Tunable Surface Properties Research Articles

CO2 reduction on p-block metal oxide overlayers on metal substrates—2D MgO as a prototype

Recently, two-dimensional (2D) metal oxide films with a thickness of one to a few atomic layers have been grown on metal substrates, which are naturally resistant to oxidation and possess highly tunable surface properties.

The Application of Carbon Nanotube/Graphene-Based Nanomaterials in Wastewater Treatment.

The treatment of organic wastewater is of great significance. Carbon nanotube (CNT)/graphene-based nanomaterials have great potential as absorbent materials for organic wastewater treatment owing to their high specific surface area, mesoporous structure, tunable surface properties, and high chemical stability; these attributes allow them to endure harsh wastewater conditions, such as acidic, basic, and salty conditions at high concentrations or at high temperatures. Although a substantial amount of work has been reported on the performance of CNT/graphene-based nanomaterials in organic wastewater systems, engineering challenges still exist for their practical application. Herein, the adsorption mechanism of CNT- and graphene-based nanomaterials is summarized, including the adsorption mechanism of CNTs and graphene at the atomic and molecular levels, their hydrophilic and hydrophobic surface properties, and the structure-property relationship required for adsorption to occur. Second, the structural modification and recombination methods of CNT- and graphene-based adsorbents for various organic wastewater systems are introduced. Third, the engineering challenges, including the molding of macroscopically stable adsorbents, adsorption isotherm models and adsorption kinetic behaviors, and reversible adsorption performance compared to that of activated carbon (AC) are discussed. Finally, cost issues are discussed in light of scalable and practical application of these materials.

Polyaniline nanotube synthesized from natural tubular halloysite template as high performance pseudocapacitive electrode

Design and preparation of nanostructured conducting polymers (CPs) is a very important research direction for high performance CPs-based supercapacitors (SCs). With hollow structure, high surface area, tunable surface properties and abundant resources, natural halloysite is a promising template agent for preparing new nanotubular-structure CPs. Here, nanotubular-structure polyaniline was successfully synthesized using natural tubular halloysite as hard template. The obtained tubular polyaniline presents high specific capacitance at various current density as electrode material for supercapacitors. After a facile carbon coating, the carbon coated tubular polyaniline shows high specific capacitance of 654 F g−1 at the current density of 1 A g−1 and excellent electrochemical stability with capacitance retentions ∼87% after 10000 cycles. This work may prove the feasibility of preparing high performance CPs-based nanostructure electrode materials for SCs application based on inexpensive natural clay minerals.

Nitrogen-doped Carbon with Modulated Surface Chemistry and Porous Structure by a Stepwise Biomass Activation Process towards Enhanced Electrochemical Lithium-Ion Storage

Controllable conversion of biomass to value-added carbon materials is attractive towards a wide variety of potential applications. Herein, hydrothermal treatment and KOH activation are successively employed to treat the cheap and abundant camellia oleifera shell as a new carbon raw material. It is shown that this stepwise activation process allows the production of porous nitrogen-doped carbon with optimized surface chemistry and porous structure compared to the counterparts prepared by a single activation procedure. Benefiting from the modulated porous structure, the as-produced porous nitrogen-doped carbon electrode delivered a high reversible capacity of 1080 mAh g−1 at a current density of 100 mA g−1, which is 3.3 and 5.8 times as high as that of the carbon materials prepared by bare hydrothermal treatment or KOH activation, respectively. Moreover, the optimized surface composition of the porous nitrogen-doped carbon endows it with a highest initial Coulombic efficiency among the three samples, showing great potentials for practical applications. This work is expected to pave a new avenue to upgrade biomass to carbon materials with tunable surface properties and microstructures for target applications.

Selective Reactivity of Myrcene for Vat Photopolymerization 3D Printing and Postfabrication Surface Modification.

Biosourced materials are gaining interest industrially, but there are still limitations on the library of available materials suitable for advanced manufacturing, especially using photopolymerization-based processing techniques. Terpenes, such as myrcene, are naturally produced materials possessing structural features, specifically alkenes, that avail themselves for such techniques. Free-radical and anionic polymerization techniques were used to explore molecular architecture, such as branching, as well as molecular weight and dispersity on physical properties prior to the production of 3D printing photopolymer resins. The polymyrcene resins were printed into dogbones and mold templates for soft materials. Model reactions with monofunctional thiols were used to demonstrate the potential for postpolymerization and fabrication functionalization, accompanying a physical demonstration where the surface hydrophobicity of polymyrcene could be tuned from superhydrophobic when using an alkyl chain monothiol (greater than 100° water contact angle) to a hydrophilic surface displaying a water contact angle of less than 45° compared with that of the unmodified surface (∼60°). Tunable bulk and surface properties are a unique feature for 3D printing materials and demonstrate the potential of polymyrcene and other biosourced photopolymers to a wide range of research applications.

An Old but Lively Nanomaterial: Exploiting Carbon Black for the Synthesis of Advanced Materials

Carbon black (CB) is an old-concept but versatile carbonaceous material prone to be structurally and chemically modified under quite mild wet conditions. Recently, we exploited the potentiality of CB for the production of a highly varied array of advanced materials with applications in energetics, water remediation and sensoristic. The proposed approaches are devised to meet specific needs: low production costs, scalable synthetic approaches, flexibility i.e. easy tuning of chemico-physical properties of the carbon-based advanced materials. Two main approaches have been exploited: modification of CB at the surface and highly CB de-structuration. The former approach allows obtaining highly homogenous CB-modified nanoparticles (around 160 nm) with tunable surface properties (hydrophilicity, typology of functional groups and surface charge density, pore size distribution), supports for ionic liquid (SILP) and composites (carbon-iron oxide). The latter approach exploiting a top-down demolition of CB produces a highly versatile graphene related material (GRM), made up by stacked short graphene-like layers (GL) particularly suitable for advanced composites synthesis and ultrathin carbon-based films production.

Preparation of Polyethylene and Ethylene/Methacrylic Acid Copolymer Blend Films with Tunable Surface Properties through Manipulating Processing Parameters during Film Blowing.

Polymer films based on polyethylene (PE) and ionomer ethylene/methacrylic acid (EMAA) copolymer blend were prepared by film blowing, whose surface properties were tuned by varying processing parameters, i.e., take up ratio (TUR). Blends of PE/EMAA copolymer were firstly prepared by the melt-mixing method, before being further blown to films. The wettability of the film was investigated by measuring the contact angle/water-film encounter time, and optical properties, i.e., the haze and transmittance. The wettability was found to be enhanced with the increase of TUR. So too was the haze, while the transmittance was found to be almost independent of TUR. The XPS and AFM results directly show the increasing polar functional groups (–COO−) on the surface and roughness with increasing TUR. Further analysis of the 2D SAXS and WAXS unveiled the origin of the invariant transmittance, which resulted from the minor change of the crystallinity and the monotonic increase of the haze, with TUR resulting from the evolution of crystal orientation. In addition to other post-modification methods, the current study provides an alternative route to prepare large-scale PE films as the template for the advanced potential applications, i.e., covering in the layer of roof, the privacy of protective windows, and multitudes of packaging.

Water Vapor Adsorption-Desorption Behavior of Surfactant-Coated Starch Particles for Commercial Energy Wheels.

This study reports on the adsorption (dehumidification)–desorption (humidification) behavior of cetylpyridinium bromide (CPB) coated starch particles (SPs), denoted as SP-CPB, as a potential desiccant material for air-to-air energy exchangers. CPB is a cationic surfactant with antibacterial activity that can be used to modify the surface properties of SPs, especially at variable CPB loading levels (SP-CPB0.5, SP-CPB2.5, and SP-CPB5.0, where the numeric suffix represents the synthetic loading level of CPB in mM). The SP-CPB0.5 sample displayed optimal surface area and pore structure properties that was selected for water sorption isotherm studies at 25 °C. The CPB-coated SPs sample (SP-CPB0.5) showed an improved water vapor uptake capacity compared to unmodified starch (SPs) and other desiccant systems such as high amylose starch (HAS15) and silica gel (SG13). Single-step and cyclic water vapor sorption tests were conducted using a small-scale exchanger coated with SP-CPB0.5. The calculated latent effectiveness values obtained from direct measurements using cyclic tests (65.4 ± 2%) agree closely with the estimated latent effectiveness from single-step tests (64.6 ± 2%) at controlled operating conditions. Compared to HAS15- and SG13-coated exchangers, the SP-CPB0.5-coated exchanger performed much better at controlled operating conditions, along with improved longevity due to the CPB surface coating. The presence of CPB did not attenuate the uptake properties of native SPs. Latent effectiveness of SP-CPB0.5-coated exchanger was enhanced (5–30% higher) over that of the SG13- or HAS15-coated exchangers, according to the wheel angular speed. This study reports on a novel and sustainable SP-CPB0.5 material as a promising desiccant coating with tunable uptake and surface properties with potential utility in air-to-air energy exchangers for ventilation systems.

Comparison of bulk and microfluidics methods for the formulation of poly-lactic-co-glycolic acid (PLGA) nanoparticles modified with cell-penetrating peptides of different architectures

The efficient and reproducible production of nanoparticles using bulk nanoprecipitation methods is still challenging because of low batch to batch reproducibility. Here, we optimize a bulk nanoprecipitation method using design of experiments and translate to a microfluidic device to formulate surface-modified poly-lactic-co-glycolic (PLGA) nanoparticles. Cell-penetrating peptides (CPPs) with a short, long linear or branched architecture were used for the surface modification of PLGA nanoparticles. The microfluidics method was more time efficient than the bulk nanoprecipitation method and allowed the formulation of uniform PLGA nanoparticles with a size of 150 nm, a polydispersity index below 0.150 and with better reproducibility in comparison to the bulk nanoprecipitation method. After surface modification the size of CPP-tagged PLGA nanoparticles increased to 160–180 nm and the surface charge of the CPP-tagged PLGA nanoparticles varied between −24 mV and +3 mV, depending on the architecture and concentration of the conjugated CPP. Covalent attachment of CPPs to the PLGA polymer was confirmed with FTIR by identifying the formation of an amide bond. The conjugation efficiency of CPPs to the polymeric PLGA nanoparticles was between 32 and 80%. The development and design of reproducible nanoformulations with tuneable surface properties is crucial to understand interactions at the nano-bio interface.

Novel Fe-Mn-O nanosheets/wood carbon hybrid with tunable surface properties as a superior catalyst for Fenton-like oxidation

Cost-effective, highly efficient and conveniently recycled heterogeneous catalyst is urgently desirable for wastewater treatment. Wood-derived monolith offers new opportunity because of its toilless functionalization and flexible processing. Herein, ferrum manganese oxide nanosheets (Fe-Mn-O NSs) were successfully grown on the microchannels of carbonized wood to construct a novel 3D wood-derived block for efficient wastewater treatment. The wood carbon not only acts as a 3D substrate to support Fe-Mn-O NSs, but also contributes to unimpeded mass diffusion benefiting from the numerous open channels and hierarchical pores on channel walls. More importantly, except for the exposure of sufficient active sites, several important surface properties (i.e. surface defects, surface charge, low-valence metal concentration and charge transfer) were improved by doping alien-metal element, resulting in greatly improved Fenton activity and stability. Notably, due to flexible processing of wood carbon, this block catalyst can be extended to filter membrane for removing pollutants in flow wastewater.

Waste-Derived Low-Cost Mycelium Nanopapers with Tunable Mechanical and Surface Properties.

Mycelium, the vegetative growth of filamentous fungi, has attracted increasing commercial and academic interest in recent years because of its ability to upcycle agricultural and industrial wastes into low-cost, sustainable composite materials. However, mycelium composites typically exhibit foam-like mechanical properties, primarily originating from their weak organic filler constituents. Fungal growth can be alternatively utilized as a low-cost method for on-demand generation of natural nanofibrils, such as chitin and chitosan, which can be grown and isolated from liquid wastes and byproducts in the form of fungal microfilaments. This study characterized polymer extracts and nanopapers produced from a common mushroom reference and various species of fungal mycelium grown on sugarcane byproduct molasses. Polymer yields of ∼10-26% were achieved, which are comparable to those of crustacean-derived chitin, and the nanopapers produced exhibited much higher tensile strengths than the existing mycelium materials, with values of up to ∼25 MPa (mycelium) and ∼98 MPa (mushroom), in addition to useful hydrophobic surface properties resulting from the presence of organic lipid residues in the nanopapers. HCl or H2O2 treatments were used to remove these impurities facilitating tuning of mechanical, thermal, and surface properties of the nanopapers produced. This potentially enables their use in a wide range of applications including coatings, membranes, packaging, and paper.

Developing a Protein Scaffolding System for Rapid Enzyme Immobilization and Optimization of Enzyme Functions for Biocatalysis.

Immobilization of enzymes is required for most biocatalytic processes, but chemistries used in enzyme immobilization are limited and can be challenging. Genetically encoded protein-based biomaterials could provide easy-to-use immobilization platforms for biocatalysts. We recently developed a self-assembling protein scaffold that covalently immobilized SpyTagged enzymes by engineering the bacterial microcompartment protein EutM from Salmonella enterica with a SpyCatcher domain. We also identified a range of EutM homologues as robust protein nanostructures with diverse architectures and electrostatic surface properties. In this work, we created a modular immobilization platform with tunable surface properties by developing a toolbox of self-assembling, robust EutM-SpyCatcher scaffolds. Using an alcohol dehydrogenase as model biocatalyst, we show that the scaffolds improve enzyme activity and stability. This work provides a modular, easy-to-use immobilization system that can be tailored for the optimal function of biocatalysts of interest.

Smart Materials by Nanoscale Magnetic Assembly

AbstractMagnetic assembly at the nanoscale level holds great potential for producing smart materials with high functional and structural diversity. Generally, the chemical, physical, and mechanical properties of the resulting materials can be engineered or dynamically tuned by controlling external magnetic fields. This Review analyzes the recent research progress on nanoscale magnetic assembly approaches toward the development of smart materials. The magnetic interactions between nanoparticles (both magnetic and nonmagnetic) and the interactions between nanoparticles and external magnetic fields are fully expatiated based on numerical simulations. In particular, the advancements of nanoscale magnetic assembly in responsive optical nanostructures, shape‐morphing systems, and advanced materials with tunable surface properties are introduced in three subsections. The key roles of magnetic interactions in nanoscale assembly toward customizable physical and chemical properties are highlighted, with focus on how to enable direct manipulation of the positional and orientational orders of the building blocks and orientational control of soft matrices through the incorporation of anisotropic magnetic structures.

High performance loose nanofiltration membranes obtained by a catechol-based route for efficient dye/salt separation

Loose nanofiltration membranes with excellent dye rejection and high inorganic salt transmission are promising for dye/salt separation. Herein, a mussel-inspired organic solvent-free method was chosen to prepare loose nanofiltration membranes with tunable surface structures and properties. A low-cost material, 1,2-dihydroxybenzene (catechol), was used to replace dopamine for the mussel-inspired surface coating strategy. With the assistance of CuSO4/H2O2, a catechol/PEI coating layer was formed on the polyethersulfone (PES) substrate in only 10 min. Through constructing the coating layer based on polyethylenimine (PEI) with different molecular weights, catechol/PEI ratios and solution deposition times, different membranes were obtained. The separation performance of the membrane is tested by a lab-scale crossflow setup under the pressure of 4 bar. Especially, LNM-3 have an ultrahigh water permeability (24.5 LMH bar−1) and an extremely low rejection for both NaCl and Na2SO4 in the concentrations between 1.0 and 50.0 g L−1. Meanwhile, LNM-3 shows superior rejection for different types of dyes, demonstrating their great potential in practical applications. Overall, such an approach enabled by an organic solvent-free process and low-cost chemicals may offer a new strategy for the environmental-friendly and economical manufacturing of multifunctional loose nanofiltration membrane.

Polyamide 6.6 thin films with distinct ratios of the main chemical groups: Influence in the primary neuronal cell culture

Neuronal cell cultures have been instrumental to the advance of our knowledge in a wide range of areas. One of the limitations of this model is the lack of stability, over time, of the substrate materials that are used in neuronal cell cultures. In this work, sputtering was used to permanently modify glass coverslips with a polyamide 6.6 thin film, using different discharge gases. Differences in the chemical composition of the films, resulting from the conditions used in deposition, were correlated with the surface properties. After characterization by SEM, TEM, AFM, XPS, zeta-potential, wettability and evaluation of the mechanical properties, some surfaces were selected for in vitro testing in the development of cultured cerebrocortical neurons. The results showed that the chemical composition and surface charge are particularly affected by the variation of the deposition parameters, although wettability, for example, did not present significant variations. In vitro tests revealed that the surfaces with higher NH 2 /COOH ratio allowed the adhesion and differentiation of neurons, with a morphology similar to that obtained after plating of the cells on poly- d -lysine-coated glass. This work opens new perspectives for the permanent modification of materials towards multifunctional neural compatible surfaces and open new areas for bioengineering applications. • Polyamide 6.6 thin films for permanent modification of glass surface for neurons adhesion • The surface of the deposited material can be preconditioned during deposition. • The tuning of surface properties potentially ensures more stable materials for cell attachment. • Polyamide permanent modified glass present similar results to the standard PDL-glass.

Electrodeposited Vanadium Dioxide Films with Unique Optical Property.

This study represents a facile but effective electrodeposition method to fabricate vanadium dioxide (VO₂) thin films on fluorine doped tin oxide (FTO) glass at room temperature. The film microstructure (thickness, surface structure, particle size and composition) and relevant optical properties were investigated by several advanced techniques. The pertinent variables that can affect the thin film formation and structure, such as deposition potential, time and post-treatment annealing temperature were also studied. It was found that the film thickness could be tuned from 35 to 130 nm by adjusting the potential from -1.22 to -1.35 V, and consequently leading to optical transmittance decreasing from ∼60% to ∼38% in the wavelength of 500-1000 nm, further confirmed by computational simulations using three-dimension (3D) finite-difference time-domain method. The hysteresis loop of the generated VO₂ film on FTO glass shows that the phase transition temperature from monoclinic to rutile is around 73 °C, a little higher than pure monoclinic VO₂ (∼68 °C) in this study. This proposed electrodeposition method is possible to extend into obtaining metal oxide films with tuneable surface properties for thermochromic smart devices.

Improvement of splitting performance of Ce0.75Zr0.25O2 material: Tuning bulk and surface properties by hydrothermal synthesis

Thermochemical cycles received renewed interest as CO2 and H2O energy-upgrading processes using solar energy as source. The two-step cycles, based on self-reduction in a solar reactor at high temperature (above 1300–1400 °C) and re-oxidation by CO2 and/or H2O flow, are the most interesting due to their simplicity and high theoretical solar-to-fuel efficiency. In the two-step cycle, ceria has been recognized as the benchmark material but it suffers from high reduction temperature, low re-oxidation kinetics as well as low stability, thus hindering practical application. In this work, the redox properties of two Ce0.75Zr0.25O2 materials prepared by hydrothermal synthesis were compared with those of a co-precipitated sample with the same nominal composition used as reference. Samples were characterized by X-Ray Diffraction (XRD), N2 physisorption, Scanning Elecron Microscopy (SEM), X-Ray Photoelectron Spectroscopy (XPS), and Electron Paramagnetic Resonance (EPR); their self-reducibility and CO2 splitting activity were tested in a Thermogravimetric (TG) balance, while H2O splitting properties were studied in an ad-hoc fixed bed reactor on H2 pre-reduced samples. Characterization results and activity tests agreed that the Ce3+ fraction both on the surface and in the bulk of ceria-zirconia can be increased by hydrothermal synthesis, thus providing improved redox properties and higher splitting activity with respect to the co-precipitated sample. So, hydrothermal synthesis, providing a controlled nucleation and growth of crystallites, appears as a promising route for the preparation of ceria-based materials with tuned oxygen vacancies.

Tuning surface properties of N-doped carbon with TiO2 nano-islands for enhanced phenol hydrogenation to cyclohexanone

Abstract ZIF-derived N-doped carbon (CN) materials were modified in this work by TiO2 nano-islands with oxygen vacancies (OV) through a sol-gel method and subsequent thermal treatment. By loading Pd nanoparticles (NPs) on CN@TiO2, Pd@CN@TiO2 catalysts were fabricated. Superior catalytic performance of Pd@CN@TiO2 was found in the selective phenol hydrogenation to cyclohexanone, with a TOF of 30.1 h−1, 2.2-fold as high as that of Pd@CN. The synergistic effect of CN and TiO2 nano-islands was responsible for the superior catalytic performance. More OV was generated due to the high specific surface area of CN. At the same time, CN could also enhance the hydrophilicity, and adsorb more phenol in non-planar fashion. The TiO2 nano-islands with OV could improve the Pd dispersion, make more Pd element on the support surface, strengthen the antioxidizability of Pd and induce electron-rich Pd NPs. Furthermore, the as-fabricated Pd@CN@TiO2 showed good recyclability in the phenol hydrogenation, and also exhibited excellent catalytic performance in the catalytic hydrogenation of phenol with diverse functional groups. These findings provide the feasibility of using the high-performance catalysts for the hydrogenation of phenol derivatives.

Erratum: Preparation of Poly(pentafluorophenyl acrylate) Functionalized SiO2 Beads for Protein Purification.

Erratum: Preparation of Poly(pentafluorophenyl acrylate) Functionalized SiO2 Beads for Protein Purification.

Recovery Behavior of Microstructured Thiol-Ene Shape-Memory Film

In this work, surface microstructurization was coupled with shape-memory polymer to generate reversibly tunable surface properties. A photopolymerizable thiol-ene composition comprising a mixture of pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT) and 2,2-dimethoxy-2-phenylacetophenone (DMPA) was used to prepare microstructured thiol-ene shape-memory film via casting and UV polymerization on the electron beam lithography fabricated arrays of 1 µm and 2 µm square pits. The mechanical deformation via compression and recovery of the surface microstructure were investigated. Results show that, after heat treatment of the deformed thiol-ene film, the recovery yields for microstructures were not worse than 90% ± 2% and 93% ± 2% for structures imprinted with 1 µm and 2 µm square pit micro imprint stamps. Additionally, heat treatment of deformed thiol-ene film resulted in the recovery of intense diffraction colors and laser diffraction patterns. This study opens up an avenue of incorporating microstructured shape-memory films for new products, e.g., optical security devices, superhydrophobic coatings, medical diagnostics and biosensors.