Surface Chemistry Of Oxides Research Articles

Orthogonal Nano‐Engineering (ONE): Modulating Nanotopography and Surface Chemistry of Aluminum Oxide for Superior Antibiofouling and Enhanced Chemical Stability

AbstractDecoupling certain material surface properties can be key to attaining critical property‐activity relationships that underpin their antibiofouling performance. Here, orthogonal nano‐engineering (ONE) is employed to decouple the influences of nanotopography and surface chemistry on surface antibiofouling. Nanotopography and surface chemistry are systematically varied with a two‐step process. Controlled nanotopography is obtained by electrochemical anodization of aluminum, which generated anodic aluminum oxide (AAO) surfaces with cylindrical nanopores (diameters: 15, 25, and 100 nm). To modify surface chemistry while preserving nanotopography, an ultrathin (≈5 nm) yet stable zwitterionic coating of poly(divinylbenzene‐4‐vinylpyridyl sulfobetaine) is deposited on these surfaces using initiated chemical vapor deposition (iCVD). Antibiofouling performance is assessed by quantifying 48‐h biomass formed by gram positive and negative bacteria. The ONE surfaces demonstrated enhanced antibiofouling performance, with small‐pore nanotopography and zwitterionic chemistry each lowered biomass accumulation by tested species, with potential additive effects. The most effective chemistry‐topography combination (ZW‐AAO15) enabled an overall reduction of 91% for Escherichia coli, 76% for Staphylococcus epidermidis, 69% for Listeria monocytogenes, and 67% for Staphylococcus aureus, relative to the uncoated nanosmooth control. Additionally, the composite ZW coating exhibited encouraging anticorrosion properties under both static and turbulent cleaning conditions, vital to antibiofouling applications in healthcare and food industries.

The surface chemistry of cuprous oxide

The chemical and electronic properties of copper combined with its large natural abundance lend this material to impact a wide range of technological applications, including heterogeneous catalysis. The reactivity of copper in its Cu1+oxidation state makes this specific configuration relevant in various chemical reactions, but the facile redox properties of copper make the isolation of individual states for fundamental studies difficult. Here we review three Cu2O model systems used to study the interaction of Cu1+ with small molecules making use of surface science techniques: Cu2O/Cu(111), thin polycrystalline Cu2O films on Cu foil, and bulk Cu2O crystals. Advantages and disadvantages of each system are discussed and exemplified through case studies of chemical adsorption and reactivity studies.

Chemically Bonded Biphase Coating of Ni-Rich Layered Oxides with Enhanced High-Voltage Tolerance and Long-Cycle Stability.

Stabilizing the crystalline structure and surface chemistry of Ni-rich layered oxides is critical for enhancing their capacity output and cycle life at a high cutoff voltage. Herein, we adopted a simple one-step solid-state method by directly sintering the Ni0.9Co0.1(OH)2 precursor with LiOH and Ta2O5, to simultaneously achieve the bulk material synthesis of LiNi0.9Co0.1O2 and in situ construction of a rock-salt Ta-doped interphase and an amorphous LiTaO3 outer layer, forming a chemically bonded surface biphase coating on LiNi0.9Co0.1O2. Such a cathode architectural design has been demonstrated with superior advantages: (1) eliminating surface residual alkali, (2) strengthening the layered oxygen lattice, (3) suppressing bulk-phase transformation, and (4) facilitating Li-ion transport. The obtained cathode exhibits excellent electrochemical performance, including a high initial reversible capacity of 180.3 mAh g-1 at 1.0 C with 85.5% retention after 300 cycles (2.8-4.35 V) and a high initial reversible capacity of 182.5 mAh g-1 at 0.2 C with 87.6% retention after 100 cycles (2.8-4.5 V). Notably, this facile and scalable electrode engineering makes Ni-rich layered oxides promising for practical applications.

Optimization of surface oxide chemistry for enhanced corrosion resistance of AlMnFeCoNi – Carbon nanotube composite coatings

AlMnFeCoNi high entropy alloy (HEA) composite coatings with different volume fractions of carbon nanotubes (CNTs) (from electrolyte bath with 2.5, 4, 5, 15, 17.5, 20 mg/L of CNT) were electrodeposited onto mild steel. Corrosion rate of HEA-CNT coatings exhibited non-monotonic variation with increasing CNT volume fraction. Corrosion resistance initially increased and then decreased with increasing CNT addition. Highest corrosion resistance exhibited by coating produced from 5 mg/L of CNT was due to higher surface uniformity, least surface roughness (732 ± 2.92 nm), induced hydrophobicity (115.44 ± 0.29˚) and presence of stable passive oxide films (Al3+, Co2+, Fe3+).

Modulating surface chemistry of copper oxides through annealing environment for enhanced selective HMF oxidation: A DFT-electrochemical approach

A comprehensive study was reported to address the effects of both copper (I) and copper (II) oxides on the electrocatalytic 5-hydroxymethylfurfural (HMF) oxidation reaction. Cu2O (1 1 1) demonstrated an outstanding selectivity (80 %) and product yield in the oxidation process towards 2,5-diformylfuran (DFF). The recorded current density of 0.12 mA/cm2 for Cu2O-dominated sample was doubled comparing to its counterpart electrocatalyst, CuO, under mild pH 9.6 condition. Periodic density functional theory calculations show that the higher DFF selectivity for the Cu2O dominant catalyst can be explained by the Cu2O (1 1 1) surface being more oxyphilic while being less carbophilic than the CuO (1 1 1) surface. As a result, all the reaction intermediates that lead to DFF are stabilized significantly more than those that lead to other products. This work deepens the understanding of copper-based oxide material for the HMF electrooxidation and provides a new window for designing electrocatalyst.

Silver-Doped Titanium Oxide Layers for Improved Photocatalytic Activity and Antibacterial Properties of Titanium Implants.

Titanium has a long history of clinical use, but the naturally forming oxide is not ideal for bacterial resistance. Anodization processes can modify the crystallinity, surface topography, and surface chemistry of titanium oxides. Anatase, rutile, and mixed phase oxides are known to exhibit photocatalytic activity (PCA)-driven bacterial resistance under UVA irradiation. Silver additions are reported to enhance PCA and reduce bacterial attachment. This study investigated the effects of silver-doping additions to three established anodization processes. Silver doping showed no significant influence on oxide crystallinity, surface topography, or surface wettability. Oxides from a sulfuric acid anodization process exhibited significantly enhanced PCA after silver doping, but silver-doped oxides produced from phosphoric-acid-containing electrolytes did not. Staphylococcus aureus attachment was also assessed under dark and UVA-irradiated conditions on each oxide. Each oxide exhibited a photocatalytic antimicrobial effect as indicated by significantly decreased bacterial attachment under UVA irradiation compared to dark conditions. However, only the phosphorus-doped mixed anatase and rutile phase oxide exhibited an additional significant reduction in bacteria attachment under UVA irradiation as a result of silver doping. The antimicrobial success of this oxide was attributed to the combination of the mixed phase oxide and higher silver-doping uptake levels.

Palladium enhanced electrochemical supercapacitive performance of chromium oxide thin films synthesized by sputtering process

Recently, the use of transition metal oxide electrodes for supercapacitor applications has increased due to the possibility of variable mixed valence states. The present study has established the use of Pd-Cr2O3 composite thin films as a working electrode for high-performance supercapacitors. The reactive dc magnetron co-sputtering method has been used for the fabrication of thin film of Cr2O3 and Pd-Cr2O3 on SS-304 substrate. X-ray diffraction and X-ray photoemission spectroscopy techniques were used to examine the surface chemistry and phase purity of chromium oxide and Pd-Cr2O3 composite thin films. The incorporation of Pd in Cr2O3 delivers a drastic change in the surface morphology. Due to the modified morphology and electronic properties, a noticeable improvement in the electrochemical properties of Pd-Cr2O3 electrode is observed. The obtained value of specific capacitance for this electrode is 401 Fg−1 at 0.1 mAcm−2 scan rate and within the potential window range 0 to +1.2 V. This value of specific capacitance is almost twice in comparison to the Cr2O3 based electrode. The Pd-Cr2O3 composite thin film shows a good cycle retention capability of 8000 cycles with 87.5 % retention. The obtained value of energy density and power density for Pd-Cr2O3 electrode was 80.2 Whkg−1 and 3.23 kWkg−1, respectively at 0.1 mAcm−2. Consequently, this composite material electrode can be seen as a promising advancement for electrodes in supercapacitor devices.

Evolution of surface oxide chemistry and its effect on the electrochemical degradation behaviour of AlCoFeCuNi high entropy alloy coating incorporated with multiwalled carbon nanotubes

AlCoFeCuNi high entropy alloy (HEA) coatings containing different volume fractions of carbon nanotubes (CNTs) were electrodeposited over mild steel substrate. Phase constitution, morphological evolution, electrochemical corrosion properties and surface oxide chemistry of the coatings were investigated as a function of their CNT content and correlated. With initial incorporation of the CNTs, the surface morphology of the composite coatings became progressively finer and compact till an optimum CNT volume fraction. Higher volume fractions of CNTs led to their agglomeration which yielded rougher and defective coating morphology. Corrosion rate of the HEA coating was highly sensitive to the CNT content and at an optimum CNT volume fraction HEA-CNT composite coatings (HEA_CNT-3 coating produced from electrolyte with 10 mg/L of CNT) with lowest corrosion rate was obtained (polarization resistance: Rp = 1178.85 Ω-cm2) while the highest corrosion rate was observed for the pristine HEA coating (Rp = 225.84 Ω-cm2). The coating with highest CNT volume fraction (HEA_CNT-6 coating produced from electrolyte with 35 mg/L of CNT) exhibited the polarization resistance value of 281.80 Ω-cm2. Contact angle measurement revealed that with increase in CNT content, coating hydrophobicity increased monotonically. Analysis of the surface oxide layer of the exposed samples exhibited increase in the relative content of Co3O4, CuO, NiO, AlO(OH) oxides with the presence of CNTs. This work shows that an optimum volume fraction of CNT which produces relatively compact morphology and facilitates evolution of stabler surface oxides leads to significant enhancement in the corrosion resistance of AlCoFeCuNi HEA-CNT composite coating.

Mechanistic and Compositional Aspects of Industrial Catalysts for Selective CO2 Hydrogenation Processes

The characteristics of industrial catalysts for conventional water-gas shifts, methanol syntheses, methanation, and Fischer-Tropsch syntheses starting from syngases are reviewed and discussed. The information about catalysts under industrial development for the hydrogenation of captured CO2 is also reported and considered. In particular, the development of catalysts for reverse water-gas shifts, CO2 to methanol, CO2-methanation, and CO2-Fischer-Tropsch is analyzed. The difference between conventional catalysts and those needed for pure CO2 conversion is discussed. The surface chemistry of metals, oxides, and carbides involved in this field, in relation to the adsorption of hydrogen, CO, and CO2, is also briefly reviewed and critically discussed. The mechanistic aspects of the involved reactions and details on catalysts’ composition and structure are critically considered and analyzed.

Hydrogen irradiation-driven computational surface chemistry of lithium oxide and hydroxide.

We have investigated, using molecular dynamics, the surface chemistry of hydrogen incident on the amorphous and crystalline lithium oxide and lithium hydroxide surfaces upon being slowed down by a collision cascade and retained in the amorphous surface of either Li2O or LiOH. We looked for the bonding of H to the resident structures in the surface to understand a possible chain of chemical reactions that can lead to surface transformation upon H atom impact. Our findings, using Density-Functional Theory (DFT) trained ReaxFF force field/electronegativity equalization method potentials, stress the importance of inclusion of polarization in the dynamics of a Li-O-H system, which is also illustrated by DFT energy minimization and quantum-classical molecular dynamics using tight binding DFT. The resulting polar-covalent chemistry of the studied systems is complex and very sensitive to the instantaneous positions of all atoms as well as the ratio of concentrations of various resident atoms in the surface.

Theoretical study on tin oxide surface chemistry mechanism and thermodynamic properties for atomic layer deposition equipment optimization

Theoretical study on tin oxide surface chemistry mechanism and thermodynamic properties for atomic layer deposition equipment optimization

Charge density wave surface reconstruction in a van der Waals layered material

Surface reconstruction plays a vital role in determining the surface electronic structure and chemistry of semiconductors and metal oxides. However, it has been commonly believed that surface reconstruction does not occur in van der Waals layered materials, as they do not undergo significant bond breaking during surface formation. In this study, we present evidence that charge density wave (CDW) order in these materials can, in fact, cause CDW surface reconstruction through interlayer coupling. Using density functional theory calculations on the 1T-TaS2 surface, we reveal that CDW reconstruction, involving concerted small atomic displacements in the subsurface layer, results in a significant modification of the surface electronic structure, transforming it from a Mott insulator to a band insulator. This new form of surface reconstruction explains several previously unexplained observations on the 1T-TaS2 surface and has important implications for interpreting surface phenomena in CDW-ordered layered materials.

Charge state of steps on anatase TiO2(1 0 1) at 78 K by AFM/KPFM

Surface steps strongly influence the surface chemistry of metal oxides, a detailed picture of step charge and structure may help to understand reactivity and predict the performance of the overall material in catalysis. In this study, we report the existence of another type of step, step BII, on the anatase TiO2(101) surface using atomic force microscopy/Kelvin probe force microscopy combined with density functional theory (DFT). By in situ measurements of current and contact potential difference (CPD) information, we found that step B II exhibits the highest charge state, followed by step C and D, which have the same structure, and step A with the weakest charge state. This finding challenges the conventional understanding that step C possesses the highest charge state. By incorporating DFT calculations, we confirmed that step B II possesses a higher charge state. This discovery also supports the observation of higher charge states in step C than in step B I. In addition, our results indicate that the valence band is predominantly governed by oxygen atoms, while titanium atoms dominate the conduction band. At the step edge, oxygen atoms act as electron donors, with electrons mainly clustering near the titanium atoms and Ti-O bonds. The present study provides a complete characterization of the charge state of the step edges on the anatase TiO2(101) surface and plays an important role in investigating the molecular adsorption as well as charge transfer in catalytic reactions on metal oxides surface.

Understanding the evolution of microstructure, phase homogeneity, electrochemical characteristics and surface chemistry of electrodeposited MnCrCoFeNiCu high entropy alloy coating with reinforcement of carbon nanotubes

MnCrCoFeNiCu high entropy alloy (HEA) coatings with varying volume fractions of carbon nanotube (CNT) were electrodeposited on mild steel. Morphology, phase constitution, wettability, surface oxide chemistry and corrosion of coatings were examined. Coating morphology became finer with initial CNT incorporation and then transformed to rougher surface for higher CNT volume fractions. Pristine HEA coating contained mixture of body centre cubic (bcc) and face centre cubic (fcc) phases. With the CNT addition phase homogenization happened and for the HEAC3 coating (from electrolyte with 5 mg/L concentration of CNT) single phase bcc microstructure was obtained. The phase mixture however re-evolved for the higher CNT incorporation due to CNT agglomeration and reduction in the metal-CNT interfaces. Water contact angle was 127° for HEA_C3 coating. All the HEA-CNT coatings exhibited higher corrosion resistance than the pristine HEA coating, corrosion rate trend was however not monotonic with CNT volume fraction and maximum corrosion resistance was observed for the HEA_C3 coating. Surface oxide chemistry of exposed sample showed stabler oxide over the HEA-CNT coatings when compared to the oxides of the pristine HEA coating. Higher corrosion resistance of the HEA_C3 coating was due to compact morphology, hydrophobicity, phase homogenization and evolution of stable surface oxides.

Electrochemical Fine-Tuning of the Chemoresponsiveness of Langmuir-Blodgett Graphene Oxide Films.

Graphene oxide has been widely deployed in electrical sensors for monitoring physical, chemical, and biological processes. The presence of abundant oxygen functional groups makes it an ideal substrate for integrating biological functional units to assemblies. However, the introduction of this type of defects on the surface of graphene has a deleterious effect on its electrical properties. Therefore, adjusting the surface chemistry of graphene oxide is of utmost relevance for addressing the immobilization of biomolecules, while preserving its electrochemical integrity. Herein, we describe the direct immobilization of glucose oxidase onto graphene oxide-based electrodes prepared by Langmuir-Blodgett assembly. Electrochemical reduction of graphene oxide allowed to control its surface chemistry and, by this, regulate the nature and density of binding sites for the enzyme and the overall responsiveness of the Langmuir-Blodgett biofilm. X-ray photoelectron spectroscopy, surface plasmon resonance, and electrochemical measurements were used to characterize the compositional and functional features of these biointerfaces. Covalent binding between amine groups on glucose oxidase and epoxy and carbonyl groups on the surface of graphene oxide was successfully used to build up stable and active enzymatic assemblies. This approach constitutes a simple, quick, and efficient route to locally address functional proteins at interfaces without the need for additives or complex modifiers to direct the adsorption process.

Reconstruction of the Indium Tin Oxide Surface Enhances the Adsorption of High‐Density Self‐Assembled Monolayer for Perovskite/Silicon Tandem Solar Cells

AbstractSelf‐assembled monolayers (SAMs) are widely used as carrier transport interlayers for enabling high‐efficiency perovskite solar cells (PSCs). However, achieving uniform and pinhole‐free monolayers on metal oxide (e.g., indium tin oxide, ITO) surfaces is still challenging due to the sensitivity of SAM adsorption to the complex oxide's surface chemistry. Here, the hydrofluoric acid and the subsequent UV–ozone treatment are employed to reconstruct the ITO surface by selectively removing the undesired terminal hydroxyl and hydrolysis product. This can significantly increase the ITO surface activity and area, thus facilitating the adsorption of high‐density SAMs. The resultant fluorinated surface can also prevent the direct contact of ITO with the perovskite active layer and passivate the perovskite bottom interface. Benefiting from the synergistically improved perovskite film formation, charge extraction, energy level alignment, and interfacial chemical stability, the corresponding PSC achieves a greatly enhanced power conversion efficiency of 21.3%, along with an enhanced long‐term stability as compared to the control counterpart. Furthermore, a semitransparent PSC with a certified efficiency of 19.0% (with a record fill factor of 84.1%) and a four‐terminal perovskite/silicon tandem with an efficiency of 28.4% are also demonstrated.

Hydrophobization of Inorganic Oxide Surfaces via Ring-Opening Polymerization of Cyclic Siloxane Vapor.

The ability to control the surface chemistry of inorganic oxides has a profound impact on numerous applications, including lubrication, antifouling, and anticorrosion. While often overlooked as potential modifying agents given their lack of traditional functional groups, siloxanes have recently been shown to react readily with and covalently attach to inorganic oxide surfaces. Herein, we examine the reactions of cyclic siloxane vapor with solid interfaces via a ring-opening polymerization (ROP) initiated by the inherent acid/base characteristics of several smooth inorganic oxide surfaces. Surfaces are characterized by ellipsometry, dynamic contact angle analysis, and X-ray photoelectron spectroscopy (XPS). This technique requires no additional solvents and very little reactant to produce nanometer-thick hydrophobic surfaces that exhibit low contact angle hysteresis. Additional studies with particulate surfaces suggest that this method prepares conformal coatings regardless of surface architecture.

Alkaline Cleaning of Zn–Al–Mg Hot-Dip Galvanized Steels: Mechanisms and Surface Oxide Chemistry

Alkaline cleaning of Zn–Al–Mg coated hot-dip galvanized steel is a central process in the industrial galvanized steel production. This process removes carbonaceous contaminants from the surface and modifies the surface chemistry profoundly. We implement a combined analytical and surface science approach to characterize the dissolution mechanism and surface chemistry of Zn-Al-Mg coatings after treatment with industrial cleaners with pH 9.3 and 12.7, respectively. Our data indicate that weak alkaline cleaning can significantly increase the surface concentration of Zn-oxide, while strong alkaline cleaning dissolves the native oxide and generates a transient Zn/Mg-hydroxide on the surface. The observed dissolution mechanisms are largely consistent with the expectations from the Pourbaix diagrams, i.e. at pH 12.7 aluminium dissolution is expected while Mg is stable and forms a transient passive film. In contrast, mild alkaline cleaning at pH 9.3 is dominated by Mg and Zn dissolution, while the native Al passive film remains stable. Hence the cleaning provides an effective direct modification of the surface chemistry for subsequent process steps during the coating. Mild alkaline cleaning offers an increase of Zn at the surface, which has important implications for subsequent conversion and adhesive applications, that have been traditionally optimized for pure Zn coatings.

Role of Water Solvation on the Key Intermediates Catalyzing Oxygen Evolution on RuO2

RuO2 and IrO2 are among the most active catalysts for the Oxygen Evolution Reaction (OER). Recently, it was demonstrated that the catalytic surface of these oxides plays a role in the reaction, where a hydrogen bond with a neighbor OH group stabilizes an unconventional −OO intermediate (−OO–H), prior to O2 evolution. Quantum chemical calculations neglecting solvation effects indicated that this intermediate is more stable than the conventional −OOH, and that deprotonation of the stabilizing −OH is the rate limiting step for OER on RuO2(110) and RuO2(100). In this work, we investigate the role of water molecules on the relative stability of −OOH and −OO–H oxygenates on RuO2 (110) by means of density functional theory calculations combined with ab initio Molecular Dynamics simulations (AIMD). We show that the two intermediates participate in a hydrogen bonding network with water to a similar extent, but leading to different interfacial water structures, with possible implications on interfacial proton dynamics and reaction kinetics. Moreover, −OOH can spontaneously convert to −OO–H through a process mediated by water, demonstrating the critical role of explicitly including water in the model. This study provides further mechanistic insights on the role of the oxide surface chemistry in the OER mechanism and highlights the importance of explicitly treating the catalyst/water interfaces including dynamical aspects to assess the stability and the interconversion mechanism of key surface species, since the adoption of static solvation approaches tends to overestimate the energetic difference between −OOH and −OO–H reaction intermediates.

Imparting Metal Oxides with High Sensitivity Toward Light‐Activated NO2 Detection Via Tailored Interfacial Chemistry

AbstractActivation of metal oxides by light is a robust yet facile approach to manipulating their surface chemistry for favorable reactions with target molecules in heterogeneous catalysis and gas sensors. However, a limited understanding of interface chemistry and the involved mechanism impedes the development of a rational design of oxide interfaces for light‐activated gas sensing. Herein, the TiOx‐assisted photosensitization of In2O3 toward NO2 sensing is investigated as a case study to elucidate the detailed mechanism of light‐activated surface chemistry at the metal/gas interface. The resultant heterogeneous oxides exhibit outstanding NO2 sensing performance under light irradiation thanks to abundant photoexcited electrons and holes that serve as adsorption and desorption sites, respectively, to accelerate both surface reactions. Furthermore, the facile transfer of electrons and holes across the TiOx‐In2O3 interface contributes to improving the reversibility of sensing kinetics. Through this study, the mechanistic understanding is established of how the surface chemistry of metal oxide surfaces can be tuned by light activation providing an effective route to the design fabrication of high‐performance gas sensors.