Simple Grinding Research Articles

Enabling a stable and dendrite-suppressed Zn anode via facile surface roughness engineering

• Smoother zinc metal anode surface exhibits better hydrophilicity. • Smoother zinc metal anode surface exhibits lower potential barrier and faster reaction kinetics. • Monitoring anode surface electrochemical behaviors during charging. • Computational simulation of the relationship between surface roughness and battery performance. The safety and cycle lifespan of zinc metal-based aqueous batteries are greatly restricted by zinc anode. The poor cycling performance of zinc metal anode is often considered to be impacted by the dendrite growth, surface passivation, zinc metal corrosion and hydrogen evolution reaction, while surface roughness is a matter that has often been ignored in past studies. Herein, a roughness gradient is constructed on the zinc anode surface by a simple grinding and pasting method. It has been found the modified zinc anodes with lower surface roughness exhibit the smaller zinc deposition overpotential and longer cycle life. Further, in situ optical microscopy photographs indicate that the zinc anode with an optimized roughness enables more uniform distribution of zinc precipitation and corrosion sites, which will facilitate a stable cycling performance of aqueous zinc ion batteries. The Zn anode dendrite-suppressing mechanism via surface roughness engineering was revealed through finite element computational simulation. These results emphasize the effectiveness of roughness engineering for tuning the surface physics of Zn anode and provide a facile strategy to develop better and safer aqueous zinc ion batteries.

Mechanochemical synthesis of gold-silver nanocomposites via diazonium salts

Mechanochemical synthesis of gold-silver nanocomposites from 4-ethynylaryl diazonium tetrachloroaurate(III) salt over chitosan is reported. The nanocomposites (AuAg-CTS NCs, CTS is chitosan) were synthesized by a simple grinding method using an agate mortar and pestle under ambient conditions. Four solid–solid reaction methods were used namely co-reduction, seeding, galvanic exchange, and immobilization. UV–visible data for the nanocomposites showed a peak at 445 nm. Transmission electron microscopy showed variable sizes for AuAg-CTS NCs such as 4.8 ± 0.9 nm (co-reduction), 74 ± 24 nm (seeding), 59 ± 26 nm (exchange), and 11.3 ± 7 nm (immobilization). X-ray photoelectron spectroscopy measurements supported the formation of gold and silver metals with a peak for Au4f7/2 at 84.8 eV and Ag3d5/2 at 368.2 eV.

Simple grinding for the synthesis of monomeric, dimeric, and trimeric pyridinium salts and its photophysical studies

AbstractSynthesis of water‐soluble‐substituted pyridinium cation which is attached with base sensitive fluorophore peripheral units with different inorganic counter anions under conventional/silica‐supported Muffle furnace methods. Solvent‐free synthetic approach has more merits than the conventional method, such as non‐toxic, shorter reaction time, easy workup procedure without purification process, and higher yields. Ultraviolet–visible spectra were recorded in neutral, acidic, and alkaline medium; it showed greater red shift in alkaline medium compared with neutral and acidic pH medium.

Ultrafast green synthesis of sub-micron Silicalite-1 zeolites by a grinding method

Sub-micron Silicalite-1 zeolite is traditionally synthesized by a prolonged synthesis approach which takes several days to complete. We herein demonstrate a rapid solvent-free synthesis route for sub-micron Silicalite-1 zeolite using TPAOH as an organic template to control the triple stage crystal growth rate and crystal morphologies of Silicalite-1 without the assistance of crystal seeds. This procedure is only achieved through simple mixing and grinding of raw materials and crystallization at 180 ​°C for 45 ​min. The fast synthesized Silicalite-1 zeolite proved to have higher crystal phases compared with the conventionally synthesized product. Through the absence of using additional solvents, all reactants were ultimately utilized without any waste, resulting in not only effectively reducing the cost of siliceous zeolites synthesis but also minimizing its environmental impact.

Simultaneous electrochemical detection of gallic acid and uric acid with p-tert-butylcalix[4]arene-based coordination polymer/mesoporous carbon composite.

Design and synthesis of an efficient electrocatalyst for simultaneous determinationof gallic acid (GA) and uric acid (UA) is vital in thebiological field. Herein, we synthesized a new p-tert-butylcalix[4]arene-based metal-organic electrocatalyst (Mn-L@MC) by combining Mn-L (H4L = tetrakis[(2-biphenylcarboxyl)oxy]-p-tertbutylcalix[4]arene) and mesoporous carbon (MC) via a simple mechanical grinding method. Synergistic effect between Mn-L and MC made the Mn-L@MC composite behave high-efficiency electrocatalytic performance toward simultaneous detection of GA and UA. Under optimal experimental conditions, the Mn-L@MC-2 electrode material featured relatively wide linear range (0.5-90µM) for the two analytes, and low determination limits of 0.043µM for GA and 0.059µM for UA. The remarkable electrochemical detection behavior of Mn-L@MC-2 electrode material toward GA and UA are comparable to those known sensors containing precious metals. TheMn-L@MC-2 material exhibited highselectivity, superior reproducibility, and acceptable stability during the determinationof the two analytes. Thesensor was assembled to simultaneously detect GA and UA in healthy human urine with satisfactory recoveries.

Optimal parameters of processing wheat grain in an ultrasonic installation

The article deals with the issues related to the process of grain processing to accelerate the process of wetting during simple grinding into wallpaper flour and decontamination of grain during storage with ultrasonic intensification of the process. A mathematical simulation of the grain processing process was carried out using the Statistica.10 program. The optimal operating parameters of the preparation of wheat grain for simple grinding were selected: water temperature – 300C, processing time – 40 seconds, the frequency of ultrasonic vibrations – 18-18.2 kHz, the intensity of the ultrasonic field – no more than 1 W/cm2.

Mechanochemical Preparation and Biological Activity of Mn (II) Complex from Ciprofloxacin

The mechanochemically prepared complex [Mn(cip)₂Cl₂] was synthesized using simple neat grinding method and analyzed using spectral studies, elemental analysis and physicochemical properties. The complex shows increase in biological activity compared with both the free ligand of ciprofloxacin and the standard. The IR spectral analysis of the complex, the ligand ciprofloxacin acts as bidentate ligand that indicate a strong band in the spectra at 1707.92 cm^-1 and 1628.81 cm^-1 which was assigned to υ(C=O) cm^-1 υ(COO) cm^-1. It shifted to a lower frequency’s regions of 1707.92 cm^-1 and 1625.40 cm^-1 in the complex indicating the involvement of carbonyl groups of both amide and carboxylic acid in the coordination, the bands at 478.20 cm^-1 and 750.39 cm^-1 which is absent in the free ligand appeared in the complex was assigned to υ(M-O) and υ(M-Cl) band. The value obtained from molar conductivity at 10.7 Ω^-1cm²mol^-1 indicate that the complex is non-electrolyte in DMSO. Both the elemental and physicochemical analysis agreed with the proposed structure of the compound and also suggested one metal to two ligands ratio. Due to environmentally friendly, shortest reactions time, inexpensive, production of higher yields the authors recommend the use of mechanochemical methods over solution-based.

A simple synthesis of surfactant-free polycrystalline CuO nanoparticles supported on carbon nanofibers for regioselective hydroboration of alkynes.

Copper oxide nanoparticles (CuO NPs) with a clean surface supported on carbon nanofibers (CNFs) in one-pot were prepared by simple solid-state grinding and aging followed by thermal treatment, yielding CuO nanoparticles with high (23.8 wt%) and uniform CuO loading in the absence of surfactants and solvent. The CuO NPs on CNFs (CuO/CNF) showed excellent catalytic activity in transforming a wide variety of alkynes into alkenyl boronates using B2Pin2 as a boron source in the absence of ligand and additives with high regioselectivity under mild conditions. Moreover, the present CuO/CNF catalyst was recyclable and possesses excellent chemoselectivity. The developed green synthetic approach is expected to offer exciting opportunities for designing monometallic or bimetallic nanoparticle catalysts on different supports applied in heterogeneous catalysis.

A hybrid borotungstate-coated metal-organic framework with supercapacitance, photocatalytic dye degradation and H2O2 sensing properties.

The compounding of polyoxometalates (POMs) with structurally well-defined and porous metal-organic frameworks (MOFs) has become a hot research topic. Here, a core-shell type hybrid, {Ag5BW12O40}@[Ag3(μ-Hbtc)(μ-H2btc)]n (called {Ag5BW12O40}@Ag-BTC-2, where BTC = 1,3,5-benzyl carboxylic acid), was successfully prepared via a simple grinding method. IR, XRD, SEM, TEM, and XPS analysis was used to confirm the structure. The specific capacitance is 179.1 F g-1 when the current density is 1 A g-1, using nickel foam as the collector, and the capacitance retention is 97.4% after 5000 cycles. The resulting aqueous-based symmetric supercapacitor has a power density of 496 W kg-1 and an energy density of 12.4 W h kg-1. In addition, the degradation rates using {Ag5BW12O40}@Ag-BTC-2 toward methylene blue (MB), rhodamine B (RhB), and methyl orange (MO) exceeded 90% in 140 min and remained essentially unchanged over five replicate experiments, showing high photocatalytic activity. Meanwhile, when {Ag5BW12O40}@Ag-BTC-2 acts as a H2O2 biosensor, it has a low detection limit (0.19 μM), a wide linear range (0.4 μM-0.27 mM) and high anti-interference properties. This shows that the synthesis of POMOFs via a grinding method is an effective strategy to improve the performance.

Sulfamic acid catalyzed grinding: A facile one-pot approach for the synthesis of polysubstituted pyrazoles under green conditions

A competent, rapid and simple grinding procedure for the synthesis of pharmacologically relevant polysubstituted pyrazoles catalyzed by sulfamic acid is reported via multicomponent reaction of substituted arylaldehydes, 4-nitrophenylacetonitrile, hydrazine hydrate, ethyl acetoacetate under solvent-free reaction conditions. In our reported protocol, four different reactants featuring diverse functional groups are assembled in one pot, enabling the synthesis of more diverse molecular structures in a facile manner.

A novel core-shell structured hybrid composed of zinc homobenzotrizoate and silver borotungstate with supercapacitor and photocatalytic dye degradation performance

Polyoxometalate-based metal-organic frameworks (POMOFs) are challenging as electrode materials for supercapacitors and catalysts for the photocatalytic degradation of organic pollutants. To this end, a novel core-shell structured zinc homobenzotrizoate and silver borotungstate ([Zn4(BTC)2(μ4-O)(H2O)2]@Ag5[BW12O40], abbreviated as Zn-BTC@Ag5[BW12O40], BTC = 1,3,5-benzylcarboxylic acid) was synthesized by wrapping polyoxometalate (POM) on metal-organic framework (MOF) by a simple grinding method. This unique synergy between the core (Zn-BTC) and shell (Ag5[BW12O40]) sets the compound more surface active sites. The composition, structure, and morphology of the title compound were discussed by infrared (IR), powder X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and other methods. In the three-electrode foam nickel system, the Zn-BTC@Ag5[BW12O40] electrode showed a higher specific capacitance (161.7 F g−1) than the Ag5[BW12O40] (97.7 F g−1) and Zn-BTC (118.4 F g−1), and the capacitance retention rate was 92.8% after 5000 cycles. Assembled into a symmetrical supercapacitor with an energy density of 9.3 Wh Kg−1 and a power density of 501.2 W Kg−1. The capacitance retention rate reached 91.4% after 5000 cycles. In addition, The photocatalytic degradation efficiency of Zn-BTC@Ag5[BW12O40] for Methylene Blue (MB), Methyl Orange (MO), and Rhodamine B (RhB) dyes are all greater than 90% in 140 min. The photocatalytic cycle test has been carried out 5 times, and the degradation effect remains the same. This indicates that the title compound has high activity in the direction of photocatalytic degradation of dyes.

Study of a water-soluble supramolecular complex of curcumin and β-cyclodextrin polymer with electrochemical property and potential anti-cancer activity

As a member of the curcuminoid compound family, curcumin (Cur) has many interesting therapeutic properties. However, its low aqueous solubility and stability have resulted in poor bioavailability and restricted clinical efficacy. Based on size matching, β-cyclodextrin polymer (β-CDP), with its hydrophilic polymer chains and hydrophobic cavities, can form an inclusion complex with Cur. To improve the water solubility and stability of Cur, a simple and eco-friendly grinding method was designed to form β-CDP inclusion complexes. According to the Boltzmann–Hamel's method and Job's method, the molar ratio of the β-CD unit in β-CDP to Cur was determined to be 1:1. The diffusion coefficient and diffusion activation energy of Cur-β-CDP were calculated in an electrochemical study. This supramolecular complex worked well in vitro to inhibit the proliferation of hepatoma carcinoma cells HepG2. Remarkably, this method visibly reduced the undesirable side effects on normal cells, without weakening the anti-cancer activity of the drugs. We expect that the obtained host–guest complex will provide a new approach for delivering natural drug molecules, having low water solubility.

Ultraviolet Light Detectable Circularly Polarized Room Temperature Phosphorescence in Chiral Naphthalimide Self-Assemblies.

The combination of circularly polarized luminescence (CPL) and pure-organic room temperature phosphorescence (RTP) potentially facilitates the construction of organic chiroptical optoelectronics and display materials, which however are challenging to use in realizing smart control of luminescent colors and switchable chiroptical properties. Here, we show a host-guest strategy to fabricate color-tunable RTP-based circularly polarized phosphorescence. Napthalimides were conjugated directly to chiral segments, of which supramolecular chirality and CPL activities in solid-states could be triggered by substituting bromine atoms on amines. Introducing tetracyanobenzene as an achiral host matrix via simple grinding would allow for the intersystem crossing to trigger red RTP and corresponding CPL by excitation lower than 320 nm, with a large Stokes shift more than 300 nm. The critical excitation wavelength of the RTP switch is determined by the absorbance of tetracyanobenzene. When the excitation wavelength was larger than 320 nm, blue fluorescence dominated with turned off RTP and CPL. The excitation wavelength-dependent RTP and CPL switch allows for detecting ultraviolet (UV) light, showing distinguishable red-blue luminescent color transition, accompanied by on/off RTP. Changing the host matrix from tetracyanobenzene to tricyanobenzene or dicyanobenzene could adjust the critical detecting wavelength limit from 320 to 300 nm. This work establishes a strategy to realize color-tunable, UV light detectable RTP and CPL under smart control.

Ball milling boosted the activation of peroxymonosulfate by biochar for tetracycline removal

Biochar materials have been commonly applied in advanced oxidation processes, and various strategies were explored to enhance the practical performance of biochar. In this study, ball milling, a simple grinding method, were used to treat biochar, and the ball-milled biochar materials were used to activate peroxymonosulfate (PMS) for tetracycline (TC) removal. It was demonstrated that the ball-milled biochar materials using different ball mass ratios and ball milling time benefited the generation of oxygen-functional groups and defects on the surface, thereby enhanced the catalytic performance of biochar to degrade TC. Besides, the different experimental conditions (initial pH, catalyst dosage, PMS dosage, and TC dosage) and coexisting substances all affected the degradation efficiency of TC. Electron paramagnetic resonance and radicals quenching experiments showed that the radicals attached to the biochar contributed greatly to the degradation of TC, and both free radicals and non-free radicals participated in the TC degradation process.

Effects of mechanical grinding on the phase behavior and anhydrous proton conductivity of imidazolium hydrogen succinate

Anhydrous organic proton conductors have attracted considerable attention as potential candidates for next-generation solid electrolytes in fuel cells. For further material development, a clear understanding of the conduction mechanism is essential, which can be accessed using crystalline materials as model systems. Recently, it has been reported that single-crystalline imidazolium hydrogen succinate (Im-Suc) exhibits a structural transition with the orientational disordering of imidazolium, which promotes proton conduction. In this study, we investigated the effects of mechanical grinding on the phase behavior and anhydrous proton conductivity of Im-Suc by comparing single-crystalline and mechanically crushed powder samples to understand the connection between ideal single crystals and highly disordered polymer systems. Thermal and structural analyses showed that grinding suppressed the structural transition through the introduction of structural disorder and mechanical stress. Moreover, the anhydrous proton conductivity was drastically enhanced with a significant decrease in activation energy in the low-temperature regime. Infrared spectroscopy indicated that the imidazolium dynamics was modulated by mechanical grinding. These findings reveal the possibility of improving the performance of anhydrous organic proton conductors and modulating their molecular dynamics properties and conduction mechanisms by simple mechanical grinding.

Punica granatum pericarp extract catalyzed green chemistry approach for synthesizing novel ligand and its metal(II) complexes: Molecular docking/DNA interactions

The gallic acid (GA) obtained from the ethanolic extract of Pomegranate(Punica granatum) pericarp, was successfully applied as a green and effective natural catalyst for the synthesis of novel quinoline based amino acid Schiff base ligand, L (C16H14N4O3) and its divalent metal complexes (where M = Fe(II), Co(II), Ni(II), Cu(II); L=(E)-2-(((2-hydroxyquinolin-3-yl)methylene)amino)-3-(1H-imidazol-5-yl)propanoic acid) through condensation of 2-hydroxyquinoline-3-carbaldehyde with L-histidine, employing a simple physical grinding technique. The ligand and the complexes denoted as [M(LH2)2] were characterized by advanced spectroscopic and analytical techniques. The configuration of the as synthesized complexes is deduced to be octahedral. The molecular docking experiments were performed by using an Autodock-4 tool to find the binding mode of the metal(II) complexes to B-DNA dodecamer. The metal complex interactions with CT-DNA were studied using spectroscopic techniques, viscosity analysis and thermal denaturation method. In UV-visible irradiation with pUC19 DNA the photo-induced cleavage studies interpreted the photonuclease characteristics of the metal(II) complexes.

A facile method of generating aluminosilicate nanoparticles: Complete fragmentation of kaolinite nanoscrolls via manual grinding

Aluminosilicate nanoparticles were prepared by the complete breakdown of the tube walls of kaolinite nanoscrolls by manual grinding. Transmission electron microscopy observation of the product showed a lack of the original hollow cylindrical morphology together with the formation of nanoparticles Hysteresis over the relative pressure range of 0.50–0.95 was present in the nitrogen adsorption/desorption isotherm of kaolinite nanoscroll but not in that of ground product. These results indicate the successful formation of kaolinite nanoparticles using a simple grinding method.

An elegant and efficient synthesis of heterocycles integrated with bis‐N‐acyl pyrazoline and bis‐1, 2, 3‐triazole via a green synthetic methodology

AbstractHighly efficient and sustainable one‐pot multicomponent synthetic protocol has been accomplished for the synthesis of novel bis‐N‐substituted pyrazolinyl‐1, 2, 3‐triazole hybrids from readily available starting materials via operationally simple mechanochemical grinding approach. The present solvent‐free synthetic protocol is advantageous for being atom economic involving short reaction time, ambient temperature, and non‐chromatographic separation of products.

Insights into the Operation of Noble-Metal-Free Cocatalyst 1T-WS2 -Decorated Zn0.5 Cd0.5 S for Enhanced Photocatalytic Hydrogen Evolution.

Due to inefficient charge separation and low surface catalytic conversion efficiencies, cocatalysts are required for achieving photocatalytic hydrogen evolution. Being a noble-metal-free cocatalyst, metallic 1T-WS2 with excellent conductivity can function for this reaction. Herein, 1T-WS2 /Zn0.5 Cd0.5 S is constructed via a simple and feasible grinding approach. The composite containing 7.5 % 1T-WS2 in 1T-WS2 /Zn0.5 Cd0.5 S achieves a hydrogen evolution rate of 61.65 mmol g-1 h-1 and an external quantum efficiency of 8.04 % at 420 nm, which is 37 times that of bare Zn0.5 Cd0.5 S (1.67 mmol g-1 h-1 ). The electrical conductivity of metallic 1T-WS2 reduces the transfer impedance at the interface and thus accelerates the non-radiative energy transfer and electron transport rate. The different Fermi levels of 1T-WS2 and Zn0.5 Cd0.5 S form a Schottky junction, which promotes the transfer of photogenerated electrons from Zn0.5 Cd0.5 S to 1T-WS2 . More importantly, the close interface contact between 1T-WS2 and Zn0.5 Cd0.5 S results in strong electron interactions, which is conducive to the spatial separation of photogenerated electrons and holes. This work will further expand the application of 1T-WS2 in the photocatalytic hydrogen evolution process.

One-pot synthesis of acid-base bifunctional catalysts for biodiesel production

Acid-base bifunctional heterogeneous solid catalysts, known as the active site with base-acid properties, exhibited relatively good performance on the transesterification for soybean oil for green fuel production. We investigated the use of niobium and three alkali metal oxides (Li, Na, and K) as MyNbOX (M = Li, Na, K) composite as acid-base catalysts for biodiesel production. MyNbOX catalysts were prepared using a simple solid-state reaction, mixing, and grinding niobium dioxide with alkali metal carbonates calcined at 800 °C in air for 4 h. XRD, BET, FE-SEM, TEM and TPD techniques were employed for catalysts characterization. The highest biodiesel yield (98.08%) was achieved under the transesterification condition of 65 °C, 6 h, 24 methanol/oil molar ratio and 2 wt% of LiNbO3 as the catalyst. The results showed that LiNbO3 could be efficiently reused at least 10 cycles with an insignificant reduction in the biodiesel yield. The physicochemical properties of the biodiesel were further studied and compared with the ASTM and the EN biodiesel specifications. The results showed that the properties of the biodiesel produced complied with the international standard specifications.