Atomic Ratio Research Articles

Tuning Flame Spray Pyrolysis for Variation of the Crystallite Size in Cu/ZnO/ZrO2 and its Influence on the Performance in CO2‐to‐Methanol Synthesis

CO2 hydrogenation to methanol (MeOH) is a key transformation in the Power‐to‐liquid concept, which aims to store energy in chemical energy carriers and chemicals. Cu/ZnO/ZrO2 (CZZ) shows great promise due to its enhanced stability in the presence of water, a critical by‐product when utilizing CO2‐based feedstocks. The structure‐sensitivity of this reaction, especially for particle sizes below 10 nm and in three‐component systems, remains highly debated. Herein, we systematically prepared a series of CZZ catalysts by flame spray pyrolysis to vary the crystallite size and to study its effect on methanol synthesis in this 3‐component system. FSP enabled us to maintain a fixed Cu/Zn/Zr ratio close to the commercial composition (61/29/10 atomic ratio), while varying the precursor feed rate. This resulted in variation in the crystallinity. The characterization by X‐ray diffraction and electron microscopy revealed an increase in crystallite size with rising feed rate for Cu and t‐ZrO2, whereas ZnO remained mostly unaffected. The testing of the materials in methanol synthesis uncovered an increase in performance, higher space time yield and MeOH selectivity, with decreasing crystallite size for two (Cu, t‐ZrO2) of its three components. The increased selectivity with smaller sizes might be attributed to an increase in interfacial sites.

Role of synthetic process parameters of nano-sized cobalt/nickel oxide in controlling their structural characteristics and electrochemical energy performance as supercapacitor electrodes

The synthesis of nano-sized bimetallic Cobalt/Nickel oxides (Ni1.5Co1.5O4) with a 1:1 Co/Ni atomic ratio has been achieved using a surfactant-free co-precipitation/hydrothermal process. The growth mechanism of Cobalt/Nickel oxides Ni1.5Co1.5O4 is elucidated by tuning the synthesis process parameters, including co-precipitation pH and hydrothermal time. The formation of Cobalt/Nickel oxides Ni1.5Co1.5O4 oxide began with the nucleation of cobalt nickel hydroxide nanoplates through the co-precipitation process, followed by dissolution-recrystallization, stacked hexagonal nano-flakes, and a flower-like microstructure. The electrochemical performances of the oxides were evaluated, with the largest surface area observed at pH 9 being the main factor for the best super-capacitive performance. As hydrothermal time increased, the structural directing growth forward, resulted in the formation of a nano-flower structure with a larger surface area. The as-prepared cobalt nickel oxide exhibited a maximum specific capacitance value of 525.5 F g-1 at a current density of 1 A g-1 and energy and power densities of 88.2 WhKg-1 and 606 WKg-1, respectively.

Controlling titanium incorporation in hydrogenated amorphous carbon films via closed-loop feedback in reactive high power impulse magnetron sputtering

A closed-loop feedback approach has been developed to control titanium incorporation in hydrogenated amorphous carbon (a-C:H) films during reactive high-power impulse magnetron sputtering (R-HiPIMS). The average discharge current measured at the magnetron target is used as the primary feedback signal to regulate the target coverage state. Hence, the titanium concentration in the films can be controlled. Significant changes were observed in the film microstructure and properties as the target state evolved with increasing target coverage. This causes the film transition from metallic titanium to a-C:H films with decreasing titanium concentration. For example, the XRD and Raman analyses indicated a microstructural change from hexagonal titanium to cubic titanium carbide and finally to amorphous carbon. The change in microstructure aligned with the density decreasing from 4.7 g∙cm‒3 to 1.6 g∙cm‒3 measured by XRR technique. In addition, a decrease in the Ti/C atomic ratio, from 1.53 to 0.03, clearly demonstrates that the titanium content can precisely be controlled. A simplified model was proposed to explain the relationship between the average HiPIMS current and the carbon coverage fraction on the target surface. The suggested relationship clarifies how adjusting the average discharge current effectively regulates the target coverage state and the consequent titanium concentration. The approach not only enhances process stability, but also offers an alternative to traditional control techniques during the deposition process.

Controllable Synthesis of BixOyBrz/TiO2 Heterojunctions with Excellent Visible‐Light‐Driven Photocatalytic Activities for Phenol

AbstractBixOyBrz/TiO2 composites have been synthesized by hydrothermal method, with TiO2 nanoparticles being employed as substrate. During the process of hydrothermal reaction, both temperature and pH have been utilized to effectively regulate the Bi/Br atomic ratio of BixOyBrz/TiO2 composites. In essence, the competitive reaction between OH− and Br− in the solution is the key factor to form BixOyBrz with different Bi/Br atomic ratios. Under visible light, the prepared Bi4O5Br2/TiO2 heterojunction demonstrates higher photocatalytic activity than other BixOyBrz/TiO2 composites for phenol and Rh B. The removal rate of phenol with Bi4O5Br2/TiO2 heterojunction is up to 92.1% after irradiation for 75 min. The excellent photocatalytic activities of Bi4O5Br2/TiO2 heterojunction are mainly attributed to its optimized microstructure and the matching band energy structure, whereby TiO2 nanoparticles with ≈10 nm diameter uniformly arranged on ≈10.2 nm thick Bi4O5Br2 nanosheets. Moreover, the heterojunction structure promotes the separation of photo‐generated electrons and holes in Bi4O5Br2/TiO2, while and h+ are the main active species during its photocatalytic processes.

Application of iron oxide and its composites containing carbon nanoparticles to the solution of environmental problems

The radioactive materials and the secondary waste after a nuclear power plant accident pose a big environmental problem. The nontoxic iron oxide and iron oxyhydroxide, and their composites with carbon materials were applied to solve the problem. Coal oxide produced by modified Brodie method using coal, NaOH, and γ-Fe2O3 were treated by a hydrothermal process. When the diluted dispersion mixture was treated with SrCl2, the composite particles were attracted to a magnet. On the other hand, the composite without SrCl2 was not attracted. This means only the SrCl2-adsorbed composite can be recovered by a magnet. Hematite doped with various amounts of Nb was synthesized. Its catalytic activities for photo-Fenton reaction were investigated for degradation of methylene blue (MB) in the presence of H2O2 under visible light. Nb-doped hematite calcined at 600 ºC produced smaller particles and showed higher catalytic activity than those calcined at 700 ºC. It was shown that the sample with higher Nb doping showed a better catalytic activity, i.e., the sample with 40 atomic percent of Nb calcined at 600 ºC has the highest catalytic activity. The hematite with 7.4 atomic percent of Nb calcined at 600 ºC showed unique characteristics since it has rapid decomposition rate of MB as well as ferrimagnetic-like characteristics, which makes it separable by a magnet. The polymorphism of iron(III) oxyhydroxide was controlled by adding acetic acid, ethylenediamine, and citric acid. The lepidocrocite obtained by adding the additive of citric acid resulted in the presence of citric acid in the particles and revealed a large specific surface area and negative Zeta potential, which showed an extremely high catalytic activity of MB decomposition for photo-Fenton reaction.

Optimizing reverse water gas shift catalysis: Minimizing metal loading and enhancing performance with Pt/ZrO2 catalysts through Rh incorporation

In this study, the optimization of catalysts for the reverse water gas shift reaction by minimizing metal loading and enhancing the performance of supported Pt catalysts through Rh incorporation was done. The catalysts were synthesized by the wet impregnation method, in which the metal noble load in bimetallic samples decreased by approximately one-third compared to the reference platinum catalyst, with varying Rh-Pt ratios. In all materials, m-ZrO2, obtained by the hydrothermal method, was used as support. In the catalytic tests in a continuous packed-bed flow reactor at atmospheric pressure, all samples were active to catalyze CO2 reduction between 200 and 300 °C. Bimetallic samples, particularly those with an Rh-Pt atomic ratio of 20–80, exhibited superior performance in the RWGS reaction despite their lower metal content. Based on the results of H2-TPR, FTIR in situ, and XPS, we propose that the enhanced CO production in bimetallic samples compared to Pt/ZrO2 catalysts can be attributed to Rh increasing the reduction extent of supported Pt. This enhancement facilitates the hydrogenation of bicarbonate species into formate species, which subsequently evolve into Pt0-CO and ultimately into CO. Additionally, Rh incorporation enables an alternative pathway for CO generation, where Pt0-carbonyls, known for their CO-producing capability, are formed via CO2 dissociation on the Pt0 surface. However, higher Rh concentrations favor the CO2 methanation rather than the RWGS reaction.

First Principles Calculation of the Influence of Alloying on the Phase Stability, Elasticity, and Thermodynamic Properties of the MoNbTiVX (X = Al/Cr) Refractory High-Entropy Alloy

In response to the poor wear resistance and high-temperature oxidation resistance of titanium alloys during service, a series of lightweight refractory high-entropy alloys (RHEAs) can be designed for the laser cladding coating of titanium alloy surfaces, with due consideration of the compositional and structural characteristics of titanium alloys. Firstly, the structural stability, mechanical and thermal properties of four lightweight RHEAs (MoNbTiV, AlMoNbTiW, CrMoNbTiV, and AlCrMoNbTiV) with equal atomic ratios were designed and calculated using first principles combined with quasi-harmonic approximation (QHA). The results indicate that all four RHEAs are stable BCC, exhibiting elastic anisotropy and ductility. The lightest density is 6.409 g/cm3. Adding Al/Cr can cause structural distortion and affect its mechanical properties. Their Young’s moduli are in the following order: AlCrMoNbTiV > MoNbTiV > CrMoNbTiV > AlMoNbTiV. The thermal expansion coefficients of the four RHEAs and titanium alloys are very close, with a difference in linear expansion coefficient of less than 1.16 × 10−5/K. Meanwhile, the metallurgical bonding of four types of RHEA coatings was successfully achieved on a Ti-6Al-4V(TC4) substrate through laser cladding technology, and all coatings exhibited a unique BCC solid solution phase.

Machine Learning-Enhanced Fabrication of Three-Dimensional Co-Pt Microstructures via Localized Electrochemical Deposition

This paper presents a novel method for fabricating three-dimensional (3D) microstructures of cobalt–platinum (Co-Pt) permanent magnets using a localized electrochemical deposition (LECD) technique. The method involves the use of an electrolyte and a micro-nozzle to control the deposition process. However, traditional methods face significant challenges in controlling the thickness and uniformity of deposition layers, particularly in the manufacturing of magnetic materials. To address these challenges, this paper proposes a method that integrates machine learning algorithms to optimize the electrochemical deposition parameters, achieving a Co:Pt atomic ratio of 50:50. This optimized ratio is crucial for enhancing the material’s magnetic properties. The Co-Pt microstructures fabricated exhibit high coercivity and remanence magnetization comparable to those of bulk Co-Pt magnets. Our machine learning framework provides a robust approach for optimizing complex material synthesis processes, enhancing control over deposition conditions, and achieving superior material properties. This method opens up new possibilities for the fabrication of 3D microstructures with complex shapes and structures, which could be useful in a variety of applications, including micro-electromechanical systems (MEMSs), micro-robots, and data storage devices.

Investigation of phase transformation and mechanical properties of silicon addition on AlCrFeMnNi high entropy alloys

Abstract This paper examines the impact of silicon in the AlCrFeMnNi high-entropy alloy system, focusing on both its microstructural and mechanical properties. Alloys with varying silicon content (x = 0, 0.3, 0.6, 0.9 atomic ratio) were synthesized using vacuum arc melting. The phase formation of these high-entropy alloys was analyzed using X-ray diffraction to comprehend the alloying process behaviour. The findings revealed that the solidification of the AlCrFeMnNi alloy occurred in dendritically, with dendrite cores containing Cr, Fe, and Ni, while interdendritic regions were enriched in Al and Ni after adding Silicon. Increasing the silicon content from 0 to 0.9 led to significant improvements in microhardness and wear resistance. This improvement is attributed to the reinforcement of grain boundaries provided by silicon. The formation of an Al and Ni rich B2 phase is crucial in resisting dislocation motion and preventing further deformation. Additionally, the addition of silicon led to improved corrosion resistance, as demonstrated by potentiodynamic polarization measurements. However, a trade-off was observed between compressive strength and ductility: compressive strength increased with higher silicon concentrations, but at the expense of ductility.

Petroleum evolution and its genetic relationship with the associated Jinding Pb[sbnd]Zn deposit in Lanping Basin, Southwest China

The spatial association of hydrocarbons with metalliferous ore deposits is found worldwide and is particularly common to MVT PbZn deposits. Heavy oil and bitumen are found in the Jinding PbZn deposit within the Lanping Basin, South China. However, the temporal and genetic associations between hydrocarbons and the deposit are still controversial. To this end, integrating Raman analysis, ReOs geochronology and transmission electron microscopy analysis of the bitumen and in situ S isotope analyses of the sulfide, the petroleum evolution of the Jinding reservoir and its genetic relationship with the PbZn deposits were discussed. Bitumen ReOs data from this study and published works indicate that the late Triassic shales underwent two distinct oil-generation events before mineralisation (~25 Ma), with initial oil generation occurring during the early Cretaceous (~116 Ma) and the second during the early Paleogene (ca. 68–59 Ma). These two ages agree with the modelled thermal history of the Jinding reservoir. Combining the oil-before-ore timing sequence, high metal abundance of the bitumen, two negative sulfur isotope peaks of the sulfide and high S/C atomic ratio of the bitumen from the Jinding deposit, the oil-containing aqueous solutions were considered as one metal carrier during the hydrocarbon migration and accumulation; further, bacterial sulfate reduction and thermo-chemically induced sulfate reduction processes could have participated in the supply of reduced sulfur for the PbZn deposit precipitation.

Temperature dependent radiative and non-radiative recombination lifetimes of luminescent amorphous silicon oxynitride systems

In our previous work, we deeply researched the absolute photoluminescence (PL) quantum yields of luminescent modulating a-SiNxOy films with various N/Si atom ratios under different measurement temperatures. In this work, we further systematically studied the temperature dependent kinetic processes of radiative and non-radiative recombinations in a-SiNxOy systems in the visible light range. First, we investigated the structure of a-SiNxOy films and obtained the concentrations of both trivalent Si and N-Si-O defects related dangling bonds through XPS, FTIR and EPR measurements. Then we further tested the transient fluorescence attenuation of a-SiNxOy films detected at different emission wavelengths. We found that the PL lifetimes of a-SiNxOy films vary with the change of N-Si-O defect state concentrations, which is different from the typical PL decay characteristics of band tail related a-SiNx films previously reported. By combining the resulting PL IQE values with the ns-PL lifetimes, we further intensively redetermined the radiative and non-radiative recombination lifetimes of a-SiNxOy systems. The related radiative recombination rates were obtained (kr∼108 s−1), which can be compared to the results in the direct band gap.

Fabrication of Ultrafine L10-FePt-Based Magnetic Patterns Enabled by Single-Step Nanoimprint-Assisted Block Copolymer Self-Assembly.

The bit islands in magnetic patterns play a crucial role in advancing magnetic recording density, but the trade-off issues between miniaturization and scalable production are still challenging. Here we present a two-in-one technique of nanoimprint lithography (NIL)-assisted self-assembly using a specially engineered FePt-containing block copolymer (BCP), offering a simple one-step fabrication for L10-FePt bit-patterned media with high throughput. This method combines top-down NIL with bottom-up self-assembly to precisely control the ultrafine magnetic bits in the nanoscale patterns. The FePt-derived BCPs, designed with an equal atomic ratio of Fe and Pt, ensure the preparation of homogeneously dispersed L10-FePt nanoparticles (NPs). Subsequent BCP pyrolysis results in NPs with enhanced magnetic properties, significantly advancing high-density data storage devices. This strategy offers a novel approach to drive the innovative creation of ordered magnetic metal alloy NPs arrays for practical applications.

Structural, Morphological, and Optical Properties of Nano- and Micro-Structures of ZnO Obtained by the Vapor–Solid Method at Atmospheric Pressure and Photocatalytic Activity

Micro- and nano-structures of ZnO were synthesized by the vapor–solid method at 600, 700, and 800 °C in atmospheres of Ar and air, at atmospheric pressure. The structural characterization XRD shows that the nano-structures synthesized in air atmosphere at 600 °C, while diffraction peaks were found due to Zn because the presence of metallic Zn remains on the surface of the pellet. SEM images show that the morphologies range from nano-wires to micro-tubes. When cathodoluminescence is measured in micro-tubes, there is a shift of the near-band edge of the ZnO toward red; this is due to structural defects in the ZnO network. This result is corroborated with panchromatic CL measurements, which exhibit a difference in brightness between the micro-tubes. Furthermore, EDS measurements show an atomic quantity ratio of Zn:O that differs from the stoichiometric composition in the micro-tubes. The photocatalytic activity of three types of structures—nano-wires, micro-tubes, and micro-rods under UV irradiation using methylene blue as a model pollutant—were evaluated. The best response was obtained for nanowires, not only because they have a larger surface area but also because of the present defects.

Catalytic performances of Ag/SiC catalysts for styrene epoxidation in O2 atmosphere

SiC supported Ag catalysts were prepared by an impregnation-reduction method for styrene epoxidation in O2 atmosphere. Under the condition of 100 °C, 0.5 MPa O2 and 4 h, 5 wt% Ag/SiC catalyst achieved styrene conversion of 98.5 % and styrene oxide selectivity of 69.7 %. Further studies show that O2 was activated on the Ag surface and then formed reactive oxygen species, 1O2 and •O2-. Based on the O2 adsorption results, the atomic ratio of O/Ag larger than 0.5 indicated that more oxygen species had spilled over to the SiC surface. In-situ diffuse reflectance Fourier transform infrared spectroscopy and Density Functional Theory calculation results showed that styrene was adsorbed on the SiC surface. The active oxygen species generated on the Ag surface could spill over to the SiC surface, reacting with the adsorbed styrene to produce styrene oxide or benzaldehyde. In addition, the catalyst exhibits good stability.

Vapor Nucleation on Hybrid-Wetting Nanoconvex Surfaces: The Competition between Intrinsic Wettability and Topography.

Hybrid-wetting surfaces with hydrophilic spots reduced from the micrometer to nanometer scale have been confirmed to enhance vapor nucleation while simultaneously minimizing droplet pinning. Given that surface topography also plays a critical role in influencing nucleation characteristics, the effect of competition between intrinsic wettability and topography on nucleation remains unclear when both surface topography and hydrophilic regions approach the critical nucleation size. This work investigated vapor nucleation on two types of hybrid-wetting nanoconvex surfaces. On random hybrid-wetting convex surfaces, the most negative potential energy sites were located at the sides of the convex structures, leading vapor to preferentially nucleate at these locations, consistent with observations on homogeneous surfaces. Despite similar average potential energy values across the surface, wettability variations in hydrophilic and hydrophobic atoms significantly alter the surface energy distribution. As the wettability difference between hydrophilic and hydrophobic atoms increases, stronger hydrophilic atoms generate relatively higher local energy regions, promoting vapor rapid nucleation. The edge effect still exists at a hydrophilic atom ratio of 10%, and competition among hydrophilic spots impedes vapor nucleation and growth. However, when the ratio increases to 40%, the increased surface average potential energy promotes the probability of vapor contacting the surface, leading to rapid vapor nucleation on the sides of the convex structures. In addition, surface potential energy analysis and the Monte Carlo method revealed that nucleation locations on nanoconvex surfaces are governed by the competition between intrinsic wettability and topography. When the magnitude of the potential energy generated by the hydrophilic atoms exceeds that from the topography, stronger solid-liquid interactions at the top of the convex structure increase the likelihood of vapor contacting the surface, resulting in nucleation at the top. Conversely, when the magnitude of the potential energy generated by hydrophilic atoms is lower than that from topography, nucleation preferentially still occurs on the sides.

Triboelectric Nanogenerator Based on Tin Doped Zinc Oxide and Polyvinyl Alcohol Composite Thin Film for Energy Harvesting Applications

The triboelectric nanogenerator (TENG) collects mechanical energy from its surroundings and converts it to electrical signals that can be used in sustainable energy harvesting technologies to help maintain the social ecosystem. However, TENG operation with pure triboelectric material may not be sufficient to power a small electronic system without modification. The optimal material capable of producing significant electrical energy with flexible structures remains a major barrier to practical application. In this study, tin-doped zinc oxide (Sn:ZnO) and polyvinyl alcohol (PVA) composite thin films were prepared using a simple solution immersion technique at various Sn atomic percentage (at.%) concentrations for use in TENG devices. The crystalline quality of a composite thin film made of Sn:ZnO and PVA was identified using x-ray diffraction. The microstructure changes of the composite thin film were found to be influenced by Sn doping, as studied using optical microscopy. The TENG with 2.5 at.% Sn:ZnO/PVA composite thin film and Kapton film achieved the highest peak voltage of 8.5 V in open circuit and 90 µW output power at 1 MΩ. The produced electrical output was then used to store energy in capacitors. According to its TENG properties, the Sn:ZnO/PVA composite thin film-based TENG has the potential to be used in low power electronic devices.

Structure and Non‐Ideal Mixing of Fe‐Ni‐S Liquid at High Temperature and Pressure and Its Implication for the Earth's Outer Core Composition

AbstractThe effect of light elements (LEs) such as sulfur on the physical properties of liquid iron‐nickel alloy under the earth's outer core conditions is critical for understanding the core composition and dynamics. First‐principles molecular dynamics simulations were employed to model Fe‐Ni‐S liquid with S concentrations in the range of (0–25) atomic percent (at%) at 4050 K and (0–33.33) at% at 5530 K and pressures relevant to the core‐mantle boundary (CMB) and inner core boundary (ICB), respectively. The thermodynamic mixing properties of Fe‐Ni‐S liquid were calculated, showing that the excess volume for Fe‐Ni‐S alloys deviates negatively from ideal mixing by −0.33% at 12.5 at% S at the CMB and −0.35% at 17 at% S at the ICB. Similarly, the excess enthalpy negatively deviated from the ideal mixing by −3.4 kJ/mole and −13 kJ/mole at the similar S concentrations at CMB and ICB, respectively, indicating non‐ideal mixing throughout the outer core. Similar behaviors are observed for isothermal bulk modulus (KT) and seismic velocity. The short‐ and intermediate‐range structures were analyzed and used to explain the non‐ideal mixing behaviors. The results suggest that extrapolations using ideal mixing underestimates the sound velocity by ∼0.14 km/s near CMB and ∼0.10 km/s near ICB, which is significant for constraining the core composition. If S is the only LE, the density at 10–12 wt% S matches the preliminary reference earth model (PREM). The seismic velocity at 12–15 wt% S matches PREM. These results suggest the presence of other LEs in the outer core.

Thermogravimetric Analysis of Combustion of Semi-Coke Obtained from Coniferous Wood and Mixtures on Their Basis

Coal remains one of the most used solid fuels for heat and electricity generation but burning coal releases large amounts of CO2 into the urban atmosphere in addition to harmful substances. In order to reduce the consumption of solid fossil fuels, it is necessary to search for fuels capable of replacing coal in terms of its thermal and environmental characteristics. One of the best alternative fuels is biomass, which is considered carbon neutral, but its thermal characteristics are worse than those of solid fossil fuels. In this work, an alternative to coal was studied for the first time, which was semi-coke, obtained by gasification at a temperature of 700–900 °C, the heat of combustion of which turned out to be higher than that of biomass before thermal treatment by 75%. We also studied fuel mixtures based on the resulting semi-coke. The aim of the work is to determine the main characteristics of combustion of semi-coke obtained from coniferous wood and mixtures based on them. The method of thermogravimetric analysis in oxidising medium at a heating rate of 20 °C/min was applied for the research. According to the results of this analysis, the ignition and burnout temperatures were determined, the combustion index was determined, the duration of coke residue combustion was determined, and synergetic interactions between the mixture components influencing the combustion characteristics were established. It was found that the ignition temperature of semi-coke is more than 50% higher than that of biomass and the burnout temperature is 10% higher. Adding 50% of biomass to semi-coke increases the combustion index by more than 30% and decreases the ignition temperature and burnout temperature. The mixture components synergistically interact with each other during combustion to reduce the value of maximum mass loss rate. It was found that the atomic ratios of O/C and H/C in semi-coke are lower than in biomass before gasification.

Changes in Soil Humin Macromolecular Structure Resulting from Long-Term Catch Cropping

The aim of this study was to assess the effect of long-term catch crop application on the structural properties of humin, which is considered the most recalcitrant fraction of soil organic matter. Soil samples from a 30-year field experiment on triticale cultivated with and without catch crops were analysed to determine the total organic carbon content and fractional composition of humic substances. Meanwhile, humin isolated from bulk soil was analysed to determine its elemental composition and spectroscopic properties measured with UV-Vis, fluorescence, and 13C-CPMAS-NMR. It was found that catch crop farming enhanced the formation of highly reactive humus substances, like low-molecular-weight fractions and humic acids, while decreasing the humin fraction. The higher H/C and O/C atomic ratios of humin and the UV-Vis, fluorescence, and 13C-CPMAS-NMR results confirmed a higher share of oxygen-containing functional groups in humin isolated from the soil with catch crop rotation, also corroborating its greater aliphatic nature. Under the conditions of our field experiment, the results indicated that organic residues from catch crops quickly undergo the decay process and are transformed mainly into highly reactive humus substances, which can potentially improve soil health, while mineral fertilisation alone without catch crops favours the stabilisation and sequestration of carbon.

Desulfurization of simulated and commercial liquid fuel on nano-ZnO fabricated walnut shells.

The current investigation involved the development of activated carbon, juglans regia activated carbon (JRACs), from walnut shells, scientifically known as Juglans regia. The ZnO nanorods were loaded on the activated carbon and referred to as ZnO@JRACs. Desulfurization efficiency was assessed through batch adsorption and compared to commercial activated carbon known as DARCO. The materials were characterized using PXRD (powder X-ray diffraction), FTIR (Fourier-transform infrared spectroscopy), ICP-AES (inductively coupled plasma atomic emission spectroscopy), BET (Brunauer-Emmett-Teller) surface area analysis, TEM (transmission electron microscopy) imaging, and TGA (thermal gravimetric analysis). The findings indicated that the materials have oxygen functionalities, a porous morphology, and a substantial specific surface area (BET) of 1269.92 m2/g for ZnO@JRACs. Zn atom concentration in the ZnO@JRACs surface was determined to be 1.16 atomic percent using ICP-AES. Desulfurization experiments were conducted on three liquid fuels, namely a single component model fuel, MSF (multicomponent simulated fuel), and commercial fuel (kerosene), under optimized conditions (8g/L adsorbent dosage in 10mL of fuel, 15min of contact time at room temperature). The conditions effectively removed ~ 98.9% of dibenzothiophene (DBT) from the single component model fuel. The observed order for adsorption capacity is as follows: ZnO@JRACs (63.6mgg-1) > JRACs (46.3mgg-1) > DARCO (26.1mgg-1). The analysis of multicomponent simulated fuel (MSF) using gas chromatography-flame photometric detector (GC-FPD) revealed significant removal percentages for different types of thiophenic sulfur. Specifically, the removal percentages were ~ 46.2%, 97.6%, and 99.4% for benzothiophene, dibenzothiophene, and 4, 6-dimethyldibenzothiophene, respectively. Kinetic studies have shown that the adsorption process is governed by a pseudo second-order reaction. Additional thermodynamic studies were conducted to further investigate the mechanism of adsorption. The spent synthesized composite ZnO@JRACs were thermally regenerated and can be reused for up to four cycles.