Post-Formation of Fused Pentagonal Structure on Fjord Region of Polyaromatic Hydrocarbons under Hydrothermal Conditions.

This study explores the synthesis of cyclopenta-fused polyaromatic hydrocarbons (CP-PAHs) via Pt-catalyzed cyclization in water, focusing on the formation of fused pentagonal rings within heavily fused PAH frameworks. Utilizing platinum catalysts at lower temperatures (200-260 °C) in water, led to the successful synthesis of singly cyclized CP-PAHs. The reaction conditions facilitated the mono-cyclization of substrates such as dibenzo[g,p]chrysene and its isomers, yielding the desired products while suppressing the formation of bis-cyclized compounds. The use of Fe2O3 as an additive in conjunction with PtO2 was effective to suppress hydrogenation of the substrates and products. The products exhibited a redshift in UV-visible absorption and photoluminescence bands due to a decrease in the HOMO-LUMO energy gap. These findings highlight the potential of Pt-catalyzed cyclization for the controlled synthesis of CP-PAHs, with implications for various applications in materials science.

Sr2[B5O8(OH)]2 ⋠[B(OH)3] ⋠H2O: A Strontium Borate That Shows Deep-Ultraviolet-Transparent Nonlinear Optical Properties.

A new noncentrosymmetric strontium borate, P1-Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O (1), has been synthesized under the hydrothermal condition. The P1-Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O shows a layered B-O network with 9-ring windows in the ab plane. Sr2+ cations, H3BO3, and H2O molecules are located in the voids of layers and interlayers, respectively. The P1-Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O is the first synthetic phase of veatchite, while the other three polymorphs are found in different natural minerals. This strontium borate is a potential deep-ultraviolet-transparent nonlinear-optical (NLO) crystal whose second-harmonic-generation (SHG) intensity is 1.7 times that of KH2PO4 (KDP) and is phase-matchable. The short wavelength cutoff edge of compound 1 is below 190 nm. Density functional theory (DFT) calculations show that the B-O units are responsible for the nonlinear optical property.

Bismuth sulfide micro flowers decorated nickel foam as a promising electrochemical sensor for quantitative analysis of melamine in bottled milk samples.

Here, we demonstrate hydrothermally grown bismuth sulfide (Bi2S3) micro flowers decorated nickel foam (NF) for electrochemical detection of melamine in bottled milk samples. The orthorhombic phase of hydrothermally grown Bi2S3is confirmed by the detailed characterization of x-ray diffraction and its high surface area micro flowers-like morphology is investigated via field emission scanning electron microscope. Furthermore, the surface chemical oxidation state and binding energy of Bi2S3/NF micro flowers is analyzed by x-ray photoelectron spectroscopy studies. The sensor exhibits a wide linear range of detection from 10 ng l-1to 1 mg l-1and a superior sensitivity of 3.4 mA cm-2to melamine using differential pulse voltammetry technique, with a lower limit of detection (7.1 ng l-1). The as-fabricated sensor is highly selective against interfering species of p-phenylenediamine (PPDA), cyanuric acid (CA), aniline, ascorbic acid, glucose (Glu), and calcium ion (Ca2+). Real-time analysis done in milk by the standard addition method shows an excellent recovery percentage of Ì´ 98%. The sensor's electrochemical mechanism studies reveal that the high surface area bismuth sulfide micro flowers surface interacts strongly with melamine molecules through hydrogen bonding and van der Waals forces, resulting in a significant change in the sensor's electrical properties while 3D skeletal Nickel foam as a substrate provides stability, enhances its catalytic activity by providing a more number /of active sites and facilitates rapid electron transfer. The work presented here confirms Bi2S3/NF as a high-performance electrode that can be used for the detection of other biomolecules used in clinical diagnosis and biomedical research.

Two new 3D Supramolecular Frameworks as Photocatalysts for Degradation of Methyl Blue.

We successfully synthesized two new supramolecular frameworks, namely {[Cu2(L1)(H2O)2]·(H2O)}n (1) and {[Ag(L2)(bpp)]2n·2(H2O)}n (2) (H2L1 = 2-hydroxy-5-sulfobenzoic acid, HL2 = 8-hydroxyquinoline-2-sulfonic acid) under hydrothermal condition. These single-crystal structures were determined via X-ray single crystal diffraction analyses. Solids 1 and 2 acted as photocatalysts and performed good photocatalytic activities for MB degradation under UV light irradiation.

A novel nanozyme doped ZnO/r-GO-based sensor for highly sensitive electrochemical determination of muscle-relaxant drug: cyclobenzaprine HCl.

A nanocomposite of Ce-doped ZnO/r-GO was synthesized using a conventional hydrothermal method. The synthesized nanocomposites were utilized for the purpose of sensitive and selective detection of cyclobenzaprine hydrochloride (CBP). The properties of the composite were extensively analyzed, including its morphology, structure, and electrochemical behavior. This study investigates the application of a modified glassy carbon electrode for the detection of CBP, a muscle relaxant used to treat musculoskeletal diseases that cause muscle spasms. The electrode is modified with Ce-doped ZnO/r-GO. Various detection methods, such as cyclic voltammetric and square wave techniques (SWV), were utilized. The composite material showed high effectiveness as an electron transfer mediator in the oxidation of CBP. The electrode showed a good response for SWV evaluations in CBP identification, with a minimum detection limit of 1.6 × 10-8 M and a wide linear range from 10 × 10-6 M to 0.6 × 10-7 M, under ideal conditions. The rate constant for charge transfer (ks) and the estimation of the electrochemical active surface area were obtained. A developed sensor exhibited desirable selectivity, long-lasting stability, and remarkable reproducibility. A sensor was used to analyze water, human serum, and urine samples, resulting in positive recovery results.

Hydrothermal synthesis of iron titanate hexagonal nanoplates for electrochemical detection of nitrofurazone.

An electrochemical sensor is established using an iron titanate (FeTiO3) modified glassy carbon electrode (GCE) to detect nitrofurazone. Various microscopic and spectroscopic analysis was performed to reveal the properties of the prepared FeTiO3 hexagonal nanoplates. The FeTiO3/GCE presents enhanced electrochemical response to nitrofurazone at the peak reduction potential of - 0.471 V with a larger peak current than the bare GCE due to high electrical conductivity, enhanced specific surface area, and abundant active sites. The superior nitrofurazone detection performance includes the low limit of detection of 0.002 µM and the sensitivity of 0.551 µA µM-1 cm-2 in the linear concentration range of 0.01-162.2 µM. The reproducibility and selectivity studies of the FeTiO3/GCE show excellent results with a relative standard deviation of < 5%. The practicability of FeTiO3/GCE is confirmed by monitoring nitrofurazone in actual samples. This work demonstrates that perovskite-type FeTiO3 has great potential in real-world sample analysis, and provides a new way to develop high-performance electrochemical sensors.

Effect of Morphology Modification of BiFeO3 on Photocatalytic Efficacy of P-g-C3N4/BiFeO3 Composites.

This current study assessed the impacts of morphology adjustment of perovskite BiFeO3 (BFO) on the construction and photocatalytic activity of P-infused g-C3N4/U-BiFeO3 (U-BFO/PCN) heterostructured composite photocatalysts. Favorable formation of U-BFO/PCN composites was attained via urea-aided morphology-controlled hydrothermal synthesis of BFO followed by solvosonication-mediated fusion with already synthesized P-g-C3N4 to form U-BFO/PCN composites. The prepared bare and composite photocatalysts' morphological, textural, structural, optical, and photocatalytic performance were meticulously examined through various analytical characterization techniques and photodegradation of aqueous rhodamine B (RhB). Ellipsoids and flakes morphological structures were obtained for U-BFO and BFO, and their effects on the successful fabrication of the heterojunctions were also established. The U-BFO/PCN composite exhibits 99.2% efficiency within 20 min of visible-light irradiation, surpassing BFO/PCN (88.5%), PCN (66.8%), and U-BFO (26.1%). The pseudo-first-order kinetics of U-BFO/PCN composites is 2.41 × 10-1 min-1, equivalent to 2.2 times, 57 times, and 4.3 times of BFO/PCN (1.08 × 10-1 min-1), U-BFO, (4.20 × 10-3 min-1), and PCN, (5.60 × 10-2 min-1), respectively. The recyclability test demonstrates an outstanding photostability for U-BFO/PCN after four cyclic runs. This improved photocatalytic activity exhibited by the composites can be attributed to enhanced visible-light utilization and additional accessible active sites due to surface and electronic band modification of CN via P-doping and effective charge separation achieved via successful composites formation.

Cellulose-Amine Porous Materials: The Effect of Activation Method on Structure, Textural Properties, CO2 Capture, and Recyclability.

CO2 capture via physical adsorption on activated porous carbons represents a promising solution towards effective carbon emission mitigation. Additionally, production costs can be further decreased by utilising biomass as the main precursor and applying energy-efficient activation. In this work, we developed novel cellulose-based activated carbons modified with amines (diethylenetriamine (DETA), 1,2-bis(3-aminopropylamino)ethane (BAPE), and melamine (MELA)) with different numbers of nitrogen atoms as in situ N-doping precursors. We investigated the effect of hydrothermal and thermal activation on the development of their physicochemical properties, which significantly influence the resulting CO2 adsorption capacity. This process entailed an initial hydrothermal activation of biomass precursor and amines at 240 °C, resulting in C+DETA, C+BAPE and C+MELA materials. Thermal samples (C+DETA (P), C+BAPE (P), and C+MELA (P)) were synthesised from hydrothermal materials by subsequent KOH chemical activation and pyrolysis in an inert argon atmosphere. Their chemical and structural properties were characterised using elemental analysis (CHN), infrared spectroscopy (IR), scanning electron microscopy (SEM), and thermogravimetric analysis (TG). The calculated specific surface areas (SBET) for thermal products showed higher values (998 m2 g-1 for C+DETA (P), 1076 m2 g-1 for C+BAPE (P), and 1348 m2 g-1 for C+MELA (P)) compared to the hydrothermal products (769 m2 g-1 for C+DETA, 833 m2 g-1 for C+BAPE, and 1079 m2 g-1 for C+MELA). Carbon dioxide adsorption as measured by volumetric and gravimetric methods at 0 and 25 °C, respectively, showed the opposite trend, which can be attributed to the reduced content of primary adsorption sites in the form of amine groups in thermal products. N2 and CO2 adsorption measurements were carried out on hydrothermal (C) and pyrolysed cellulose (C (P)), which showed a several-fold reduction in adsorption properties compared to amine-modified materials. The recyclability of C+MELA, which showed the highest CO2 adsorption capacity (7.34 mmol g-1), was studied using argon purging and thermal regeneration over five adsorption/desorption cycles.

Hydrothermally Synthesized ZnCr- and NiCr-Layered Double Hydroxides as Hydrogen Evolution Photocatalysts.

The layered double hydroxides (LDHs) of transition metals are of great interest as building blocks for the creation of composite photocatalytic materials for hydrogen production, environmental remediation and other applications. However, the synthesis of most LDHs is reported only by the conventional coprecipitation method, which makes it difficult to control the catalyst's crystallinity. In the present study, ZnCr- and NiCr-LDHs have been successfully prepared using a facile hydrothermal approach. Varying the hydrothermal synthesis conditions allowed us to obtain target products with a controllable crystallite size in the range of 2-26 nm and a specific surface area of 45-83 m2∙g-1. The LDHs synthesized were investigated as photocatalysts of hydrogen generation from aqueous methanol. It was revealed that the photocatalytic activity of ZnCr-LDH samples grows monotonically with the increase in their average crystallite size, while that of NiCr-LDH ones reaches a maximum with intermediate-sized crystallites and then decreases due to the specific surface area reduction. The concentration dependence of the hydrogen evolution activity is generally consistent with the standard Langmuir-Hinshelwood model for heterogeneous catalysis. At a methanol content of 50 mol. %, the rate of hydrogen generation over ZnCr- and NiCr-LDHs reaches 88 and 41 µmol∙h-1∙g-1, respectively. The hydrothermally synthesized LDHs with enhanced crystallinity may be of interest for further fabrication of their nanosheets being promising components of new composite photocatalysts.

Lamellar Crystal Structure and Haldane Magnetism in NH4 VPO4 OH.

A novel vanadium hydroxide-phosphate, NH4 VPO4 OH, was synthesized hydrothermally in V2 O5 -NH4 H2 PO4 -citric acid system at 230 °C. It was characterized by XRD, TG-DSC, SEM-EDX, FTIR and NMR spectroscopy. NH4 VPO4 OH is isostructural with NH4 GaPO4 OH and features edge-sharing chains of VO6 octahedra. These chains running along [010] direction of the unit cell are connected by phosphate tetrahedra to form infinite layers parallel to the (100) plane. Ammonium cations are embedded between the heteropolyhedral layers. According to the thermodynamic and NMR measurements supported by the first-principles calculations, NH4 VPO4 OH presents a rare case of Haldane spin system with spin S=1 based on V3+ ions.

Active Site Engineering and Theoretical Aspects of "Superhydrophilic" Nanostructure Array Enabling Efficient Overall Water Electrolysis.

The rational design of noble metal-free electrocatalysts holds great promise for cost-effective green hydrogen generation through water electrolysis. In this context, here, the development of a superhydrophilic bifunctional electrocatalyst that facilitates both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline conditions is demonstrated. This is achieved through the in situ growth of hierarchical NiMoO4 @CoMoO4 ·xH2 O nanostructure on nickel foam (NF) via a two-step hydrothermal synthesis method. NiMoO4 @CoMoO4 ·xH2 O/NF facilitates OER and HER at the overpotentials of 180 and 220 mV, respectively, at the current density of 10 mA cm-2 . The NiMoO4 @CoMoO4 ·xH2 O/NF ǁ NiMoO4 @CoMoO4 ·xH2 O/NF cell can be operated at a potential of 1.60 V compared to 1.63 V displayed by the system based on the Pt/C@NFǁRuO2 @NF standard electrode pair configuration at 10 mA cm-2 for overall water splitting. The density functional theory calculations for the OER process elucidate that the lowest ΔG of NiMoO4 @CoMoO4 compared to both Ni and NiMoO4 is due to the presence of Co in the OER catalytic site and its synergistic interaction with NiMoO4 . The preparative strategy and mechanistic understanding make the windows open for the large-scale production of the robust and less expensive electrode material for the overall water electrolysis.

Construction of Pd-Co-Doped CdS Heterojunctions as Efficient Platforms in Photocatalysis.

In this work, we present the structural, optical and photocatalytic properties of CdS semiconducting nanostructures, doped with palladium- and cobalt-based species. XRD analysis, corroborated by Raman and XPS, demonstrated the growth of CdS crystallites in the hexagonal structure, whereas solvothermal conversion of neat precursor metal salts resulted in the formation of metallic Pd and cobalt oxide, respectively. Scanning electron microscopy imaging certified the dendritic structure of hybrids, especially in the case where CdS was grown in the presence of either palladium- or cobalt-based nanoparticles. XPS surface analysis revealed that a major fraction of metallic Pd nanoparticles was converted to PdO during the in situ growth of CdS nanoparticles. The oxidation of Pd nanoparticles could be ascribed to chemisorption of oxygen phases onto the metal surface. The presence of cocatalyst nanoparticles resulted in an appreciable shift of the absorption edge of the ternary hybrids by about 50 nm. The optimized hybrid was found to photodegrade Orange G dye almost quantitatively within 2 h, by simulated solar light irradiation. Scavenging experiments revealed that hydroxy radicals were the main transient intermediate, leading to the oxidative degradation of the dye.

Recognizing the Minimum Structural Units Driving the Crystallization of SAPO-34 in a Top-Down Process.

Recognizing the structure and nature of the nuclei for zeolites crystallization on an atomic level is of great importance, which can provide guidance on the control of crystallization kinetics and the rational synthesis of zeolites. However, it remains a long-standing challenge due to the difficulty in characterization of amorphous precursor with limited crystal nuclei. Herein, a top-down synthesis system was designed for SAPO-34 molecular sieve and well investigated. A clear precursor solution with abundant SAPO-34 crystal nuclei was obtained under a depolymerization-dominant condition. The species in the liquid precursor were identified by FT-ICR MS, solid-state MAS NMR and atomic pair distribution function analyses. In combination with various designed experiments, it is revealed that both the formation of small species containing Si-O-Al bonds and reaching a certain concentration, is crucial for driving the crystallization of SAPO-34, rather than structural units with specific spatial conformation. This work provides an important understanding on the (pre)nucleation of SAPO-34 and sheds light on the synthesis control of SAPO molecular sieves.

Green and Fast Strategies for Energy-Efficient Preparation of the Covalent Organic Framework TpPa-1.

Three synthesis procedures for the covalent-organic framework (COF) TpPa-1 are studied with the purpose of setting up the most promising one in a fast and green way, leading to a more environmentally friendly and sustainable process. With conventional heating, good crystallinity and a high BET specific surface area (SSA) of up to 1007 m2 ⋅ g-1 are achieved at 170 °C for 3 days using water as the quintessential green solvent. However, the application of microwave radiation in the synthesis for this crystalline porous polymer allows reaction times to be shortened to 30 min while maintaining structural and textural properties (BET SSA of 928 m2 ⋅ g-1 ) and obtaining yields close to 98 % (vs. 90 % in the hydrothermal synthesis). The water-assisted mechanochemical synthesis is also an environmentally friendly synthetic approach; with heating at 170 °C in a two-step process (10+10 min), high crystallinity is achieved, a BET SSA of 960  m2 ⋅ g-1 and a yield of 98 % for TpPa-1.

Orange Peel Biomass-derived Carbon Supported Cu Electrocatalysts Active in the CO2 -Reduction to Formic Acid.

We report a green, wet chemistry approach towards the production of C-supported Cu electrocatalysts active in the CO2 reduction to formic acid. We use citrus peels as a C support precursor and as a source of reducing agents for the Cu cations. We show that orange peel is a suitable starting material compared to lemon peel for the one-pot hydrothermal synthesis of Cu nanostructures affording better Cu dispersion as well as productivity and selectivity towards formic acid. We rationalize this finding in terms of the beneficial chemical composition of the orange peel, which favors both the reduction of the Cu precursor as well as the carbon matrix. This work demonstrates new viable opportunities for the reuse of citrus waste on a rational basis.

Tin oxide-polyaniline nanocomposite modified nickel foam for highly selective and sensitive detection of cholesterol in simulated blood serum samples.

Cholesterol (CH) is a vital diagnostic marker for a variety of diseases, making its detection crucial in biological applications including clinical practice. In this work, we report the synthesis of tin oxide-polyaniline nanocomposite-modified nickel foam (SnO2-PANI/NF) for non-enzymatic detection of CH in simulated human blood serum. SnO2was synthesized via the hydrothermal method, followed by the synthesis of SnO2-PANI nanocomposite throughin situchemical polymerization of aniline using ammonium persulfate as the oxidizing agent. Morphological studies display agglomerated SnO2-PANI, which possess diameters ranging from an average particle size of ∼50 to ∼500 nm, and the XRD analysis revealed the tetragonal structure of the SnO2-PANI nanocomposite. Optimization studies demonstrating the effect of pH and weight percentage are performed to improve the electrocatalytic performance of the sensor. The non-enzymatic SnO2-PANI/NF sensor exhibits a linear range of 1-100µM with a sensitivity of 300µAµM-1/cm-2towards CH sensing and a low limit of detection of 0.25µM (=3 S m-1). SnO2-PANI/NF facilitates the electrooxidation of CH to form cholestenone by accepting electrons generated during the reaction and transferring them to the nickel foam electrode via Fe (III)/Fe (IV) conversion, resulting in an increased electrochemical current response. The SnO2-PANI/NF sensor demonstrated excellent selectivity against interfering species such as Na+, Cl-, K+, glucose, ascorbic acid, and SO42-. The sensor successfully determined the concentration of CH in simulated blood serum samples, demonstrating SnO2-PANI as a potential platform for a variety of electrochemical-based bioanalytical applications.

Hydrothermal synthesis and formation mechanism of controllable magnesium silicate nanotubes derived from coal fly ash.

A novel controllable magnesium silicate nanotube (MSN) material derived from coal fly ash was successfully synthesized via a hydrothermal process for the first time, and the reaction conditions and mechanism of synthesizing MSN materials from magnesium oxide and sodium silicate extracted from the fly ash were studied. The optimal preparation conditions are temperature = 220 °C, pH = 13.5, and Mg: Si molar ratio = 3:2, and the tubular structure gradually appeared and showed controllable and regular growth with the increase of synthesis time. The mechanism revealed that with the gradual dissolution of brucite into the sodium silicate solution, the reaction product begins to crystallize and transform from an initial sheet-like structure to a tubular structure, and finally becomes a uniformly arranged nanotube. The formation process of MSN follows Pauling's fourth rule, Si-O tetrahedral coordination and Mg-OH octahedral coordination is further condensed to form a two-layer structure by the action of active oxygen, then the sheet is rolled into a tube under its structural stress. The growth of both outer tubular diameter and inner tubular diameter has good linear law and controllable, and the growth rate are 0.289 nm h-1and 0.071 nm h-1, respectively.

Effect of intercalated molybdenum atoms on structure and electrochemical properties of Mo1+xS2synthesized by hydrothermal method.

As an alternative anode to graphene, molybdenum disulfide (MoS2) has attracted much attention due to its layered structure and high specific capacity. Moreover, MoS2can be synthesized by hydrothermal method with low cost and the size of its layer spacing can be controlled. In this work, the results of experiment and calculation proved that the presence of intercalated Mo atoms, leading to the expansion of MoS2layer spacing and weakening of Mo-S bonding. For the electrochemical properties, the presence of intercalated Mo atoms causes the lower reduction potentials for the Li+intercalation and Li2S formation. In addition, the effective reduction of diffusion resistance and charge transfer resistance in Mo1+xS2leads to the acquisition of high specific capacity for battery applications.

Fluorescence of D-Glucose-Derived Carbon Dots: Effect of Process Parameters.

The aim of this study was to synthesize highly fluorescent carbon dots (CDs) from glucose using a microwave hydrothermal method. It explored the impact of glucose concentration, process time, molar ratio of KH2PO4 to glucose, and homogenization time on the resulting CDs, employing a fractional plan 3(k-1) with four independent parameters for twenty-seven synthesis. Results showed that longer process times at 200°C increased the fluorescence intensity of the CDs. The molar ratio of KH2PO4 to glucose, glucose concentration, and process time significantly influenced fluorescence. Homogenization was crucial for obtaining small particles, though an anti-aggregation agent might still be needed. UV-vis spectroscopy, spectrofluorimetry, and DLS were used to analyze the synthesized CDs. The UV-vis absorption maxima were observed around 230 nm and 282 nm, with peak shifts at different excitation wavelengths. Out of the twenty-seven samples, six CDs samples were identified to be below 10 nm and a total of twelve below 50 nm. Analyzing the results, the study concluded that the CDs possess strong fluorescence and are suitable for diverse applications. For enhanced fluorescence, longer process times at 200°C and the use of KH2PO4 were recommended, while shorter processes were preferred for obtaining smaller particles. Hierarchical clustering, the k-means method, Pareto charts, and profiles for predicted values and desirability were used to analyze the results. It was confirmed that higher fluorescence is favored by longer process time at 200°C and the use of KH2PO4. In order to obtain smaller particles, shorter processes should be used.

One Pot Hydrothermal Synthesis and Application of Bright-yellow-emissive Carbon Quantum Dots in Hg2+ Detection.

Carbon quantum dots (CQD) have drawn great interest worldwide for their extensive application as sensors due to their extraordinary physical and chemical characteristics, good biocompatibility, and high fluorescence in nature. Here, we demonstrate a technique for detecting mercury (Hg2+) ion using a fluorescent CQD probe. Ecology is concerned about the accumulation of heavy metal ions in water samples due to their harmful effects on human health. Sensitive identification and removal of metal ions from water samples are required to reduce heavy metals' risk. To find out Mercury in the water sample, carbon quantum dots were used and synthesized by 5-dimethyl amino methyl furfuryl alcohol and o-phenylene diamine through the hydrothermal technique. The synthesized CQD shows yellow emission when exposed to UV irradiation. Mercury ion was used to quench carbon quantum dots, and it was found that the detection limit was 5.2 nM with a linear range of 15-100 µM. The synthesized carbon quantum dots were demonstrated to efficiently detect Mercury ions in real water samples.