Oxygen Diffusion Research Articles

Component regulation and high-entropy engineering for enhanced antioxidant and high-temperature mechanical properties of protective films

Transition metal nitrides (TMNs) have gained widespread application in protecting structural components due to their high strength and hardness. However, TMNs still have the challenge of structural instability and mechanical deterioration caused by oxidation under harsh high temperature conditions. Herein, we present a strategy combining component regulation with high-entropy engineering to develop an advanced high-temperature Al-containing high-entropy nitrides (HENs) material. To prevent the phase decomposition of AlN within the (NbMoTaWAl)N, theoretical simulations were employed to determine a critical atomic percent of 25.0% Al for maintaining the stability of the high-entropy structure. Ensuing experimental synthesis creates three NbMoTaWAlN films with varying Al content: a high-entropy film with 0.0% Al (HEN), a high-entropy film with 21.2% Al (HEN-Al), and an amorphous transition metal nitride film with 30.2% Al (a-TMN-Al), validating key high-entropy engineering benchmarks. It is found that the unique HEN-Al film exhibits excellent oxidation resistance and high-temperature hardness, attributed to the uniform distribution of Al atoms in the robust high-entropy structure, which creates conditions for forming a dense and continuous Al2O3 barrier layer, effectively hindering the diffusion of oxygen into the film interior. This study provides new insights to develop a new generation of high-temperature protective materials.

In-situ synchrotron x-ray photoelectron spectroscopy study of medium-temperature baking of niobium for SRF application

In order to determine optimal parameters of vacuum thermal processing of superconducting radiofrequency niobium cavities exhaustive information on the initial chemical state of niobium and its modification upon a vacuum heat treatment is required. In the present work the chemical composition of the niobium surface upon ultra-high vacuum baking at 200 ∘C–400 ∘C similar to ‘medium-temperature baking’ and ‘furnace baking’ of cavities is explored in-situ by synchrotron x-ray photoelectron spectroscopy (XPS). Our findings imply that below the critical thickness of the Nb2O5 layer ( ≈1nm ) niobium starts to interact actively with surface impurities, such as carbon and phosphorus. By studying the kinetics of the native oxide reduction, the activation energy and the rate-constant relation have been determined and used for the calculation of the oxygen-concentration depth profiles. It has been established that the controlled diffusion of oxygen is realized at temperatures 200 ∘C–300 ∘C, and the native-oxide layer represents an oxygen source, while at 400 ∘C the pentoxide is completely reduced and the doping level is determined by an ambient oxygen partial pressure. Fluorine (F to Nb atomic ratio is 0.2) after the buffered chemical polishing was found to be incorporated into the surface layer probed by XPS ( ≈4.6nm ), and its concentration increased during the low-temperature baking (F/Nb = 0.35 at 230 ∘C) and depleted at higher temperatures (F/Nb = 0.11 at 400 ∘C). Thus, the influence of fluorine on the performance of mid-T baked, nitrogen-doped and particularly mild-baked (120 ∘C/48 h) cavities must be considered. The possible role of fluorine in the educed Nb+5→Nb+4 reaction under the impact of an x-ray beam at room temperature and during the thermal treatment is also discussed. The range of temperature and duration parameters of the thermal treatment at which the niobium surface would not be contaminated with impurities is determined.

Thermal stability and flame retardancy of cotton fabric coated with PVA-boric acid-cellulose nanofiber hybrid: Role of chemical interactions

An ecofriendly, polymer coating to impart fire retardancy to cotton fabric is introduced in the current study. Polyvinyl alcohol-boric acid-cellulose nanofiber (PVA-BA-CNF) hybrid coating with different compositions of boric acid and 2.5 wt% cellulose nanofiber (CNF) were coated over cotton fabric. The CNF used in the study was extracted from onion skin, an agricultural waste. The nanofibrous morphology of extracted CNF was confirmed from Transmission Electron Microscopic (TEM) images. The surface morphology of treated cotton was compared with that of bare cotton using scanning electron microscope (SEM) and optical microscope (OM). The dispersion of the coating formulation over the cotton fabric and the porosity after coating were confirmed. Chemical interactions developed in the coating formulations were characterized by Fourier transform infrared spectroscopy (FTIR). In addition to hydrogen bonding established between the coating formulation and cotton fabric, the existence of chemical bonding (B-O-C) between the components of the coating formulation and between the crosslinked coating and cotton fabric has been evident. The thermal stability of the coated cotton fabrics was evaluated using thermogravimetric analysis (TGA). The high char residue recorded for PVA-BA-CNF coated fabric, especially with 17phr BA content indicated the efficiency of crosslinked coating matrix in enhancing the thermal stability of the cotton fabric. The coated cotton degraded in two stages and with a different degradation kinetics than that of uncoated cotton fabric. Flame retardant performance of the coated fabric has been evaluated by vertical flammability tests and pyrolysis combustion flow calorimetry (PCFC). The peak temperature of heat release rate (pHRR) showed 32 % reduction for PVA-BA-CNF coating with 17phr BA content compared with pure cotton indicating a decreasing flame spreading rate due to the inhibition of oxygen diffusion by chemically crosslinked PVA-BA-CNF coating.

Effect of Yttrium Additions on the High-Temperature Oxidation Behavior of GH4169 Ni-Based Superalloy.

The effect of the active element yttrium and its content on the oxidation behavior of GH4169 Ni-based superalloy at extreme temperature was studied by isothermal oxidation experiments. The results show that the oxide scale of GH4169 alloy presents a multi-layer structure, in which the continuous and dense Cr2O3 oxide layer is located in the subouter layer (II layer) and the continuous Nb-rich layer is in the subinner layer (III layer). These layers can inhibit the diffusion of oxygen and alloying elements, preventing the further oxidation of the alloy. The appropriate addition of yttrium can promote the selective oxidation of Cr element, reduce the thickness of the oxide scale and the oxidation rate of the alloy, inhibit the formation of voids at the interface of the oxide scale/alloy matrix, improve the resistance of the alloy to spalling as well as the adhesion of the oxide scale, and improve the high-temperature oxidation resistance of the alloy. Of those tested, the alloy containing 0.04 wt.%Y has the lowest oxidation weight gain, the slowest oxidation rate, and less oxide scale spalling. Based on this, the effect of yttrium on the high-temperature oxidation behavior of GH4169 Ni-based superalloy and its mechanism were revealed.

Polishing methods for composites restoration: the influence on human gingival fibroblasts behaviour

BackgroundCarious/Non-carious cervical lesions with gingival recessions may require both dental and periodontal reconstructive therapy, where flaps/grafts may be placed in contact with a dental filling material. Human Gingival Fibroblasts (HGF-1) response during the early phase of healing could vary according to the procedures employed to cure the dental composite. Moreover, oxygen diffusion into dental composite inhibits the polymerization reaction, creating an oxygen-inhibited layer (OIL) that presents residual unreacted monomers. The aim of this study was to assess the effect of different polishing techniques and OIL on HGF-1.MethodsComposite discs polished with different techniques (diamond rubber, abrasive discs and tungsten carbide burr) were used. An additional not polished smooth group obtained with and without OIL was used as control. Samples were physically characterized through the analysis of their hydrophilicity and surface topography through contact angle measurement and SEM, respectively; afterwards the biologic response of HGF-1 when cultured on the different substrates was analyzed in terms of cytotoxicity and gene expression.ResultsThe finishing systems caused alterations to the wettability, even if without a proportional relation towards the results of the proliferation essay, from which emerges a greater proliferation on surfaces polished with one-step diamond rubber and with abrasive discs as well as a direct effect of the glycerin layer, confirming that surface roughness can heavily influence the biological response of HGF-1.ConclusionsSurfaces wettability as well as cellular behavior seem to be affected by the selection of the finishing system used to lastly shape the restoration. Especially, the presence of OIL act as a negative factor in the regards of human gingival fibroblasts. The present study may provide the first clinical instruction regarding the best polishing system of composite material when the restoration is placed directly in contact with soft tissue cells. Understanding HGF-1 behavior can help identifying the polishing treatment for direct restoration of carious/non-carious cervical lesions associated with gingival recessions.

Oxygen diffusion in freestanding body centered cubic tantalum structural thin films in air and in high vacuum

Sensors and actuators constructed from freestanding tantalum thin films show promise for micromachining applications and for the study of thin film mechanical behavior. To assess this promise, it is necessary to gain further understanding of the performance of Ta as a structural material. We first evaluate the coefficient of thermal expansion, αTa, using micromachined bent beams, which amplify displacement compared to linear expansion. The value for αTa is 6.8 × 10−6 m/m °C, in good agreement with the bulk value. This validation enables the study of interstitial oxygen diffusion in Ta, for which literature values of activation energy vary widely, from 0.60 to 1.98 eV. Displacement in air due to oxygen diffusion becomes measurable after 30 min exposure at 180 °C. We extract an activation energy for interstitial oxygen in Ta of 0.53 eV/atom. Analysis indicates that lattice rather than grain boundary diffusion is the associated mechanism. To inhibit the oxidation, we construct a thermal stage that controls specimen temperature in 10−5 Pa vacuum. Then, after a 24 h hold, oxidation is suppressed up to 400 °C. This result is discussed in terms of O dissolution from its native oxide, coupled with further absorption from background gases.

Highly Stable and Reversible Coloration of Oxide Nanoparticles Film by Ultrafast‐CW Laser Induced Band Engineering

AbstractColoration in oxides meets the challenge in achieving high stability and repeatability simultaneously. In this work, reversible coloration of TiO2 nanoparticles (NPs) film is demonstrated by alternate ultrafast (UF) laser and continuous wave (CW) laser irradiation. Under UF laser irradiation, oxygen vacancies are introduced in the TiO2 lattice, which lead to the bandgap reduction (2.73 to 1.50 eV) and surface blackening. The blackened area can achieve high resolution with size down to ≈1.1 µm. This coloration in TiO2 also shows excellent thermal stability that color fading is negligible even after thermal annealing at 700 K for 2 h in air. The generated high temperature by CW irradiation is known to be beneficial for the O2 dissociation on defected TiO2, thus promoting the internal oxygen diffusion to eliminate the vacancies. The energy band structure of TiO2 can be recovered accordingly, and decoloration is achieved. TiO2‐NPs film shows stable microstructures with barely changed optical properties after 12 cycles of coloration–decoloration process. This band engineering‐induced reversible coloration can also be applicable for broad oxides, e.g., ZnO, HfO2, and Ga2O3. Such highly stable and reversible coloration is promising in high‐performance micro/nano‐devices development for color display and optical encryption.

High temperature oxidation behavior of liquid phases sintered SiC ceramics with ZrB2 addition

The oxidation property of liquid-phase sintered silicon carbide (LPS-SiC) ceramics with ZrB2 addition was studied after oxidation test in air at 1400 °C. The results indicate that the addition of ZrB2 decreased the degree of polymerization (DOP) of the silicate networks in the oxide layer, suppressing the additional oxidation caused by residual bubbles in the oxide layer of LPS-SiC, which bypassed the layer and directly corroded the material internally. After 100 h of oxidation, the additional oxidation depth was found to be 125 μm in the sample without ZrB2 and 0 μm in those containing 10 wt% ZrB2. Simultaneously, the decrease in DOP facilitates the migration of crystalline phases. The generated ZrSiO4 can migrate and aggregate at the interface between the surface oxide layer and the SiC/ZrB2 matrix, forming a continuous ZrSiO4 barrier. This impedes the diffusion of the oxidant and enhances the oxidation resistance. However, an insufficient ZrB2 content leads to a discontinuous ZrSiO4 layer, thereby weakening its protective effect. Simultaneously, a decrease in DOP increases the rate of oxygen diffusion, resulting in an increase in the oxidation layer thickness. This study contributes to a better understanding of the failure mechanisms of LPS-SiC in oxidizing environments and provide a reference for the design of oxidation-resistant LPS-SiC materials.

Reignition characteristics of lignite affected by pre-oxidation and liquid nitrogen cold soaking

The propensity of residual oxidized coal to be reignited within enclosed fire areas in coal mines under liquid nitrogen (LN2) cold soaking remains unclear. Therefore, scanning electron microscopy (SEM), low-temperature nitrogen adsorption (LTNA), and thermogravimetric (TG) experiments were conducted to characterize the pore structure and secondary oxidation of oxidized cold-soaked coal. The results indicate that pre-oxidation or cold soaking alone can promote the generation and merging of pores and make the pore structure more complex, especially when pre-oxidized. However, pore evolution is suppressed and then improves when lignite is simultaneously subjected to pre-oxidation and cold soaking. In particular, the macropore volume and specific surface area decrease and then increase. The cryogenic shrinking of the LN2 results in the collapse of the loose coal matrix, which subsequently blocks the macropores. In contrast, vaporization expansion enhances pore connectivity with continuous LN2 injections, transforming mesopores into macropores, especially in the pore ranges of 2–5 nm and >50 nm. Additionally, pre-oxidation or cold soaking alone improves the oxidizing activity and combustion performance of raw coal. However, continuous cold soaking initially increases and subsequently decreases the characteristic temperatures and activation energy of oxidized coal. Oxidization at 200 °C with one cold soaking can further lower reignition propensity. The average activation energy of oxidized coal decreases by 22.9%–29 % when soaked more than three times. The improvement in combustion property is closely related to the increasing number of macropores because a larger pore volume and specific surface area are conducive to oxygen diffusion and adsorption. Therefore, pre-oxidation and cold soaking promote and inhibit the reignition of coal when performed simultaneously. These results provide theoretical guidance for rational liquid-nitrogen injection to control coal fires.

Tailored high-temperature corrosion behavior of Cr coatings using high power impulse magnetron sputtering on ZIRLO alloys for accident-tolerant fuel application

To further enhance the oxidation resistance of Zirconium alloys during Loss of Coolant Accident (LOCA), protective Cr coatings were deposited in synchronized pulse bias mode through high power impulse magnetron sputtering (HiPIMS). The results showed the weight gain of the Cr coatings with synchronized pulse bias was reduced by approximately 61.7 % compared to that of the Cr coatings without synchronized pulse bias after 90 min of steam oxidation at 1200 °C. This was mainly attributed to the formed intense (200) preferred orientation of the Cr coatings with synchronized pulse bias during deposition, accelerating the recrystallization growth of the residual Cr layer in a high-temperature steam environment, thereby reducing the rapid diffusion pathways for oxygen. Moreover, the synchronized pulse bias induced Cr grains refinement, favoring the formation of a more compact Cr2O3 scale, and therefore efficiently inhibiting the diffusion of external oxygen to the underlying alloy.

Enhanced reactivity over Ce2(SO4)3/MgO with NiO modification for chemical looping partial oxidation of methane

Chemical looping partial oxidation of methane to syngas is a promising process. Thermodynamic and kinetic analysis both forecast the NiO/Ce2(SO4)3–MgO is a prospective oxygen carrier (OC) to this process, which enables with 100% syngas selectivity, 2.15H2/CO ratio, excellent methane conversion and stable cycling characteristic. Compared with Ce2(SO4)3, the methane conversion rate rise by 73.19% because of the excellent lattice oxygen availability, less carbon deposit, and large specific surface area. The distinctive pore structure also provides a favorable reaction environment. Through the density functional theory, Ni doping can lower the energy barrier (Eb), promote lattice oxygen activation and diffusion, and the oxygen vacancy (Ov) can further promote these processes. CH3 → CH2 + H (TS2) is the rate-limiting step. Compared with Ce2(SO4)3, the Ni doping can reduce Eb by 16.8%, and the Ov can further reduce it by 43.0%. It does not change when the Ov concentration is more than 1.96%.

High-temperature oxidation behavior of double glow plasma Cr-Y alloyed layers on Ti2AlNb alloy

A Cr-Y alloyed layer was synthesized on the surface of Ti2AlNb by double glow plasma surface alloying technique. The morphology, phase composition and oxidation behaviors at 750 °C, 800 °C, and 850 °C of Cr-Y alloyed layers were systematically investigated. The results illustrated that Cr-Y alloyed layer was approximately 10 μm thick, which the morphology of alloyed layer was uniform and compact, with a flat and uniform interface to the matrix. Oxidation kinetics for the Cr-Y alloyed layer approximately followed the parabolic law, with an oxidation weight gain significantly lower than that of Ti2AlNb. The predominant oxides of Cr-Y layer were CrNbO4, Cr2O3, and Y2O3, which effectively hindered oxygen diffusion into the substrate.

A novel naturally aspirated cathode for efficient electrosynthesis of hydrogen peroxide and wastewater purification in electro-Fenton systems

Electrochemical synthesis of hydrogen peroxide (H2O2) has developed rapidly in recent years as an alternative process to the anthraquinone method. However, the low H2O2 production and high energy consumption limit its further application. In this study, we propose a simple method to fabricate a naturally aspirated cathode (NAC), which significantly reduces the mass transfer resistance of oxygen and achieves a high oxygen diffusion coefficient (7.11 × 10-6 m2 s−1) and oxygen utilization efficiency (39.6 %). Additionally, the NAC provides a high density of reaction sites to achieve efficient production of H2O2 (0–84.33 mg h−1 cm−2) at near industrial current densities (0–240 mA cm−2) without external aeration. Meanwhile, the prepared NAC can degrade over 97.5 % of dyes within 10 min during the electro-Fenton process. The NAC exhibits excellent H2O2 production performance and great stability during long-term operation, which offers huge potential for industrial-scale electrochemical H2O2 production and the advanced oxidation processes (AOP) derived from it.

Hierarchical pore engineering of MOF-5 derived electrocatalysts with high mass transfer for zinc-air flow batteries

From micro to macro level, the performance of zinc-air flow battery (ZAFB) hinges on two crucial factors: the effective oxygen reduction reaction (ORR) electrocatalysts, and the durable triple-phase electrodes. However, sluggish kinetic process always occurs due to insufficient active sites and hysteretic mass transfer. In this work, a well-confined iron phthalocyanine (FePc) structure onto carbonized metal-organic framework (C-MOF5) electrocatalyst is constructed through a pyrolysis-free strategy. The macrocyclic skeleton of MOF-5 has been confirmed to offer a stronger and more abundant environment for hosting FePc molecules. Attributing to the hierarchical pore engineering of MOF-5, the FePc@C-MOF5 electrocatalyst reveals a high content of Fe (5.68 wt%) with multiple exposed active sites. Notably, the FePc@C-MOF5 exhibits a remarkably high half-wave potential of 0.915 V for ORR in 0.1 M KOH, surpassing that of commercial Pt/C by nearly 60 mV. From a higher-level device perspective, the highest oxygen diffusion velocity and local current density of the FePc@C-MOF5 electrode is verified by computational fluid dynamics (CFD) simulations. As a result, the as-assembled ZAFB demonstrates long-term stability with 200 h’ cycling. This work not only presents the hierarchical pore tailoring strategy for designing ORR electrocatalysts but also offers a deeper understanding of the essence of interfacial mass transfer.

In-vitro fretting tribocorrosion and biocompatibility aspects of laser shock peened Ti-6Al-4V surfaces

Laser shock peening without coating (LSPwC), a prospective surface modification technique for improving the mechanical aspects of Ti-6Al-4V alloy for automotive/aerospace sector, is also expected to dictate the efficiency of this material class for implant application. Here we unravel the impact of LSPwC on Ti-6Al-4V material surface characteristics, in-vitro tribocorrosion and biocompatibility. Micrography shows the presence of nano and sub-micron sized pores after LSPwC process. The role of nano and sub-micron sized pores along with topography modification induced by LSPwC to serve as cues for controlling gene expressions, cell adhesion and activities offer novel insights in this research direction. A detailed X-ray photoelectron spectroscopy analysis detected local chemical non-stoichiometry with reduced number of oxygen diffusion channels. A crucial outcome of this oxide layer modification is the negative skewness (−0.55 ± 0.11) and reduced kurtosis (3.49 ± 0.14) of the surface, along with localized plastic deformation. These factors are correlated with the shift in potential during fretting tribo-corrosion from −800 to −250 mV after LSPwC, accompanied by a lower coefficient of friction of 0.4. Furthermore, the presence of well-spread cells and the up-regulation of beneficial genetic markers (Ki67) on LSPwC surfaces have the potential to form a better bone-material interface. The findings open new frontiers of the LSPwC-treated Ti-6Al-4V surface to synergistically modulate the tribocorrosion and biocompatibility aspects, with exciting possibilities for biomedical implants.

Low nitrate under waterlogging triggers exodermal suberization to form a barrier to radial oxygen loss in rice roots.

To acclimate to hypoxic waterlogged conditions, the roots of wetland plants form a radial oxygen loss (ROL) barrier that can promote oxygen diffusion to the root tips. We hypothesized that the low-nitrate concentrations that occur after molecular oxygen is consumed in waterlogged soils are an environmental trigger for ROL barrier formation in rice (Oryza sativa). We previously identified 128 tissue-specific up/downregulated genes during rice ROL barrier formation. The RiceXPro database showed that many of these genes were differentially regulated in response to nitrogen deficiency. Therefore, we assessed changes in the concentrations of ionic species of nitrogen under stagnant conditions, i.e. in a nutrient solution that mimics waterlogged soil conditions, and examined the effects of an increase or decrease of nitrate in the nutrient solution on ROL barrier formation and exodermal suberization. Preventing nitrate deficiency in the stagnant nutrient solution suppressed the formation of an ROL barrier. Conversely, a decrease in nitrate strongly induced ROL barrier formation, even under aerated conditions. In parallel with ROL barrier formation, suberin lamellae formed at the exodermis. Nitrate deficiency also promoted aerenchyma formation and the enlargement of root diameters. These findings suggest that the severe decline of nitrates under waterlogged conditions is an environmental cue for exodermal suberization to form an ROL barrier in rice roots.

A device for rapid calorimetric measurements on small biological tissue samples

A new calorimetric technique is described that allows high-throughput heat production rate measurements on small biological tissue samples. The technique is based on the widely used thermopile chip technology combined with an innovative method for precise transport and positioning of samples of different biological materials at the thermal power detector inside the calorimeter. The new transport and positioning technique is a combination of fluidic and mechanical transport, where the latter is realized by a magneto-motor drive. The transport facility ensures good diffusive oxygen penetration into the sample, which is essential for highly metabolically active materials. The proper functioning of the device is demonstrated by measuring the heat production of metabolically active brown adipose tissue, biopsied tegu lizard muscle, and live Drosophila larvae at different stages and temperatures.

How quickly does FLASH need to be delivered? A theoretical study of radiolytic oxygen depletion kinetics in tissues

Purpose. Radiation delivered over ultra-short timescales (‘FLASH’ radiotherapy) leads to a reduction in normal tissue toxicities for a range of tissues in the preclinical setting. Experiments have shown this reduction occurs for total delivery times less than a ‘critical’ time that varies by two orders of magnitude between brain (∼0.3 s) and skin (⪆10 s), and three orders of magnitude across different bowel experiments, from ∼0.01 to ⪆(1–10) s. Understanding the factors responsible for this broad variation may be important for translation of FLASH into the clinic and understanding the mechanisms behind FLASH. Methods. Assuming radiolytic oxygen depletion (ROD) to be the primary driver of FLASH effects, oxygen diffusion, consumption, and ROD were evaluated numerically for simulated tissues with pseudorandom vasculatures for a range of radiation delivery times, capillary densities, and oxygen consumption rates (OCR’s). The resulting time-dependent oxygen partial pressure distribution histograms were used to estimate cell survival in these tissues using the linear quadratic model, modified to incorporate oxygen-enhancement ratio effects. Results. Independent of the capillary density, there was a substantial increase in predicted cell survival when the total delivery time was less than the capillary oxygen tension (mmHg) divided by the OCR (expressed in units of mmHg/s), setting the critical delivery time for FLASH in simulated tissues. Using literature OCR values for different normal tissues, the predicted range of critical delivery times agreed well with experimental values for skin and brain and, modifying our model to allow for fluctuating perfusion, bowel. Conclusions. The broad three-orders-of-magnitude variation in critical irradiation delivery times observed in in vivo preclinical experiments can be accounted for by the ROD hypothesis and differences in the OCR amongst simulated normal tissues. Characterization of these may help guide future experiments and open the door to optimized tissue-specific clinical protocols.

Modeling the phase boundaries in Cu(100)-(2√2 × √2)R45°-O missing row reconstruction (MRR) structure

Although the structure of Cu(100)-(22×2)R45°-O missing row reconstruction (MRR) has been well-established for decades, the detailed structure of its various boundaries remains an untilled area due to the difficulties in obtaining atomically resolved images. Herein, atomic arrangement of the phase boundaries existing in MRR structure was modeled on the basis of scanning tunneling microscopy (STM) investigations. By determining the periodicity and unit structure of MRR in STM images and extending them to boundary region, several types of phase boundaries were identified, resulted respectively from: (1) the mismatch between c(2 × 2)-O patches, (2) the regulation by step edges, and (3) the mismatch between Cu missing rows (MRs). With the modeled structure, it was revealed that the types of the c(2 × 2)-O mismatch induced phase boundaries (OMIPBs) are mainly dominated by the oxygen exposure and in-diffusion barrier. The step edge regulated phase boundaries (SERPBs) are always terminated with Cu-O chain and may represent an intermediate growth stage to larger MRR structure. Comparatively, Cu MRs mismatch is often reconciled by the differently oriented domains between them. As a result, the Cu MRs mismatch induced phase boundaries (CMRMIPBs) are only occasionally observed as Cu-O chains between mismatched Cu MRs that encounter shoulder-to-shoulder. For all studied boundaries, the surrounding MRR domains exhibit obvious orientation preference through inclined packing along the SP direction with the degree closely related with the width of the boundaries.

Mesoporous Pdx-Nix aerogels for electrocatalytic evaluation of urea-assisted electrolysis

This work presents the synthesis and evaluation of Pd-Ni aerogels toward the urea oxidation reaction (UOR). The incorporation of Ni led to a 0.13 V reduction in the energy required for the oxidation and reduction of PdO compared to monometallic Pd, both in alkaline medium with and without urea. Varying the Ni ratios in Pd (Pd-Ni 4:1, Pd-Ni 1:1, and Pd-Ni 1:4) led to significant changes in the electrochemical behaviour. In alkaline medium without urea, PdNi 4:1 showed the formation of NiOOH at 1.35 V, which promoted oxygen diffusion on the electrode surface and increased the current density, confirming the increase in the active sites of NiOOH and NiPdOOH and enabling urea-based electrolysis at these sites. While palladium aerogels alone are ineffective for UOR, the presence of nickel plays a key role in enhancing the UOR efficiency. On the other hand, physicochemical characterisation revealed that PdNi 4:1 has a crystal size of 4.37 nm and a larger shift in the 2θ positions of the (111) and (200) planes, which favours electronic changes that were investigated by XPS. These changes affected the electrocatalytic activity, which is primarily related to electronic effects. The results of SEM and TEM studies and nitrogen adsorption-desorption isotherm confirmed that the aerogels are highly porous and have an effective surface area and abundant active sites for reactions that allow efficient mass transfer and low diffusion resistance. TEM observations revealed interconnected nanochains indicating optimal electrocatalytic activity for both ORR and UOR due to high mass transfer. These interconnected networks are crucial for improving electrocatalytic activity in the urea oxidation reaction.