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Oxidation-Assisted ZnCl2 Activation of Pitch-Derived Hard Carbon with Abundant Closed Pores for Efficient Sodium Storage
As a low-cost precursor for hard carbon (HC) anodes in sodium-ion batteries, oxidized asphalt (OP) suffers from excessive carbon-layer ordering and insufficient development of closed-pore structure during pyrolysis, which limits low-voltage sodium storage and initial Coulombic efficiency. Herein, a synergistic strategy combining HNO3 oxidation with ZnCl2 activation is developed to regulate the microstructure of oxidized asphalt-derived HC. The oxygen-containing functional groups introduced by oxidation promote the anchoring of Zn species and facilitate the in situ generation of ZnO intermediates during pyrolysis, thereby reconfiguring the activation process and carbonization behavior. As a result, the ordered stacking of carbon layers is effectively suppressed, leading to an enlarged interlayer spacing of 0.391 nm and a closed-pore-rich structure. The obtained N–Zn–OP exhibits a defect-rich turbostratic framework with a specific surface area of 359.67 m2 g–1. Benefiting from the cooperative optimization of carbon layers and pore structure, the N–Zn–OP anode delivers a reversible capacity of 403.52 mAh g–1 at 15 mA g–1, with 51.13% of the capacity contributed by the low-voltage plateau, and retains 90% of its capacity after 100 cycles at 0.1C.
Uranyl separation from wastewater on the porous Fe-BC synthesized through coupling carbothermal reduction and ZnCl2 activation
Nano zero-valent iron (nZVI) has been widely reported to attract uranium (U(VI)) from wastewater through surface adsorption and reduction. However, surface oxidation and agglomeration of nZVI significantly limited the application of nZVI in removing U(VI) from wastewater. In this study, a novel porous nZVI/BC composite (Fe 1 Zn 3 -BC(900)) was synthesized via a one-step process coupling carbothermal reduction and ZnCl 2 activation. In this process, ferric chloride and zinc chloride were employed as the Fe and Zn precursors, while starch was utilized as the biochar precursor. Zn and Fe were formed in the carbothermal reduction process. The Zn was sacrificed through evaporation to increase the porosity, providing sufficient inner space for well-dispersing the nZVI, what could be wrapped and protected by the porous carbon. Besides, the galvanic cell between the nZVI-C interface was formed, accelerating the electron transfer for reduction of U(VI) into U(IV). As expected, the Fe 1 Zn 3 -BC(900) performed a high efficiency of 94.3% for separating the U(VI) in an initial concentration of 10 mg/L within 30 min, confirming the positive effect of ZnCl 2 sacrifice on enhancing separation of U(VI) onto the Fe 1 Zn 3 -BC(900). The high uranium removal efficiency can be attributed to the fact that the enhanced porosity resulting from Zn evaporation facilitates U(VI) adsorption. The reduction of U(VI) is further facilitated by the high dispersion of nZVI and the formation of Fe/C galvanic cell. Therefore, this work has developed a promising method to address the agglomeration of nZVI in the separation of U(VI) from wastewater, which provides a new idea for the subsequent efficient uranium removal.
Influence of magnesium chloride on the electrodeposition of zinc from the 1,3-dimethyl-2-imidazolidinone/ZnCl2 system
The effect of magnesium chloride (MgCl 2 ) on the electrodeposition of zinc in 1,3-dimethyl-2-imidazolidinone (DMI)/ZnCl 2 solvate ionic liquids was investigated. Cyclic voltammetry and Chronoamperometry are employed to study the electrochemical behavior of Zn. The crystal structure, microscopic morphology, and roughness of Zn coatings were measured by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Non-contact Optical Surface Profiler (OSP). The results reveal that adding MgCl 2 is favorable to the electrodeposition of Zn and leads to the formation of a new zinc-containing species in the electrolyte, which was confirmed by Raman spectra. Importantly, this addition does not affect the nucleation mechanism of zinc. Furthermore, the zinc grows preferentially on the (1 0 1) plane and a more smooth and uniform zinc coating was obtained. Corrosion resistance testing is conducted in a 3.5 wt% NaCl solution using the Tafel method. Coatings obtained at 4 mA/cm 2 and 343 K with 0.1 mol/L MgCl 2 addition exhibit lower corrosion current density of 38.10 μA/cm 2 compared to zinc coatings obtained without MgCl 2 .
Cellulose Paper Modified by a Zinc Oxide Nanosheet Using a ZnCl2-Urea Eutectic Solvent for Novel Applications
Cellulose paper has been functionalized by nanoparticles such as Ag nanoparticles, TiO2, and BaTiO3for versatile applications including supercapacitor, sensors, photoactivity, and packaging. Herein, zinc oxide (ZnO) nanosheet-modified paper (ZnO@paper) with excellent antibacterial properties was fabricated via a mild ZnCl2-urea eutectic solvent. In this proposed method, cellulose fibers as the raw material for ZnO@paper were treated by an aqueous solvent of ZnCl2-urea; the crystalline region was destroyed and [ZnCl]+-based cations were adsorbed on the surface of cellulose fibers, facilitating more ZnO growth on ZnO@paper. A flexible paper-based triboelectric nanogenerator (P-TENG) was made of ZnO@paper paired with a PTFE film. The P-TENG presents high triboelectric output performance and antibacterial activity. For instance, the output voltage and current of the P-TENG were 77 V and 0.17 μA, respectively. ZnO@paper showed excellent antibacterial activity againstE. coliandS. aureus, suggesting that a P-TENG can restrain and kill the bacteria during the working process. The results also indicated that ZnO could improve the surface roughness of cellulose paper, enhancing the output performance of a flexible P-TENG. In addition, the potential application of a P-TENG-based pressure sensor for determining human motion information was also reported. This study not only produced a high-performance P-TENG for fabricating green and sustainable electronics, but also provides an effective and novel method for ZnO@paper preparation.Keywords:cellulose paper;zinc oxide;triboelectric nanogenerator;antibacterial activity;pressure sensor
Facile preparation of cellulose nanocrystals/ZnO hybrids using acidified ZnCl2 as cellulose hydrolytic media and ZnO precursor
Hybridization of nanocellulose with zinc oxide nanoparticles can improve the dispersibility of the zinc oxide and bring new functions to the bio-based products. In this study, cellulose nanocrystal/zinc oxide (CNC/ZnO) nanohybrids with reinforcing and antibacterial properties were prepared via a facile one-pot route. Microcrystalline cellulose (MCC) was first treated with acidified zinc chloride and hydrolyzed into CNCs, which then served as a stabilizing and supporting agent for the in-situ growth of ZnO nanoparticles during subsequent chemical precipitation. The acidified ZnCl 2 solution played a dual role, acting both as cellulose hydrolytic media and as ZnO precursor. By adjusting the pH of the zinc precursor solution (pH = 9–12), well-dispersed rod-like (length: 137.0–468.0 nm, width: 54.1–154.1 nm) and flower-like (average diameter: 179.6 nm) ZnO nanoparticles with hexagonal wurtzite structure were obtained. CNC/ZnO nanohybrids were incorporated into waterborne polyurethane (WPU) films. The Young's modulus and tensile strength of the nanocomposite films increased gradually from 154.8 to 509.0 MPa and from 16.5 to 29.9 MPa, respectively, with increasing CNC/ZnO nanofiller content up to 10 wt%. The 10 % CNC/ZnO composites showed inhibition rates to both E. coli and S. aureus above 88.8 %.
Efficient and safe conversion of 5-hydroxymethylfurfural to 5-hydroxymethyl-2-furancarbonitrile with hydroxylamine zinc chloride salt
Efficient and safe conversion of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarbonitrile (HMFC) with hydroxylamine zinc chloride salt (ZnCl 2 ·2NH 2 OH) obtained from a novel method was developed. Without a catalyst, free NH 2 OH could react with HMF to produce HMFC with a yield of 41% at 55 °C. ZnCl 2 was an appropriate catalyst that increased HMFC yield to 64%. However, the reaction has a potential explosion safety hazard and a low effective utilization rate of NH 2 OH due to the easy decomposition property of free NH 2 OH. To address these issues, ZnCl 2 ·2NH 2 OH was prepared to serve as a hydroxylamine stabilizer, catalyst, and nitrogen source in the synthesis of HMFC. Therefore, NH 2 OH could be slowly released to participate in the reaction, slowing the invalid decomposition and increasing the utilization rate of elemental N. Under optimal conditions of n(HMF): n(NH 2 OH) = 1:1.5, 100 °C for 20 min with acetonitrile as solvent, the yield of HMFC was 100%. A plausible reaction mechanism for HMFC synthesis was also proposed.
Realizing High Thermoelectric Performance in ZnCl2-Doped N-Type Polycrystalline SnSe Through Band Engineering and Incorporating Multiple Defects
SnSe-based compounds, as promising thermoelectric materials, are well-known for their intrinsically low thermal conductivity and outstanding thermoelectric performance. However, the suboptimal electrical transport capacity for n-type polycrystalline SnSe significantly hinders the improvement of its thermoelectric performance. In this work, an effective approach for enhancing the thermoelectric performance of n-type SnSe polycrystalline materials through ZnCl2 doping has been investigated. The enhanced density of state effective mass, which is related to the introduction of an impurity level and the facilitation of multivalley degeneracy after ZnCl2 doping, can significantly improve the electrical transport coefficient. Additionally, multiple defects caused by ZnCl2 doping, such as multiscale precipitates, amorphous tin chloride, and twin boundaries, effectively decrease the lattice thermal conductivity, leading to a subsequently enhanced quality factor. As a result, the SnSe0.95–2%ZnCl2 sample achieves a maximum zT of ∼1.3 at 873 K parallel to the pressing direction, being 4 orders higher than that of the pristine SnSe0.95 sample and better than that of most other halide-doped SnSe samples. This study presents a cost-effective and environmentally friendly strategy for improving the thermoelectric properties of n-type polycrystalline SnSe.
The synthesis of glycerol carbonate from glycerol and urea using deep eutectic solvent ZnCl2:Acetamide as a catalyst
A series of deep eutectic solvents (DESs) with ZnCl 2 as hydrogen bonding acceptor and monoethanolamine (MEA) or acetamide as hydrogen bonding donor were prepared and used as catalysts for the reaction of glycerol and urea to synthesize glycerol carbonate (GC) without any additional organic solvent and co-catalyst. FT-IR, TGA, DSC and pH value were used to characterize the physicochemical properties of the prepared DESs. The effect of reaction temperature, urea to glycerol molar ratio, catalyst amount, and reaction time on the reaction were further investigated. The results show that ZnCl 2 :Acetamide (1:2) DES possess the highest catalytic activity because of the strong hydrogen bond network between ZnCl 2 and acetamide and the hydrogen bonding interactions between ZnCl 2 :Acetamide (1:2) and reactants, which were shown by FTIR spectra. The glycerol conversion of 93.85 % and GC yield of 90.77 % were obtained at reaction temperature of 140 °C, urea to GL molar ratio of 1:1, catalyst amount of 5 wt% (based on the GL weight) and reaction time of 2 h. Based on the experimental results and characterization by FTIR and ESI-MS, the reaction mechanism was proposed.
Preparation of porous carbon derived from a lignin-based polymer through ZnCl2 activation for effective capture of iodine
Lignin-based porous carbon, a derivative of lignin, is acknowledged for its cost-effectiveness, stability, and environmental sustainability. It exhibits significant adsorption capacity for the removal of heavy metals and in wastewater treatment, rendering it a highly esteemed adsorbent material. However, the potential of lignin-derived porous carbon for the capture of iodine in environmental contexts has yet to be thoroughly investigated. This research aims to examine the iodine capture capabilities of lignin-derived porous carbon in both iodine vapor and iodine/cyclohexane solution. Initially, lignin derivatives (ADL) (Mn = 2.85 × 10 4 , Mw / Mn = 1. 73) were synthesized through the graft copolymerization of lignin (Mn ≈ 2500), 4-acetoxystyrene, and dienopropyl terephthalate in ethylene glycol, utilizing azobisisobutyronitrile (AIBN) as the initiator. Subsequently, ADL was transformed into layered lignin-based porous carbon (ADLC) by one-step carbonization and zinc chloride activation. The iodine adsorption capacity of ADLC was determined to be 2340 mg/g in an iodine vapor environment and 354 mg/g in a 500 mg/L iodine/cyclohexane solution. These findings indicate that the layered porous carbon (ADLC) derived from lignin represents a promising material for iodine capture, providing an economical, stable, and environmentally friendly approach to nuclear waste management.
Template-activated bifunctional soluble salt ZnCl2 assisted synthesis of coal-based hierarchical porous carbon for high-performance supercapacitors
A series of coal-based hierarchical porous carbons with adjustable pores were successfully prepared with the assistance of the soluble salt Zinc chloride (ZnCl 2 ). During the carbonization process , ZnCl 2 , with a low melting point (238 °C), “in situ occupied” and “occupied” within the coal solids to generate interconnected pores, which acted as a template. Simultaneously, the activation of ZnCl 2 reduced the oxygen content of products and further improves their electrical conductivity . Optimization of the mass of the salt and the carbonization temperature resulted in targeted product with a suitable specific surface area (1581 m 2 g −1 ) and unique pores (V meso /V total = 45%), which exhibited a high specific capacitance (470.7 F g −1 at 0.5 A g −1 ) in 6 M KOH electrolyte. The symmetrical supercapacitor of targeted product has favorable rate performance (256.7 F g −1 at 0.5 A g −1 , 84.8% capacity retention at 30 A g −1 ) and excellent cycling performance (after 10000 cycles, the specific capacitance increases to 115% of the initial capacity at 10 A g −1 ). In the EMIMBF 4 electrolyte system, the energy density is 95.31 Wh kg −1 at 213.13 W kg −1 . Therefore, this work provides an effective method to improve the green and efficient use of coal.
Synergistic catalysis of species in molten salt hydrate for conversion of cellulose to 5-hydroxymethylfurfural
The one-pot approach was developed by using molten salt hydrate consisting of ZnCl 2 ·4H 2 O and LiCl·3H 2 O to produce 5-hydroxymethylfurfural (5-HMF) from cellulose . Cellulose was dissolved and regenerated to study the interaction of cellulose and molten salt hydrate. The effects of ZnCl 2 ·4H 2 O concentration, reaction time, and temperature on the conversion of cellulose to 5-HMF were investigated. 5-HMF yield increased when ZnCl 2 ·4H 2 O was mixed with LiCl·3H 2 O, and the maximum value (44.1%) was reached at 160 °C and 90 min when ZnCl 2 ·4H 2 O concentration was 64.9 mol%. The species of ZnCl 2 ·4H 2 O–LiCl·3H 2 O were analyzed, and the function of species concentration was correlated with the 5-HMF yield from the conversion of glucose and fructose. It was found that the synergistic catalysis of ZnCl 3 − , Zn 2+ , Zn(OH) + , H + as well as Li + promoted the efficiently cellulose conversion to 5-HMF.
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