Carbon Quantum Dots: Properties, Preparation, and Applications.

Carbon quantum dots are a novel form of carbon material. They offer numerous benefits including particle size adjustability, light resistance, ease of functionalization, low toxicity, excellent biocompatibility, and high-water solubility, as well as their easy accessibility of raw materials. Carbon quantum dots have been widely used in various fields. The preparation methods employed are predominantly top-down methods such as arc discharge, laser ablation, electrochemical and chemical oxidation, as well as bottom-up methods such as templates, microwave, and hydrothermal techniques. This article provides an overview of the properties, preparation methods, raw materials for preparation, and the heteroatom doping of carbon quantum dots, and it summarizes the applications in related fields, such as optoelectronics, bioimaging, drug delivery, cancer therapy, sensors, and environmental remediation. Finally, currently encountered issues of carbon quantum dots are presented. The latest research progress in synthesis and application, as well as the challenges outlined in this review, can help and encourage future research on carbon quantum dots.

Electronic Lieb lattice signatures embedded in two-dimensional polymers with a square lattice.

Exotic band features, such as Dirac cones and flat bands, arise directly from the lattice symmetry of materials. The Lieb lattice is one of the most intriguing topologies, because it possesses both Dirac cones and flat bands which intersect at the Fermi level. However, the synthesis of Lieb lattice materials remains a challenging task. Here, we explore two-dimensional polymers (2DPs) derived from zinc-phthalocyanine (ZnPc) building blocks with a square lattice (sql) as potential electronic Lieb lattice materials. By systematically varying the linker length (ZnPc-xP), we found that some ZnPc-xP exhibit a characteristic Lieb lattice band structure. Interestingly though, fes bands are also observed in ZnPc-xP. The coexistence of fes and Lieb in sql 2DPs challenges the conventional perception of the structure-electronic structure relationship. In addition, we show that manipulation of the Fermi level, achieved by electron removal or atom substitution, effectively preserves the unique characteristics of Lieb bands. The Lieb Dirac bands of ZnPc-4P shows a non-zero Chern number. Our discoveries provide a fresh perspective on 2DPs and redefine the search for Lieb lattice materials into a well-defined chemical synthesis task.

Bottom-Up Synthesis of Crystalline Covalent Organic Framework Nanosheets, Nanotubes, and Kippah Vesicles: An Odd-Even Effect Induction.

Few-layer organic nanosheets are becoming increasingly attractive as two-dimensional (2D) materials due to their precise atomic connectivity and tailor-made pores. However, most strategies for synthesizing nanosheets rely on surface-assisted methods or top-down exfoliation of stacked materials. A bottom-up approach with well-designed building blocks would be the convenient pathway to achieve the bulk-scale synthesis of 2D nanosheets with uniform size and crystallinity. Herein, we have synthesized crystalline covalent organic framework nanosheets (CONs) by reacting tetratopic thianthrene tetraaldehyde (THT) and aliphatic diamines. The bent geometry of thianthrene in THT retards the out-of-plane stacking, while the flexible diamines introduce dynamic characteristics into the framework, facilitating nanosheet formation. Successful isoreticulation with five diamines with two to six carbon chain lengths generalizes the design strategy. Microscopic imaging reveals that the odd and even diamine-based CONs transmute to different nanostructures, such as nanotubes and hollow spheres. The single-crystal X-ray diffraction structure of repeating units indicates that the odd-even linker units of diamines introduce irregular-regular curvature in the backbone, aiding such dimensionality conversion. Theoretical calculations shed more light on nanosheet stacking and rolling behavior with respect to the odd-even effects.

Efficiency and mechanisms of cadmium removal via core-shell zeolite/Zn-layer double hydroxides.

To investigate the removal mechanisms of cadmium (Cd) by Zn-layer double hydroxides-modified zeolites substrates in constructed rapid infiltration systems (CRIS), the ZnAl-LDHs and ZnFe-LDHs were synthesized and in-situ coated on the original zeolites through co-precipitation method. The prepared Zn-LDHs-modified and original zeolites were characterized by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) methods, whose results provided the evidences that the Zn-LDHs were successfully coated on the original zeolites. From the results of purification experiments, the average Cd removal rates of ZnAl-LDHs-modified, ZnFe-LDHs-modified and original zeolites were 88.40, 86.00 and 32.52%, respectively; demonstrating that the removal rates of zeolites could significantly improve. Additionally, the modification of Zn-LDHS could enhance the theoretical adsorption ability. According to the results of isothermal adsorption and desorption tests, the desorption rates of Zn-LDHs-modified zeolites were higher than that of original zeolites. Cd adsorption capacity of ZnFe-LDHs-modified zeolites was 1428.57 mg kg-1 and original zeolites was 434.783 mg kg-1. In the adsorption kinetic studies, the pseudo-second-order models were used to well describe the experimental results of Zn-LDHs-modified zeolites, indicating that their adsorption types were attributed to be more stable chemisorption. Besides, the relevant microbial tests also confirmed that microbial enzymatic activity and extracellular polymeric substances (EPS) were significantly promoted on surface of Zn-LDHs-modified zeolites. The contents of EPS on the surface of zeolites were as following: ZnAl-LDHs-modified zeolites (78.58128 µg/g) > ZnFe-LDHs-modified zeolites (71.85445 µg/g) > original zeolites (68.69904 µg/g). Meanwhile, the results of high-throughput sequencing showed that modification by Zn-LDHs improved microbial diversity and relative abundance. The Proteobacteria was the dominant phylum and the Acidobacteria was conducive to Cd removal. Overall, it could be concluded that ZnAl-LDHs-modified zeolites might be applied as an efficient substrate for Cd removal in CRIS.

Hexavalent chromium removal from aqueous solution by adsorption on modified zeolites coated with Mg-layered double hydroxides.

In this study, MgAl-LDHs and MgFe-LDHs were synthesized via co-precipitation method and in situ coated on pre-washed zeolites through dipping process in beaker. The obtained modified zeolites and original zeolites were utilized as substrates of constructed rapid infiltration systems (CRIS) to remove hexavalent chromium (Cr(VI)) in wastewater. Micro-morphology features and chemical composition of zeolites before and after modification were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray fluorescence spectrometer (XRF). The SEM, XRD, and XRF results demonstrated the feasibility of LDHs coated on the surface of the original zeolites. Purification experiments in simulated CRIS showed that the Cr(VI) removal rates of zeolites/MgAl-LDHs increased by 110.03% on average every concentration (0.5-16 mg L-1) compared with the original zeolites under 24-h HRT. The adsorption capacity of zeolites/MgAl-LDHs reached 66.98 mg kg-1 at 32 mg L-1 initial Cr(VI) concentration, which is nearly twice that of the original zeolites (33.24 mg kg-1) and 1.5 times higher than that of zeolites/MgFe-LDHs (42.01 mg kg-1). Isothermal adsorption tests showed that the Freundlich isotherm equations gave better fitting to the adsorption process. And zeolites/MgAl-LDHs showed a best fit with pseudo-second-order model which meant that the adsorption of Cr(VI) by zeolites/MgAl-LDHs was dominated by chemisorption. Thermodynamic parameters showed that the process of adsorption for the three substrates was spontaneous and endothermic intrinsically. Zeolites/MgAl-LDHs also displayed nearly 60% desorption rate with low concentration eluent (0.01 mol L-1 NaCl). Therefore, zeolites/MgAl-LDHs were chosen out as an optimal substrate for removing Cr(VI) from wastewater in CRIS. Graphical Abstract.

Microbial action and mechanisms for Cr(VI) removal performance by layered double hydroxide modified zeolite and quartz sand in constructed wetlands.

This study was conducted to evaluate the performance underlying the removal of hexavalent chromium Cr(VI) associated with Zn-layered double hydroxides (Zn-LDHs)-modified substrates utilized in simulated constructed wetlands (CWs) from a microbial perspective. To accomplish this, Zn-LDHs-modified substrates (zeolite and quartz sand (QS)) were synthesized at various Zn2+/Al3+ and Fe3+ molar ratios by co-precipitation under alkaline conditions. The experimental group was then compared with a control group to determine the microbial action responsible for Cr(VI) removal during the Cr(VI) removal experiments. The removal experiment revealed that the average Cr(VI) removal rates of the Zn-LDHs-modified substrates were superior to those of natural substrates. Subsequent evaluation of the microbial structure by Illumina high-throughput sequencing revealed that the relative abundance of Novosphingobium, Brevundimonas, Methylophilus, and Acidovorax related to Cr(VI) removal was relatively high in Zn-LDHs-modified substrates. Moreover, the extracellular polymeric substance (EPS) content was significantly influenced by the Zn-LDHs coating according to the relative microbial experiments. Similar trends were observed in enzyme activity. Taken together, these findings illustrated that the Zn-LDHs coating had a significant impact on microbial action, and the Cr(VI) removal efficiency of the Zn-LDHs-modified QS (zeolite) substrate was better than that of the natural substrate because of intracellular and extracellular removal mechanisms. Briefly, the microbial action of Zn-LDHs-modified QS played an important role in Cr(VI) removal, since the EPS content possessed the appropriate concentrations. Moreover, the microbial activity of ZnAl-LDHs-modified QS (zeolite) may have been higher than that of ZnFe-LDHs-modified QS (zeolite) because Al had a stronger promoting effect on Cr(VI) bio-removal than Fe. Therefore, the microbial Cr(VI) removal supported by ZnAl-LDHs-modified QS is a better choice for CWs.

Removal of Cd(II) by modified maifanite coated with Mg-layered double hydroxides in constructed rapid infiltration systems.

To improve the adsorption performance of Cd(II) by maifanite in constructed rapid infiltration systems (CRIS), Mg-layered double hydroxides (MgAl-LDHs, MgFe-LDHs) are prepared by a co-precipitation method and in-situ coated on the surface of original maifanite. Characterization of the successful LDHs-coating modification is realized by the following: scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Brunauer Emmett Teller (BET). In the purification experiments, the average removal rates of Cd(II) were 97.66% for maifanite/MgAl-LDHs and 97.54% for maifanite/MgFe-LDHs, approximately 11% greater than for the original maifanite. Isothermal adsorption experiments and adsorption kinetic experiments were conducted to explore the Cd(II) adsorption mechanism. The modified maifanite demonstrated a higher Langmuir adsorption capacity and stronger surface bond energies compared to the original maifanite. The adsorption type of Cd(II) by maifanite/Mg-LDHs and original maifanite was monolayer adsorption based mainly on chemical adsorption. Furthermore, the extracellular polymeric substances and dehydrogenase activities of the microorganisms were measured and analyzed to study the effect of microorganisms on the removal of Cd(II) in the test columns. High-throughput sequencing technology was also applied to analyze the composition and diversity of bacterial communities. Based on a simple estimation, the synthesis cost of maifanite/MgAl-LDHs was only ¥ 0.33/Kg. In brief, maifanite/Mg-LDHs is an efficient and economical substrate for a CRIS for Cd(II) removal.

[Adsorption of Cr(â ¥) in Water by Maifanite Modified with Different LDHs Coatings].

Under alkaline conditions, the hydrothermal coprecipitation method was used to form different layered double hydroxides (LDHs) by combining different bivalent and trivalent metal compounds, such as ZnCl2, MgCl2, AlCl3, and FeCl3, and then LDHs were coated on the surface of the original maifanite. The effect of LDHs coating-modified maifanite on the improvement of Cr(Ⅵ) adsorption in water was studied using isothermal adsorption, desorption, non-isothermal adsorption, adsorption kinetics, pH, and competitive adsorption tests, respectively. The results show that the maximum theoretical adsorption capacity of modified maifanite for Cr(Ⅵ) is close to ten times that of original maifanite at 15℃. The adsorption effect of ZnAl-LDHs coating-loaded modified maifanite is better than that of other LDHs-coating modified maifanites. In contrast, the results of the desorption experiments show that maifanite coated with LDHs enhances the reuse of substrates. The thermodynamic parameters of the substrate for Cr(Ⅵ) adsorption in the experiment were △Gθ < 0, △Hθ < 0, △Sθ > 0, indicating that the substrate adsorption process of Cr(Ⅵ) is spontaneous and exothermic. Based on the adsorption kinetics study, the adsorption process of Cr(Ⅵ) by maifanite could be fitted using a pseudo-secondary reaction process. The adsorption type was mainly chemisorption. By selecting the suitable metal ion combination method to prepare different LDHs-coating modified maifanites, the Cr(Ⅵ) performance can effectively be improved.

Removal of hexavalent chromium ions by core-shell sand/Mg-layer double hydroxides (LDHs) in constructed rapid infiltration system.

This study aimed to determine the efficiencies and mechanisms of hexavalent chromium (Cr(VI)) removal with modified sand coated by Mg-LDHs in constructed rapid infiltration system (CRIS). Mg-LDHs (MgAl-LDHs, MgFe-LDHs) were prepared by co-precipitation method and in situ coated onto the surface of original sand. Scanning Electron Microscope (SEM) and X-Ray Fluorescence Spectrometer (XRFS) were used to analyze physicochemical properties of sand/Mg-LDHs composites. Results obtained confirmed the successful LDHs-coating modification. During the purification experiments, the average removal rates of Cr(VI) were 47.62% for sand/MgAl-LDHs, 34.15% for sand/MgFe-LDHs and 11.61% for original sand, respectively. The sand/Mg-LDHs had a higher Langmuir adsorption capacity and desorption capability for Cr(VI) compared to original sand. The adsorption kinetic data of different adsorbents were better described by pseudo-second-order model. Intra-particle diffusion model was also used to elucidate the adsorption mechanism. Moreover, extracellular polymeric substances, biomass and enzymatic activity of microbes on the modified and original sand were testified and analyzed to study microbial effect on Cr(VI) removal in test columns. Through a rough economic estimation, the reagent cost of sand/MgAl-LDHs synthesis was only RMB ¥ 0.24/Kg. It could be concluded that MgAl-LDHs modified sand is an efficient and economical substrate of CRIS for Cr(VI) removal.

Sequentially Reinforced Additive Coating for Transparent and Durable Superhydrophobic Glass.

Now that there are various routes to prepare superhydrophobic surfaces for self-cleaning, anti-icing, liquid collecting, etc., attentions are moving toward low-cost upscaling of routes and increasing the reliability for actual applications. However, the required micro-nano structures for superhydrophobicity are light scattering and very vulnerable to abrasion. This intrinsically conflicts with the transparency and durability of superhydrophobic glass, which are the major barriers for its commercialization. In this study, we present a novel sequentially reinforced additive coating (SRAC) process to realize robust and transparent micro-nano structured film with tough intergranular sintering. A benign aqueous-based ink with poly(furfuryl alcohol) (PFA) and silica species is carefully designed and sprayed on glass to enable self-phase separation and morphology construction. The coatings reach the static contact angle (SCA) for water over 166° and withstand a 6H pencil scratching, the cross-cut test, and sand abrasion. Moreover, we also performed a 90 day outdoor performance test and the glass maintained superhydrophobicity with an SCA of 154°. These results provide a low-cost waterborne ink formula, and the high throughput and upscalable SRAC process could be a convenient technology for the fabrication of large area, robust superhydrophobic coatings.

Enhanced removal performance of Cr(VI) by the core-shell zeolites/layered double hydroxides (LDHs) synthesized from different metal compounds in constructed rapid infiltration systems.

Nine kinds of LDHs were synthesized by the co-precipitation method under alkaline conditions with different combinations of trivalent metal compounds (FeCl3, AlCl3, CoCl3) and divalent metal compounds (CaCl2, MgCl2, ZnCl2), which were then coated in situ on the surface of zeolites to synthesize core-shell zeolites/LDHs composites. The zeolites before and after modification were characterized by SEM and X-ray fluorescence spectrometry. Using the different core-shell zeolites/LDHs and original zeolite substrates, the constructed rapid infiltration systems (CRIS) simulated test columns were set to treat the municipal sewage containing hexavalent chromium, Cr(VI). Isothermal adsorption tests were subsequently performed. The average removal efficiencies of the small-sized zeolites were much higher than those of the large-sized zeolites. For the small-sized zeolites, the Cr(VI) removal performances of the Mg-LDHs- and Al-LDHs-modified zeolite substrates were efficiently enhanced in particular, which could reach over 90%. And the removal rate of core-shell zeolites/ZnAl-LDHs reached 94.5%. Meanwhile, the maximum adsorption capacity of ZnAl-LDHs-modified zeolites could reach 51.0 mg/kg, indicating that the adsorption properties could be enhanced by ZnAl-LDHs coating. During the purification experiments, most of the LDHs-modified zeolites maintained their predominant chemical adsorption ability for the removal of Cr(VI). Therefore, the small-sized core-shell zeolites/ZnAl-LDHs composites could be used as potential substrates for the efficient removal of Cr(VI) in CRIS.