Role Of Surface Chemistry Research Articles

Adsorption of cytochrome c on different self-assembled monolayers: The role of surface chemistry and charge density.

In this work, the adsorption behavior of cytochrome c (Cyt-c) on five different self-assembled monolayers (SAMs) (i.e., CH3-SAM, OH-SAM, NH2-SAM, COOH-SAM, and OSO3--SAM) was studied by combined parallel tempering Monte Carlo and molecular dynamics simulations. The results show that Cyt-c binds to the CH3-SAM through a hydrophobic patch (especially Ile81) and undergoes a slight reorientation, while the adsorption on the OH-SAM is relatively weak. Cyt-c cannot stably bind to the lower surface charge density (SCD, 7% protonation) NH2-SAM even under a relatively high ionic strength condition, while a higher SCD of 25% protonation promotes Cyt-c adsorption on the NH2-SAM. The preferred adsorption orientations of Cyt-c on the negatively-charged surfaces are very similar, regardless of the surface chemistry and the SCD. As the SCD increases, more counterions are attracted to the charged surfaces, forming distinct counterion layers. The secondary structure of Cyt-c is well kept when adsorbed on these SAMs except the OSO3--SAM surface. The deactivation of redox properties for Cyt-c adsorbed on the highly negatively-charged surface is due to the confinement of heme reorientation and the farther position of the central iron to the surfaces, as well as the relatively larger conformation change of Cyt-c adsorbed on the OSO3--SAM surface. This work may provide insightful guidance for the design of Cyt-c-based bioelectronic devices and controlled enzyme immobilization.

A mini review on the applications of artificial intelligence (AI) in surface chemistry and catalysis

Abstract This review critically analyzes the incorporation of artificial intelligence (AI) in surface chemistry and catalysis to emphasize the revolutionary impact of AI techniques in this field. The current review examines various studies that using AI techniques, including machine learning (ML), deep learning (DL), and neural networks (NNs), in surface chemistry and catalysis. It reviews the literature on the application of AI models in predicting adsorption behaviours, analyzing spectroscopic data, and improving catalyst screening processes. It combines both theoretical and empirical studies to provide a comprehensive synthesis of the findings. It demonstrates that AI applications have made remarkable progress in predicting the properties of nanostructured catalysts, discovering new materials for energy conversion, and developing efficient bimetallic catalysts for CO2 reduction. AI-based analyses, particularly using advanced NNs, have provided significant insights into the mechanisms and dynamics of catalytic reactions. It will be shown that AI plays a crucial role in surface chemistry and catalysis by significantly accelerating discovery and enhancing process optimization, resulting in enhanced efficiency and selectivity. This mini-review highlights the challenges of data quality, model interpretability, scalability, and ethical, and environmental concerns in AI-driven research. It highlights the importance of continued methodological advancements and responsible implementation of artificial intelligence in catalysis research.

The Unseen Threat of the Synergistic Effects of Microplastics and Heavy Metals in Aquatic Environments: A Critical Review

Abstract Purpose of Review The synergistic effects of microplastics (MPs) and heavy metals are becoming major threats to aquatic life and human well-being. Therefore, understanding synergistic interactions between MPs and heavy metals is crucial to comprehend their environmental impacts. Recent Findings The mechanisms such as electrostatic attraction, surface interactions, ion exchange, hydrogen bonding, hydrophobic forces, and π–π interactions behind the synergistic effects of MPs and heavy metals were critically reviewed and justified. In addition, the roles of surface chemistry in these interactions were also emphasized. Finally, efficient remediation techniques aligning with a circular economy-based initiative to promote sustainable solutions were recommended to mitigate plastic-heavy metal pollution to achieve a cleaner environment. Summary This review examines the combined impact of MPs and heavy metals in aquatic ecosystems, detailing their mechanistic interactions, and consequences with proposed sustainable solutions. Additionally, this review highlights the MP-heavy metal contamination risks and emphasizes the need for further research to safeguard aquatic life and human health.

Role of Surface Chemistry in Pyrrole Autoxidation.

Chemical compounds in liquid hydrocarbon fuels that contain five-membered pyrrole (Py) rings readily react with oxygen from air and polymerize through a process known as autoxidation. Autoxidation degrades the quality of fuel and leads to the formation of unwanted gum deposits in fuel storage vessels and engine components. Recent work has found that the rate of formation of these gum deposits is affected by material surfaces exposed to the fuel, but the origins of these effects are not yet understood. In this work, atomic layer deposition (ALD) is employed to grow aluminum oxide, zinc oxide, titanium dioxide, and manganese oxide films on silicon substrates to control material surface chemistry and study Py adsorption and gum nucleation on these surfaces. Quartz crystal microbalance (QCM) studies of gas-phase Py adsorption indicate 1.5-2.8 kcal/mol exergonic adsorption of Lewis basic Py onto Lewis acidic surface sites. More favorable Py adsorption onto Lewis acidic surfaces correlates with faster polypyrrole (PPy) film nucleation in vapor phase oxidative molecular deposition (oMLD) polymerization studies. Liquid-phase studies of Py autoxidation reveal primarily particulate formation, indicating a homogeneous PPy propagation step rather than a completely surface-based polymerization mechanism. The amount of PPy particulate formation is positively correlated with more acidic surfaces (lower pH-PZC values), indicating that the rate-limiting step for Py autoxidation involves Lewis acidic surface sites. These studies help to establish new mechanistic insights into the role of surface chemistry in the autoxidation of pyrrolic species. We apply this knowledge to demonstrate a polymer coating formed by vapor phase polymer deposition that slows autoxidation by 2 orders of magnitude.

Effect of Surface Modification on the Luminescence of Individual Upconversion Nanoparticles.

Lanthanide-doped upconversion nanoparticles (UCNPs) hold promise for single-molecule imaging owing to their excellent photostability and minimal autofluorescence. However, their limited water dispersibility, often from the hydrophobic oleic acid ligand during synthesis, is a challenge. To address this, various surface modification strategies' impact on single-particle upconversion luminescence are studied. UCNPs are made hydrophilic through methods like ligand exchange with dye IR806, HCl or NOBF4 treatment, silica coating (SiO2 or mesoporous mSiO2), and self-assembly with polymer of DSPE-PEG or F127. The studies revealed that UCNPs modified with NOBF4 and DSPE-PEG exhibited notably higher single-particle brightness with minimal quenching (3% and 8%, respectively), followed by SiO2, F127, IR806, mSiO2, and HCl (84% quenching). HCl disrupted UCNPs's crystal lattice, weakening luminescence, while mSiO2 absorbed solvent molecules, causing luminescence quenching. Energy transfer to IR806 also reduced the brightness. Additionally, a prevalence of upconversion red emission over green is observed, with the red-to-green ratio increasing with irradiance. UCNPs coated with DSPE-PEG exhibited the brightest single-particle luminescence in water, retaining 48% of its original emission due to a lower critical micelle concentration and superior water protection. In summary, the investigation provides valuable insights into the role of surface chemistry on UCNPs at the single-particle level.

Soft Surface Activated Bonding of Hydrophobic Silicon Substrates

Surface Activated Bonding (SAB) is interesting for strong silicon to silicon bonding at room temperature without any annealing needed, afterwards (1). Although it is a well-known technique, the activation step, in particular, is scarcely documented. This paper offers insights about the impact of soft activation parameters on the amorphous region at the bonding interface. In addition, the adherence energy of hydrophobic silicon bonding with SAB is quantified to better understand bonding mechanisms.With very low dose and acceleration activation parameters, the surface preparation prior to bonding becomes of paramount importance. Indeed, the silicon native oxide is typically removed during the activation step. The thin amorphous silicon region is a side effect of this singular surface preparation(2).In order to work around this potential roadblock, we used instead hydrophobic surface preparation to remove the native oxide, before entering into the activation step. Two types of preparation were evaluated in this study. First, a standard “HF-Last” chemical treatment was used on standard silicon wafers. This treatment removed the silicon native oxide and passivated the surface with Si-H and, to a lesser extent, Si-F bonds (3). We otherwise used epitaxy-reconstructed silicon wafers with fully hydrophobic surfaces (4). Silicon native oxide was removed thanks to an ultra-pure H2 bake at 1100°C, 20 Torr for 2 minutes in an epitaxy chamber. Then, several tens of nm of Silicon were deposited at 950°C to obtain, after another H2 bake, a silicon surface fully passivated by hydrogen atoms with atomically smooth terraces and mono-atomic step edges.Our EVG®ComBond® bonding tool, operating under ultra-high vacuum (UHV), is equipped with an accelerated argon ion beam to perform the activation step. The softest functional settings, on our set up, are 50V (acceleration) and 26 mA (dose). After beam initialization, the two sets of substrates pass through the activation chamber. Activated substrates are then transferred to the bonding chamber within 5 minutes of handling.The exposure time in the activation chamber was evaluated, the aim being to remove adsorbed hydrogen atoms on the silicon surface without any amorphous silicon generation. Different characterization techniques such as transmission electron microscopy or FTIR-MIR were used to quantify the amorphous layer formation and the potential Si-H bonds remaining (after activation). The adherence energy of the bonded pair was measured by a double cantilever beam method under prescribed displacement control in anhydrous atmosphere (5).Figure 1 shows the adherence energy (Gc=2γc) in mJ/m² as a function of activation exposure time with soft activation parameters for both wafer preparations. The 0s reference bonding was conducted without passing through the activation module. We then had very low adherence energies, around 50 mJ/m², as expected for standard hydrophobic silicon wafer bonding under UHV (6). Upon Ar+ exposure, behaviors were very different depending on surface preparation. The adherence energy barely increased with the Ar+ exposure time for “HF-Last” surfaces. Meanwhile, even 1s of exposure to Ar+ had a definite impact on the adherence energy of epi-reconstructed, atomically smooth silicon surfaces, which was definitely higher. The maximum difference between both wafer preparations occurred for 30 up to 60 seconds exposure times. This indicate a change in the bonding mechanism as the comparatively high roughness of the “HF-Last” silicon wafer started to be counter-balanced by activation.The experimental set up, the manufacturing process, as well as further characterizations will be presented. Cross-sectional TEM imaging of the bonding interface, FTIR-MIR and AFM measurements after surface preparation will help us better understand the specificities of such soft activation process on the SAB of hydrophobic surfaces. The impact of the amorphous silicon layer on bonding will be discussed. Suga T et al. STRUCTURE OF A1-A1 A N D A1-Si3N4 INTERFACES BONDED AT ROOM TEMPERATURE BY MEANS OF THE SURFACE ACTIVATION METHOD. Acta Metallurgica et Materialia 1992.Takagi H et al. Surface activated bonding of silicon wafers at room temperature. Appl Phys Lett. 1996.Abbadie A et al. Low thermal budget surface preparation of Si and SiGe. Appl Surf Sci. 2004.Sordes D et al. Nanopackaging of Si(100)H Wafer for Atomic-Scale Investigations. 2017.Maszara WP et al. Bonding of silicon wafers for silicon‐on‐insulator. J Appl Phys. 15 nov 1988;64(10):4943-50.Tong QY et al. The Role of Surface Chemistry in Bonding of Standard Silicon Wafers. J Electrochem Soc. 1997. Figure 1

The role of surface chemistry in the synthesis of supported CuPd bimetallic/intermetallic catalysts for selective hydrogenation reactions

Understanding and controlling the structure of supported bimetallic/intermetallic catalysts are crucial for many heterogeneous catalytic reactions. However, commonly used synthesis techniques such as coimpregnation and coadsorption often yield nonuniform alloying and phase segregation, largely owing to the lack of interactions between different metal precursors. Here we show that by adopting sequential adsorption of complex metal cations and anions with the assistance of a proper ligand, the interaction between different metal precursors is enhanced, thus resulting in uniformly alloyed intermetallic catalysts. The supported CuPd intermetallic catalyst exhibits greatly improved selectivity towards monoolefins in the semihydrogenation of acetylene and butadiene compared to those random CuPd alloys synthesized via coimpregnation and coadsorption methods.

Different Roles of Surface Chemistry and Roughness of Laser-Induced Graphene: Implications for Tunable Wettability.

The control of surface wettability is a technological key aspect and usually poses considerable challenges connected to high cost, nanostructure, and durability, especially when aiming at surface patterning with high and extreme wettability contrast. This work shows a simple and scalable approach by using laser-induced graphene (LIG) and a locally inert atmosphere to continuously tune the wettability of a polyimide/LIG surface from hydrophilic to superhydrophobic (Φ ∼ 160°). This is related to the reduced amount of oxygen on the LIG surface, influenced by the local atmosphere. Furthermore, the influence of the roughness pattern of LIG on the wettability is investigated. Both approaches are combined, and the influence of surface chemistry and roughness is discussed. Measurements of the roll-off angle show that LIG scribed in an inert atmosphere with a low roughness has the highest droplet mobility with a roll-off angle of ΦRO = (1.7 ± 0.3)°. The superhydrophobic properties of the samples were maintained for over a year and showed no degradation after multiple uses. Applications of surfaces with extreme wettability contrast in millifluidics and fog basking are demonstrated. Overall, the proposed processing allows for the continuous tuning and patterning of the surface properties of LIG in a very accessible fashion useful for "lab-on-chip" applications.

Tuning the Microstructures of ZnO To Enhance Photocatalytic NO Removal Performances

Effective removal of kinetically inert dilute nitrogen oxide (NO, ppb) without NO2 emission is still a challenging topic in environmental pollution control. One effective approach to reducing the harm of NO is the construction of photocatalysts with diversified microstructures and atomic arrangements that could promote adsorption, activation, and complete removal of NO without yielding secondary pollution. Herein, microstructure regulations of ZnO photocatalysts were attempted by altering the reaction temperature and alkalinity in a unique ionic liquid-based solid-state synthesis and further investigated for the removal of dilute NO upon light irradiation. Microstructure observations indicated that as-tuned photocatalysts displayed unique nucleation, diverse morphologies (spherical nanoparticles, short and long nanorods), defect-related optical characteristics, and enhanced carrier separations. Such defect-related surface-interface aspects, especially Vo″-related defects of ZnO devoted them to the 4.16-fold enhanced NO removal and 2.76 magnitude order decreased NO2 yields, respectively. Improved NO removal and toxic product inhabitation in as-tuned ZnO was disclosed by mechanistic exploitations. It was revealed that regulated microstructures, defect-related charge carrier separation, and strengthened surface interactions were beneficial to active species production and molecular oxygen activation in ZnO, subsequently contributing to the improved NO removal and simultaneous avoidance of NO2 formation. This investigation shed light on the facile regulation of microstructures and the roles of surface chemistry in the oxidation of low concentration NO in the ppb level upon light illumination.

Structure of the Poly(methyl methacrylate) Adsorbed Layer Determined by the Surface Chemistry of the Substrate

The adsorbed polymer layer on the inorganic solid surface is crucial in improving the physical properties of composite nanomaterials; therefore, the properties could be tuned by altering the structure of the adsorbed layer. We investigated poly(methyl methacrylate) (PMMA) adsorbed layers on SiO2–Si substrates by varying the hydroxyl (OH) group content on the substrate surface. The results indicated that the thicknesses of the flattened layer and loosely adsorbed layer decreased with decreasing OH group content and the flattened layer disappeared when the content was ∼31%. The OH groups controlled the formation of the adsorbed layer, providing anchor points through hydrogen bonding with the carbonyl groups in PMMA. With decreasing OH group content, fewer anchor points possibly prevented train conformation and the relatively stable loosely adsorbed chains still formed, which enhanced the segmental dynamics of the ultrathin PMMA film. These results provide novel insight into the role of surface chemistry in forming adsorbed polymer layers on substrates.

Rational design of β-cyclodextrins-derived hierarchically porous carbons for CO2 capture: The roles of surface chemistry and porosity on CO2 capture

CO2 capture, storage and utilization (CCSU) is the most promising strategy for ameliorating the ever-increasing atmospheric CO2 concentrations problem. The development of advanced porous solid adsorbents for efficient CCSU is a burgeoning interest in materials science. Currently, porous carbon-based adsorbents face the major challenge of balancing the structural features of porosity and surface chemistry for CCSU in a durable and scalable material. To this end, we designed hierarchically porous carbons with tailorable porosity and adjustable surface chemistry, and clarify the influence of porosity and surface chemistry on CO2 capture. Meanwhile, the systematic study revealed the synergetic effect of microporosity of less than 10 Å and surface chemistry on CO2 capture, and the synergistic effect mechanism of various surface groups on CO2 capture property was also ascertained in detail. Porosity was found to be the determinant role on CO2 capture, in particular the microporosity of < 10 Å and ultramicroporosity of < 7.0 Å. While, surface chemistry played a significant role on the improvement of CO2 capture, especially the CO2/N2 selectivity at higher temperature. Importantly, this work provided an instructive guideline for rational design of high-efficient porous carbon CO2 adsorbents with a balanced porosity and surface chemistry property.

Design Guidelines for Sulfonyl/Sulfamoyl Fluoride Electrolyte Additives for Modulation of Lithium Anode Coulombic Efficiency

Owing to its high theoretical capacity (3860 mAh/g, over 10 times that of graphite) and its lowest theoretical electrochemical potential (-3.04 V vs SHE), Li metal is an ideal anode material for improving the capacity of rechargeable Li batteries [1]. However, the practical application of the Li anode is severely hindered by its high reactivity with standard electrolyte compositions, which results in limited Coulombic efficiency (CE) in those electrolytes (for instance, 85-90% with 1 M LiPF6 EC:DEC [2]). Strategies to improve CE have focused on electrolyte engineering, including development of highly concentrated electrolytes (HCE) and more recently, local high-concentration electrolytes (LHCE) [3]. A feature shared by these strategies is the promotion of contact-ion pairing, which enhances anion contributions to the solid electrolyte interphase (SEI). Among the best-performing salts are fluorinated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), which are believed to promote stable inorganic-rich SEIs and correlate with higher CE [4]. A second strategy of interest is to pursue development of additives incorporated at relatively low concentrations (e.g., 2-5 wt%) that can favorably alter the SEI, such as carbonates (e.g., vinylene carbonate (VC) [5] and fluoroethylene carbonate (FEC) [6]), sulfates (e.g., ethylene sulfate (DTD) and 1,3-propanesulfonate (PS) [7]), and borates (e.g., lithium difluoro(oxoalate) borate (LiDFOB) [8] and tris (2,2,2-trifluoroethyl) borate (TTFEB) [9]). An advantage of this strategy is the possibility to ultimately lower reliance on high fluorinated salt concentrations, which are costly and can be corrosive towards the Al current collector, and potentially expand the versatility of available electrolyte frameworks having competitive CE. However, compared to the principles developed for salt and solvent selection in HCE and LHCE, the mechanism behind successful additive activation needs elucidation.In this work, we examined the potential of "FSI-like," neutral sulfonyl/sulfamoyl fluorides (R-SO2F and R-R’-NSO2F, Figure 1) as functional additives for Li cycling, motivated by their structural similarity to the high-performance FSI- anion. The examined baseline electrolytes include high-CE systems consisting of LiFSI dissolved in various solvents: fluoroethylene carbonate (FEC, 1 and 4 M salt), 1,2-dimethoxyethane (DME, 4 M), and dimethyl carbonate (DMC, 6 M). The ability for each additive to coordinate with Li+ was first examined by NMR, with trends rationalized in part by supporting microcalorimetry data on the degree of solvent coordination strength. We relate these to CE and cycling outcomes in each electrolyte. Interestingly, we find that additives have negligible effect on CE in FEC-based electrolytes, whereas significant impacts were observed in DME and DMC. We relate these diverse outcomes to the SEI chemical compositions and gases evolved during galvanostatic cycling, as characterized by X-ray photoelectron spectroscopy (XPS) and gas chromatography (GC), which help to rationalize competitive reactions among solvent, anion, and additive. Unfortunately, additives had a negative-to-neutral impact on CE in these systems. Thus, we finally examined a LiPF6 in carbonate electrolyte, 1 M LiPF6 in EC/DMC (LP40), where we hypothesized that competitive reduction of coordinating additives over problematic carbonate solvent would lead to performance gains. Indeed, significant improvements (up to 94%, compared to baseline 89% over the initial 50 cycles) in CE were observed for two additives, with their structural advantages further discussed. Overall, our findings provide insights into the effects of sulfonyl/sulfamoyl fluoride additive structures on Li metal cyclability and the compositions of baseline electrolytes whose electrochemical cycling stability can be effectively modulated by these additives. Xu, W., et al., Lithium metal anodes for rechargeable batteries. Energy & Environmental Science, 2014.7(2):p.513-537.Genovese, M., et al., Combinatorial methods for improving lithium metal cycling efficiency. Journal of The Electrochemical Society, 2018.165(13):p.A3000.Hobold, G.M., et al., Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes. Nature Energy, 2021.6(10):p.951-960.Suo, L., et al., Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries. Proceedings of the National Academy of Sciences, 2018.115(6):p.1156-1161.Aurbach, D., et al., On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries. Electrochimica acta, 2002.47(9):p.1423-1439.Markevich, E., et al., Fluoroethylene carbonate as an important component in electrolyte solutions for high-voltage lithium batteries: role of surface chemistry on the cathode. Langmuir, 2014.30(25):p.7414-7424.Han, B., et al., Poor Stability of Li2CO3 in the Solid Electrolyte Interphase of a Lithium ‐Metal Anode Revealed by Cryo ‐Electron Microscopy. Advanced Materials, 2021.33(22):p.2100404.Liu, J., et al., Lithium difluoro (oxalato) borate as a functional additive for lithium-ion batteries. Electrochemistry communications, 2007.9(3):p.475-479.Ma, Y., et al., Enabling reliable lithium metal batteries by a bifunctional anionic electrolyte additive. Energy Storage Materials, 2018.11:p.197-204. Figure 1. (a) Sulfonyl/sulfamoyl fluoride chemical structures and (b) R-S and S-F bond lengths calculated by density functional theory. Figure 1

Role of surface chemistry in determining the heteroepitaxial growth of Ir films on a-plane α-Al2O3 single crystals

Heteroepitaxy has increased in importance as the development of the semiconductor industry has advanced and a number of heteroepitaxial devices have been developed. In this study, Ir films of (001) or (111) preferred orientation were deposited onto a-plane α-Al2O3 surfaces pretreated via annealing in air and/or Ar+ ion etching. Ir (001) films were epitaxially grown on α-Al2O3 substrates with an in-plane orientation relationship of Ir (001)[110]//α-Al2O3 (112¯0)[0001]. In contrast, (111) films were non-epitaxial with the out-of-plane orientation relationship of Ir (111)// α-Al2O3 (112¯0). The effects of annealing in air and Ar+ ion etching on Ir film growth were then analyzed. Annealing in air can lead to a terrace morphology and a lower Al/O atomic ratio of 1/2 than 2/3 for α-Al2O3 surfaces, and a better Ir film crystallinity due to the step-flow mechanism; however, this was not the key factor for Ir heteroepitaxy. Ar+ ion etching was regarded as an irreplaceable pretreatment procedure. The surface chemistry of α-Al2O3 substrates was characterized via X-ray photoelectron spectroscopy. Carbon adsorbate (C = O, CC, CO, etc.) on substrate surfaces was drastically reduced after etching. Interfacial structures were observed by transmission electron spectroscopy. Two different stacking sequences were observed along the out-of-plane direction of α-Al2O3 (112¯0) surface, representing the 〈111〉 and 〈001〉 crystal directions, respectively; C element enrichment was observed at the interface without etching. Finally, the interaction between Ir films and α-Al2O3 substrates, which is probably influenced by the surface chemistry, is considered to be the growth mechanism of Ir films. This study provides significant insights into the role of the surface chemistry in the epitaxial growth of films.

The Role of Surface Chemistry in the Orientational Behavior of Water at an Interface.

Molecular dynamics studies have demonstrated that molecular water at an interface, with either a gas or a solid, displays anisotropic orientational behavior in contrast to its bulk counterpart. This effect has been recently implicated in the like-charge attraction problem for colloidal particles in solution. Here, negatively charged particles in solution display a long-ranged attraction where continuum electrostatic theory predicts monotonically repulsive interactions, particularly in solutions with monovalent salt ions at low ionic strength. Anisotropic orientational behavior of solvent molecules at an interface gives rise to an excess interfacial electrical potential which we suggest generates an additional solvation contribution to the total free energy that is traditionally overlooked in continuum descriptions of interparticle interactions in solution. In the present investigation we perform molecular dynamics simulation based calculations of the interfacial potential using realistic surface models representing various chemistries as well as different solvents. Similar to previous work that focused on simple model surfaces constructed by using oxygen atoms, we find that solvents at more realistic model surfaces exhibit substantial anisotropic orientational behavior. We explore the dependence of the interfacial solvation potential on surface properties such as surface group chemistry and group density at silica and carboxylated polystyrene interfaces. For water, we note surprisingly good agreement between results obtained for a simple O-atom wall and more complex surface models, suggesting a general qualitative consistency of the interfacial solvation effect for surfaces in contact with water. In contrast, for an aprotic solvent such as DMSO, surface chemistry appears to exert a stronger influence on the sign and magnitude of the interfacial solvation potential. The study carries broad implications for molecular-scale interactions and may find relevance in explaining a range of phenomena in soft-matter physics and cell biology.

The role of surface chemistry on CO2 adsorption in biomass-derived porous carbons by experimental results and molecular dynamics simulations

Biomass-derived porous carbons have been considered one of the most effective adsorbents for CO2 capture, due to their porous structure and high specific surface area. In this study, we successfully synthesized porous carbon from celery biomass and examined the effect of external adsorption parameters including time, temperature, and pressure on CO2 uptake in experimental and molecular dynamics (MD) simulations. Furthermore, the influence of carbon’s surface chemistry (carboxyl and hydroxyl functionalities) and nitrogen type on CO2 capture were investigated utilizing MD simulations. The results showed that pyridinic nitrogen has a greater tendency to adsorb CO2 than graphitic. It was found that the simultaneous presence of these two types of nitrogen has a greater effect on the CO2 sorption than the individual presence of each in the structure. It was also revealed that the addition of carboxyl groups (O=C–OH) to the carbon matrix enhances CO2 capture by about 10%. Additionally, by increasing the simulation time and the size of the simulation box, the average absolute relative error for simulation results of optimal structure declined to 16%, which is an acceptable value and makes the simulation process reliable to predict adsorption capacity under various conditions.

Ruthenium Icosahedra and Ultrathin Platelets: The Role of Surface Chemistry on the Nanoparticle Structure

The control of the crystalline structure and shape (crystal habit) of nanoparticles (NPs) is the key to controlling their physical and chemical properties. Among the different metals, the crystallogenesis of ruthenium NPs has been less studied, and until recently, the Ru NP crystal structure and morphology have been considered as presenting less versatility than the face-centered cubic (fcc) metals of the platinum group. Here, we show that while the hydrogenation of [Ru(COD)(COT)] in solutions containing a long-chain amine (hexadecylamine, HDA) in large excess leads to isotropic NPs adopting the expected hexagonal close-packed (hcp) structure of bulk Ru, a long-chain carboxylic acid (lauric acid, LA) in large excess induces the formation of Ru nano-objects of two original structures: ultrathin platelets and icosahedra. The latter have never been produced so systematically by other methods. We show that carbon monoxide, produced in situ by the decarbonylation of lauric acid, plays a pivotal role in the stabilization of the Ru icosahedra. This result is supported by density functional theory (DFT) calculations, which show that above a critical surface coverage of CO, small Ru icosahedra are more stable than the Ru bipyramid polyhedra crystallizing in the hcp structure. Thus, in situ production of CO results in a competition between icosahedral and hcp seeds, which explains the mixture of icosahedra and ultrathin platelets. Another effect of the large excess of lauric acid is the stabilization of the ruthenium precursors in solution, limiting the nucleation extent and slowing down the NP growth. While the growth of the icosahedral seeds is limited because of the structural strains, the growth of the hcp seeds preferentially develops the (0001) facets, leading to ultrathin platelets and threefold stars.

The Role of Surface Chemistry in the Osseointegration of PEEK Implants.

Poly(etheretherketone) (PEEK) implants suffer from poor osseointegration because of chronic inflammation. In this study, we hypothesized that adding NH2 and COOH groups to the surface of PEEK could modulate macrophage responses by altering protein adsorption and improve its osseointegration. NH2 and COOH-functionalized PEEK surfaces induced pro- and anti-inflammatory macrophage responses, respectively, and differences in protein adsorption patterns on these surfaces were related to the varied inflammatory responses. The macrophage responses to NH2 surfaces significantly reduced the osteogenic differentiation of mesenchymal stem cells (MSCs). MSCs cultured on NH2 surfaces differentiated less than those on COOH surfaces even though NH2 surfaces promoted the most mineralization in simulated body fluid solutions. After 14 days in rat tibia unicortical defects, the bone around NH2 surfaces had thinner trabeculae and higher specific bone surface than the bone around unmodified implants; surprisingly, the NH2 implants significantly increased bone-binding over the unmodified implants, while COOH implants only showed a trend for increasing bone-binding. Taken together, these results suggest that both mineral-binding and immune responses play a role in osseointegration, and PEEK implant integration may be improved with mixtures of these two functional groups to harness the ability to reduce inflammation and bind bone strongly.

Roles of Surface Chemistry and Texture of Nanoporous Activated Carbons in CO2 Capture

Roles of Surface Chemistry and Texture of Nanoporous Activated Carbons in CO₂ Capture

Role of surface chemistry of activated carbon for anchoring iron particles by forced hydrolysis and evaluation of iron-loaded adsorbents for Cr (VI) adsorption

ABSTRACT This research aimed to assess the role of granular activated carbon (GAC) functional groups for anchoring iron particles by forced hydrolysis and the effect of iron-loaded GAC for the adsorption of Cr (VI). First, to modify the surface chemistry of the GAC, the adsorbent was treated by oxidation, heating, and ammonia soaking. Next, the anchorage of iron on raw and modified GAC by forced hydrolysis was conducted. Subsequently, adsorbents were characterized, and adsorption tests were performed at pH 6 and 25°C. Findings revealed that the incorporation of acid functional groups on the GAC surface by oxidation allowed an iron anchoring (1.5%) higher than the heat-treated GAC (0.2%). Besides, forced hydrolysis treatment significantly improved the Cr (VI) adsorption capacity at equilibrium concentrations lower than 150 mg/L. Heat-treated GAC with iron achieved the best Cr (VI) uptake capacity (57 mg/g) and the fastest adsorption kinetics of the studied adsorbents. Cr (VI) desorption (98%) from the best adsorbent (iron-loaded and heat-treated GAC) was attained with a 0.1 N NaOH-NaCl solution, suggesting an adsorption mechanism mainly by physical attraction. In conclusion, the surface chemistry of GAC plays a significant role in the anchorage of iron particles, and iron particles improve Cr (VI) adsorption.

Rational Design of Β-Cyclodextrins-Derived Hierarchically Porous Carbons for Co2 Capture: The Roles of Surface Chemistry and Porosity on Co2 Capture

Rational Design of Β-Cyclodextrins-Derived Hierarchically Porous Carbons for Co2 Capture: The Roles of Surface Chemistry and Porosity on Co2 Capture