in actual livestock wastewater. SIGNIFICANCE: The strategy based on MOF pore-confined quantum dots can effectively enhance the photocurrent response of the photosensitive substrate. Simultaneously, the MIP constructed by in-situ rapid UV-polymerization showed excellent anti-interference and reusable properties. This work provides a promising MIP-PEC cathodic sensing method for the rapid and sensitive detection of antibiotics in complex-matrix environmental samples.

Green and effective remediation of heavy metals contaminated water using CaCO3 vaterite synthesized through biomineralization.

Heavy metal pollution has attracted significant attention due to its persistent presence in aquatic environments. A novel vaterite-based calcium carbonate adsorbent, named biogenic CaCO3, was synthesized utilizing a microbially induced carbonate precipitation (MICP) method to remediate heavy metal-contaminated water. The maximum Cd2+ removal capacity of biogenic CaCO3 was 1074.04 mg Cd2+/g CaCO3 with a high Cd2+ removal efficiency greater than 90% (initial Cd2+ concentration 400 mg/L). Furthermore, the biogenic CaCO3 vaterite, induced by microbial-induced calcium carbonate precipitation (MICP) process, demonstrated a prolonged phase transformation to calcite and enhanced stability. This resulted in a sustained high effectiveness (greater than 96%) following six consecutive recycling tests. Additionally, X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses revealed that the semi-stable vaterite type of biogenic CaCO3 spontaneously underwent dissolution and recrystallization to form thermodynamic stable calcite in aquatic environments. However, the presence of Cd2+ leads to the transformation of vaterite into CdCO3 rather than undergoing direct converting to calcite. This transformation is attributed to the relatively low solubility of CdCO3 compared to calcite. Meanwhile, the biogenic CaCO3 proved to be an efficient and viable method for the removal of Pb2+, Cu2+, Zn2+, Co2+, Ni2+ and Mn2+ from water samples, surpassing the performance of previously reported adsorbents. Overall, the efficient and promising adsorbent demonstrates potential for practical in situ remediation of heavy metals-contaminated water.

Recent Trends in Self-Powered Photoelectrochemical Sensors: From the Perspective of Signal Output.

Revolutionary developments in analytical chemistry have led to the rapid development of self-powered photoelectrochemical (PEC) sensors. Different from conventional PEC sensors, self-powered PEC sensors do not require an external power source or complex devices for the sensitive detection of targets. As a result, these sensors have enormous application potential for the development of novel portable sensors. An increasing body of work is making excellent progress toward the implementation of self-powered PEC sensors for detection, but there have been no reviews to date. The present review first introduces the state of the art in the development of self-powered PEC sensors. Then, different types of self-powered PEC sensors are summarized and discussed in detail, including their current, power, and potential. Additionally, single- and dual-photoelectrode systems are classified and systematically compared. Finally, the current developments and major challenges that need to be addressed are also summarized. This review provides valuable insights into the current state of self-powered PEC sensors to promote further progress in this field.

Gold nanocluster-confined covalent organic frameworks as bifunctional probes for electrochemiluminescence and colorimetric dual-response sensing of Pb2.

The development of bifunctional signal probes based on a single component is highly desirable for sensitive and simple dual-mode detection of Pb2+. Here, novel gold nanocluster-confined covalent organic frameworks (AuNCs@COFs) were fabricated as a bisignal generator to enable electrochemiluminescence (ECL) and colorimetric dual-response sensing. AuNCs with both intrinsic ECL and peroxidase-like activity were confined into the ultrasmall pores of the COFs via an in situ growth method. On the one hand, the space-confinement effect of the COFs closed the ligand motion-induced nonradiative transition channels of the AuNCs. As a result, the AuNCs@COFs exhibited a 3.3-fold enhancement in anodic ECL efficiency compared to the solid-state aggregated AuNCs using triethylamine as the coreactant. On the other hand, due to the outstanding spatial dispersibility of the AuNCs in the structurally ordered COFs, a high density of active catalytic sites and accelerated electron transfer were obtained, leading to the promotion of the enzyme-like catalytic capacity of the composite. To validate its practical applicability, a Pb2+-triggered dual-response sensing system was proposed based on the aptamer-regulated ECL and peroxidase-like activity of the AuNCs@COFs. Sensitive determinations down to 7.9 pM for the ECL mode and 0.56 nM for the colorimetric mode were obtained. This work provides an approach for designing single element-based bifunctional signal probes for dual-mode detection of Pb2+.

Electrochemical sensor based on Bi/Bi2O3 doped porous carbon composite derived from Bi-MOFs for Pb2+ sensitive detection.

It is of great significance to develop electrochemical sensors based on novel functional nanomaterials for heavy metal ions detection. In this work, a novel Bi/Bi2O3 co-doped porous carbon composite (Bi/Bi2O3@C) was prepared by simple carbonization of bismuth-based metal-organic frameworks (Bi-MOFs). The micromorphology, internal structure, crystal and elemental composition, specific surface area and porous structure of the composite were characterized by SEM, TEM, XRD, XPS, and BET. Further, a sensitive electrochemical sensor for Pb2+ detection was constructed by modifying Bi/Bi2O3@C on the surface of the glassy carbon electrode (GCE) based on the square wave anodic stripping voltammetric (SWASV). The different factors affecting the analytical performance were optimized systematically, such as material modification concentration, deposition time, deposition potential, and pH value. Under optimized conditions, the proposed sensor exhibited a wide linear range from 37.5 nM to 2.0 µM with a low detection limit of 6.3 nM. Meanwhile, the proposed sensor showed good stability, acceptable reproducibility, and satisfactory selectivity. The reliability of the as-proposed sensor was confirmed by the ICP-MS method for Pb2+ detection in different samples.

Highly Fluorescent Magnetic ATT-AuNCs@ZIF-8 for All-in-One Detection and Removal of Hg2+: An Ultrasensitive Probe to Evaluate Its Removal Efficiency.

The development of multifunctional materials for the synchronous detection and removal of mercury ions (Hg2+) is in high demand. Although a few multifunctional materials as a fluorescent indicator and adsorbent have achieved this aim, the feedback of their removal efficiency still depends on other methods. Herein, magnetic Fe3O4 nanoparticles (MNPs) and 6-aza-2-thiothymine-protected gold nanoclusters (ATT-AuNCs) were rationally assembled into a zeolitic imidazolate framework 8 (ZIF-8) structure via a one-pot method. The coordination assembly of ATT-AuNCs and ZIF-8 not only strengthened the aurophilic interactions of adjacent ATT-AuNCs but also induced the restriction of intramolecular motion of ATT with a six-membered heterocyclic structure. As a consequence, the fluorescence (FL) quantum yield of MNPs/ATT-AuNCs@ZIF-8 was 12.5-fold higher than that of pristine ATT-AuNCs. Benefiting from the enhanced FL emission, MNPs/ATT-AuNCs@ZIF-8 showed improved sensitivity for Hg2+ detection and therefore could evaluate the removal efficiency via FL detection, without relying on another detection method. Additionally, the nanocomposite also displayed a satisfactory removal capability for Hg2+, including a short capture time (20 min), a high removal efficiency (>96.9%), and excellent reusability (10 cycles). This work provides an approach for customizing functional nanocomposites to concurrently detect and remove Hg2+ with superior performance, especially for high detection sensitivity.

Photoactivities regulating of inorganic semiconductors and their applications in photoelectrochemical sensors for antibiotics analysis: A systematic review.

Efficient and rapid detection methods for antibiotics are of great practical importance to achieve environmental safety and protect human health. PEC sensors have been widely employed in antibiotics analysis due to their advantages of low background signal, high sensitivity, simple operation, and wide dynamic response range. This review is focused on the recent progress in photoactivities regulating of inorganic semiconductors from metal oxides/sulfides, metal-based quantum dots to metal-free carbon nitride and various types of PEC sensors in antibiotics monitoring which covers sensing strategies without or with a recognition element (antibody, molecularly imprinted polymer and aptamer). Finally, the challenges and the development prospects of the PEC sensors for antibiotics detection are discussed.

Removal of Chromium(VI) by Nanoscale Zero-Valent Iron Supported on Melamine Carbon Foam.

The overuse of chromium (Cr) has significantly negatively impacted human life and environmental sustainability. Recently, the employment of nano zero-valent iron (nZVI) for Cr(VI) removal is becoming an emerging approach. In this study, carbonized melamine foam-supported nZVI composites, prepared by a simple impregnation-carbonization-reduction method, were assessed for efficient Cr(VI) removal. The prepared composites were characterized by XPS, SEM, TEM, BET and XRD. Batch experiments at different conditions revealed that the amount of iron added, the temperature of carbonization and the initial Cr(VI) concentration were critical factors. Fe@MF-12.5-800 exhibited the highest removal efficiency of 99% Cr(VI) (10 mg/L) at neutral pH among the carbonized melamine foam-supported nZVI composites. Its iron particles were effectively soldered onto the carbonaceous surfaces within the pore networks. Moreover, Fe@MF-12.5-800 demonstrated remarkable stability (60%, 7 days) in an open environment compared with nZVI particles.

Boosting the singlet oxygen production from H2O2 activation with highly dispersed Co-N-graphene for pollutant removal.

Singlet oxygen (1O2) is a promising reactive species for the selective degradation of organic pollutants. However, it is difficult to generate 1O2 from H2O2 activation with high efficiency and selectivity. In this work, a graphene-supported highly dispersed cobalt catalyst with abundant Co-N x active sites (Co-N-graphene) was synthesized for activating H2O2. The Co-N-graphene catalyzed H2O2 reaction system selectively catalyzed 1O2 production associated with the superoxide radical (O2˙-) as the critical intermediate, as proven by scavenger experiments, electron spin resonance (ESR) spin trapping and a kinetic solvent isotope effect study. This resulted in excellent degradation efficiency towards the model organic pollutant methylene blue (MB), with an outstanding pseudo-first-order kinetic rate constant of 0.432 min-1 (g Lcatalyst -1)-1 under optimal reaction conditions (C H2O2 = 400 mM, initial pH = 9). Furthermore, this Co-N-graphene catalyst enabled strong synergy with HCO3 - in accelerating MB degradation, whereas the scavenger experiment implied that the synergy herein differed significantly from the current Co2+-HCO3 - reaction system, in which contribution of O2˙- was only validated with a Co-N-graphene catalyst. Therefore, this work developed a novel catalyst for boosting 1O2 production from H2O2 activation and will extend the inventory of catalysts for advanced oxidation processes.

Highly dispersed and stable nano zero-valent iron doped electrospun carbon nanofiber composite for aqueous hexavalent chromium removal.

In this work, a nZVI doped electrospun carbon nanofiber (nZVI-CNF) composite was prepared and applied for aqueous hexavalent chromium (Cr(vi)) removal. Firstly, FeCl3/PAN nanofibers were prepared by a simple electrospinning method; Then, nZVI-CNFs were obtained by carbonization of FeCl3/PAN nanofibers at 800 °C. The surface morphology and internal structure of nZVI-CNFs were characterized by SEM and TEM, showing that the uniformly dispersed nZVI particles were well integrated into the carbon layer structure. The Cr(vi) removal efficiency of nZVI-CNFs was 91.5% with a Cr(vi) concentration of 10 mg L-1 and the mechanism was further studied by XRD and XPS. Meanwhile, the nZVI-CNFs exhibited good stability over a wide range of pH values from 4-8 and a long time placement stability. Furthermore, nZVI-CNFs can be used as a filter membrane for continuous treatment of wastewater, suggesting great potential for practical application.

Preparation and Characterization of Multi-Doped Porous Carbon Nanofibers from Carbonization in Different Atmospheres and Their Oxygen Electrocatalytic Properties Research.

Recently, electrocatalysts for oxygen reduction reaction (ORR) as well as oxygen evolution reaction (OER) hinged on electrospun nanofiber composites have attracted wide research attention. Transition metal elements and heteroatomic doping are important methods used to enhance their catalytic performances. Lately, the construction of electrocatalysts based on metal-organic framework (MOF) electrospun nanofibers has become a research hotspot. In this work, nickel-cobalt zeolitic imidazolate frameworks with different molar ratios (NixCoy-ZIFs) were synthesized in an aqueous solution, followed by NixCoy-ZIFs/polyacrylonitrile (PAN) electrospun nanofiber precursors, which were prepared by a simple electrospinning method. Bimetal (Ni-Co) porous carbon nanofiber catalysts doped with nitrogen, oxygen, and sulfur elements were obtained at high-temperature carbonization treatment in different atmospheres (argon (Ar), Air, and hydrogen sulfide (H2S)), respectively. The morphological properties, structures, and composition were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Moreover, the specific surface area of materials and their pore size distribution was characterized by Brunauer-Emmett-Teller (BET). Linear sweep voltammetry curves investigated catalyst performances towards oxygen reduction and evolution reactions. Importantly, Ni1Co2-ZIFs/PAN-Ar yielded the best ORR activity, whereas Ni1Co1-ZIFs/PAN-Air exhibited the best OER performance. This work provides significant guidance for the preparation and characterization of multi-doped porous carbon nanofibers carbonized in different atmospheres.

Flexible, Porous, and Metal-Heteroatom-Doped Carbon Nanofibers as Efficient ORR Electrocatalysts for Zn-Air Battery.

Developing an efficient and durable oxygen reduction electrocatalyst is critical for clean-energy technology, such as fuel cells and metal-air batteries. In this study, we developed a facile strategy for the preparation of flexible, porous, and well-dispersed metal-heteroatom-doped carbon nanofibers by direct carbonization of electrospun Zn/Co-ZIFs/PAN nanofibers (Zn/Co-ZIFs/PAN). The obtained Zn/Co and N co-doped porous carbon nanofibers carbonized at 800 °C (Zn/Co-N@PCNFs-800) presented a good flexibility, a continuous porous structure, and a superior oxygen reduction reaction (ORR) catalytic activity to that of commercial 20 wt% Pt/C, in terms of its onset potential (0.98 V vs. RHE), half-wave potential (0.89 V vs. RHE), and limiting current density (- 5.26 mA cm-2). In addition, we tested the suitability and durability of Zn/Co-N@PCNFs-800 as the oxygen cathode for a rechargeable Zn-air battery. The prepared Zn-air batteries exhibited a higher power density (83.5 mW cm-2), a higher specific capacity (640.3 mAh g-1), an excellent reversibility, and a better cycling life than the commercial 20 wt% Pt/C + RuO2 catalysts. This design strategy of flexible porous non-precious metal-doped ORR electrocatalysts obtained from electrospun ZIFs/polymer nanofibers could be extended to fabricate other novel, stable, and easy-to-use multi-functional electrocatalysts for clean-energy technology.

Facile fabrication of PAN/PDMS core-shell nanofibers from synchronous photopolymerization.

Different from the traditional method for fabricating core-shell structure nanofiber, the PAN/PDMS nanofibers with core-shell structure (PAN as the core layer and PDMS as the shell layer) have been illustrated, which combines with the synchronous photopolymerization during emulsion electrospinning process. The morphology and structure of as-fabricated PAN/PDMS nanofibers are characterized by SEM and TEM. The composition of PAN/PDMS nanofibers is characterized by FTIR, XPS, TG, and DTG, successfully. The photopolymerization process is characterized by UV-vis spectroscopy indirectly. The WCA tests show that it has good hydrophobicity, which makes it possible as functional material. Meanwhile, the most important thing is that the method provides a flexible design strategy of core-shell structure nanofibers.