Adsorption Structure Research Articles

Study on the effects of a novel imidazoline siliconophilic collector in the desilication process of magnesite: Separation experiments, adsorption mechanisms, and separation model

This study innovatively introduced heptadecenyl amine ethyl imidazoline quaternary ammonium salt (ODD) as a siliconophilic flotation collector, effectively facilitating the achievement of high-efficiency separation of magnesite from quartz. ODD exhibits unique properties such as high selectivity and environmental friendliness. Through a comprehensive series of experiments, including flotation tests, zeta potential characterization, atomic force microscopy (AFM) imaging, Fourier-transform infrared (FTIR) spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS), the flotation performance and selective adsorption mechanisms of ODD were thoroughly investigated. The experiments demonstrated that at a pH of 7.00 and an ODD concentration of 40 mg/L, quartz achieved a flotation recovery rate of 95.16 %, while magnesite was only 2.99 %, underscoring the high selectivity of ODD in mineral separation. Zeta potential measurements indicated that ODD exhibits strong adsorption interactions with quartz over magnesite. AFM observations confirmed that ODD forms significant adsorption structures on quartz surfaces, in contrast to weaker interactions with magnesite. FTIR analysis further revealed the robust interactions between ODD and quartz through hydrogen bonds and electrostatic forces, which were significantly diminished on magnesite surfaces. ToF-SIMS analysis provided direct evidence of ODD’s selective adsorption on quartz, contributing to a better understanding of the flotation mechanisms involved. This research not only offers a novel approach for the purification of magnesite and effective removal of quartz but also demonstrates the potential of ODD as an eco-friendly collector in mineral processing, potentially advancing a green transformation in the industry. The findings provide a solid theoretical and experimental basis for future industrial applications and innovative development of flotation collectors.

Assessment of Hydrophilicity/Hydrophobicity in Mesoporous Silica by Combining Adsorption, Liquid Intrusion, and Solid-State NMR Spectroscopy.

We have developed a comprehensive strategy for quantitatively assessing the hydrophilicity/hydrophobicity of nanoporous materials by combining advanced adsorption studies, novel liquid intrusion techniques, and solid-state NMR spectroscopy. For this, we have chosen a well-defined system of model materials, i.e., the highly ordered mesoporous silica molecular sieve SBA-15 in its pristine state and functionalized with different amounts of trimethylsilyl (TMS) groups, allowing one to accurately tailor the surface chemistry while maintaining the well-defined pore structure. For an absolute quantification of the trimethylsilyl group density, quantitative 1H solid-state NMR spectroscopy under magic angle spinning was employed. A full textural characterization of the materials was obtained by high-resolution argon 87 K adsorption, coupled with the application of dedicated methods based on nonlocal-density functional theory (NLDFT). Based on the known texture of the model materials, we developed a novel methodology allowing one to determine the effective contact angle of water adsorbed on the pore surfaces from complete wetting to nonwetting, constituting a powerful parameter for the characterization of the surface chemistry inside porous materials. The surface chemistry was found to vary from hydrophilic to hydrophobic as the TMS functionalization content was increased. For wetting and partially wetting surfaces, pore condensation of water is observed at pressures P smaller than the bulk saturation pressure p0 (i.e., at p/p0 < 1) and the effective contact angle of water on the pore walls could be derived from the water sorption isotherms. However, for nonwetting surfaces, pore condensation occurs at pressures above the saturation pressure (i.e., at p/p0 > 1). In this case, we investigated the pore filling of water (i.e., the vapor-liquid phase transition) by the application of a novel, liquid water intrusion/extrusion methodology, allowing one to derive the effective contact angle of water on the pore walls even in the case of nonwetting. Complementary molecular simulations provide density profiles of water on pristine and TMS-grafted silica surfaces (mimicking the tailored, functionalized experimental silica surfaces), which allow for a molecular view on the water adsorbate structure. Summarizing, we present a comprehensive and reliable methodology for quantitatively assessing the hydrophilicity/hydrophobicity of siliceous nanoporous materials, which has the potential to optimize applications in heterogeneous catalysis and separation (e.g., chromatography).

Lignin-derived porous carbon with interconnected pores for bulky dye adsorption in fixed-bed systems

The porous structure of adsorbents is an important factor of their adsorption performance, especially in fixed-bed systems. In this study, we fabricated lignin-derived porous carbon (LPC-Mg) with interconnected pores, which exhibited low resistance for the transport of contaminants in water. The maximum adsorption capacity of LPC-Mg toward Rhodamine B (RhB) and Congo red (CR) was 403.2 and 735.3 mg·g−1 in the batch adsorption mode and 330.5 and 718.6 mg·g−1 in the column adsorption mode. Microporous, hierarchical porous, and commercial activated carbon were used as carbonaceous adsorbents for comparison. The RhB and CR adsorption capacity of LPC-Mg was 1.8–26.6 and 4.0–33.6 times those of other carbonaceous adsorbents at the breakthrough points in fixed-bed systems, respectively. This study developed an effective strategy toward the improvement in the adsorption efficiency of carbon-based adsorbents in fixed-bed systems.

Multi‐Task Mixture Density Graph Neural Networks for Predicting Catalyst Performance

AbstractGraph neural networks (GNNs) have drawn more and more attention from material scientists and demonstrated a strong capacity to establish connections between structures and properties. However, with only unrelaxed structures provided as input, few GNN models can predict the thermodynamic properties of relaxed configurations with an acceptable level of error. In this work, a multi‐task (MT) architecture based on DimeNet++ and mixture density networks is developed to improve the performance of such task. Taking CO adsorption on Cu‐based single‐atom alloy catalysts as an example, the method can reliably predict CO adsorption energy with a mean absolute error of 0.087 eV from the initial CO adsorption structures without costly first‐principles calculations. Compared to other state‐of‐the‐art GNN methods, the model exhibits improved generalization ability when predicting the catalytic performance of out‐of‐distribution configurations, built with either unseen substrate surfaces or doping species. Further, the enhancement of expressivity has also been demonstrated on the IS2RE predicting task in the Open Catalyst 2020 project. The proposed MT GNN strategy can facilitate the catalyst discovery and optimization process.

Adsorption structure and properties of Ni/Fe electrodeposition interface: a DFT study

The density functional theory calculations of the adsorption model of NiCl2, Ni, and Cl on the Fe surface, as well as interface electronic properties, provide theoretical guidance for improving the Ni electrodeposition process. The adsorption properties of these three species on the Fe (100) crystal surface at different coverages, and the adsorption properties of the single Ni on three different crystal surfaces of Fe (100), Fe (110), and Fe (111), were studied through calculations of adsorption energy, charge density, charge occupancy, and DOS. The results indicate that the H sites are the most favorable for the adsorption of Ni and Cl on the Fe (100) surface. T sites, B sites, and H sites are all potential adsorption sites for NiCl2. The order of adsorption strength is Ni > Cl > NiCl2. In response to changes in charge, the adsorption effect exhibits a negative correlation with surface coverage. In addition, the hybridization of Ni’s 3d orbitals, Cl’s 3p orbitals, and Fe’s 3d orbitals changes the distribution of the interface charge, resulting in an increase of the charge in the Fe surface. Ni exhibits better adsorption performance on Fe (100) surface, driven by the lattice structure, surface electron configuration, and Ni–Fe atomic interactions.

Spectroscopic studies under properties of chlorpromazine conjugated to gold nanoparticles

Scientific studies have demonstrated that conjugates of anticancer drugs with metal nanoparticles (MeNPs) lead to a more effective deactivation of tumor cells compared to free drugs. Similarly, it has been established that conjugates of antibiotics with MeNPs exhibit higher biocidal activity against bacteria than their unbound counterparts. However, limited information is available regarding conjugates formed from drugs other than anticancer and antibiotics. Therefore, our research aims to develop synthesis methods for conjugates of chlorpromazine (CPZ), a neuroleptic, with gold nanoparticles (AuNPs). CPZ-AuNP conjugates were prepared through a ligand exchange reaction conducted on the surface of quasi-spherical, negatively charged citrate-stabilized TC-AuNPs with an average size of 55 ± 5 nm. UV–vis spectroscopy was employed to determine the stability range of the conjugates under controlled conditions of pH and ionic strength. Based on electrokinetic measurements, it was observed that the zeta potential of CPZ-AuNP conjugates strongly depends on the amount of CPZ adsorbed on the TC-AuNP surface. Additionally, the conjugates exhibited an isoelectric point at pH 8.8. Surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRA) were employed to elucidate the adsorption structure of CPZ on TC-AuNPs. The interpretation of the spectra was conducted based on the Raman and FTIR spectra of CPZ, along with calculations performed using Density Functional Theory (DFT). The results indicated that CPZ primarily interacts with the TC-AuNP surface through the angularly oriented phenothiazine ring and the propylene bridge. Furthermore, it was demonstrated that the C-N-C fragment is perpendicular to the surface of the TC-AuNP with which it interacts. The findings from this analysis suggest the potential for further research on the use of these conjugates in biomedical applications.

Granulated graphene oxide-activated carbon for adsorptive removal of diclofenac sodium and ibuprofen in a continuous fixed-bed column

The granular graphene oxide-activated carbon (GGA) composite was synthesized with polyvinyl alcohol (PVA) and malonic acid (MA) as chemical crosslinker at different conditions. GGA synthesis was performed at different parameters including binder-to-powder ratio in the range of 0.5–1.2, synthesis time in the range of 2–24 h, and drying temperature in the range of 60–110 °C. Response surface methodology (RSM) was used to optimize the synthesis parameters of the adsorbent synthesis. The optimum parameters for synthesis were achieved at a binder-to-powder ratio of 0.875, a synthesis time of 23.992 h, and a drying temperature of 60.071 °C. XRD, FTIR, FE-SEM, BET and TGA analyses were used to discuss the characteristics of the adsorbent structures. The surface area and mechanical stability were found to be 156.59 m2/g and 95.417 %, respectively. The adsorption behavior of mono-components (diclofenac sodium (DCF)/ibuprofen (IBP)) and bi-components (DCF + IBP) on the GGA was evaluated in a fixed-bed column. The effects of column operating parameters, including bed mass (m: 0.25–0.75 g), flow rate (Q: 5–9 mL/min), and adsorbate concentration for DCF (C: 20–100 mg/L) and IBP (C: 5–15 mg/L) on the breakthrough curves were investigated. The experimental data of fixed-bed column were correlated with breakthrough models such as Thomas, Bohart-Adams, Yoon-Nelson, Yan, Gompertz, and Log-Gompertz via both linear (under different column operating conditions) and nonlinear (for DCF (Co of 60 mg/L; m of 0.5 g and Q of 7 mL/min) and IBP (Co of 10 mg/L; m of 0.5 g and Q of 7 mL/min)) regression analysis. The maximum adsorption capacities calculated by the Thomas model were 110.068 and 34.912 mg/g for DCF and IBP, respectively. In bi-component systems, antagonistic behavior was observed in the adsorption of DCF and IBP. The results showed that the GGA can successfully remove DCF and IBP through a fixed-bed adsorption column.

Study on the competitive reduction mechanism of C and CO on Fe2O3 in blast furnace ironmaking

The competitive reduction behaviour of C and CO on the surface of Fe2O3 in blast furnaces was studied based on experiments and the first-principles calculations. The material morphology and element distribution of Fe2O3 under the conditions of C, CO and C + CO reduction were compared. In order to further investigate the competitive reduction behaviour of C and CO on the Fe2O3 surface, based on the first-principles calculation, the adsorption mechanism of C and CO on the α-Fe2O3(001) surface was studied by calculating the parameters of bond length, adsorption energy, charge density and state density. The results showed that under the condition of C + CO co-reduction, the reduction degree of Fe2O3 is better. When CO was adsorbed on the α-Fe2O3 (001) surface alone, the adsorption energy of the adsorption structure was −0.549 eV. The state density peak of the CO molecule on the left side of the Fermi level was sharper, and the electron delocalization around the CO molecule was weaker. Compared with the C atom, the CO molecule was less easily adsorbed on the α-Fe2O3 (001) surface, and the structure stability of the adsorbed products generated by the CO molecule was also lower. Compared with the adsorption of C and CO on the α-Fe2O3 (001) surface alone, the co-adsorption energy of C atom and CO molecule was relatively low, which was −7.755 eV, and the co-adsorption structure was more stable, and the presence of CO was more conducive to the interactions between C and α-Fe2O3 (001) surface.

Theoretical and experimental study on gas sensing properties of SnO2-graphene sensor for SF6 decomposition products

Based on theoretical calculation and experimental detection, SnO2-modified graphene (SnO2-graphene) was proposed as a gas-sensing material for the SF6 characteristic decomposition products (SO2, H2S, SOF2, SO2F2) in SF6-insulated equipment. Based on density functional theory calculations, the most stable modifying structure of single and double SnO2 on the surface of graphene is optimized. The adsorption structure, adsorption energy, and charge transfer of four gas molecules on the surface of SnO2-graphene are calculated and analyzed. Then the total density of states (DOS) and partial density of states (PDOS) of the system before and after gas adsorption were compared and analyzed to explore the interaction mechanism between different gases and SnO2-graphene. In experimental study, graphene was prepared by the modified Hummers oxidation–reduction method in the laboratory. four concentration gradients of SnO2 modified on the surface of graphene, and then specific gas sensing experiments were carried out with 10, 25, 50, 100 ppm of the SF6 characteristic decomposition products. The gap between simulation and experiment is compared and analyzed, which lays a theoretical and experimental foundation for the development of new specific sensors.

Imaging fibrinogen assembly on calcium-doped titanium by using scanning electrochemical microscopy

Fibrinogen adsorption is a critical host response to the insertions of various medical devices. Scanning electrochemical microscopy (SECM) has the power to probe the local interactions between proteins and bulk solids in liquid environments; however, our knowledge of the distribution or the assembly structures of protein adsorption is limited. Here, fibrinogen assembly behaviors on calcium-doped titanium are imaged by resolving the strength of the SECM probe’s negative feedback in two-dimensional micro-regions. By using ion implantation techniques, calcium and/or silver were doped into polished titanium surfaces. The calcium-doped titanium was capable of releasing calcium, while the clean titanium and silver-doped titanium did not release their constituents. The two-dimensional discontinuous distribution of the probe current/steady current (i/i0) values were only detectable in calcium-doped groups, and this was incubating duration dependent, showing the micro-regions preferential for fibrinogen assembly in calcium-doped groups. This was consistent with the fibrinogen adsorption morphologies on calcium-doped titanium examined by dye-assisted scanning electron microscopy. It is concluded that protein assembly behaviors on bulk solid surfaces in liquid environments can be imaged by resolving the distribution of the SECM probe currents in two-dimensional areas. The method is promising in illuminating the true surface-protein interactions and the protein adsorption structure–function relations.

Amine-impregnated natural inorganic nanotubes via layer-by-layer electrostatically self-assembly approach for efficient CO2 adsorption

Developing cost-effective and high-performance solid amine adsorbents has considered as an important way to alleviate the greenhouse effect. How to precisely regulate its pore structure and surface interface characteristics, and how to cooperate to optimize the dynamic mass transfer and adsorption–desorption behavior of gas in the adsorbent are still challenging work. Herein, we demonstrated a facile and efficient approach to construct polyethyleneimine (PEI) impregnated halloysite nanotubes (HNTs) as an emerging nanocomposite for CO2 capture. Based on the natural electrostatic differences of inner and outer walls for HNTs, the hollow tubular structures of adsorbents were constructed by selective surface modification and layer-by-layer electrostatic self-assembly technology to improve the CO2 uptake capacity and cyclic stability, in which poly(sodium-p-styrene sulfonate) (PSS) and PEI were used as polyanionic and polycationic layer, respectively, to coat the inner walls of HNTs. The loading capacity of PSS-PEI composite ionic layers in HNTs and the influence of PSS polyanionic layer on PEI dispersion were specifically discussed according to the CO2 uptake capacity, adsorption heat, thermodynamics and kinetics of the adsorbents. The optimal PEI20-0.5PHNTs adsorbent exhibited a higher CO2 uptake of 0.87 mmol/g at 80 °C in the flow of 40 vol% N2/60 vol% CO2 than that of PEI20-HNTs, owing to the high amine efficiency due to the uniform dispersion of PEI in the electrostatic composite ionic layers. Furthermore, PEI20-0.5PHNTs reached 75 % of the maximum adsorption capacity at the 5th min of the adsorption process and released the most heat during adsorption at − 18.28 kJ/mol due to the presence of electrostatic composite ionic layers. PEI20-0.5PHNTs showed excellent cyclic stability with a slight loss of 7.4 %. The electrostatic self-assembled adsorbent obtained by layer-by-layer loading of PSS and PEI based on the unique surface charge characteristics of HNTs is an inspiration for the synthesis of cost-effective solid amine adsorbents for practical CO2 capture and separation.

Effect of voltage gradients on EK-PRB remediation: Experimental and molecular dynamics simulations

Electrokinetic-Permeable Reaction Barrier (EK-PRB) coupled remediation technology can effectively treat heavy metal-contaminated soil near coal mines. This study was conducted on cadmium (Cd), a widely present element in the soil of the mining area. To investigate the impact of the voltage gradient on the remediation effect of EK-PRB, the changes in current, power consumption, pH, and Cd concentration content during the macroscopic experiment were analyzed. A three-dimensional visualized kaolinite-heavy metal-water simulation system was constructed and combined with the Molecular Dynamics (MD) simulations to elucidate the migration mechanism and binding active sites of Cd on the kaolinite (001) crystalline surface at the microscopic scale. The results showed that the voltage gradient positively correlates with the current, power consumption, and Cd concentration during EK-PRB remediation, and the average removal efficiency increases non-linearly with increasing voltage gradient. Considering power consumption, average removal efficiency, and cost-effectiveness, the voltage range is between 1.5 and 3.0 V/cm, with 2.5 V/cm being the optimal value. The results of MD simulations and experiments correspond to each other. Cd2+ formed a highly stable adsorption structure in contrast to the Al–O sheet on the kaolinite (001) crystalline surface. The mean square displacement (MSD) curve of Cd2+ under the electric field exhibits anisotropy, the total diffusion coefficient DTotal increases and the Cd2+ migration rate accelerates. The electric field influences the microstructure of Cd2+ complexes. With the enhancement of the voltage gradient, the complexation between Cd2+ and water molecules is enhanced, and the interaction between Cd2+ and Cl− in solution is weakened.

Structure of Graphene Grown on Cu(111): X-Ray Standing Wave Measurement and Density Functional Theory Prediction.

We report the quantitative adsorption structure of pristine graphene on Cu(111) determined using the normal incidence x-ray standing wave technique. The experiments constitute an important benchmark reference for the development of density functional theory approximations able to capture long-range dispersion interactions. Electronic structure calculations based on many-body dispersion-inclusive density functional theory are able to accurately predict the absolute measure and variation of adsorption height when the coexistence of multiple moiré superstructures is considered. This provides a structural model consistent with scanning probe microscopy results.

Density and volume of adsorbed methane in key applications for in-situ gas content: Insights from molecular simulation

The evaluation of the in-situ gas content in deep coal seams, potentially containing free gas in saturated-oversaturated reservoirs, holds practical significance for exploration and production compared with shallow undersaturated-saturated reservoirs dominated by adsorbed gas. However, owing to the inherent limitations of volumetric and gravimetric methods, the accurate assessment of adsorbed and free gases faces significant challenges. In this study, based on molecular simulations, we focused on slit-shaped pores to explore the microscopic interaction mechanisms between coal and methane molecules under different pore sizes, temperatures, and pressures. By combining isothermal adsorption and pore structure experiments, the distribution characteristics of the adsorbed phase density (APD) and adsorbed phase volume (APV) were determined. The results showed that, in pores smaller than 1.5 nm, methane exhibited an aggregated state distribution (containing only adsorbed methane) characterized by micropore filling adsorption. In pores larger than 1.5 nm, methane showed a dispersed state distribution (coexistence of adsorbed and free methane) characterized by monolayer adsorption. The APD increased with pressure and decreased with temperature and pore size, whereas the APV remained independent of the pressure and temperature. In the in-situ gas content evaluation, three adsorption models (SL, SDR, and SL + SDR models) considering APV and APD were utilized to describe the methane adsorption behavior. The SDR model considering the APV was consistent with the actual physical properties and molecular simulation results. Traditional correction methods often lead to an overestimation of the adsorbed methane content, and neglecting the APV can result in an overestimation of the free methane content. In summary, the SDR model considering the APV can provide more rigorous scientific support for the refined study of methane occurrence states and gas content distribution.

Adsorption of toxic gases by Janus MoSeTe monolayers doped with transition metals and surface defects: A first-principles study

In recent years, two-dimensional TMDs materials have been proved to be high-performance gas sensor materials. Janus material is a member of the TMD family, and its gas sensing performance research is particularly important. Gas sensing mechanism of toxic gases on transition metal dichalcogenides based Janus MoSeTe monolayers is investigated using the density functional theory. Six transition metals are considered to modify the MoSeTe surface, by comparing the adsorption energies of the transition metal on both sides of the MoSeTe monolayer, it is found that the transition metal doping is more stable on the Se side. The MoSeTe surface is activated by transition metal modification, and the gas behavior is improved by transition metal modification, it is found that Ir-MoSeTe had the best sensing performance for NO2, Os-MoSeTe had the best sensing performance for CO, and Ru-MoSeTe had the best sensing performance for H2S, NO, and SO2. After that, we explain the adsorption mechanism of gas molecules by calculating the band structure, state density, differential charge density and work function of the adsorption structure, and the recovery time explain the reuse performance of the sensor. The results show that transition metal doped MoSeTe is a promising toxic gas sensor, which provides a theoretical basis for the development of new gas sensors.

Adsorption Structures, Vibrational Raman Spectra and Chemical Binding Properties of Thioglycolic Acid on Cu(111) Surfaces: A DFT Study.

Copper is widely used in everyday life and industrial production because of its good electrical and thermal conductivity. To overcome copper oxidation and maintain its good physical properties, small organic molecules adsorbed on the surface of copper make a passivated layer to further avoid copper corrosion. In this work, we have investigated thioglycolic acid (TGA, another name is mercaptoacetic acid) adsorbed on copper surfaces by using density functional theory (DFT) calculations and a periodical slab model. We first get five stable adsorption structures, and the binding interaction between TGA and Cu(111) surfaces by using density of states (DOS), indicating that the most stable configuration adopts a triple-end binding model. Then, we analyze the vibrational Raman spectra of TGA adsorbed on the Cu(111) surface and make vibrational assignments according to the vibrational vectors. Finally, we explore the temperature effect of the thermodynamically Gibbs free energy of TGA on the Cu(111) surface and the antioxidant ability of the small organic molecular layer of copper oxidation on the copper surface. Our calculated results further provide evidences to interpret the stability of adsorption structures and antioxidant properties of copper.

Structural and interfacial microenvironment modulation of two-dimensional layered niobium phosphate to enhance uranium adsorption

To address the environmental and resource challenges arising from the advancement of the nuclear power industry, it becomes imperative to foster the development of efficient and expeditious materials for uranium adsorption. Here, for the first time, a kind of niobium phosphate with improvement of interlayer spacing and hydrophilicity (NbP-8) is employed by crystal phase modulation for uranium adsorption, which synergistically realizes structural and interfacial microenvironment modulation. Characterizations demonstrate that the expanded interlayer spacing contributes to accommodation of uranyl which increases adsorption capacity, and the enhanced hydrophilicity reduces infiltration time and greatly accelerates the adsorption rate. Consequently, NbP-8 possesses exceptional adsorption capacity of 1470.4 mg g−1, ultra-fast adsorption rate with an equilibrium time of 1 min and high selectivity, delivering one of the best phosphate uranium adsorbents. Moreover, this work opens a new venue for optimizing performance of phosphate by changing the crystal phase to modulate structure and interfacial microenvironment for uranium adsorption.

DFT studies of the structural and electronic properties of PdGe n (n = 1–11) clusters and adsorption capacity for some gas molecules

Density functional theory calculations have been employed for the theoretical studies of the geometric structures and electronic characteristics of PdGe n (n = 1−11) clusters. An analysis of the second- order energy differences indicates that PdGe7 and PdGe10 clusters possess superior thermodynamic stability. PdGe10 displays the highest chemical stability and the lowest chemical activity, due to its largest energy gap value (E g). Vertical ionization potential and vertical electron affinity exhibit the decreasing and increasing trends, respectively, with the increase of the number n of Ge atoms. PdGe10 presents the highest electronegativity among these clusters. The analysis on the adsorption properties of PdGe n (n = 7,10) clusters for gas molecules (e.g. CO, NO, NO2, NH3, SO2 and H2S) yields the adsorption structures, adsorption energies, Mulliken charge transfer and the changes in the electronic properties. All the listed gas molecules chemically adsorb onto PdGe7. PdGe10 has a better adsorption performance for NO2, while its adsorption ability for CO is poorer. The potentiality of PdGe n (n = 7, 10) clusters as gas sensors is also evaluated and reveals that NO adsorption significantly affects the electronic properties, especially conductivity, of the systems. PdGe10 has an appropriate NO adsorption capacity and significant charge transfer, with the adsorption energy of −0.278 eV and the recovery time of about 10−9s, indicating its fast response and hence good potentiality as the NO sensor. In contrast, PdGe7 has a higher adsorption capability towards NO with a lower adsorption energy of −1.16 eV, leading to the difficulty in desorption and a longer recovery time of over 12 h.

Low gelatin concentration assisted cellulose nanocrystals stabilized high internal phase emulsion: The key role of interaction

Low concentrations of gelatin (0.02–0.20 wt%) were applied to regulate the surface and interface properties of CNC (0.50 wt%) by forming CNC/G complexes. As gelatin concentration increased from 0 to 0.20 wt%, the potential value of CNC/G gradually changed from −44.50 to −17.93 mV. Additionally, various gelatin concentrations led to micromorphology changes of CNC/G complexes, with the formation of particle interconnection at gelatin concentration of 0.10 wt%, followed by network structure and enhanced aggregation at gelatin concentration of 0.15 and 0.20 wt% respectively. The water contact angle (25.91°-80.23°) and interface adsorption capacity of CNC/G were improved due to hydrophobic group exposure of gelatin. When gelatin concentration exceeded 0.10 % at a fixed oil phase volume fraction (75 %), a high internal phase emulsion (HIPE) stabilized by CNC/G can be formed with a good storage stability. The rheological and microstructure results of HIPE confirmed that low gelatin concentration can assist CNC to form stable emulsion structure. Especially, the auxiliary stabilization mechanism of various gelatin concentration was different. CNC/G-0.10 % and CNC/G-0.15 % stabilized HIPE mainly depended on the enhanced interface adsorption and network structure, while CNC/G-0.20 % stabilized HIPE mainly relied on enhanced interface adsorption/accumulation due to weak electrostatic repulsion and aggregate granular morphology of CNC/G-0.20 %.

Melon seed shell synthesis N, S-carbon quantum dots as ultra-high performance corrosion inhibitors for copper in 0.5 M H2SO4

This work reports on the preparation of N, S-CQDs from melon seed shell, a common household waste that can inhibit the corrosion of copper in a 0.5 M H2SO4 solution. Additionally, by varying the preparation time and preparation temperature, the effects of N, S-CQDs on the capacity of copper to resist corrosion in 0.5 M H2SO4 solution were compared. It was also used to prove its inhibitory effect on copper in 0.5 M H2SO4 solution by a series of test methods. The corrosion inhibition rate of N, S-CQDs was 99.66 % and 99.87 % when the N, S-CQDs prepared at 160 ℃ for 6 h and 200 ℃ for 10 h were added. The results indicate that the corrosion inhibition rate of N, S-CQDs increases with increasing preparation time and temperature. XPS (X-ray photoelectron spectroscopy) and ATR-FTIR (Fourier transform infrared) were used to describe the composition and functional groups adsorbed on the surface of copper. N, S-CQDs' corrosion inhibition property was demonstrated by using an AFM (Atomic force microscope) and SEM (Scanning electron microscopy) to examine the corrosion surface morphology. Using the Langmuir adsorption model, it was found that the corrosion of copper was inhibited by both physical and chemical adsorption. A number of experimental findings demonstrate that preparation temperature and time impact the degree of carbonization, size, and functional group content of the N, S-CQDs, which in turn influences the corrosion inhibition of the N, S-CQDs. By means of heteroatom adsorption and surface structure, N, S-CQDs generate new chemical coordination bonds on the copper surface, thereby forming a protective layer, reducing the interaction between copper and 0.5 M H2SO4 solution, and generating a corrosion inhibition effect.