Cobalt-Modified Black Phosphorus Nanosheets-Enabled Ferrate (VI) Activation for Efficient Chemiluminescence Detection of Thiabendazole.

The development of chemiluminescence-based innovation sensing systems and the construction of a sensing mechanism to improve the analytical performance of compounds remain a great challenge. Herein, we fabricated an advanced oxidation processes pretreated chemiluminescence (AOP-CL) sensing system via the introduction of cobalt-modified black phosphorus nanosheets (Co@BPNs) to achieve higher efficient thiabendazole (TBZ) detection. Co@BPNs, enriched with lattice oxygen, exhibited a superior catalytic performance for accelerating the decomposition of ferrate (VI). This Co@BPNs-based ferrate (VI) AOP system demonstrated a unique ability to selectively decompose TBZ, resulting in a strong CL emission. On this basis, a highly selective and sensitive CL sensing platform for TBZ was established, which exhibited strong resistance to common ions and pesticides interference. This was successfully applied to detecting TBZ in environmental samples such as tea and kiwi fruits. Besides, the TBZ detection mechanism was explored, Co@BPNs-based ferrate (VI) AOP system produced a high yield of ROS (mainly 1O2), which oxidized the thiazole-based structure of TBZ, generating chemical energy that was transferred to Co@BPNs via a chemical electron exchange luminescence (CIEEL) mechanism, leading to intense CL emission. Notably, this study not only proposed an innovative approach to enhance the chemical activity and CL properties of nanomaterials but also offered a new pathway for designing efficient CL probes for pollutant monitoring in complex samples.

Phosphorous nitride dots induced efficient advanced oxidation with intrinsic chemiluminescence for organic pollutant degradation.

In this work, we introduced new metal-free catalysts, phosphorus nitride dots (PNDs), into an environmentally friendly H2O2-SO32- system to generate abundant reactive oxygen species (O2˙-, ˙OH and SO4˙-) with strong intrinsic chemiluminescence (CL). The excellent catalytic ability of PNDs not only improved the degradation efficiency of organic pollutants, but also provided a promising prospect for deeply probing the mechanism of advanced oxidation processes (AOPs) by combining with CL.

Europium-Functionalized Graphitic Carbon Nitride for Efficient Chemiluminescence Detection of Singlet Oxygen.

Enhancing the sensitivity and selectivity of chemiluminescence (CL) sensors for detecting chemical species in complex samples poses a significant challenge in nanoparticle surface engineering. Graphitic carbon nitride (CN) shows promise but suffers from weak CL intensity and unknown luminescence mechanisms. In this study, we propose a nitrogen defect strategy to enhance the CL efficiency of europium-functionalized graphitic carbon nitride (Eu-CNNPs). By controlling the dosage of the europium modification, we can adjust the nitrogen defect content to reduce the energy gap and improve the CL performance. Remarkably, Eu-CNNPs with rich nitrogen defects exhibit strong chemiluminescence emission specifically for singlet oxygen (1O2) without responding to other reactive oxygen species (ROS). Building upon this finding, we developed a direct, selective, and sensitive CL sensing platform for 1O2 in PM2.5 and monitored 1O2 production in photosensitizers without interference from metal ions. Through extensive experiments, we attribute the 1O2-driven CL response to the presence of abundant nitrogen defects in the CN material, accelerating electron transfer and yielding a high generation of 1O2. Furthermore, chemiluminescence resonance energy transfer (CRET) between (1O2)2* (1O2 dimeric aggregate) and Eu-CNNPs contributes to strong CL emission. This work provides insights into enhancing the CL performance of CN and offers new possibilities for advancing the practical analysis of nanomaterials using the intriguing mechanism of nitrogen defects.

Modulated oxygen vacancies in europia clusters/black phosphorus induced signal amplification for efficient chemiluminescence sensing.

In this work, we proposed an oxygen vacancy engineering strategy to boost the chemiluminescence (CL) efficiency in europia clusters/black phosphorus quantum dots (Eu2O3/BPQDs), which could dramatically amplify the ClO- CL emission through electron transfer. Accordingly, a sensitive and direct CL sensing platform for hypochlorite and titanium ions was constructed. This work provides a neoteric methodology by modulating the surface state of nanoparticles to boost the CL sensitivity.

Europium functionalized black phosphorus quantum dots as a CRET platform for synergistically enhanced chemiluminescence.

In this work, we synthesize stable europium ion modified black phosphorus quantum dots (Eu-BPQDs) using a microwave irradiation technique, which can react with organic amines exhibiting unique chemiluminescence (CL). The mechanism of the Eu-BPQDs/organic amines CL system accounting for the efficient CRET is induced by the chelation of organic amines with the surface functionalized europium.

Efficient generation of sulfate radicals in Fe(ii)/S(iv) system induced by WS2 nanosheets and examined by its intrinsic chemiluminescence.

In this study, the generation of more SO4˙- and strong intrinsic chemiluminescence (CL) were achieved through activating sulfite (SO32-) with ferrous ions (Fe2+) on 5 nm-thick WS2 nanosheets. The blend of CL with the Fe2+/SO32- system by introducing WS2 nanosheets not only improved the efficiency of the degradation of pollutants but also revealed the potential of using CL to study the mechanism of SO4˙--based advanced oxidation processes (SR-AOPs).

Off/On Amino-Functionalized Polyhedral Oligomeric Silsesquioxane-Perylene Diimides Based Hydrophilic Luminescent Polymer for Aqueous Fluoride Ion Detection.

Fluoride ion detection in water focuses much attention due to the serious healthy impact in human pathologies. For fluoride recognition, the chemical affinity between fluoride and silicon has been developed on the basis of the degradation mechanism. However, most fluorescent probes are the "turn off" type due to the aggregation of the degradational products. Herein, we first developed an "off-on" hydrophilic luminescent polymer composed of amino-functionalized polyhedral oligomeric silsesquioxane (AE-POSS) and perylene diimides (PDIs) for fluoride ion in water. The AE-PDI polymer was "turned off" because of the photoinduced electron transfer (PET) between PDI and AE-POSS, and then after reaction with F-, the fluorescent emission could "turn on" obviously because the PET was blocked by the degradation of the cage. The PET from amino-POSS to PDI was proved by FL spectrum and energies of HOMO and LUMO orbitals. 29Si, 19F NMR, and 1H NMR titration, XRD, FTIR, size analysis, and ion chromatography were applied to demonstrate the degradation mechanism. These results indicated that the higher quantum yield could be obtained by introducing the amide group in the PDI and the products of AE-PDI polymer might exist in the form of complex compounds with partial condensation of organosiloxane. With high selectivity and sensitivity (detection limit of 16.2 ppb), this probe was successfully applied for F- detection in actual water samples.

Engineering the energy gap of black phosphorene quantum dots by surface modification for efficient chemiluminescence.

In this work, NH2-functionalized BPQDs (N-BPQDs) were purposely synthesized by using an ultrasound exfoliation technique combined with solvothermal treatment. The surface modification of BPQDs allowed engineering the energy gap and accelerating the electron transfer between the electron/hole donors and N-BPQDs, which played an important role in producing efficient chemiluminescence (CL) with the assistance of persulfate (K2S2O8). This work sheds new light on revealing the relationship between the BPQD structures and their optical properties.

Chemiluminescence of Oleic Acid Capped Black Phosphorus Quantum Dots for Highly Selective Detection of Sulfite in PM2.5.

Quantum dots (QDs), especially metal-free QDs with their unique optoelectronic properties, environmental friendliness, and excellent biocompatibility, have opened a new avenue to explore novel chemiluminescence (CL) systems for analytical applications. However, the unknown CL properties, relatively weak emission, and instability of some of them in water (e.g., black phosphorus QDs) often seriously hinder their further practical applications. Chemical modification trends have offered new properties for materials and have been proved to be desirable ways to establish sensing platforms with improved sensitivity and stability. Herein, oleic acid capped black phosphorus QDs (OA-BP QDs) with improved stability and optical properties were successfully synthesized. More importantly, an extraordinary CL emission when OA-BP QDs reacted with SO32- was first observed. In the CL process, OA-BP QDs acted as the catalyst to trigger singlet oxygen (1O2) generation in NaHSO3, and then a chemiluminescence resonance energy transfer (CRET) between (1O2)2* (1O2 dimeric aggregate) and OA-BP QDs was produced. On this basis, a new CL system for directly monitoring SO32- in airborne fine particulate matter (PM2.5) was fabricated. The study opens attractive perspectives of modified metal-free QDs for the practice of CL in monitoring the chemical species in PM2.5.

Chemiluminescence of black phosphorus quantum dots induced by hypochlorite and peroxide.

For the first time, black phosphorus quantum dots (BP QDs) were found to show chemiluminescence (CL) properties in the presence of hydrogen peroxide (H2O2) and hypochlorite (ClO-). Excited phosphorus oxides (HPO) resulting from the oxidation of BP QDs account for CL emission. Taking triacetone triperoxide (TATP) as an example, the potential application of a new CL system was evaluated. This work sheds new light on the characteristics and broader applications of black phosphorus (BP).