Reactive Gas Research Articles

The impact of internal climate variability on OH trends between 2005 and 2014

The hydroxyl radical (OH) lies at the nexus of climate and air quality as the primary oxidant for both reactive greenhouse gases and many hazardous air pollutants. To better understand the role of climate variability on spatiotemporal patterns of OH, we utilize a 13-member ensemble of the Community Earth System Model version 2-Whole Atmosphere Community Climate Model version 6 (CESM2-WACCM6), a fully coupled chemistry-climate model, spanning the years 1950–2014. Ensemble members vary only in their initial conditions of the climate state in 1950. We focus on the final decade of the simulation, 2005–2014, when prior studies disagree on the signs of the global OH trends. The ensemble mean global airmass-weighted mean tropospheric column OH ( ΩTOH ), which is an estimate of the forced signal, increases by 0.06%/year between 2005 and 2014 while regional ΩTOH trends range from −0.56%/year over Southern Europe to +0.64%/year over South America. We show that ten-year ΩTOH trends are strongly affected by internal climate variability, as the spread of ΩTOH trends across the ensemble varies between 0.23%/year in Asia and 1.53%/year in South America. We train a fully connected neural network to emulate the ΩTOH simulated by the CESM2-WACCM6 model and combine it with satellite observations to interpret the role of OH chemical proxies. While the OH chemical proxies are subject to internal variability, the impact of internal variability on ΩTOH trends is primarily due to the meteorological parameters except for South America. Forced trends in global mean ΩTOH do not unambiguously emerge from trends driven by internal variability over the 2005–2014 period. The observation-constrained ΩTOH presents opposite trends due to climate variability, resulting in varying conclusions on the attribution of OH to CH4 trends.

Investigation of Proton Exchange Membrane Fuel Cell Performance by Exploring the Synergistic Effects of Reaction Parameters via Power Curve and Impedance Spectroscopy Analysis

In this paper, a comprehensive analysis of the parameters that affect polymer electrolyte membrane fuel-cell performance is presented. Experiments were conducted on a single fuel cell membrane with an active area of 5 cm2. To study the fuel cell operation, parametric studies of temperature, pressure and relative humidity values were conducted under cyclic voltammetry for impedance analysis. The impact of the behavior of all three parameters on the fuel-cell performance were recorded and analyzed. As the temperature increased from 50 °C to 74 °C, the Pt catalyst surface areas demonstrated lower activation losses as the membrane conductivity increased. It is confirmed that an increase in temperature accompanied higher humidity levels to provide sufficient cell hydration that resulted in a higher performance output. The impedance measurements indicate that low humidity levels resulted in higher cell resistance and mass transport losses. As the back pressure increased, the membrane resistance decreased, which also reduced mass transport losses. The results indicate that the important factors affecting the fuel cell performance are mass transport limitation and membrane resistance. Based on the results of this study, the optimum performance can be achieved by operating at higher pressures and temperatures with humidified reactant gases.

MieAI: a neural network for calculating optical properties of internally mixed aerosol in atmospheric models

Aerosols influence weather and climate by interacting with radiation through absorption and scattering. These effects heavily rely on the optical properties of aerosols, which are mainly governed by attributes such as morphology, size distribution, and chemical composition. These attributes undergo continuous changes due to chemical reactions and aerosol micro-physics, resulting in significant spatio-temporal variations. Most atmospheric models struggle to incorporate this variability because they use pre-calculated tables to handle aerosol optics. This offline approach often leads to substantial errors in estimating the radiative impacts of aerosols along with posing significant computational burdens. To address this challenge, we introduce a computationally efficient and robust machine learning approach called MieAI. It allows for relatively inexpensive calculation of the optical properties of internally mixed aerosols with a log-normal size distribution. Importantly, MieAI fully incorporates the variability in aerosol chemistry and microphysics. Our evaluation of MieAI against traditional Mie calculations, using number concentrations from the ICOsahedral Nonhydrostatic model with Aerosol and Reactive Trace gases (ICON-ART) simulations, demonstrates that MieAI exhibits excellent predictive accuracy for aerosol optical properties. MieAI achieves this with errors well within 10%, and it operates more than 1000 times faster than the benchmark approach of Mie calculations. Due to its generalized nature, the MieAI approach can be implemented in any chemistry transport model which represents aerosol size distribution in the form of log-normally distributed internally mixed modes. This advancement has the potential to replace frequently employed look-up tables and plays a substantial role in the ongoing attempts to reduce uncertainties in estimating aerosol radiative forcing.

Optical properties of low-pressure DC Ar plasma torch with N2–SiH4–B2H6 gas mixture injection for Si–B–N thin film deposition

Si–B–N ceramic hard films were prepared by injecting N2+SiH4+B2H6 reaction gas into an argon DC arc plasma jet at reduced pressure. XPS, FT-IR, SEM, and microhardness tester were used to characterize the samples, and the optical properties of Ar discharge plasma jet with and without reaction gas injection were studied by a multichannel high-resolution spectroscopy and a wide spectral range spectroscopy. It is found that the deposited films are mainly composed of Si, B, N and O. The film surface presents a dense structure with hundred-nanometer-sized clusters, and the hardness of sample is greatly enhanced. When the reaction gas is injected into the plasma jet, the emission of excited atoms in the background plasma is greatly reduced, and the growth rate of Si–B–N film shows a significant downward trend as the reaction gas injection ring or substrate holder is moved away from the torch nozzle. A slight enhancement of background plasma emission is observed near the substrate surface with increasing the distance between gas injection ring and torch nozzle, which indicates that the suppression effect of the reactive gas injection on the background plasma emission and the activation efficiency of the reaction gas are weakened, thereby reducing the deposition rate.

Visualizing the gas-sensitive structure of the CuZn surface in methanol synthesis catalysis

Methanol formation over Cu/ZnO catalysts is linked with a catalytically active phase created by contact between Cu nanoparticles and Zn species whose chemical and structural state depends on reaction conditions. Herein, we use variable-temperature scanning tunneling microscopy at elevated pressure conditions combined with X-ray photoelectron spectroscopy measurements to investigate the surface structures and chemical states that evolve when a CuZn/Cu(111) surface alloy is exposed to reaction gas mixtures. In CO2 hydrogenation conditions, Zn stays embedded in the CuZn surface, but once CO gas is added to the mixture, the Zn segregates onto the Cu surface. The Zn segregation is CO-induced, and establishes a new dynamic state of the catalyst surface where Zn is continually exchanged at the Cu surface. Candidates for the migrating few-atom Zn clusters are further identified in time-resolved imaging series. The findings point to a significant role of CO affecting the distribution of Zn in the multiphasic ZnO/CuZn/Cu catalysts.

Technical note: Characterization of a single-beam gradient force aerosol optical tweezer for droplet trapping, phase transition monitoring, and morphology studies

Abstract. Single particle analysis is essential for a better understanding of the particle transformation process and to predict its environmental impact. In this study, we developed an aerosol optical tweezer (AOT) Raman spectroscopy system to investigate the phase state and morphology of suspended aerosol droplets in real time. The system comprises four modules: optical trapping, reaction, illumination and imaging, and detection. The optical trapping module utilizes a 532 nm laser and a 100 × oil immersion objective to stably trap aerosol droplets within 30 s. The reaction module allows us to adjust relative humidity (RH) and introduce reaction gases into the droplet levitation chamber, facilitating experiments to study liquid–liquid phase transitions. The illumination and imaging module employs a high-speed camera to monitor the trapped droplets, while the detector module records Raman scattering light. We trapped sodium chloride (NaCl) and 3-methyl glutaric acid (3-MGA) mixed droplets to examine RH-dependent morphology changes. Liquid–liquid phase separation (LLPS) occurred when RH was decreased. Additionally, we introduced ozone and limonene/pinene to generate secondary organic aerosol (SOA) particles in situ, which collided with the trapped droplet and dissolved in it. To determine the trapped droplet's characteristics, we utilized an open-source program based on Mie theory to retrieve diameter and refractive index from the observed whispering gallery modes (WGMs) in Raman spectra. It is found that mixed droplets formed core–shell morphology when RH was decreased, and the RH dependence of the droplets' phase transitions generated by different SOA precursors varied. Our AOT system serves as an essential experimental platform for in situ assessment of morphology and phase state during dynamic atmospheric processes.

Large time existence and asymptotic stability of the generalized solution to flow and thermal explosion model of reactive real micropolar gas

We study the long time behavior of the generalized solution of the flow and thermal explosion model of the reactive real micropolar gas. The dynamics of the chemical reaction involved and the usual laws of conservation of mass, momentum, angular momentum, and energy generate a complex governing system of partial differential equations. The fluid is nonideal and non‐Newtonian. In this work, we prove that the problem can be solved in an infinite time domain and establish the asymptotic properties of the solution. Namely, we conclude that for certain parameter values, the solution stabilizes exponentially to a steady‐state solution, while for others the stabilization occurs but at power decay rate. At the end, we conducted a few numerical tests whereby we experimentally confirmed theoretical findings about long‐term behavior of the solution.

Tantalum-doped tin oxide thin films using hollow cathode gas flow sputtering technology

SnO2 and tantalum doped SnO2 (TTO) thin films were prepared using reactive hollow cathode gas flow sputtering (GFS) on glass substrates. An in-situ heating process under vacuum preceded the sputtering. The resistivity of the tin oxide films was reduced to a remarkable low of 2.02 × 10−3 Ω cm, with a carrier concentration of 2.55 × 1020 cm−3 and a mobility of 12.11 cm2V−1s−1. As the substrate temperature increased, the film resistivity decreased. Notably, at a substrate temperature of 270 °C, the effect of Ta doping on the film resistivity and carrier concentration was significantly stronger compared to higher temperatures. Elevating the substrate temperature and Ta doping resulted in a lower refractive index (n). This effect was consistently strong at higher temperatures, attributed to the higher film-free carrier concentration (4.54 × 1020 cm−3) compared to lower temperatures (2.35 × 1020 cm−3). The film's structure was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and atomic force microscope (AFM). The preferred direction of film growth was discussed. The successful and reproducible fabrication of tin oxide films underscores the advantages of gas flow sputtering (GFS) technology. GFS offers stable operating conditions across various oxygen flow levels without requiring target oxidization control, as is required in magnetron sputtering when managing gas status and film quality.

Impacts assessment of nitrification inhibitors on U.S. agricultural emissions of reactive nitrogen gases

Fertilizer-intensive agriculture leads to emissions of reactive nitrogen (Nr), posing threats to climate via nitrous oxide (N2O) and to air quality and human health via nitric oxide (NO) and ammonia (NH3) that form ozone and particulate matter (PM) downwind. Adding nitrification inhibitors (NIs) to fertilizers can mitigate N2O and NO emissions but may stimulate NH3 emissions. Quantifying the net effects of these trade-offs requires spatially resolving changes in emissions and associated impacts. We introduce an assessment framework to quantify such trade-off effects. It deploys an agroecosystem model with enhanced capabilities to predict emissions of Nr with or without the use of NIs, and a social cost of greenhouse gas to monetize the impacts of N2O on climate. The framework also incorporates reduced-complexity air quality and health models to monetize associated impacts of NO and NH3 emissions on human health downwind via ozone and PM. Evaluation of our model against available field measurements showed that it captured the direction of emission changes but underestimated reductions in N2O and overestimated increases in NH3 emissions. The model estimated that, averaged over applicable U.S. agricultural soils, NIs could reduce N2O and NO emissions by an average of 11% and 16%, respectively, while stimulating NH3 emissions by 87%. Impacts are largest in regions with moderate soil temperatures and occur mostly within two to three months of N fertilizer and NI application. An alternative estimate of NI-induced emission changes was obtained by multiplying the baseline emissions from the agroecosystem model by the reported relative changes in Nr emissions suggested from a global meta-analysis: −44% for N2O, −24% for NO and +20% for NH3. Monetized assessments indicate that on an annual scale, NI-induced harms from increased NH3 emissions outweigh (8.5–33.8 times) the benefits of reducing NO and N2O emissions in all agricultural regions, according to model-based estimates. Even under meta-analysis-based estimates, NI-induced damages exceed benefits by a factor of 1.1–4. Our study highlights the importance of considering multiple pollutants when assessing NIs, and underscores the need to mitigate NH3 emissions. Further field studies are needed to evaluate the robustness of multi-pollutant assessments.

Morphology evolution and non-uniformity removal mechanism analysis of diamond nanocone arrays by reactive ion etching

Microstructures of diamond can be fabricated by reactive ion etching and during this process the evolution of surface morphology can affect the electric field near the microstructure. These changes in the electric field will alter the trajectory of ions, thereby affecting the number of ion bombardments on the surface regions of the microstructure. Consequently, this will affect the removal rate of the material on the microstructure surface and consequently affects the evolution of microstructure morphology. In order to understand the morphology evolution process of diamond during etching. H2 and Ar were used as the reactive gases to etch the nanocrystalline diamond (NCD) films with masks. The electric field near the microstructure and the trajectories of reactive ions was stimulated. The number of H+ and Ar+ bombardments at various regions on the diamond microstructure surface has been recorded and analyzed. By observing the cross-sectional morphology of the microstructure at different periods, the etching process of nanocones was analyzed. The study found that the microstructure of the diamond surface would gradually be etched into convex shaped and waist drum shaped and cone. By stimulating the electric field near the microstructure, it was found that the electric field distorted near the microstructure, causing the electric field lines initially perpendicular to the diamond surface to be diverted. As a result, the trajectory of the particles originally arrived perpendicularly to the diamond surface was distorted and hence they bombarded against the sidewall of the diamond microstructures. The angle between the ion trajectory and the electric field line also increased gradually.

Numerical study on improved mass and heat transfer performance in a solid oxide electrolysis cell with sine wave flow field

In this paper, the periodic variation of sine wave is used to promote the transport and diffusion process of reactive gases; and the relationship between the performance of a solid oxide electrolysis cell (SOEC) and the mass and heat transfer capabilities of its flow field is thoroughly examined. The impact of variations in the amplitude and frequency of the sine wave on the SOEC's electrolysis efficiency, its mass and heat transfer properties, and fluid flow dynamics are explored. The results indicate that longitudinal flow velocity of the gas in the sine wave flow channel is increased by 26.96–80.76% at a current density of 10000 A/m2, and this kind of flow channel exhibits superior gas transport performance. Moreover, the temperature-uniformity index and the maximum thermal stress of the positive-electrolyte-negative (PEN) structure are decreases by 18.93–22.67% and 20%, respectively. It indicates that this configuration is capable of reducing thermal stress and enhancing the uniformity of temperature distribution at high current-densities. Increasing the amplitude and frequency improves the comprehensive performance of the flow field. More specifically, frequency has a greater impact on flow field performance than amplitude.

Combined ns pulsed-RF excitation and impedance matching considerations for the production of moderate E/n atmospheric pressure discharges for gas conversion

Sub-breakdown radiofrequency (RF) discharges enabled by a nanosecond (ns) pulse ignition source are studied at atmospheric pressure in a range of gas mixtures from completely inert (in Ar) to completely reactive (in CO2). An electrical characterisation of the continuous wave (CW) RF discharge (13.56 MHz) is performed to determine plasma impedance and plasma power dissipation. Two different measurement methods to electrically characterize the system are described and compared. One method uses in-situ measurements of discharge parameters (voltage, current and the phase angle), and the other method performs ex-situ measurements of the load circuit using a vector network analyser. It was found that RF plasma power deposition depended on the applied RF power as well as the gas mixture composition. Using the in-situ voltage, current and phase angle measurements, plasma power deposition was calculated to be as much as 85% and 76% of the applied RF power for the pure Ar and pure CO2 cases, respectively. A preliminary qualitative assessment of the plasma composition was performed by optical emission spectroscopy, and CO2 conversion by mass spectrometry. CO2 to CO conversions of 11.2% and 5.5% in a 20:80 (CO2:Ar) mixture and in 100% CO2, respectively, were observed. This study demonstrates a RF plasma source for gas conversion applications at atmospheric pressure in a completely reactive gas.

Ultrathin and Deformable Graphene Etch Mask for Fabrication of 3D Microstructures.

Three-dimensional (3D) microfabrication techniques play a crucial role across various research fields. These techniques enable the creation of functional 3D structures on the microscale, unlocking possibilities for diverse applications. However, conventional fabrication methods have limits in producing complex 3D structures, which require numerous fabrication steps that increase the costs. Graphene is an atomically thin material known for its deformability and impermeability to small gases and molecules, including reactive gases like XeF2. These features make graphene a potential candidate as an etch mask for 3D microfabrication. Here, we report the fabrication of various 3D microstructures using graphene etch masks directly grown and patterned on a Si substrate. The patterned graphene deforms and wraps the etched structures, allowing for the fabrication of complicated 3D microstructures, such as mushroom-like and step-like microstructures. As a practical demonstration of the graphene etch mask, we fabricate an omniphobic surface of reentrant 3D structures on a Si substrate. Our work provides a method for fabricating complex 3D microstructures using a graphene etch mask, contributing to advancements in etching and fabrication processes.

Nitric oxide signaling through three receptors regulates virulence, biofilm formation, and phenotypic heterogeneity of Legionella pneumophila.

The highly reactive diatomic gas molecule nitric oxide (NO) is produced by eukaryotes and bacteria to promote short-range and transient signaling within and between neighboring cells. Despite its importance as an inter-kingdom and intra-bacterial signaling molecule, the bacterial response and the underlying components of the signaling pathways are poorly characterized. The environmental bacterium Legionella pneumophila forms biofilms and replicates in protozoan and mammalian phagocytes. L. pneumophila harbors three putative NO receptors, one of which crosstalks with the Legionella quorum sensing (Lqs)-LvbR network to regulate various bacterial traits, including virulence and biofilm architecture. In this study, we used pharmacological, genetic, and cell biological approaches to assess the response of L. pneumophila to NO and to demonstrate that the putative NO receptors are implicated in NO detection, bacterial replication in phagocytes, intracellular phenotypic heterogeneity, and biofilm formation.

Zirconium Oxynitride Thin Films for Photoelectrochemical Water Splitting.

Transition metal oxynitrides are a promising class of functional materials for photoelectrochemical (PEC) applications. Although these compounds are most commonly synthesized via ammonolysis of oxide precursors, such synthetic routes often lead to poorly controlled oxygen-to-nitrogen anion ratios, and the harsh nitridation conditions are incompatible with many substrates, including transparent conductive oxides. Here, we report direct reactive sputter deposition of a family of zirconium oxynitride thin films and the comprehensive characterization of their tunable structural, optical, and functional PEC properties. Systematic increases of the oxygen content in the reactive sputter gas mixture enable access to different crystalline structures within the zirconium oxynitride family. Increasing oxygen contents lead to a transition from metallic to semiconducting to insulating phases. In particular, crystalline Zr2ON2-like films have band gaps in the UV-visible range and are n-type semiconductors. These properties, together with a valence band maximum position located favorably relative to the water oxidation potential, make them viable photoanode candidates. Using chopped linear sweep voltammetry, we indeed confirm that our Zr2ON2 films are PEC-active for the oxygen evolution reaction in alkaline electrolytes. We further show that high-vacuum annealing boosts their PEC performance characteristics. Although the observed photocurrents are low compared to state-of-the-art photoanodes, these dense and planar thin films can offer a valuable platform for studying oxynitride photoelectrodes, as well as for future nanostructuring, band gap engineering, and defect engineering efforts.

Dust Transport from North Africa to the Middle East: Synoptic Patterns and Numerical Forecast

Every year, large quantities of dust are transported from North Africa to the Americas, Europe, and West Asia. The purpose of this study is to analyze four intense and pervasive dust storms that entered the Middle East from Northern Africa. Satellite products, ground-based remote sensing measurements, reanalysis data, and the outputs of the Aire Limitée Adaptation dynamique Développement InterNational-Dust (ALADIN-Dust) and the ICOsahedral Nonhydrostatic weather and climate model with Aerosols and Reactive Trace gases (ICON-ART) forecasting models were synergized. The dust storms originated from different source regions located in the north, northeastern, and central parts of the Sahara Desert. The transport height of the main dust plumes was about 3–5 km, triggered by the westerly zonal winds. The presence of a closed low over the Eastern Mediterranean and the penetration of a deep trough into North Africa at 500 hPa were the main synoptic circulation patterns favoring long-range dust transport during the four dust events. A comparison of aerosol optical depth (AOD) outputs from the two models with satellite data revealed that although both models forecasted dust transport from Africa to the Middle East, they considerably underestimated the AOD values, especially near the dust sources. The ICON-ART model performed slightly better than ALADIN in forecasting these dust storms, and for longer forecasting leading time, although the performance of both models decreased, the superiority of the ICON-ART model became more apparent.

Nanostructured Niobium and Titanium Carbonitrides as Electrocatalyst Supports.

Nanostructured niobium-titanium carbonitrides, (Nb,Ti)C1-xNx, with the cubic-rock salt structure are prepared without the use of reactive gases via thermal treatment (700-1200 °C) under nitrogen of mixtures of guanidine carbonate and ammonium niobate (V) oxalate hydrate, with addition of ammonium titanyl oxalate monohydrate as a titanium source. The bulk structure and chemical composition of the materials are characterized using powder X-ray diffraction (XRD) and powder neutron diffraction, elemental homogeneity is studied using energy dispersive spectroscopy (EDS) mapping using transmission electron microscopy (TEM), and surface chemical analysis is examined using X-ray photoelectron spectroscopy (XPS). Nanoscale crystallites of between 10 and 50 nm are observed by TEM, where EDS reveals the homogeneity of metal distribution for the mixed-metal materials. Titanium carbonitrides are found to be air sensitive, reacting with air under ambient conditions, while titanium-niobium carbonitrides are found to degrade in aqueous sulfuric acid. The niobium carbonitrides, however, show some stability toward acidic solutions. Materials are produced with composition NbC1-xNx with x between 0.35 and 0.45, and more carbon-rich materials (x ≈ 0.35) are found as the synthesis temperature is increased, as proven by Rietveld refinement of crystal structure against powder neutron diffraction data. Despite phase purity seen by diffraction and negligible bulk carbon content, XPS shows a complex surface chemistry for the NbC1-xNx materials, with evidence for Nb2O5-like oxide species in a carbon-rich environment. The NbC1-xNx prepared at 900 °C has a surface area around 50 m2 g-1, making it suitable as a catalyst support. Loading with iridium provides a material active for the oxygen evolution reaction in 0.1 M sulfuric acid, with minimal leaching of either Nb or Ir after 1000 cycles.

Mo-based bimetallic oxide catalysts for the reverse water gas shift reaction

The reverse water gas shift (RWGS) is of great significance to the resource utilization of CO2. In this paper, based on the features of MoO3, the Mo-based catalysts doped with Ga, Ti and Ce were prepared, and the effects of oxygen vacancies and basic sites on the RWGS reaction were studied. When the volume ratio of H2 and CO2 is 1 : 1, the yield of CO can reach 26.66%. Because it exposes higher concentration of Ce sites and moderate alkaline active sites on the surface. When the proportion of H2 in the reaction gas increases, the highest yield of CO can reach 54.53%, which is mainly attributed to a large number of oxygen vacancies on the surface of MoTi. This study can be used as a reference for the design of catalysts for RWGS reaction under different reaction conditions.

Optimization of syngas production via methane bi-reforming using CeO2 promoted Cu/MnO2 catalyst

Currently, syngas plays an important role in renewable and sustainable energy production. The idea of manufacturing syngas via bi-reforming methane, which involves the combination of methane (CH4), carbon dioxide (CO2), and steam, appears very promising. As a result, the goal of this research is to improve syngas output by improving process parameters in methane bi-reforming using a 3%Ce-15%Cu/MnO2 catalyst. Optimization analysis was performed using response surface methodology (RSM). The ultrasonic impregnation (UI) method was employed to synthesize the catalysts used in this study. Following that, the catalyst was characterized using several techniques such as Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption (TPD), and temperature programmed oxidation (TPO). The findings of the characterization show that the presence of CeO2 promoters has a dual effect on the size of CuO crystallites. Firstly, it reduces the size from 19.07 nm to 13.66 nm because to the dilutive effect generated by the inclusion of CeO2. Second, the presence of CeO2 promoter accelerates the transition from CuO to Cu0 metallic phase. Furthermore, the addition of CeO2 boosts the CH4 and CO2 conversion rates by 23.65% and 24.93%, respectively. As a result, the H2 yield increases significantly when compared to the unpromoted catalyst. The study investigates the influence of process parameters, specifically the reaction temperature (700–900℃), CO2 ratio (0.2–1), and gas hourly space velocity (GHSV) (16–36 L g cat−1 hr−1), on the conversion of CH4 and CO2, as well as the H2/CO ratio. The optimization study finds that the highest conversion rates for CH4 and CO2 are 78.32% and 72.45%, respectively, when the reaction temperature is 800 °C, the CO2 ratio is 0.6, and the gas hourly space velocity (GHSV) is 26 L g cat−1 hr−1. The optimum conditions result in the highest syngas ratio of 1.77. The results of the optimization are then assessed using the mean errors. The H2/CO ratio, as well as the average errors for CH4 and CO2 conversions, are discovered to be 0.15%, 0.95%, and 0%, respectively.

Characterization of cosputtered (TiZrHfY)Nx films

Medium-entropy TiZrHfY alloy films and corresponding nitride (TiZrHfY)Nx films were fabricated through cosputtering. The Ti0.24Zr0.23Hf0.27Y0.26 film had the form of a hexagonal close-packed (HCP) solid solution with a mixing enthalpy of 9.09 kJ/mol, mixing entropy of 11.50 J/mol·K (1.38 R), atomic size difference of 7.72 %, and valence electron concentration of 3.73. Moreover, this film had a hardness of 6.0 GPa and an elastic modulus of 106 GPa. (TiZrHfY)Nx films with various stoichiometric ratios (x) were fabricated by adjusting the reactive gas flow ratio fN2 [N2/(N2 + Ar)] in the range 0.1–0.7. Adding N to the TiZrHfY matrix resulted in a change of phase from an HCP structure to a face-centered cubic phase. The (Ti0.23Zr0.18Hf0.24Y0.35)N0.71 film (with fN2 = 0.2) exhibited the most favorable mechanical properties, having a hardness of 19.1 GPa and an elastic modulus of 244 GPa. Moreover, the film had the highest critical loads (LC3 = 46.6 N) among the films analyzed in the scratch test. The anticorrosive properties of the TiZrHfY and (TiZrHfY)Nx films were evaluated using potentiodynamic polarization curves, obtained in 3.5 wt% NaCl aqueous solution. High polarization resistance of 1.1 × 106 Ω·cm2 was obtained for the (Ti0.23Zr0.18Hf0.24Y0.35)N0.71 film, which was 145 times higher than that of the bare SUS420 substrate. The (Ti0.23Zr0.18Hf0.24Y0.35)N0.71 film had the most favorable mechanical and anticorrosive properties of the surveyed (TiZrHfY)Nx films.