The surface charge components of 2 Georgia kaolinites of differing degrees of crystallinity (KGa-1 and KGa-2) were determined using procedures based on charge balance concepts. Permanent structural charge density (σ0) was determined by measuring the surface excess of Cs, which is highly selective to permanent charge sites. The values of σ0 determined were -6.3 ± 0.1 and -13.6 ± 0.5 mmol kg−1 for kaolinites KGa-1 and KGa-2, respectively. The net proton surface charge density (σH) was determined as a function of pH by Potentiometrie titration in 0.01 mol dm-3 LiCl. Correction from apparent to absolute values of σH was made by accounting for Al release during dissolution, background ion adsorption and charge balance. Lithium and C1 adsorption accounted for the remainder of the surface charge components. Changes in surface charge properties with time were measured after mixing times of 1, 3 and 15 h, the latter representing “equilibrium”. Time-dependent behavior is believed to be caused by mineral dissolution followed by readsorption or precipitation of Al on the mineral surface. Both the point of zero net charge (p.z.n.c.) and the point of zero net proton charge (p.z.n.p.c.) changed with mixing time, generally increasing. The “equilibrium” p.z.n.c. values were approximately 3.6 for KGa-1 and 3.5 for KGa-2, whereas the corresponding p.z.n.p.c. values were about 5.0 and 5.4. The p.z.n.c. results were in good agreement with previous studies, but the values of p.z.n.p.c. were higher than most other values reported for specimen kaolinite.

Two-line ferrihydrite is an important adsorbent of many toxics in natural and anthropogenic systems; however, the specific structural sites responsible for the high adsorption capacity are not well understood. A combination of chemical and spectroscopic techniques have been employed in this study to gain further insight into the structural nature of sites at the ferrihydrite surface. The kinetics of iron isotopic exchange demonstrated that there are at least two types of iron sites in ferrihydrite. One population of sites, referred to as labile sites, approached iron isotopic equilibrium within 24 hr in 59Fe-NTA solutions, while the second population of sites, referred to as non-labile, exhibited a much slower rate of isotopic exchange. Adsorbed arsenate reduced the degree of exchange by labile sites, indicating that the anion blocked or greatly inhibited the rate of exchange of these sites. Mössbauer spectra were collected from a variety of samples including 56Fe-ferrihydrite samples with 57Fe in labile sites, samples containing 57Fe throughout the structure, and samples with 57Fe in non-labile sites. The spectra showed characteristic broad doublets signifying poor structural order. Refined fits of the spectra indicated that labile sites have larger quadrupole splitting, hence more local distortion, than non-labile sites. In all cases, the spectra demonstrated some degree of asymmetry, indicating a distribution of Fe environments in ferrihydrite. Overall spectral findings, combined with recent EXAFS results (Waychunas et al., 1993), indicate that labile sites likely are more reactive (with respect to iron isotopic exchange) because they have fewer neighboring Fe octahedra and are therefore bound less strongly to the ferrihydrite structure. The labile population of sites probably is composed of end sites of the dioctahedral chain structure of 2-line ferrihydrite, which is a subset of the entire population of surface sites. Mössbauer spectra of samples containing adsorbed arsenate indicated that the anion may slightly decrease the distortion of labile sites and stabilized the structure as a whole by bidentate bonding.

Three-dimensional porous materials with the hydrophobic/oleophilic surface have attracted significant interest in the fields of oil/water separation. In this paper, superhydrophobic magnetic polyurethane sponge was fabricated by the self-polymerization of dopamine to bind the Fe3O4 nanoparticles tightly on the sponge and then soaking in cheap stearic acid aqueous solution. The obtained sponge has the superhydrophobic property and good magnetic property. The surface structure, composition, and properties of the modified sponges were characterized by scanning electron microscopy, energy dispersive spectrometer, Fourier-transform infrared spectrum, and water contact angle (WCA) measurements. The as-prepared superhydrophobic magnetic sponge was able to collect a wide range of oils and organic solvents from oil–water mixture with an absorption capacity up to 16–60 times of its own weight. Under an external magnetic field, it can be guided to a designated area. In addition, combined with the vacuum system, continuous oil separation can be carried out, which is of great significance for removing a good deal of dirty oil on the water surface. Furthermore, the WCA of sponge remains above 141°, and the oil absorption is basically unchanged through repeated cyclic experiments.

Molecular weight (Mw) effects in poly(vinylidene fluoride) (PVDF) influence both processability and combustion behavior in energetic Al–PVDF filaments. Results show decreased viscosity in unloaded and fuel-lean (i.e., 15 wt% Al) filaments. In highly loaded filaments (i.e., 30 wt% Al), reduced viscosity is minimal due to higher electrostatic interaction between Al particles and low Mw chains as confirmed by Fourier-transform infrared spectroscopy. Thermal and combustion analysis further corroborates this story as exothermic activity decreases in PVDF with smaller Mw chains. Differential scanning calorimetry and Thermogravimetric analysis show reduced reaction enthalpy and lower char yield in low Mw PVDF. Enthalpy reduction trends continued in nonequilibrium burn rate studies, which confirm that burn rate decreases in the presence of low Mw PVDF. Furthermore, powder X-ray patterns of post-burn products suggest that low Mw PVDF decomposition creates a diffusion barrier near the Al particle surface resulting in negligible AlF3 formation in fuel-rich filaments.

Graphene and its functionalization are still one of the most prominent two-dimensional crystals. In recent years, the wetting properties of graphene for water (i.e., its hydrophobic, hydrophilic, and also icophobic features) were controversially discussed as well as water intercalation and confined water, that have unusual characteristics. The dispute about wetting properties was originally based on contact angle (/engineering) measurements conducted at ambient pressure. In the meanwhile, detailed ultra-high vacuum (UHV) surface science works and theoretical studies are available. This brief review describes the current knowledge available in the literature about the water/graphene system as well as our own work using experimental UHV surface science techniques. The review starts with a definition of hydrophobicity and briefly touches on a possible correlation with icephobicity as well as discusses briefly confined water. Next, theoretical studies are reviewed, and finally, experimental works are described on which the review focusses. Finally, a brief outlook section discusses water adsorption on functionalized graphene.

Hydrogen lithography has been used to template phosphine-based surface chemistry to fabricate atomic-scale devices, a process we abbreviate as atomic precision advanced manufacturing (APAM). Here, we use mid-infrared variable angle spectroscopic ellipsometry (IR-VASE) to characterize single-nanometer thickness phosphorus dopant layers (δ-layers) in silicon made using APAM compatible processes. A large Drude response is directly attributable to the δ-layer and can be used for nondestructive monitoring of the condition of the APAM layer when integrating additional processing steps. The carrier density and mobility extracted from our room temperature IR-VASE measurements are consistent with cryogenic magneto-transport measurements, showing that APAM δ-layers function at room temperature. Finally, the permittivity extracted from these measurements shows that the doping in the APAM δ-layers is so large that their low-frequency in-plane response is reminiscent of a silicide. However, there is no indication of a plasma resonance, likely due to reduced dimensionality and/or low scattering lifetime.

Boron nitride nanotubes (BNNTs) and hexagonal boron nitride platelets (h-BNs) have received considerable attention for aerospace insulation applications due to their exceptional chemical and thermal stability. Presently, making BN nanomaterials compatible with polymer and composite matrices is challenging. Due to their inert and highly stable structure, h-BN and BNNTs are difficult to covalently functionalize. In this work, we present a novel sonochemical technique that enables covalent attachment of fluoroalkoxy substituents to the surface of BN nanomaterials in a controlled and metered process. Covalent functionalization is confirmed via colloidal stability analysis, FT-IR, and x-ray photoelectron spectroscopy (XPS).

Polyhydroxyalkanoates (PHAs) are degradable (co)polyesters synthesized by microorganisms with a variety of side-chains and co-monomer ratios. PHAs can be efficiently hydrolyzed under alkaline conditions and by PHA depolymerase enzymes, altering their physicochemical properties. Using 2D Langmuir monolayers as model system to study the degradation behavior of macromolecules, we aim to describe the the interdependency between the degradation of two PHAs and the surface potential, which influences material-proteins interaction and cell response. We hypothesize that the mechanism of hydrolysis of the labile ester bonds in (co)polyesters defines the evolution of the surface potential, owing to the rate of accumulation of charged insoluble degradation products. The alkaline hydrolysis and the enzymatically catalyzed hydrolysis of PHAs were previously defined as chain-end scission and random-scission mechanisms, respectively. In this study, these two distinct scenarios are used to validate our model. The surface potential change during the chain-end scission of poly(3-R-hydroxybutyrate) (PHB) under alkaline conditions was compared to that of the enzymatically catalyzed hydrolysis (random-scission) of poly[(3-R-hydroxyoctanoate)-co-(3-R-hydroxyhexanoate)] (PHOHHx), using the Langmuir monolayer technique. In the random-scission mechanism the dissolution of degradation products, measured as a decrease in the area per molecule, was preceded by a substantial change of the surface potential, provoked by the negative charge of the broken ester bonds accumulated in the air-water interface. In contrast, when chains degraded via the chain-ends, the surface potential changed in line with the dissolution of the material, presenting a kinetic dependent on the surface area of the monolayers. These results provide a basis for understanding PHAs degradation mechanism. Future research on (co)polymers with different main-chain lengths might extend the elucidation of the surface potential development of (co)polyesters as Langmuir monolayer.

A scalable preparation of in situ N-doped disordered carbon nanosheets from reduced melamine formaldehyde resin is demonstrated. For the first time, nanosheets prepared by such a process have been tested as anodes for lithium ion and sodium ion batteries. Li-ion battery half-cell delivers a reversible capacity of about 500 mA h/g at a specific current of 100 mA/g, and also a capacity of 250 mA h/g at a specific current of 500 mA/g is retained after 600 cycles. For Na-ion batteries, a reasonable capacity of about 150 mA h/g is recorded at a specific current of 50 mA/g, and a capacity of 120 mA h/g at a specific current of 250 mA/g is retained after 350 cycles. The sloppy low-voltage profile obtained for both the lithium ion and sodium ion cells corresponds to the nanosheet anodes, being soft carbon-like, thereby demonstrating superior cycling stability and safety by avoiding metal plating and dendrite formation.

In this work, we studied an atomic layer deposition (ALD) process of ZrO2 with the precursors of tetrakis(dimethylamido)zirconium(IV) and water. We investigated the growth characteristics and mechanism of the ALD ZrO2 in the temperature range of 50–275 °C. Furthermore, the evolutions of film thickness and morphology were studied and discussed. It was found that the growth rate of ZrO2 decreased almost linearly with the increasing temperature from ∼1.81 Å/cycle at 50 °C to ∼0.8 Å/cycle at 225 °C. Interestingly, it was revealed that the growth of ZrO2 films ceased after a certain number of ALD cycles at a temperature higher than 250 °C. We also verified that the crystallinity of ZrO2 evolved with deposition temperature from amorphous to crystalline phase. In addition, the wettability of ZrO2 films was studied, showing a hydrophobic nature.

The initial steps of the thermal chemistry of Cu(I)-2-(tert-butylimino)-5,5-dimethyl-pyrrolidinate on metal surfaces were characterized using temperature-programmed desorption experiments and density functional theory (DFT). The relative stability of the initial dimer relative to its dissociation on metal surfaces was evaluated. Several molecular desorption temperatures were identified on Ni(110), but all correspond to dimers, either containing the initial Cu ions or after their removal; no monomer was ever detected. DFT calculations also indicated preferential bonding on Cu(110) as a dimer, albeit with a distorted configuration, via the Cu atoms and in registry with the lattice of the substrate. A potential dissociation pathway of the adsorbed dimer was identified involving the partial detachment of the ligands via the scission of one Cu–N bond at the time and migration to adjacent surface sites. This process is accompanied by the reduction of the Cu centers of the metal–organic complex, indicating that it may be the rate-limiting reaction that leads to further fragmentation of the ligands.

Wire-shaped supercapacitors (WSSCs) hold great promise in portable and wearable electronics. Herein, a novel kind of high-performance coaxial WSSCs has been demonstrated and realized by scrolling porous carbon dodecahedrons/Al foil film electrode on vertical FeOOH nanosheets wrapping carbon fiber tows (FeOOH NSs/CFTs) yarn electrode. Remarkably, ionogel is utilized as solid-state electrolyte and exhibits a high thermal/electrochemical stability, which effectively ensures the great reliability and high operating voltage of coaxial WSSCs. Benefiting from the intriguing configuration, the coaxial WSSCs with superior flexibility act as efficient energy storage devices and exhibit low resistance, high volumetric energy density (3.2 mW h/cm3), and strong durability (82% after 10,000 cycles). Importantly, the coaxial WSSCs can be effectively recharged by harvesting sustainable wind source and repeatedly supply power to the lamp without a decline of electrochemical performance. Considering the facile fabrication technology with an outstanding performance, this work has paved the way for the integration of sustainable energy harvesting and wearable energy storage units.

Using ethanol adsorption calorimetry, the surface energetics of two carbon substrates and two products in microwave-assisted carbon nanotube (CNT) growth was studied. In this study, the ethanol adsorption enthalpies of the two graphene-based samples at 25 °C were measured successfully. Specifically, the near-zero differential enthalpies of ethanol adsorption are −75.7 kJ/mol for graphene and −63.4 kJ/mol for CNT-grafted graphene. Subsequently, the differential enthalpy curve of each sample becomes less exothermic until reaching a plateau, −55.8 kJ/mol for graphene and −49.7 kJ/mol for CNT-grafted graphene, suggesting favorable adsorbate–adsorbent binding. Moreover, the authors interpreted and discussed the partial molar entropy and chemical potential of adsorption as the ethanol surface coverage (loading) increases. Due to the low surface areas of carbon black–based samples, adsorption calorimetry could not be performed. This model study demonstrates that using adsorption calorimetry as a fundamental tool and ethanol as the molecular probe, the overall surface energetics of high–surface area carbon materials can be estimated.

Polypropylene plastic (PP) was chosen as additives for the preparation of activated carbon (AC), considering that PP promotes pore formation during the preparation of AC. When the addition ratio of PP was 20%, AC having a maximum specific surface area of 1916.1 m2/g was prepared. Fourier transform–infrared spectroscopy (FT-IR) analysis exhibited the types of functional groups on the surface of AC, such as–OH, C=O, C–C, and –CH. The SEM analysis revealed the formation of disordered pores over the AC. Furthermore, iodine value of the AC is 1460 mg/g. Additionally, adsorption test revealed the AC is suitable for adsorbing methylene blue (MB). The adsorption equilibrium data of MB onto AC were most suitable for Redlich–Peterson model. The maximum adsorption capacity of the single layer was 476.88 mg/g, indicating that AC has high adsorption capacity. The kinetic data fitted well with the pseudo-second-order model.

Tribology—the study of contacting, sliding surfaces—seeks to explain the fundamental mechanisms underlying friction, adhesion, lubrication, and wear, and to apply this knowledge to technologies ranging from transportation and manufacturing to biomedicine and energy. Investigating the contact and sliding of materials is complicated by the fact that the interface is buried from view, inaccessible to conventional experimental tools. In situ investigations are thus critical in visualizing and identifying the underlying physical processes. This article presents key recent advances in the understanding of tribological phenomena made possible by in situ experiments at the nanoscale. Specifically, progress in three key areas is highlighted: (1) direct observation of physical processes in the sliding contact; (2) quantitative analysis of the synergistic action of sliding and chemical reactions (known as tribochemistry) that drives material removal; and (3) understanding the surface and subsurface deformations occurring during sliding of metals. The article also outlines emerging areas where in situ nanoscale investigations can answer critical tribological questions in the future.

Magnetic iron oxide nanoparticles (MIONPs) are particularly attractive in biosensor, antibacterial activity, targeted drug delivery, cell separation, magnetic resonance imaging tumor magnetic hyperthermia, and so on because of their particular properties including superparamagnetic behavior, low toxicity, biocompatibility, etc. Although many methods had been developed to produce MIONPs, some challenges such as severe agglomeration, serious oxidation, and irregular size are still faced in the synthesis of MIONPs. Thus, various strategies had been developed for the surface modification of MIONPs to improve the characteristics of them and obtain multifunctional MIONPs, which will widen the applicational scopes of them. Therefore, the processes, mechanisms, advances, advantages, and disadvantages of six main approaches for the synthesis of MIONPs; surface modification of MIONPs with inorganic materials, organic molecules, and polymer molecules; applications of MIONPs or modified MIONPs; the technical challenges of synthesizing MIONPs; and their limitations in biomedical applications were described in this review to provide the theoretical and technological guidance for their future applications.

Heteroatom-doped carbon plays a vital role in the field of energy storage and conversion, and the synthesis of them has intimate relation with doping pathways. In this work, a facile two-step doping pathway, i.e., hydrothermal method followed by thermal annealing process, was employed to prepare annealed three-dimensional N,S-codoped graphene framework (3D A-NSG). The morphology, structure, composition, and related electrochemical performance were all studied. The results showed that A-NSG possessed typical 3D thin nanosheets, much increased specific surface area and structural defects, strengthened conductivity, and optimized N and S configurations (especially for dominated pyridinic N as well as graphitic N and –C–S–C–). As a result, A-NSG presented much better capacitance and oxygen reduction reaction performance than the counterparts. Apparently, our work offers a good guidance on the synthesis of advanced heteroatom-doped carbon materials by adjusting the doping strategy.

Density functional theory (DFT) has proved to be exceptionally successful in rationalizing trends in activity and functionality for electrochemical functional materials. With continued increases in computing power, there has been an increased interest in “high-throughput” materials discovery and design based on a few descriptors to scan the phase space en masse for thousands of potential candidates, which could be made technologically and commercially viable. However, given fundamental accuracy limitations associated with DFT, the success of high-throughput material discovery efforts has been limited. In this review, we suggest an additional dimension to aid in high-throughput material discovery related to uncertainty quantification and propagation, which provides a more realistic picture of the likelihood of new candidate materials to improve upon known materials. We demonstrate the approach and its utility through two case studies: (1) electrocatalyst materials for their activity and selectivity for the oxygen reduction reaction, and (2) cathode materials for Li-ion batteries based on Ni-Mn-Co oxides. The ease with which uncertainty quantification and propagation can be incorporated into traditional high-throughput material discovery with almost no additional computational cost allows for its proposed wide usage.

Surface water can affect the properties of metal oxide nanoparticles. Investigations on several systems revealed that nanoparticles have different thermodynamic properties than their bulk counterparts due to adsorbed water on their surfaces. Some thermodynamically metastable phases of bulk metal oxides become stable when reduced to the nanoscale, partially due to interactions between high energy surfaces and surface water. Water adsorption microcalorimetry and high-temperature oxide melt solution calorimetry, low-temperature specific heat calorimetry, and inelastic neutron scattering are used to understand the interactions of surface water with metal oxide nanoparticles. Computational methods, such as molecular dynamics simulations and density functional theory calculations, have been used to study these interactions. Investigations on titania, cassiterite, and alumina illustrate the insights gained by these measurements. The energetics of water on metal oxide surfaces are different from those of either liquid water or hexagonal ice, and there is substantial variation in water interactions on different metal oxide surfaces.