Surface dissolution and amorphization of electrocatalysts during oxygen evolution reaction: Atomistic features and viewpoints

Electrochemical electrolysis with an aqueous electrolyte is a key method to obtain green hydrogen energy, convert carbon dioxide into high value-added carbon-based chemicals, and produce ammonia by nitrogen reduction at ambient conditions. For better efficiency of these electrolysis processes, lowering the comparatively large activation barrier of the sluggish oxygen evolution reaction (OER) at the anode side is necessary. Therefore, suitable electrocatalysts should be adopted to facilitate the OER. As a highly oxidizing environment along with high overpotential is unavoidable at the anode during electrolysis, degradation of both the activity and durability of OER catalysts inevitably takes place. In this Review, we classify four significant origins directly affecting the stability of oxide-based OER catalysts: (1) Alkali and alkaline-earth metal dissolution; (2) transition-metal leaching; (3) lattice oxygen evolution; and (4) rapid dissolution of phosphorus and chalcogens. In particular, because these origins usually induce amorphization or reconstruction at the surface, we systematically summarize atomic-level evidence largely based on transmission electron microscopy in each section. Providing integrated viewpoints for a better understanding of catalyst degradation, we believe that this Review offers valuable insight toward designing new OER catalysts with enhanced durability and activity.     

Characterization of indium tin oxide film and practical ITO film by electron microscopy

In order to clarify the structure of indium oxide film containing tin and tin oxides, various In₂O₃ based films prepared by vacuum evaporation were studied using high-resolution electron microscope (HREM). Indium tin oxide (ITO) film was composed of In₂O₃ and SnO. SnO crystal also contained (110) or (101) crystallographic shear (CS) structures that indicate excess amounts of tin. The CS structure was also found in a commercial ITO film having the resistivity of 2×10⁻⁴ Ω cm.     

Using ZrNb and ZrMo oxide nanoparticles as catalytic activity boosters supported on Printex L6 carbon for H2O2 production

Oxygen reduction reaction (ORR) is an important reaction which is widely applied in advanced oxidative processes (AOP) through the in-situ electrogeneration of hydrogen peroxide. Oxygen gas can either be reduced to hydrogen peroxide via two-electron pathway or be converted to water in a competitive way via four-electron pathway. In this study, we report the effective enhancement of H₂O₂ generation in K₂SO₄ 0.1 mol/L (pH 2) through the application of Printex L6 carbon (PL6C) modified with zirconium/niobium (ZrNb) and zirconium/molybdenum (ZrMo) oxides compared to unmodified PL6C. The proposed catalysts were prepared by the polymeric precursors synthesis method (on carbon). The catalysts were analyzed by X-ray fluorescence (FRX), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), and were electrochemically characterised by cyclic voltammetry (CV) and hydrodynamic linear sweep voltammetry (LSV). The electroactivity of ZrNb/PL6C and ZrMo/PL6C oxides was analyzed in the ratio of 50/50 w/w. The results obtained from the electrochemical characterisations of the electrodes showed that the application of 5% ZrNb/PL6C and 1% ZrMo/PL6C yielded H₂O₂ selectivity of 84.3 and 77%, respectively, compared to 84.3% recorded for the unmodified PL6C. Also, based on the application of a determined current density, 5% ZrNb/PL6C and 1% ZrMo/PL6C recorded a potential shift of 200 and 400 mV to less negative potentials, respectively, compared to the unmodified PL6C, which implies in less energy consumption. The results obtained from the morphological and surface characterisations of the materials pointed to a practically homogeneous distribution of ZrO₂, Nb₂O₅, and MoO₃ with particle size of ca. 5 nm on the PL6C surface compared to the unmodified PL6C which exhibited particle size of ca. 30–50 nm.     

氮掺杂石墨烯的制备及其电催化氧气还原性能

通过改良Hummers法制备氧化石墨(Graphite oxide,GO),采用爆炸辅助还原法将GO还原剥离并原位掺杂得到氮掺杂石墨烯(Nitrogen-doped graphene,N-RGO)。采用TEM、SEM、FI-IR、XPS、XRD及Raman等分析手段对N-RGO的形貌、组成以及结构进行了表征,利用旋转环盘电极技术测试了其电催化氧气还原活性。TEM和SEM结果表明,爆炸条件下GO被很好地剥离开来,得到只有几层厚度的石墨烯;FI-IR及XPS结果表明,GO中大部分含氧官能团被脱除,C/O原子比达到26.2,是目前所得GO还原程度非常高的方法之一,且氮元素成功掺杂进石墨烯晶格中,掺杂氮的原子质量分数约为2.11%;电化学测试结果显示,氧气还原的极限扩散电流由非氮掺杂石墨烯(Reduced graphene oxide,RGO)的0.24mA提高到N-RGO的0.49 mA,尽管爆炸辅助还原得到的RGO对氧气还原也显示出较好的催化活性,但掺杂之后的N-RGO具有更高的催化活性。     

Anodic oxide growth on aluminium surfaces modified by cathodic deposition of Ni and Co

Surface conditions similar to those found in aluminium alloys of practical use were assessed by cathodic deposition of transitions metals (Ni and Co) from different electrolytes. Fundamental aspects concerning with the growth of anodic oxide films at potentials lower than 10 V in neutral acetate buffer solution on these modified surfaces were analysed by common electrochemical techniques complemented with scanning electron microscopy and transmission electron microscopy. In both potentiodynamic and galvanostatic modes, the growth of aluminium oxide competes with the dissolution of deposited metal particles. The formation of a thin aluminium barrier oxide film beneath them shifts the dissolution potential over to 1.5 V towards more positive values. Some particles get progressively embedded in the matrix of the growing alumina and act as cation sources, increasing the film conductivity and diminishing the established electric field in the oxide. This effect is more pronounced with Co deposits due to its high active dissolution rate, before passivation occurs. Then, the generation of a two-layer film is explained in terms of the precipitation of metal hydroxide at the solution side on the oxide barrier film.     

Flower-like zinc oxide deposited on the film of graphene oxide and its photoluminescence

The graphene oxide films have been fabricated by simply filtering the graphene oxide solution through the micropore filter. Then the flower-like ZnO grows on the graphene layer by immersing the seed-coated graphene oxide films in the dilute growing solution containing NH₃·H₂O and Zn(NO₃)₂·6H₂O. The morphologies of the as-obtained ZnO deposited on the graphene oxide layer are characterized by using scanning electron microscope (SEM), X-ray powder diffraction (XRD) and photoluminescence (PL). The formation mechanism of the flower-like ZnO has also been investigated. The results show that the morphology of the finally-obtained ZnO is tunable by seeds, the concentration of growing solution and the reaction time.     

Facile synthesis,magnetic and optical properties of double-shelled Co3O4 hollow microspheres

Double-shelled Co₃O₄ hollow spheres are successfully synthesized by chemically induced self-assembly in the hydrothermal environment. The morphology, chemical composition, and crystalline structure of the double-shelled Co₃O₄ hollow spheres are characterized by different techniques, such as powder X-ray diffraction (PXRD), Raman spectrum, X-ray photoelectron spectrum (XPS), field emission scanning electron microscope (FESEM), and high resolution transmission electron microscope (HRTEM) with selected area electron diffraction (SAED). Magnetic measurements and optical spectra suggest the double-shelled Co₃O₄ hollow spheres exhibit close to a weak ferromagnetic behaviour and enhanced photogenerated carrier separation. Since this synthetic route is simple, convenient, and “green”, it is possible to extend this synthetic method to preparation of a wide range of the multishelled hollow spheres of metal oxides for semiconductor device applications.     

Montmorillonite/graphene oxide nanocomposite as superior adsorbent for the adsorption of Rhodamine B and Nickel ion in binary system

A series of montmorillonite reduced graphene oxide (MrGO) composites were synthesized using different ratios (5, 10, 15 and 20) of montmorillonite (MMt) to GO. The synthesized composites were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, surface area analyzer (BET), and Fourier transform- infrared spectroscopy. The adsorption capacity and efficiency of the synthesised composites were examined towards removal of Rhodamine B (RhB) and Nickel ion (Ni²⁺). The results were compared with that of GO and commercial MMt clay. The kinetic sorption models were evaluated, and it was observed that sorption follows the pseudo-second-order kinetics. Adsorption isotherm was best fit into the Langmuir model (R²?=?0.996 for RhB & 0.957 for Ni²⁺). Among all the synthesized composites, MrGO-2, a composite of GO and montmorillonite with (1:10) ratio, showed maximum activity towards the adsorption of Rhodamine B and Ni²⁺ calculated to be 625?mg/g and 178?mg/g respectively at neutral pH condition. From the calculated ΔG⁰ (?3.99 & ?0.71?kJ?mol^?1), ΔH (28.6 & 4.61?kJ?mol^?1) and ΔS (?107.5 & ?17.8?J?mol^?1 K) values for RhB & Ni²⁺ respectively, it can be unambiguously inferred that the adsorption process was feasible, endothermic and exhibiting least randomness, respectively. The prepared MrGO composites showed good adsorption capacity towards efficient removal of RhB and Ni²⁺ in single as well as binary system.     

On the photoluminescence of multilayer arrays of silicon rich oxide with high silicon content prepared by low pressure chemical vapor deposition

The photoluminescence emission of multilayer structures composed of layers of silicon rich oxide with high silicon content and layers of silicon rich oxide with low silicon content obtained by low pressure chemical vapor deposition is here presented. Different parameters for the preparation of the multilayers have been varied such as the Si concentration and the thicknesses of the layers. Additionally, the samples were oxidized at different temperatures. For all samples the photoluminescence seems to have the same origin: defects in the oxide matrix and defects at the interfaces between the Si nanocrystals. The structural and compositional properties of the multilayer structures are discussed.     

Transmission electron microscope study of the topotactic reaction of (0 0 1), (0 1 1) and (1 1 1) Ag films and Te

The formation, structure and morphology of silver telluride was investigated in the reaction of (0 0 1), (0 1 1) and (1 1 1) single crystalline Ag films with vacuum deposited Te. Silver films 30–40 nm in thickness were deposited by thermal evaporation onto water- and chlorine-treated NaCl. Onto this silver 1–40 nm of tellurium were deposited at 100 and 200 °C. The Ag–Te reaction occurred during Te deposition. Accordingly, formation of the compound phase was investigated from the nucleation stage through complete tellurization on either side of the polymorphic phase transformation temperature (T_c=150 °C). Transmission electron microscope and selected area electron diffraction showed that monoclinic silver telluride (Ag₂Te) of different morphology and texture was always formed. The orientation of silver and monoclinic phase upon differently oriented monocrystalline Ag films and at deposition temperatures around T_c is discussed.     

Modifying the morphology and structure of graphene oxide provides high-performance LiFePO4/C/rGO composite cathode materials

In this study we synthesized LiFePO₄/carbon/reduced graphene oxide (LFP/C/rGO) composite cathode materials using a method involving sol–gel processing, spray-drying, and calcination. To improve the electrochemical performance of LFP/C, we tested graphene oxides (GOs) of various morphologies as conductive additives, including pristine GO, three-dimensional GO, and hydrothermal porous GO (HTGO). Among our samples, the cathode material prepared through spray-drying with the addition of 1 wt% of HTGO (denoted SP-LFP/C/1%rHTGO) displayed the best electrochemical performance; its discharge capacities at 0.1C, 1C, 5C, and 10C were 160.5, 151.8, 138.8, and 130.3 mA h g⁻¹, respectively. From measurements of its long-term cycling performance, the discharge capacity in the first cycle and the capacity retention after 30 cycles at 0.1C were 160.2 mA h g⁻¹ and 99.6%, respectively; at 10C, these values were 132.2 mA h g⁻¹ and 91.8%, respectively. The electronic conductivity of SP-LFP/C/1%rHTGO (6.58 × 10⁻⁵ S cm⁻¹) was higher than that of the pristine LFP/C (9.24 × 10⁻⁶ S cm⁻¹). The Li⁺ ion diffusivities (D_Li⁺) of the SP-LFP/C/1%HTGO cathode, measured using AC impedance (3.91 × 10⁻¹³ cm² s⁻¹) and cyclic voltammetry (6.66 × 10⁻¹⁰ cm² s⁻¹ for discharge), were superior to those of the LFP/C cathode (9.31 × 10⁻¹⁵ cm² s⁻¹ and 1.79 × 10⁻¹⁰ cm² s⁻¹ for discharge, respectively). Galvanostatic intermittent titration revealed that the value of D_Li⁺ was located in a reasonable range from 1 × 10⁻¹⁰ to 1 × 10⁻¹⁷ cm² s⁻¹; its value dropped to its lowest point when the state of charge was close to 50%. Thus, the use of spray-drying and the addition of conductive HTGO (having a 3D wrinkled morphology and interconnected pore structure) can enhance the electronic conductivity and Li⁺ ion diffusivity of LFP/C cathode materials, thereby improving the electrochemical performance significantly.     

Native oxide consumption during the atomic layer deposition of TiO2 films on GaAs (100) surfaces

The consumption of the surface native oxides is studied during the atomic layer deposition of TiO₂ films on GaAs (100) surfaces. Films are deposited at 200 °C from tetrakis dimethyl amido titanium and H₂O. Transmission electron microscopy data show that the starting surface consists of ~2.6 nm of native oxide and X-ray photoelectron spectroscopy indicates a gradual reduction in the thickness of the oxide layer as the thickness of the TiO₂ film increases. Approximately 0.1-0.2 nm of arsenic and gallium suboxide is detected at the interface after 250 process cycles. For depositions on etched GaAs surfaces no interfacial oxidation is observed.     

On the role of activation mode in the plasma- and hot filaments-enhanced catalytic chemical vapour deposition of vertically aligned carbon nanotubes

Catalytic chemical vapor deposition (CCVD) with different activation modes (thermal; hot filaments-enhanced; direct current plasma-enhanced and both hot filament and direct current plasma-enhanced) are achieved in order to grow vertically aligned carbon nanotubes (VA CNTs). By widely varying the power of the different activation sources of the gas (plasma, hot filaments, substrate heating) while keeping identical the substrate temperature (973 K) and the catalyst preparation, the results point out the important role of ions in the nucleation of carbon nanotubes (CNTs), as well as the etching behaviour of highly activated radicals such as H˙ in the selective growth of vertically aligned films of CNTs. Moreover, it is demonstrated that, within the deposition conditions (temperature, pressure, flow rate) used in this study, oriented carbon nanotubes can be grown only when both ions, mainly generated by the gas discharge plasma, and highly reactive radicals, mainly formed by the hot filaments, are produced in the gas phase. We propose that highly energetic ions are needed to nucleate the carbon nanotubes by increasing the carbon concentration gradient whereas the highly reactive radicals allow the selective growth of vertically aligned CNTs by preventing carbon deposition on the whole surface through chemical etching of edge carbons in graphene sheets.     

Templated growth of superparamagnetic iron oxide nanoparticles by temperature programming in the presence of poly(vinyl alcohol)

Magnetite (Fe₃O₄) nanostructures with different morphologies including uniform nanoparticles, magnetic beads and nanorods were synthesized via a co-precipitation method. The synthesis process was performed at various temperatures in the presence of polyvinyl alcohol (PVA) at different concentrations. It is shown that small amounts of PVA act as a template in hot water (70 °C), leading to the oriented growth of Fe₃O₄ nanorods, which was confirmed by selected area electron diffraction. Individually coated magnetite nanoparticles and magnetic beads were formed at a relatively lower temperature of 30 °C in the folded polymer molecules due to the thermo-physical properties of PVA. When a moderate temperature (i.e. 50 °C) was used, nanorods and nanobeads co-existed. At higher concentrations of PVA (polymer/iron mass ratio of 5), however, the formation of magnetic beads was favored. The nanorods were shown to be unstable upon exposure to electron beams. Freezing/thawing process was applied post synthesis as temperature programming to fabricate stable nanorods with rigid walls.     

In-situ investigation on the deformation and damage behaviour of diamond-like carbon coated thin films under uniaxial loading

In the present work, the failure behaviour of diamond-like carbon (DLC) coatings on thin steel substrate under uniaxial tensile loading is analyzed in-situ in scanning electron microscopy as well as ex-situ using focused ion beam cross section and transmission electron microscopy. Aim of the work is to find correlations between the failure behaviour of the coating system, the adhesion and the stress-strain behaviour of a DLC coating system under tensile loadings conditions. Therefore thin amorphous DLC films were coated onto thin stainless steel foils using a plasma assisted chemical vapour deposition technique. It is found from the in-situ investigations that at increasing strains cracks were formed in the coating, with decreasing spacing at higher strains. By comparing uncoated steels foils with coated systems the stress-strain behaviour of a DLC coating was determined. The DLC coating, although already strongly cracked, bears loads up to a total strain of 15%. Cross section analyses with a focused ion beam and microscopy techniques supported these investigations. During straining the formation of two deformation bands adjacent to the Cr adhesion layer was observed. This deformation bands also indicate a high interfacial adhesion.     

Structure and stimulated emission of a high-quality zinc oxide epilayer grown by atomic layer deposition on the sapphire substrate

A high-quality ZnO epilayer was grown on the (0001) sapphire substrate by atomic layer deposition (ALD) and followed by high-temperature rapid thermal annealing (RTA). The layer-by-layer growth and low deposition temperature of ALD, as well as the RTA treatment, prevent the formation of columnar structures in the ZnO epilayer. A distorted ZnO layer at the ZnO/sapphire interface, which relaxes the misfit in ZnO leads to a low threading dislocation density in the ZnO epilayer. Optically-pumped stimulated emission was achieved with a low-threshold intensity of 153 kW/cm² at room temperature. The good crystalline quality and low-threshold stimulated emission indicate that the ALD approach is appropriate for preparing high-quality ZnO epilayers.     

Enhanced photoelectrochemical properties and photocatalytic activity of porous TiO2 films with highly dispersed small Au nanoparticles

Small Au nanoparticles (NPs) with mean diameter of 4.1 nm were highly deposited on TiO₂ films via a simple electrostatic self-assembly method. The physically separated Au NPs, with a high surface density of 6.3 × 10¹¹ NPs/cm², were mainly distributed on the top layer of porous TiO₂ films. The deposition of Au NPs induced a negative shift (~ 100 mV) of the apparent flat band potential of Au-TiO₂ electrodes. The charge separation efficiency of the TiO₂ electrode increased from 72.1% to 88.5% by dispersing Au NPs. Whatever redox species were present in the electrolyte, the Au-TiO₂ electrode had higher photovoltage than the TiO₂ electrode. The photovoltage was very sensitive to added redox species such as O₂, O₃, and methanol, and the effect of adsorbed redox species on electron accumulation was discussed. The electrochemical impedance spectroscopic measurements revealed that the charge transfer resistance (R_ct) of Au-TiO₂ films was reduced to 16% of bare TiO₂ electrode, and the decreased R_ct corresponded to the increased photocatalytic activity of Au-TiO₂ films. The beneficial role of uniformly dispersed small Au NPs on the charge separation was discussed. By modifying TiO₂ films with small Au NPs, the photocatalytic activity of TiO₂ films for formaldehyde degradation increased about 2.5 times.     

The impact of non-uniform channel layer growth on device characteristics in state of the Art Si/SiGe/Si p-metal oxide semiconductor field effect transistors

In this study we have highlighted the effect of non-uniform channel layer growth by the direct correlation of the microstructure and electrical characteristics in state-of-the-art pseudomorphic Si/SiGe p-channel metal oxide semiconductor field effect transistor devices fabricated on Si. Two nominally identical sets of devices from adjacent locations of the same wafer were found to have radically different distributions in gate threshold voltages. Due to the close proximity and narrow gate length of the devices, focused ion beam milling was used to prepare a number of thin cross-sections from each of the two regions for subsequent analysis using transmission electron microscopy. It was found that devices from the region giving a very narrow range of gate threshold voltages exhibited a uniform microstructure in general agreement with the intended growth parameters. However, in the second region, which showed a large spread in the gate threshold voltages, profound anomalies in the microstructure were observed. These anomalies consisted of fluctuations in the quality and thickness of the SiGe strained layers. The non-uniform growth of the strained SiGe layer clearly accounted for the poorly controlled threshold voltages of these devices. The results emphasize the importance of good layer growth uniformity to ensure optimum device yield.     

The effect of temperature and strain rate on the deformation behaviour, structure development and properties of biaxially stretched PET-clay nanocomposites

The inclusion of a synthetic fluoromica clay in PET affects its processability via biaxial stretching and stretching temperature (95 °C and 102 °C) and strain rate (1 s⁻¹ and 2 s⁻¹) influence the structuring and properties of the stretched material. The inclusion of clay has little effect on the temperature operating window for the PET-clay but it has a major effect on deformation behaviour which will necessitate the use of much higher forming forces during processing. The strain hardening behaviour of both the filled and unfilled materials is well correlated with tensile strength and tensile modulus. Increasing the stretching temperature to reduce stretching forces has a detrimental effect on clay exfoliation, mechanical and O₂ barrier properties. Increasing strain rate has a lesser effect on the strain hardening behaviour of the PET-clay compared with the pure PET and this is attributed to possible adiabatic heating in the PET-clay sample at the higher strain rate. The Halpin-Tsai model is shown to accurately predict the modulus enhancement of the PET-clay materials when a modified particle modulus rather than nominal clay modulus is used.     

Study on the supercooling degree and nucleation behavior of water-based graphene oxide nanofluids PCM

This article aimed to study the supercooling degree and nucleation behavior of nanofluids phase change material. The nanofluids were prepared by adding small fraction of graphene oxide nanosheets in deionized water without any dispersants. The supercooling degree of nanofluids with different concentrations was tested experimentally. The results show that the supercooling degree can be reduced by 69.1%, and the nucleation was started in advance, shorting the time by 90.7%. Theoretical analysis based on the heterogeneous nucleation theory indicates that ice crystal nucleus cannot grow on the thickness surface of the graphene oxide nanosheet, while it can grow on the top or bottom surface of the nanosheet only when the supercooling degree ΔT and the nanosheets size D meet the formulaD⋅ΔT≥4.2×10⁻⁸. Our study implies that graphene oxide nanofluids have the potential to be used as PCMs in cold storage applications because of their low supercooling degree and rapid nucleation behavior.