MgO Surface Research Articles

Unraveling the Synergy of Au and Polar MgO(111) Surface in Photothermal Catalytic Oxidative Coupling of Methane

AbstractDirect and selective catalytic oxidative coupling of methane (OCM) into high‐carbon products is a great challenge in C1 chemistry. Herein, the successful fabrication of a series of Au clusters loaded on different MgO facets of (111), (110), and (100) is reported. This work demonstrates the Au‐loaded MgO(111) (denoted as Au/MgO(111)) shows the highest C2H6 yield of 12733.4 µmol g−1 h−1 and selectivity of 90.4%, which is 2.46 times higher than that of Au/MgO(110) (5171.4 µmol g−1 h−1) and 25.14 times higher than that of Au/MgO(100) (506.4 µmol g−1 h−1). Moreover, the high activity of Au/MgO(111) can be well maintained over 100 h. Detailed in situ experiments and theoretical calculation reveal such great performance can be attributed to 1) the strong electronic affinity of the surface oxygen species on polar MgO(111) and CH4with the lowest adsorption energy of −0.82 eV; 2) the Au/MgO(111) shows the lowest ΔERDS of 0.53 eV in the rate‐deterime step of OCM that comes in activating the second CH4 molecule; 3) the Au can act as a hole acceptor under light irradiation and adsorb *CH3 with a strong d‐σ hybridization, resulting in an increased C2H6 selectivity.

Unveiling the adsorption mechanism of propanehydrazine derivatives on magnesium oxide surface: Insights from computational approach

The use of green and effective inhibitors for preventing metal oxide (MgO) corrosion in industrial applications is highly significant in promoting environmental protection and sustainable development. This study delves into the adsorption behavior and interfacial mechanism of environmentally friendly inhibitor derived from propane hydrazine (PH) on MgO surface. Specifically, PH1, PH2, PH3, and PH4 were explored for their effectiveness in preventing corrosion by using advanced theoretical simulations-based density functional theory (DFT) for assessing the reactivity and adsorption characteristics. The study considered a detailed exploration of local and global reactivity descriptors, providing insights into the inhibitors’ reactivity and adsorption abilities in both isolated and adsorbed states. These findings focus more in the mechanisms underlying organic-inorganic interactions and present promising prospects for further development and application. Using first-principles DFT calculations alongside quantitative molecular surface analyses, we examined the adsorption patterns of PHs on the MgO(100) surface. These investigations are boosted by the application of independent gradient model (IGM) framework, providing robust verification of PHs' adsorption behavior on MgO(100) surface. Our calculations reveal a substantial decrease in the energy gap following complex formation, suggesting that charge density changes occur upon interaction with MgO surfaces, thereby facilitating direct electron transfer in all the studied systems. Noreover, the results highlight the crucial role of intermolecular interactions in boosting the interaction between PHs and the [Mg(H2O)6]2+ cation. First-principles DFT calculations show that all PH molecules consistently display parallel adsorption on the MgO surface, where the oxygen atoms form bonds with adjacent magnesium atoms. The bond lengths vary from 2.18 to 2.35 Å when PHs bind to the Mg atoms in parallel orientations through the oxygen atom, suggesting a stable parallel arrangement for PH molecules on the MgO surface. The calculated adsorption energy (Eads) varies in the following order: MgO-PH3 (−815.14 Kcal mol−1) > MgO-PH2 (−803.85 Kcal mol−1)) > MgO-PH4 (−695.38 Kcal mol−1) > MgO-PH1 (−125.77 Kcal mol−1). This trend indicates that parallel interactions enhance the adsorption behavior and binding of PH compounds through inter- and intra-molecular interactions, resulting in the PHs being centered at specific sites on the MgO surface. The potential enhancement in electrochemical properties is believed to stem from the synergistic interaction between the PHs and the MgO surface, which theoretically allows for a precise adjustment of their adsorption and interaction within the composite structure. This understanding provides a fundamental framework for examining the complex interfacial dynamics between inhibitor structures and elucidating how these molecular interactions influence the selection of corrosion inhibitors and their adsorption behaviors on the corrosion layer's surface, rather than on metallic Mg.

A plasma-catalytic system with MgO/NiO/Ni cathode for SF6 degradation

In this work, a plasma-catalytic system in DC discharge with MgO/NiO/Ni (MNN) cathode is proposed for the degradation of SF6 greenhouse gas. The discharge power with MNN cathode is significantly increased compared with Ni cathode due to its good electron emission characteristics, and an effective and stable SF6 degradation performance is achieved in this multi-needle plate discharge system. Besides, surface discharge occurs on the MNN cathode in addition to the needle tips, which is believed to be conducive to the catalytic decomposition of SF6 on the MgO surface. Nontoxic products of MgF2 and MgSO4 are detected on the MgO layer after discharge from various characterizations (XRD, XPS, FTIR and Raman, etc.), suggesting that there is a series of catalytic reactions between SF6/intermediates and MgO. The addition of appropriate O2 (O2:SF6 = 1:1) in the background is not only conducive to the defluorination decomposition of SF6 in ionization region, but also O atom generated from O2 discharge promotes the formation of MgF2 and MgSO4, thus resulting in an effective SF6 degradation performance. Then, the possible degradation mechanism of SF6 in gas phase and on the MgO layer is discussed and the possible degradation pathways are proposed. This research first demonstrates the effectiveness of enabling degrading SF6 gases in a plasma-catalytic system with MNN cathode.

Direct quantitative assessment of single-atom metal sites supported on powder catalysts

Rational design of effective catalyst demands a profound understanding of active-site structures. Single-atom supported powder catalysts, depicting unique features like enhanced metal dispersion, hold promise in different applications. Here, we present an approach to directly quantify the detailed structural nature of metal sites in single-atom, high surface area, powder catalysts. By combining advanced high-resolution scanning-transmission electron microscopy, deep learning and density functional theory calculations, we determine, with statistical significance, the exact location and coordination environment of Pd single-atoms supported on MgO nanoplates. Our findings reveal a preferential interaction of Pd single-atoms with cationic vacancies (V-centers), followed by occupation of anionic defects on the {001} MgO surface. The former interaction results in stabilization of PdO species within V-centers, while partially embedded Pd states are found in F-defects. This methodology opens a route to the ultimate structural analysis of metal-support interaction effects, key in the design of advanced nanocatalysts for sustainable and energy-efficient processes.

Unveiling Carbon Cluster Coating in Graphene CVD on MgO: Combining Machine Learning Force field and DFT Modeling.

In this study, we investigate the behavior of carbon clusters (Cn, where n ranges from 16 to 26) supported on the surface of MgO. We consider the impact of doping with common impurities (such as Si, Mn, Ca, Fe, and Al) that are typically found in ores. Our approach combines density functional theory calculations with machine learning force field molecular dynamics simulations. It is found that the C21 cluster, featuring a core-shell structure composed of three pentagons isolated by three hexagons, demonstrates exceptional stability on the MgO surface and behaves as an "enhanced binding agent" on MgO-doped surfaces. The molecular dynamics trajectories reveal that the stable C21 coating on the MgO surface exhibits less mobility compared to other sizes Cn clusters and the flexible graphene layer on MgO. Furthermore, this stability persists even at temperatures up to 1100K. The analysis of the electron localization function and potential function of Cn on MgO reveals the high localization electron density between the central carbon of the C21 ring and the MgO surface. This work proposes that the C21 island serves as a superstable and less mobile precursor coating on MgO surfaces. This explanation sheds light on the experimental defects observed in graphene products, which can be attributed to the reduced mobility of carbon islands on a substrate that remains frozen and unchanged.

Wannier Function Localization Using Bloch Intrinsic Atomic Orbitals.

We extend the intrinsic atomic orbital (IAO) method for the localization of molecular orbitals to calculate well-localized generalized Wannier functions in crystals in the spirit of the Pipek-Mezey method. We furthermore present a one-shot diabatic Wannierization procedure that aligns the phases of the Bloch functions, providing immediate Wannier localization, which serves as an excellent initial guess for optimization. We test our Wannier localization implementation on a number of solid-state systems, highlighting the effectiveness of the diabatic preparation, especially for localizing core bands. Partial charges of Wannier functions generated using Bloch IAOs align well with chemical intuition, which we demonstrate through the example of the adsorption of CO on a MgO surface.

Evaluation of rheo-viscoelasticity of magnesium-silicate-hydrate mixes incorporating different superplasticizers

This study investigated rheo-viscoelastic behaviors of MgO-SiO2 pastes with three phosphate additives (sodium hexametaphosphate (SHMP), sodium trimetaphosphate (STMP), and sodium orthophosphate (SOP)) as superplasticizers. Static yield stress, dynamic yield stress, median differential viscosity, thixotropic loop area, structural recovery rate, and non-destructive structural build-up were analyzed. Furthermore, assessment of hydration and particle dispersion stability was facilitated by employing isothermal calorimetry, XRD, DTG, and zeta potential techniques. SHMP significantly decreased the static and dynamic rheology, thixotropy, and viscoelastic evolution. Samples incorporating 2 wt% SOP exhibited enhanced rheological parameters, particularly static yield stress, owing to increased brucite formation and a denser microstructure in the fresh paste. Adsorption of phosphate additives on MgO surfaces inhibited formation of brucite and improved interparticle electrostatic repulsion, thereby increasing suspension stability. High-efficiency adsorption of SHMP on MgO surfaces, coupled with the retardation of brucite nucleation-and-growth, and enhancement in suspension stability, greatly restrained the rheo-viscoelastic evolution of MgO-SiO2 system.

Green and energy-saving tread rubber by constructing chemical cross-linking interface between graphene oxide and natural rubber

The dispersibility of fillers and interfacial interaction are crucial for polymer nanocomposites. Developing a simple, efficient and green method to simultaneously reduce and functionalize graphene oxide (GO) for preparing graphene/rubber composites with excellent dispersibility and enhanced interfacial interactions remains one of the main trends in developing and expanding the application of graphene in the rubber industry. In this work, VOC (volatile organic compound) -free and environmentally friendly L-methionine (L-Met) was selected as the functional modifier of GO. Then, L-Met-modified GO (MGO) was blended with natural rubber (NR) in an aqueous phase to prepare MGO/NR composites. The amphiphilic property of L-Met not only reduced GO but also endowed it with less agglomeration and excellent water dispersibility, which was a prerequisite for achieving uniform dispersion of GO in the NR matrix. In addition, the amino acids on the surface of MGO enhanced the compatibility between GO and the protein-phospholipid layer on the outer layer of NR latex particles. Meanwhile, L-Met containing sulfur bonds promoted rubber vulcanization, resulting in the formation of a cross-linked network between the modified GO and NR molecular chains. Compared to unmodified GO/NR composites, MGO/NR composites exhibited excellent mechanical properties and low heat build-up. More importantly, the solid tire prepared by using L-Met as the interface modifier for GO filled rubber showed lower rolling resistance and temperature rise, and the energy saving efficiency was improved. This strategy is expected to provide a new insight into the green production of organically modified graphene and the preparation of low-energy-consumption green graphene tires.

Study on the homologous effects on the performance of alkali metal-doping MgO-based adsorbents for CO2 capture

In this article, MgO-based adsorbents with different structure and surface property were prepared by combustion of the colloids containing Mg and alkali metal. At the same time, CO2 adsorption performance tests are conducted to compare the doping effect of alkali metal on MgO adsorbents. As confirmed, the introduction of lithium, sodium, and potassium can reduce the grain size of MgO and enhance the basicity, especially increasing the concentration of oxygen vacancies on MgO surface which exposed more basic adsorption active sites and was more conducive to CO2 adsorption. Among them, the one doped with 0.5 % K which had more electron shell numbers showed larger surface area and smaller crystal size. Most importantly, it provided more number of basic sites along with the improved strength of surface basicity due to the more oxygen vacancies. As a result, the maximum CO2 uptake (1.09 mmol/g) at the adsorption time of 60 min can be obtained which still remained at 0.67 mmol/g after 16 cycles of CO2 adsorption–desorption. With the aid of N2 physical adsorption, inductively coupled plasma-optical emission spectroscopy, powder X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and chemical adsorption, the relationship between CO2 adsorption capacity of MgO-based adsorbent and homologous regularity of alkali metal was disclosed. In other words, by comparing the CO2 adsorption performance of MgO adsorbents prepared by doping different alkali metals, CO2 adsorption capacity increased with the increase of electron shell numbers. Such a configuration is in favor of the electron supply of the p-orbitals and weakens the Mg–O bonds which promoted the formation of oxygen vacancies. The found will provide in-depth understanding for the modification and performance improvement of MgO-based adsorbents.

Selective hydrogenation of biphenyl to cyclohexylbenzene over Cu based catalysts

The Cu/Al2O3, Cu/MgAlO, Cu/MgO and Cu-Ni/MgAlO catalysts (60 wt%) were studied for the selective hydrogenation of biphenyl (BP) to cyclohexylbenzene (CHB). The results showed the relatively high dispersion but low reducibility of Cu in the Cu/Al2O3. The acidic surface of Al2O3 caused the electron-deficient Cu that enhanced the adsorption of aromatic rings and thus led to the higher intrinsic activity for the hydrogenation of aromatic rings over the Cu/Al2O3, while the basic surface of MgO played the just opposite roles. The Cu/MgAlO possessed the suitable surface acidity and basicity and thus the high density of surface Cu active sites. Thus, it exhibited the higher overall activity than the Cu/Al2O3 and Cu/MgO for the hydrogenation of BP. However, the heats for the adsorption of toluene and H2 were significantly lower on Cu than those on Ni, which accounted for that the Ni was much more active than Cu for the hydrogenation of BP and CHB. Further studies showed that the activation energies for the hydrogenation of BP and CHB on Cu were high and differ greatly, resulting in the high conversion of BP with high selectivity to CHB over the Cu catalysts. On the other hand, the activation energies were significantly lower and did not differ so much on Ni, leading to the high conversion of BP and CHB for the formation of bicyclohexyl. Finally, the addition of a small amount of Ni (1 wt%) into the Cu/MgAlO greatly increased the conversion of BP under relative lower temperature while maintained the high selectivity to CHB.

A comprehensive evaluation of crumb rubber modified asphalt-aggregate interfacial behavior and the effect of water: Molecular dynamics simulation and experimental investigation

The incorporation of crumb rubber (CR) makes the asphalt-aggregate interfacial properties highly complex and uncertain, while water is a key environmental factor causing interfacial failure. This paper aims to evaluate the characteristics of crumb rubber modified asphalt (CRMA)-aggregate interaction and the interfacial failure mechanism under the influence of different material properties and water at ambient temperature. Firstly, the CRMA-aggregate interfacial behavior before and after water intrusion is investigated using molecular dynamics simulations at the molecular scale. Next, the failure process and characteristics of the CRMA-aggregate interface were analyzed using the disk-shaped compact tension (DCT) test at the macro scale. Finally, the effect of water intrusion on the interface failure mode was analyzed through image processing. The results show that CR enhances binder cohesion and significantly affects its adhesion to aggregates with high CaO and MgO contents regardless of the presence of water. The asphalt concentration distribution on the CaO and MgO surfaces is more concentrated with higher peak concentration, leading to superior interfacial adhesion and water damage resistance with binder, while Al2O3 and SiO2 were inferior. The use of asphalt with higher creep stiffness, high-strength alkaline aggregates, and smaller CR particle size is beneficial for enhancing the CRMA binder-aggregate interfacial fracture performance. Water intrusion severely affected the interfacial adhesion, resulting in a significant increase in the proportion of adhesion failure, which is the main cause of the deterioration of the interface properties. The findings of this study provide insights into the factors affecting the CRMA-aggregate interfacial behavior, which facilitate the accurate design and application of high-strength durable CRMA mixtures.

CO2 adsorption on a K-promoted MgO surface: A DFT theoretical study

The primary cause of global warming is the emission of greenhouse gases such as CO2. So reducing CO2 emissions is vital. This paper investigates the impact of the atom K as a promoter of MgO on the CO2 adsorption properties using the DFT theoretical computational method. By analyzing the adsorption energy, bader charge as well as the density of states and COHP, it was found that K-promoting the MgO (100) surface resulted in a redistribution of charge on the MgO surface and enhanced CO2 adsorption compared to the pure MgO surface. The presence of K atoms causes orbital hybridization among O (CO2) and Mg atoms, O (CO2) atoms and K atoms, and the surface O atoms and K atoms. These interactions lead to the formation of (MgO)Mg-O(CO2) and (CO2)O−K−O(MgO) chemical bonds. The adsorption energy of CO2 on the K-promoted MgO surface increased from -0.32 eV to -1.01 eV compared to the pure surface, enhancing the adsorption of CO2.

Preparation of molten salt promoted MgO for efficient CO2 capture by microwave method: Performance evaluation and mechanism exploration

MgO’s great potential for capturing CO2 has drawn a lot of attention, but the limited O2– sites prevents its further development. This work proposed a microwave-induced method (microwave hydrothermal and microwave sintering) to produce high-performance MgO CO2 adsorbent and was further modified using carbonates (K2CO3) and nitrates of alkali metals (NaNO3, KNO3). The outcomes demonstrated that the small particle size MgO nanocrystals (6.20 nm) with a CO2 uptake of 1.8 mmol·g−1 could be produced by a unique method of microwave heating from the inside out. Among the modified samples, addition of 20 mol% NaNO3 on the surface of MgO exhibited the highest CO2 uptake (11.91 mmol·g−1), and the uptake was still 7.9 mmol·g−1 after 10 cycles. The addition of molten salt changed the adsorbent’s active sites, resulting in an increase in O2– alkaline sites and the activation of MgO lattice defects, both of which improved the sample’s CO2 adsorption performance. This work could offer a new idea for creating affordable and effective CO2 solid adsorbents to capture CO2.

Enhanced antibacterial effect with MgO nanoplates: Role of oxygen vacancy and alkalinity

The rational design of MgO nanomaterials with rich oxygen vacancies has garnered significant attention. However, the influence of oxygen vacancies and alkalinity on the generation and stability of active oxygen, particularly regarding the antibacterial activity of MgO nanomaterials, remains uncertain. In this work, the defective MgO nanoplates with adjustable oxygen vacancy and alkalinity were successfully designed by thermal treatment in different atmospheres (air, vacuum, and N2). MgO nanoplates calcined in N2 atmosphere exhibited superior antibacterial activity against Escherichia coli (ATCC 25922), reducing colony counts from 571.5 to 53.5 CFU/mL at 750 μg/mL compared with MgO nanoplates calcined in air. At a low concentration (100 μg/mL), MgO nanoplates calcined in N2 atmosphere exhibited remarkable antibacterial performance, achieving a colony survival ratio of only 6.8 %. This enhanced performance was correlated with a higher oxygen vacancy (OA) content (51.3 %) in MgO nanoplates calcined in N2 compared to those calcined in air (26.5 %). Advanced characterization techniques and alkalinity measurements revealed that calcination in a N2 atmosphere promoted oxygen vacancy formation on the MgO surface, accelerated MgO surface hydrolysis owing to oxygen vacancies, and increased OH− production. Consequently, this process enhances the participation of adsorbed oxygen in surface reaction, leading to the increased generation and stability of active oxygen in an alkaline environment. These findings provide valuable insights into the design of oxygen vacancies and offer a potential approach for constructing highly antibacterial nanomaterials. Such materials could find applications in personal protection and public health.

Interfacial Engineering of Fluorescent Carbon Dots with Metal Oxides for Real-Time Visualization of Oxygen Vacancy Dynamics.

Oxygen vacancy (Vo), as one of the most common surface defects, significantly influence the physiochemical properties of metal oxides. However, it remains a challenge for existing techniques to visualize the evolution of Vo during redox process due to its heterogeneous distribution, small size, and dynamic nature. Herein, the real-time monitoring of such microscopic interfacial events is reported by advantage of the high-contrast fluorescence response of carbon dots (H-CDs) to Vo. The green emissive H-CDs possess a unique disc-shaped structure and exceptional hydrophilicity, allowing their tight adhesion to the surfaces of Vo-rich MgO by simple mixing. Subsequently, a water involved interfacial reaction occurred between H-CDs and Vo, resulting in gradual quenching of the original green emission and simultaneously emergence of bright red fluorescence. Moreover, the spatiotemporal diffusion dynamics and reaction kinetics are investigated by confocal laser scanning microscopy, revealing the time-dependent reorganization and structural heterogeneity at the interface. The finding provides a new toolbox for in situ imaging of Vo-triggered phenomena at a microscopic level, which will be helpful in promoting the rational design of oxide materials.

Simultaneous removal of diclofenac sodium, cadmium and bacterial inactivation from aqueous solutions by activated MgO nanoparticles

This study investigated whether MgO nanoparticles (NPs) produced via the sol–gel process can simultaneously remove the pharmaceutical diclofenac sodium (DCF) and cadmium ions (Cd2+) from water. The UV spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX) were used to confirm the composition, morphology and particle size of the MgO NPs. The adsorption performance of MgO NPs was compared to that of bentonite-nano zero valent iron (B-nZVI) and activated carbon (AC). The impact of contact time, adsorbate concentration, pH, and temperature on the removal efficacy of DCF and Cd2+ via MgO NPs in aqueous solutions were investigated, and the removal data was best described by the kinetic model of pseudo-second-order and the Langmuir isotherm model (R 2 > 0.996). The maximum removal capacity of MgO for DCF and Cd2+ at pH 7 was 66.2 mg.g−1 (%R = 90) and 50.8 mg.g−1 (%R = 80), respectively. The average adsorption enthalpy for DCF and Cd2+ (ΔH° 50 kJ. mol−1) demonstrates the occurrence of physical adsorption process, while the negative value of ΔG° reveals the spontaneous nature of DCF and Cd2+ adsorption on the surface of MgO NPs. The DCF and Cd2+ adsorbed MgO surfaces were reused against various gram-positive bacteria. Finally, it was shown that MgO and sand column were more effective for removal of persistent substances and heavy metal residues than a column packed by a mixture of B-nZVI and sand.

Basic magnesium carbonate template assisted co-carbonization of potassium citrate toward hierarchical porous carbon for supercapacitors

Hierarchical porous carbon (HPC) as the ideal host material for supercapacitors has received extensive attention. However, traditional methods of fabricating HPC often rely on organic macromolecules and complex procedures. Herein, a simple and straightforward approach is developed for the synthesis of HPC through basic magnesium carbonate template assisted co-carbonization of potassium citrate. Potassium citrate can be effectively embedded and encapsulated with basic magnesium carbonate due to the large bulk density difference between them. In the pyrolysis process, the carbon-containing small molecules produced by the pyrolysis of potassium citrate are deposited on the surface of MgO surface obtained from the decomposition of basic magnesium carbonate, and the etching reaction of potassium salt, CO2 and primary carbon structure occurs. The competitive rate of carbon deposition reaction and etching reaction can be easily controlled by changing the ratio of potassium citrate and basic magnesium carbonate. The obtained carbon materials show the morphology changes of nanoparticle accumulations, discontinuous carbon frames and carbon planar blocks, and the hierarchical porous structure of carbon materials can also be controlled in a wide range. HPC-2 exhibits the morphology of nanoparticle accumulation and generates abundant meso-macropores, which accelerates the rapid transport of electrolytic ions. The micropores inside the nanoparticles provide an accessible room for ionic adsorption. Benefited from this unique microstructural framework, HPC-2 shares a high capacitance of 305.5 F g−1 at 0.5 A g−1 and 173.1 F g−1 at 50 A g−1. Furthermore, the assembled symmetric supercapacitors exhibit a high energy density and power density than YP-50 F throughout the test range. The versatility of this synthetic strategy provides an insight into directional tailoring fine pore structure and micro-morphology of carbon materials based on small molecule deposition.

Revealing the Role of MgO in Sorption‐Enhanced Water Gas Shift Reaction for H2 Production: A DFT Study

AbstractThe sorption‐enhanced water gas shift (SEWGS) process has emerged as a promising technology for high‐purity H2 production. MgO serves as a competitive sorbent in SEWGS, removing CO2 in situ. Yet the reaction mechanism of SEWGS employing MgO is not well understood. In this work, the reaction mechanism of SEWGS on the MgO surface is revealed by density functional theory (DFT) analysis. The MgO(110) surface shows a remarkable enhancement for SEWGS. Spontaneous dissociation of H2O is observed whether in the presence of CO or CO2, leading to the enrichment of hydroxyl groups for subsequent reactions. CO2 generated is captured by surface basic sites, resulting in the formation of MgCO3. The presence of the generated hydroxyl group enhances the dehydrogenation reaction on the surface, facilitating hydrogen production. The reaction pathway is described as follows. First, spontaneous dissociation of H2O occurs when co‐adsorbed with CO on the MgO surface. Then, two hydroxyl groups interact, yielding atomic O for CO oxidization and atomic H for H2 generation. Ultimately, CO2 is captured by the surface while H2 desorbs from the surface. The rate‐limiting step is H2 generation with an energy barrier of 0.68 eV. The calculation results elucidate the enhancement mechanism of MgO on the SEWGS process.

Excellent catalytic activity for NO decomposition on Rhn supported on grain-boundary terminations of the MgO (0 0 1) surface

In the present study, we first propose the grain-boundary termination of the MgO (001) surface (referred as GB@MgO(001)) as the substrate to support a series of Rhn clusters to trap and dissociate NO. Using van der Waals density functional theory calculations, we have studied the interaction between the Rhn (n = 1 ∼ 8) cluster and the MgOΣ5(210)GB@MgO(001) and the properties of the adsorption and dissociation of NO on Rhn/GB@MgO(001) systems. The Rhn clusters can tightly bond to the GB@MgO(001), with interfacial interactions comparable to those at the Rhn/MgO-nanotube interface. Stable quasi-two-dimensional Rhn clusters provide more active sites to NO. Moreover, NO dissociation is activated, with all the complete reaction paths occur below the reference state, indicating the possibility of the NO decomposition. An extremely small energy barrier of 0.037 eV was obtained for NO dissociating on the square-Rh4/GB@MgO(001) system. Molecular dynamic (MD) calculations reveal that NO can be completely decomposed at 527 K without obvious structure distortions of the complex. The adsorption of NO yields a change in the total magnetic moment of the Rhn/GB@MgO(001) system, but it has a minimal impact on the adsorption energy of NO. Our results also show that the optimal Rhn clusters that are good at trapping and dissociating NO are not the most stable structures, but rather clusters of relatively low dimension that are bound to the substrate with a moderate strength. As a result, the modification and tuning of the substrate structure can effectively enrich the structure of Rh cluster catalyst and improve its physical properties so that it can potentially play a greater role in other redox reactions, which motivates us to continue designing various types of GB@MgO(001) for different purposes.

Hydration of MgO, CaO, SrO, and BaO (001) Surfaces from First Principles

AbstractIn this work we present a computational study of alkaline earth oxides (001) surfaces interfaced with water by means of density functional theory (DFT) in conjunction with ab initio molecular dynamics (AIMD) calculations. We studied the nature of MgO, CaO, SrO, and BaO (001) surfaces in contact with water. Results show that water dissociation is promoted as the alkaline earth metal becomes heavier. Similarly, the coordination number of the cation atoms with water molecules follows the same trend, indicating a more favorable interaction. The combined analysis of rumpling and pair distribution functions allows to provide a correspondence between reactivity of atoms on the surface and capability to coordinate water molecules. Except for MgO, the remaining surfaces display strong structural changes upon hydration, a relevant message when modelling hydrated surfaces. We also investigated the effect of the water thickness by adsorbing a water monolayer and bilayer to the surface. The findings of the study and the adopted approach could be of help for future studies of more complex systems or to provide fundamental rationalizations.