Metal Oxide Surfaces Research Articles

Van der Waals interactions between nonpolar alkyl chains and polar oxide surfaces prevent catalyst deactivation in aldehyde gas sensing

Catalysis-based electrical sensing of volatile organic compounds on metal oxide surfaces is a powerful method for molecular discrimination. However, catalyst deactivation caused by the poisoning of catalytic sites by analytes and/or catalyzed products remains a challenge. This study highlights the underestimated role of van der Waals interactions between hydrophobic aliphatic alkyl chains and hydrophilic ZnO surfaces in mitigating catalyst deactivation during aliphatic aldehyde sensing. By immobilizing octadecylphosphonic acid (ODPA) on ZnO nanowire sensors, recovery times for nonanal detection are significantly reduced without compromising sensitivity. Temperature-programmed measurements demonstrate a reduction in desorption temperature of carboxylates on ODPA-modified ZnO to below 150 °C, whereas carboxylates on bare ZnO remain above 300 °C, indicating a significant decrease in catalyst deactivation. Density functional theory calculations reveal that accumulated van der Waals interactions between alkyl chains and ZnO surfaces significantly contributed to adsorption molecular kinetics. IR spectroscopy using deuterated self-assembled monolayers (SAMs) reveals conformational changes of alkyl chains within the SAMs caused by aldehyde adsorption, supporting the suggested adsorption kinetics. A model is proposed based on the dynamic surface-covering by alkyl chains destabilizes catalytically oxidized carboxylic acids.

Adsorption grand potential of OH on metal oxide surfaces.

Describing chemical processes at solid-liquid interfaces as a function of a fixed electron chemical potential presents a challenge for electronic structure calculations and is essential for understanding electrochemical phenomena. Grand Canonical Density Functional Theory (GCDFT) allows treating solid-liquid interfaces in such a way that studying the influence of a fixed electron potential arises naturally. In this work, GCDFT is used to compute the adsorption grand potential (AGP), a key parameter for understanding and predicting the behavior of adsorbates on surfaces. We focused on the adsorption of an OH molecule on three metallic surfaces commonly used in electrochemical processes, such as the oxygen evolution reaction (OER). Our study aims to offer insights into how AGP can be used to compare adsorption strengths under different fixed electron chemical potentials, which is crucial for designing efficient electrode materials. By determining the average number of electrons self-consistently under varying chemical potentials, we showed how one can distinguish between electron acquisition and depletion during the adsorption process, offering a deeper understanding of the adsorbate-surface interactions. The approach used in this work employs the Kohn-Sham-Mermin formulation of the Grand Canonical Density Functional Theory. The computations were performed using the periodic open-source density functional theory software, JDFTx, with the Garrity-Bennett-Rabe-Vanderbilt library of ultrasoft pseudopotentials. Calculations were made using truncated Coulomb potentials and the auxiliary Hamiltonian method with the PBE exchange-correlation functional, along with DFT-D2 long-range dispersion corrections. The implicit solvation model CANDLE was used to describe the electrolyte with a 1M concentration.

A Procedure for Solid-Phase Extractions Using Metal-Oxide-Coated Silica Column in Lipidomics.

Lipid enrichment is indispensable for enhancing the coverage of targeted molecules in mass spectrometry (MS)-based lipidomics studies. In this study, we developed a simple stepwise fractionation method using a titanium- and zirconium-dioxide-coated solid-phase extraction (SPE) silica column that separates neutral lipids, phospholipids, and other lipids, including fatty acids (FAs) and glycolipids. Chloroform was used to dissolve the lipids, and neutral lipids, including steryl esters, diacylglycerols, and triacylglycerols, were collected in the loading fraction. Second, methanol with formic acid (99:1, v/v) was used to retrieve FAs, ceramides, and glycolipids, including glycosylated ceramides and glycosylated diacylglycerols, by competing for affinity with the Lewis acid sites on the metal oxide surface. Finally, phospholipids strongly retained via chemoaffinity interactions were eluted using a solution containing 5% ammonia and high water content (45:50 v/v, 2-propanol:water), which canceled the electrostatic and chelating interactions with the SPE column. High average reproducibility of <10% and coverage of ∼100% compared to those of the non-SPE samples were demonstrated by untargeted lipidomics of human plasma and mouse brain, testis, and feces. The advantage of our procedure was showcased by characterizing minor lipid subclasses, including dihexosylceramides containing very long-chain polyunsaturated FA in the testis, monogalactosyl and digalactosyl monoacylglycerols in feces, and acetylated and glycolylated derivatives of gangliosides in the brain that were not detected using conventional solvent extraction methods. Likewise, the value of our method in biology is maximized during glycolipidome profiling in the absence of neutral lipids and phospholipids that cover more than 80% of the chromatographic peaks.

“Grafting-from” and “Grafting-to” Poly(N-isopropyl acrylamide) Functionalization of Glass for DNA Biosensors with Improved Properties

Surface-based biosensors have proven to be of particular interest in the monitoring of human pathogens by means of their distinct nucleic acid sequences. Genosensors rely on targeted gene/DNA probe hybridization at the surface of a physical transducer and have been exploited for their high specificity and physicochemical stability. Unfortunately, these sensing materials still face limitations impeding their use in current diagnostic techniques. Most of their shortcomings arise from their suboptimal surface properties, including low hybridization density, inadequate probe orientation, and biofouling. Herein, we describe and compare two functionalization methodologies to immobilize DNA probes on a glass substrate via a thermoresponsive polymer in order to produce genosensors with improved properties. The first methodology relies on the use of a silanization step, followed by PET-RAFT of NIPAM monomers on the coated surface, while the second relies on vinyl sulfone modifications of the substrate, to which the pre-synthetized PNIPAM was grafted to. The functionalized substrates were fully characterized by means of X-ray photoelectron spectroscopy for their surface atomic content, fluorescence assay for their DNA hybridization density, and water contact angle measurements for their thermoresponsive behavior. The antifouling properties were evaluated by fluorescence microscopy. Both immobilization methodologies hold the potential to be applied to the engineering of DNA biosensors with a variety of polymers and other metal oxide surfaces.

Palladium-Functionalized Nanostructured Nickel-Cobalt Oxide as Alternative Catalyst for Hydrogen Sensing Using Pellistors.

To meet today's requirements, new active catalysts with reduced noble metal content are needed for hydrogen sensing. A palladium-functionalized nanostructured Ni0.5Co2.5O4 catalyst with a total Pd content of 4.2 wt% was synthesized by coprecipitation to obtain catalysts with an advantageous sheet-like morphology and surface defects. Due to the synthesis method and the reducible nature of Ni0.5Co2.5O4 enabling strong metal-metal oxide interactions, the palladium was highly distributed over the metal oxide surface, as determined using scanning transmission electron microscopy and energy-dispersive X-ray investigations. The catalyst tested in planar pellistor sensors showed high sensitivity to hydrogen in the concentration range below the lower flammability limit (LFL). At 400 °C and in dry air, a sensor response of 109 mV/10,000 ppm hydrogen (25% of LFL) was achieved. The sensor signal was 4.6-times higher than the signal of pristine Ni0.5Co2.5O4 (24.6 mV/10,000 ppm). Under humid conditions, the sensor responses were reduced by ~10% for Pd-functionalized Ni0.5Co2.5O4 and by ~27% for Ni0.5Co2.5O4. The different cross-sensitivities of both catalysts to water are attributed to different activation mechanisms of hydrogen. The combination of high sensor sensitivity to hydrogen and high signal stability over time, as well as low cross-sensitivity to humidity, make the catalyst promising for further development steps.

Robust Metal Oxide Adhesion Layers for Cellulose Nanofiber-Based QCM Sensors.

Here, we demonstrate the significant role of robust metal oxide adhesion layers on the cellulose nanofiber (CNF)-based quartz crystal microbalance (QCM) humidity sensor characteristics including sensitivity and stability. In this study, we deposited various metal oxide films (NiO, TiO2, ZnO, and WO3) onto QCM Au electrodes as adhesion layers before drop-casting CNF dispersion water. These metal oxide adhesion layers significantly enhanced the stability of CNF films on QCM sensors even in a high-humidity environment where a conventional adhesion layer (polyethylenimine) for CNF could not maintain stable adhesion. There was a significant difference between different metal oxide layers in the QCM data for humidity sensing. We found a negative correlation between the QCM sensitivity and the water wettability of metal oxide surfaces. Morphology analysis of the deposited CNF films revealed that the center-concentrated CNF microstructures on the metal oxide adhesion layers rigorously explained the observed negative correlation between the sensitivity and the wettability of metal oxide surfaces. This trend was further confirmed by gradually changing the hydrophobicity of the NiO adhesion surfaces. Thus, the proposed strategy using robust metal oxide adhesion layers will be a foundation for further development of various CNF-based QCM gas sensors.

Does H2 Temperature‐Programmed Reduction Always Probe Solid‐State Redox Chemistry? The Case of Pt/CeO2

Redox reactions on the surface of transition metal oxides are of broad interest in thermo, photo, and electrocatalysis. H2 temperature‐programmed reduction (H2‐TPR) is commonly used to probe oxide reducibility by measuring the rate of H2 consumption during temperature ramps, assuming that this rate is controlled by oxide reduction. However, oxide reduction involves several elementary steps, such as H2 dissociation and H‐spillover, before surface reduction and H2O formation occur. In this study, we evaluated the kinetics of H2 consumption over CeO2 and Pt/CeO2 with varying Pt loadings and structures to identify the elementary steps probed by H2‐TPR. Literature often attributes changes in H2‐TPR characteristics with Pt addition to increased CeO2 reducibility. However, our analysis revealed that the H2 consumption rate is measurement of the rate of H‐spillover at Pt‐CeO2 interfaces and is determined by the concentration of Pt species on Pt nanoclusters that dissociate H2. Therefore, lower temperature H2 consumption observed with Pt addition does not indicate higher CeO2 reducibility. Measurements on samples with mixtures of Pt single‐atoms and nanoclusters demonstrated that H2‐TPR can effectively quantify dilute Pt nanocluster concentrations, suggesting caution in directly linking H2‐TPR characteristics to oxide reducibility while highlighting alternative material insights that can be gleaned.

Does H2 Temperature-Programmed Reduction Always Probe Solid-State Redox Chemistry? The Case of Pt/CeO2.

Redox reactions on the surface of transition metal oxides are of broad interest in thermo, photo, and electrocatalysis. H2 temperature-programmed reduction (H2-TPR) is commonly used to probe oxide reducibility by measuring the rate of H2 consumption during temperature ramps, assuming that this rate is controlled by oxide reduction. However, oxide reduction involves several elementary steps, such as H2 dissociation and H-spillover, before surface reduction and H2O formation occur. In this study, we evaluated the kinetics of H2 consumption over CeO2 and Pt/CeO2 with varying Pt loadings and structures to identify the elementary steps probed by H2-TPR. Literature often attributes changes in H2-TPR characteristics with Pt addition to increased CeO2 reducibility. However, our analysis revealed that the H2 consumption rate is measurement of the rate of H-spillover at Pt-CeO2 interfaces and is determined by the concentration of Pt species on Pt nanoclusters that dissociate H2. Therefore, lower temperature H2 consumption observed with Pt addition does not indicate higher CeO2 reducibility. Measurements on samples with mixtures of Pt single-atoms and nanoclusters demonstrated that H2-TPR can effectively quantify dilute Pt nanocluster concentrations, suggesting caution in directly linking H2-TPR characteristics to oxide reducibility while highlighting alternative material insights that can be gleaned.

Anchoring Frustrated Lewis Pair Active Sites on Copper Nanoclusters for Regioselective Hydrogenation.

In recent years, the concept of Frustrated Lewis Pairs (FLPs), which consist of a combination of Lewis acid (LA) and Lewis base (LB) active sites arranged in a suitable geometric configuration, has been widely utilized in homogeneous catalytic reactions. This concept has also been extended to solid supports such as zeolites, metal oxide surfaces, and metal/covalent organic frameworks, resulting in a diverse range of heterogeneous FLP catalysts that have demonstrated notable efficiency and recyclability in activating small molecules. This study presents the successful immobilization of FLP active sites onto the surface of ligand-stabilized copper nanoclusters with atomic precision, leading to the development of copper nanocluster FLP catalysts characterized by high reactivity, stability, and selectivity. Specifically, thiol ligands containing 2-methoxyl groups were strategically designed to stabilize the surface of [Cu34S7(RS)18(PPh3)4]2+ (where RSH = 2-methoxybenzenethiol), facilitating the formation of FLPs between the surface copper atoms (LA) and ligand oxygen atoms (LB). Experimental and theoretical investigations have demonstrated that these FLPs on the cluster surface can efficiently activate H2 through a heterolytic pathway, resulting in superior catalytic performance in the hydrogenation of alkenes under mild conditions. Notably, the intricate yet precise surface coordination structures of the cluster, reminiscent of enzyme catalysts, enable the hydrogenation process to proceed with nearly 100% selectivity. This research offers valuable insights into the design of FLP catalysts with enhanced activity and selectivity by leveraging surface/interface coordination chemistry of ligand-stabilized atomically precise metal nanoclusters.

Insights into the synergistic effects between deposited Fe oxides and dissolved organic matter in influencing perfluorooctanoic acid transport in saturated porous media

Perfluorooctanoic acid (PFOA) transport in the subsurface environment is relevant to drinking water safety, while the compounding effects of soil components on PFOA migration are poorly understood. Laboratory miscible-displacement experiments were conducted using saturated sand columns to explore how metal oxide surfaces and dissolved organic matter (DOM) jointly affect PFOA transport in porous media. Retardation factors indicated that Fe oxide coating inhibited PFOA migration due to electrostatic interaction. However, PFOA recovery rates changed insignificantly, decreasing by less than 4 % when the proportion of Fe oxide-coated sand reached 50 %. DOM (1 mg/L humic acid) in the pore water slightly decreased PFOA recovery rates (by about 10 %) in quartz sand, indicating the effect of hydrophobic interaction on PFOA migration. When the PFOA solution containing 1 mg/L humic acid was injected into the column containing Fe oxide-coated sand, PFOA recovery was significantly decreased by nearly 20 %, and the retardation factor was more than doubled. This could be attributed to the stronger hydrophobic effect provided by the higher DOM deposition on the Fe oxide surface. These results, supported by SEM-EDS, zeta potential, and model fitting data, highlight the microscopic mechanisms by which interactions between metal oxides and DOM influence PFOA transport. However, this inhibitory effect disappeared at higher humic acid concentrations (20 mg/L), indicating the risk of PFOA re-migration when the DOM concentration greatly exceeds the adsorption capacity of the media for it. The findings of this work have implications for predicting or controlling the environmental risks of PFOA in soil and groundwater.

Elusive supported surface M2Ox dimer active site (M = Re, W, Mo, Cr, V, Nb, and Ta)

Supported transition metal oxide catalysts are extensively used as heterogeneous catalysts for various energy, chemical, and environmental applications. The molecular structures of dehydrated surface metal oxide phases are crucial for understanding structure-activity/selectivity relationships that guide the design of enhanced catalysts. Some early studies suggested that dimeric (aka binuclear) surface metal oxide sites were more active/selective than monomeric (aka mononuclear) sites, prompting interest in synthesizing catalysts with supported dimeric metal oxide structures. This review examines the literature on dehydrated silica-based supported group 7-5 MOx catalysts (ReOx, WOx, MoOx, CrOx, VOx, NbOx, and TaOx on SiO2, MCM-41, AlOx/SiO2, and H-ZSM-5) for their surface metal oxide structures. In situ Raman, extended x-ray absorption fine structure, and ultraviolet-visible spectroscopy indicate that monomeric surface MOx structures predominate in all such catalysts. Therefore, the cursory use of dimeric surface M2Ox sites in catalytic mechanisms and reaction models in heterogeneous catalysis by supported metal oxides is questionable, and moving forward, the invoking of supporting dimeric surface M2Ox sites should be critically examined and backed up with direct spectroscopic methods.

Biogenic fabrication of NiO-ZnO-CaO ternary nanocomposite using Azadirachta Indica (Neem) leaves extract with proficient photocatalytic degradation of rhodamine B dye

In the current study, a ternary nanocomposite (NiO–ZnO–CaO) was successfully synthesized through the co-precipitation method using Azadirachta Indica (neem) leaves extract as green approach. The characterization of prepared nanocomposite was conducted using FT-IR, XRD, SEM and EDS to determine the metal oxides absorption bands, structural properties, elemental composition, and surface morphology of the nanocomposite. FT-IR analysis revealed characteristic vibrational peaks at 621, 684, and 721 cm−1, corresponding to Ni-O, Zn-O, and Ca-O bond vibrations, respectively. XRD patterns showed distinct diffraction peaks, indicative of the hexagonal structure of ZnO and the cubic structures of NiO and CaO. EDS analysis confirmed the presence of calcium, nickel, zinc, and oxygen with weight percentages of 9.2%, 14.4%, 15.1%, and 20.9%, respectively. SEM images displayed an irregular cube like morphology with noticeable clustering within the nanocomposite. The ternary nanocomposite was employed as photocatalyst and exhibited degradation efficiency (97%) against rhodamine B dye under 180 min of irradiation time. The kinetic studies of dye on the photocatalyst surface were accurately explained by a first-order kinetics model, with all R2 &gt; 95, signifying a strong correlation between time and dye concentration. The potocatalytic degradation mechanism of ternary nanocomposite was proposed based on band positions of of NiO, ZnO and CaO forming double type II heterojunction. Furthermore, species trapping experiments employing different scavengers were carried out, revealing the active participation of OH● and O2●─ radicals in the degradation mechanism.

CO2 hydrogenation to light olefins over highly active and selective Ga-Zr/SAPO-34 bifunctional catalyst

The production of light olefins from the hydrogenation of CO2 is an efficient way to utilize CO2, where the surface oxygen vacancy in metal oxide plays an important role in CO2 adsorption and activation. Here, the Ga-Zr metal oxides were prepared by hydrolysis of urea at different temperatures and combined with SAPO-34 to prepare the bifunctional catalyst for CO2 hydrogenation to light olefins. The surface oxygen vacancy content of Ga-Zr oxide increases with increasing urea hydrolysis temperature, and a high CO2 conversion of 26.4% and C2=–C4= hydrocarbon selectivity of 87.2% were obtained by a well-matched amount of desorbed CO2 and H2. Using the CO2 and H2/HCOOH/CH3OH as probe molecules, the in-situ DRIFT spectra reveal that the CO2 could be activated on surface oxygen vacancy and converted to CO3* and HCO3* species, which were further hydrogenated to HCOO* and CH3O* species. While the by-product CO mainly originates from the decomposition of HCOO* and the presence of SAPO-34 converts CH3O* to C2=–C4=. The current study illustrates that boosting the surface oxygen vacancy in defected surfaces of metal oxide and providing a matching H2 dissociation ability is the key to improve the performance of CO2 hydrogenation to light olefins.

Chemistry of Formate and Water Ligands on Metal Oxide Cluster Nodes of Metal-Organic Framework hcp Hf-UiO-66: Keys to Understanding Reactivity of Paired μ2-OH and Defect Sites.

Many metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters, and ligands that have been observed on these nodes include formates, acetates, water, hydroxyl groups, and others, all of which are potentially important in affecting reactivities for applications in separations, catalysis, and sensing. Formate is a common node ligand, arising from formic acid used as a modulator and from N,N-dimethylformamide used as a solvent in MOF syntheses. Yet only little work has been reported characterizing the reactivities of node formate ligands. Infrared spectra reported here show that formate bonds to two types of sites on the paired Hf6O8 nodes of hcp UiO-66, namely, defect and μ2-OH sites. Quantifying the number of formate ligands by 1H NMR spectroscopy of digested samples showed an almost equal number of formate ligands on the two sites, indicating the likelihood that they neighbor each other. These formate ligands interact with water molecules, reversibly switching their bonding from bidentate to monodentate. The formates on μ2-OH sites of hcp Hf-UiO-66 interact much more strongly with water than those on defect sites of the same node, and both interact more strongly than isolated defect sites of Hf-UiO-66. Correspondingly, the catalytic activities of hcp UiO-66 determined as turnover frequencies on each site are approximately twofold higher than those on UiO-66, bolstering the inference that methanol dehydration is catalyzed by a node defect site and a neighboring node μ2-OH site. The results show how MOFs, with their well-defined node structures, provide unprecedented opportunities to understand details of reactivities and catalysis on metal oxide clusters, in contrast to bulk metal oxide surfaces.

Hydrogen reduction and baking process of Pb-silicate microchannel plate and their performance studies

Microchannel plate (MCP) are honeycomb structures consisting of numerous parallel, hollow micro glass fiber channels renowned for their exceptional secondary electron multiplication. This paper investigates changes in MCP properties under hydrogen reduction temperatures ranging from 300 °C to 500 °C. The findings reveal that higher temperatures reduce surface metal oxides, which then accumulate within and darken the microchannels, affecting electron transport. Bulk resistance decreases before increasing, while gain increases and then decreases. At 350 °C, lead oxide begins to reduce to its conductive state, enhancing electron multiplication. However, increased temperatures cause clustering and roughening of the inner channel walls, which diminishes the efficiency of secondary electron release. These alterations are associated with the reduction dynamics of lead ions and temperature-induced microstructural changes. As the hydrogen reduction temperature increases, internal stresses shift outward, and the uniformity of gain varies, reaching its peak at 400 °C. Additionally, an aluminum oxide film enhances resistance to baking and ensures consistent bulk resistance. This study elucidates the relationship between MCP performance and reduction temperature, providing valuable insights for design improvement.

A durable superhydrophobic surface with bud-particle structure prepared by one-step spray method

Superhydrophobic surfaces play an essential role in numerous applications such as anti-fouling, waterproofing, and drag reduction due to their water-repellent. However, for most fabrication methods, there are high requirements for the preparation process and conditions. Meanwhile, the superhydrophobic surfaces generally have the problem of insufficient durability. In this study, a one-step method to fabricate a stable superhydrophobic surface by spraying is proposed. A new bud-particle structure is obtained by modifying micron and nano Aluminium hydroxide(Al(OH)3) particles, which helps the coated surface to demonstrate excellent superhydrophobicity with the water contact angle ∼157.0° and rolling angle ∼2.0°, and it shows great repellency to water droplet impact. Due to the compatibility of Al(OH)3with the pretreatment substrate and the reinforcing effect of nanoparticles, the coating maintained the superhydrophobicity well in the sandpaper wear and the ultrasonic damage test, which reflects the outstanding robustness of the coating.Moreover,benefiting from the control of the wetting state by micronand nanoparticles doping,the coating showed an excellent underwater drag reduction effect in the rheometer experiment, with a drag reduction rate of ∼67.7 %. The one-step spraying method proposed is a simple and convenient way to create the surface with excellent superhydrophobicity and durability, which has great potential applications in improving metal surface oxidation resistance and underwater reducing drag.

MOF-derived metal oxides with hollow porous nanocube structure realize ultra-wideband, lightweight, and anticorrosion microwave absorber

High density, skin effect, and environmental instability are significant limitations that restrict the application of metal-based microwave absorbers in achieving lightweight, high performance, and long service life. This study broke from traditional methods for preparing a microwave absorber Mn2O3-Fe3O4@PPy (polypyrrole) by employing an innovative annealing process to convert metal into metal oxide by the introduction of metal organic framework (MOF), which effectively achieving a more lightweight absorber material with hollow porous nanocube structure. Subsequently, PPy was coated onto the metal oxide surface to form a core-shell structure by a situ chemical oxidation synthesis method. The combination of metal oxide of the hollow porous nanocube structure and the core-shell structure formed by highly conductive PPy shell significantly enhanced heterogeneous interfaces and electromagnetic (EM) wave reflection. Excellent dielectric loss and impedance matching contributed evidently to the ultra-wideband EM wave absorption performance. It was demonstrated that, with a filling amount of only 20 wt%, the prepared Mn2O3-Fe3O4@PPy achieved an effective bandwidth (EAB) of 10.0 GHz at a thickness of 3.08 mm, with EABmax reaching 13 GHz. At a filling amount of only 10 wt%, the reflection loss (RL) was −62.13 dB, achieving an EAB of 7.4 GHz at 2.98 mm thickness, with EABmax reaching 11.4 GHz. Furthermore, the proposed strategy incorporating metal oxide and PPy enhanced corrosion resistance with higher charge transfer resistance.

Water Vapor Adsorption-Desorption Hysteresis Due to Clustering of Water on Nonporous Surfaces.

Water vapor is continuously adsorbed onto and desorbed from all kinds of surfaces depending on changes in relative humidity. Adsorption-desorption hysteresis of water that occurs on various nonporous surfaces and extends down to low relative humidities has been reported for decades, but remains unexplained. Here we show experimentally that such hysteresis is a common phenomenon on metal oxide and mineral surfaces and can be divided into two distinct categories based on the wettability of the adsorbent surface. Type I hysteresis occurs on more hydrophobic surfaces and is associated with adsorption isotherms that behave rather linearly as water saturation is approached, whereas type II hysteresis occurs on more hydrophilic surfaces and is associated with adsorption isotherms that curve steeply upward close to saturation. Our model calculations strongly indicate that adsorption in both types occurs cluster-wise, and the type I hysteresis is caused by contact angle hysteresis, while type II hysteresis is associated with film formation close to saturation. The understanding of water vapor adsorption and desorption mechanisms may be key for explaining and quantifying physical and chemical interfacial phenomena in atmospheric and industrial environments.

Reverse Hydrogen Spillover on Metal Oxides for Water-Promoted Catalytic Oxidation Reactions.

Understanding the water-involved mechanism on metal oxide surface and the dynamic interaction of water with active sites is crucial in solving water poisoning in catalytic reactions. Herein, this work solves this problem by designing the water-promoted function of metal oxides in the ethanol oxidation reaction. In situ multimodal spectroscopies unveil that the competitive adsorption of water-dissociated *OH species with O2 at Sn active sites results in water poisoning and the sluggish proton transfer in CoO-SnO2 imparts water-resistant effect. Carbon material as electron donor and proton transport channel optimizes the Co active sites and expedites the reverse hydrogen spillover from CoO to SnO2. The water-promoted function arises from spillover protons facilitating O2 activation on the SnO2 surface, leading to crucial *OOH intermediate formation for catalyzing C-H and C-C cleavage. Consequently, the tailored CoO-C-SnO2 showcases a remarkable 60-fold enhancement in ethanol oxidation reaction compared to bare SnO2 under high-humidity conditions.

Performance of mesoporous ceria supported Ru catalysts for oxidative degradation of aqueous solution of plastic monomer bisphenol A in a fixed bed flow reactor: Structure-activity insights, optimization of reaction conditions, kinetics, catalyst stability, and characterization

One of the important defects is the oxygen vacancy on metal oxide surfaces, and the defects function as the active sites in different catalytic reactions. Herein, Ru/CeO2-rod and Ru/CeO2-cube catalysts were prepared via the ESI method, and CeO2-rod and CeO2-cube supports were synthesized by hydrothermal processes. The activity of these catalysts was tested in a high-pressure fixed-bed reactor, and the oxidative degradation of industrial organic raffinate containing the plastic chemical bisphenol A (BPA) was compared with their oxygen vacancy concentration estimated after calcination. The Ru/CeO2-rod catalyst showed higher catalytic activity with 90 % BPA conversion at 453 K, 30 bar, 0.5 % Ru metal content, 15 O2 to BPA molar ratio, and 2 g−1.h−1 BPA feed weight hourly space velocity (WHSV). In contrast, 80 % BPA degradation was achieved using the Ru/CeO2-cube catalyst under similar reaction conditions. The higher oxygen vacancy concentration and the higher interfacial surface area between metal and the support of the CeO2-rod supported Ru catalyst triggered the higher BPA degradation at low oxidation conditions. Besides, the atomic ratio, Ce3+/Ce4+, is lower in the Ru/CeO2-rod catalyst than that of the Ru/CeO2-cube catalyst, indicating the higher Ce4+ available in the catalyst, leading to the higher degradation of BPA. Moreover, the Ru/CeO2-rod catalyst possesses {111} planes that boost the generation of energetic Ru to improve the pursuit of the catalyst. The Weisz-Prater modulus and Thiele modulus values indicated that the surface reaction is the rate limitation step and there is no diffusion limitation. TEM, HRTEM, XPS, Raman, H2-TPR, XRD, CO chemisorption and BET surface area analyzers were used to characterize the catalysts.