Dissociative Adsorption Research Articles

Revealing Dynamics and Competitive Mechanism of Gas-Induced Surface Segregation of PdFe0.08 Dilute Alloy by Multi-Dimensional Imaging.

The restructuring of dilute alloys under gas environments has shown a great impact on their catalytic performance due to intriguing structural sensitivity, but the structural dynamics and underlying mechanism remains elusive. Herein, we directly resolved the distinct dynamic behaviors of PdFe0.08 dilute alloys under CO or O2 environment by multidimensional imaging. The stronger binding of gaseous CO with Fe atoms stimulates Fe segregation out of the PdFe0.08, resulting in 3D growth of Fe islands, whereas the dissociative adsorption of O2 results in 2D layer-by-layer growth of segregated FeO as encapsulation overlayers that bind strongly with the Pd surface underneath. Such varied structures remarkably tune the catalytic activity for CO oxidation, showing a considerably high activity for a CO-treated sample. Our results reveal the competitive mechanism between adsorbate-metal and metal-metal interaction for gas-induced surface segregation, which should be highly considered for the rational design of dilute alloys with dynamically tuned structure and reactivity.

Mechanism insights and experimental feasibility of using boron nitride nanocones for rapid adsorption and degradation of SF6 decomposition compounds

Gas-insulated switchgear (GIS) employs sulfur hexafluoride (SF6) as an insulating medium to shield electrical gadget. However, SF6 can decompose under sure situations, generating dangerous sulfur-based totally compounds which include SO2, SOF2, and SO2F2. These byproducts pose enormous dangers to both protection and environmental integrity. Efficiently adsorbing and disposing of those compounds is critical for ensuring operational reliability and reducing environmental dangers. This study investigates the adsorption and degradation mechanisms of SF₆ decomposition compounds (SO₂, SOF₂, and SO₂F₂) on boron nitride nanocones (BNNCs) using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Our comprehensive analysis covers five distinct systems, exploring individual and combined adsorption scenarios. The findings reveal that the apex of BNNCs plays a crucial role in the adsorption process, showing high efficiency in adsorbing SO₂ (adsorption energy − 1.22 eV) and facilitating the catalytic breakdown of SOF₂ (adsorption energy − 1.57 eV). The positively charged potential at the nanocone’s apex significantly influences the dissociation and subsequent adsorption of fluorine atoms, with an energy barrier for F dissociation at the apex (1.8 kcal/mol) much lower than at the sidewall (5.3 kcal/mol). In gas mixtures, SO₂ preferentially binds to the apex region of BNNCs, with a bond length of approximately 1.38 Å. BNNCs demonstrate superior adsorption capabilities for SO₂ and SOF₂ compared to other boron nitride nanostructures, with adsorption energies up to 89% higher. The electron transfer analysis reveals that BNNC complexes act as potent electron donors, particularly in the case of BNNC@3SO₂F₂. Additionally, BNNCs show significant potential as sensors for detecting SO₂F₂, with a rapid recovery time of 4.67 ps and a notable decrease in the Fermi level energy to -4.97 eV upon adsorption. The study also provides insights into the angular distribution and charge density difference profiles, offering a detailed understanding of the adsorption mechanisms. These findings have important implications for improving the safety and efficiency of gas-insulated switchgear (GIS) and contribute to the development of more effective environmental protection solutions in electrical power systems.

Thermal Rates and High-Temperature Tunneling from Surface Reaction Dynamics and First-Principles.

Studying dynamics of the dissociative adsorption and recombinative desorption of hydrogen on copper surfaces has shaped our atomic-scale understanding of surface chemistry, yet experimentally determining the thermal rates for these processes, which dictate the outcome of catalytic reactions, has been impossible so far. In this work, we determine the thermal rate constants for dissociative adsorption and recombinative desorption of hydrogen on Cu(111) between 200 and 1000 K using data from reaction dynamics experiments. Contrary to current understanding, our findings demonstrate the predominant role of quantum tunneling, even at temperatures as high as 400 K. We also provide precise values for the reaction barrier (0.619 ± 0.020 eV) and adsorption energy (0.348 ± 0.026 eV) for H2 on Cu(111). Remarkably, the thermal rate constants are in excellent agreement with a first-principles quantum rate theory based on a new implementation of ring polymer molecular dynamics for reactions on surfaces, paving the way to discovering better catalysts using reliable and efficient computational methods.

A comparative theoretical study: Reaction mechanism of Hg0 and H2S/H2Se on α-Fe2O3 (0 0 1) surface

Selenium has emerged as a modifier of mercury sorbent in recent years following sulfur, and H2Se is expected to be helpful for mercury capture as H2S do. To explore the differences in the impact of H2S and H2Se on mercury control, the reaction mechanism of Hg and H2S/H2Se on the α-Fe2O3(0 0 1) surface was investigated by density functional calculations. The results show that the H2S and H2Se perform similar adsorption behaviors on α-Fe2O3 (0 0 1) surface, and they tend to undergo a complete dissociative adsorption, with H atoms bonding to surface O atoms, and S/Se atoms bonding to surface Fe atoms. Comparatively, the adsorption of H2Se is more favorable than H2S in both thermodynamics and kinetics. The active S/Se site, derived from the dissociative adsorption of H2S/H2Se, can stabilize Hg atoms firmly through the generation of HgS/HgSe with a negligible energy barrier. However, HgS and HgSe are unlikely to desorb from α-Fe2O3 (0 0 1) surface indicated by their high adsorption energy of above 320 kJ/mol. These findings not only elucidate the reaction mechanisms involved in the interaction between H2Se and mercury on the α-Fe2O3 (0 0 1) surface but also predict the superior performance of H2Se compared to H2S in enhancing mercury capture over sorbents.

Enhanced ethanol synthesis via CO2 hydrogenation using La-Doped CuFeOx catalysts

CO2 hydrogenation is an effective solution for direct ethanol production as it realizes a high-value utilization of waste CO2. As it requires a synergistic multi-step process of CO2 activation, asymmetric hydrogenation of CO, and precise coupling of C-C bonds, the design of highly active and selective catalysts for such procedures remains challenging. In this study, we prepared a series of La-doped CuFe catalysts using a simple and green solvent-free ball milling method to accelerate the rate of CO2 hydrogenation to ethanol generation. HRTEM, in situ XRD, EPR, and CO2-TPD analyses indicated that the doping of moderate amounts of La can significantly improve the dispersion of the Cu and Fe species, enhance the interaction between the CuFe species, decrease the reduction temperatures of CuO and Fe2O3, promote the formation of oxygen vacancies during the reaction process, and enhance CO2 adsorption and activation ability. DFT calculations, XPS, in situ FTIR, and CO-TPSR-MS analyses indicated that the transfer of electrons from the Fe to La species decreased their electron cloud densities, weakened the bridge type adsorption of CO, enhanced the linear adsorption of CO, and optimized the ratio of the dissociative and non-dissociative adsorption of CO intermediates, which ultimately resulted in a better matching of the rates of generation of CHx* and C(H)O* intermediates. The occurrence of C-C coupling at the abundant Cu0-Fe5C2 interface promoted the highly efficient synthesis of ethanol, achieving yields as high as 13.5 % over the 5La-CuFeOx catalyst, ranking the top level among the reported catalysts in the literature. This study presents a feasible strategy for the targeted regulation of multicomponent active centers.

Work function and electrochemistry of ZnO (wurtzite) single crystals (F-1:L07)

The work functions of two polar surfaces of ZnO (wurtzite), i.e., O-(000–1) and Zn-(0001) are determined by photoelectron spectroscopy in ultrahigh vacuum or in the presence of oxygen or water vapor at near-ambient pressures, and by Kelvin probe in air. The work functions were also determined by Mott-Schottky analysis in aqueous or aprotic (acetonitrile) electrolyte solutions. The values obtained by different techniques and in different environments are much less scattered compared to the fluctuations, reported for TiO2 (anatase or rutile). The Zn-(0001) surface has a smaller work function for all the solid/vacuum and solid/gas interfaces, and also in the acetonitrile electrolyte solution. Solely at the aqueous electrochemical interface, the difference is small or even opposite. We propose a hypothesis that the dissociative water adsorption on the O-(000–1) is responsible for this irregular downshift of the work function in aqueous medium.

Glucose oxidation on gold in alkaline solution: A DEMS and microkinetic modeling study

The mechanism and kinetics of the electrochemical oxidation of glucose on gold surfaces in 0.1 M NaOH solution are investigated by rotating disk electrode and differential electrochemical mass spectrometry coupled to microkinetic modeling. For this purpose, the glucose mass-transport parameters (solution viscosity and density, glucose diffusion coefficient) were determined in the relevant conditions. Koutecký–Levich analysis of rotating disk electrode current-potential curves revealed that the glucose oxidation reaction (GOR) follows a one-electron mechanism at 0.6 V vs RHE, while H2 production could be evidenced by DEMS in this potential range. This suggests that the glucose oxidation selectively produces gluconate at 0.6 V vs RHE through an electrochemical oxidative dehydrogenation (EOD) mechanism. A microkinetic model of the current-potential curves was developed, taking into account the hydrogen electrode reactions kinetics, the dissociative adsorption/desorption of glucose, and the glucose electrooxidation on gold surfaces. The dissociative adsorption of glucose was found to be the rate-determining step of the reaction. It is also revealed that the release of anodic H2 through the Tafel step is triggered by the consumption of the adsorbed reaction intermediates. The gluconate electrooxidation into further products has to be considered for potential above 0.7 V vs RHE.

Pd-Co Supported on Anodized Aluminium for VOCs Abatement: Reaction Mechanism, Kinetics and Applicability as Monolithic Catalyst

It has been found out that Pd-Co-based catalyst, supported on anodized aluminum, possesses very high activity in combustion reactions of C1–C6 alkanes and toluene. The catalyst characterization has been made by N2-pysisorption, XRD, SEM, XPS, FTIR, TEM, and EPR methods. In view of the great interest, methane combustion was investigated in detail. It is ascertained that the complete oxidation of methane proceeds by dissociative adsorption on PdO and formation of hydroxyl and methyl groups, the former being highly reactive, and it undergoes further reaction to oxygen-containing intermediates, whereupon HCHO is one of them. The presence of Co2+ cations promotes greatly oxygen adsorption. The dissociative adsorption is favored on neighboring Co2+ cations, leading to the formation of bridging peroxides. Further, the oxygen dissociates on the nearest Pd2+ cations. According to the results from the experimental data, instrumental methods, and the observed kinetics and DFT model calculations, it can be concluded that the reaction pathway over Pd+Co/anodic alumina support (AAS) catalyst proceeds most probably through Mars–van Krevelen. The obtained data on the kinetics were used for simulation of the methane combustion in a full-scale adiabatic reactor.

Effect of transition and alkali metals on Mo2C/Al2O3 catalysts for syngas to higher alcohols

Direct production of higher alcohols remains a great challenge in syngas conversion process. Herein, MMo2C/Al2O3 and KMMo2C/Al2O3 catalysts promoted by different transition metals M (M=Co, Fe, Cu, Ni, Zn, Nb) and alkali metal (K) were prepared by impregnation method to investigate the effect on CO hydrogenation to higher alcohols under milder reaction conditions (300°C, 3.0 MPa). The catalysts were characterized with XRD, H2-TPR, and XPS. It was found that the addition of transition metals and K resulted in the decrease of low-valent Mo species on the catalyst surface, which facilitated the generation of Mo4+ during the reaction. Increase in Mo4+ content facilitates the conversion of CO to CO*, which provides more CO insertion sites for the generation of alcohols. Moreover, the introduction of K also enhances the interaction of transition metals with Mo, which accelerates the formation of alcohols in the reaction. Meanwhile, the transition metal and Mo2C work together to promote the dissociative adsorption of CO. The production of higher alcohols is facilitated by the synergistic effect of the two mentioned above. Overall, the KCoMo/Al2O3 and KFeMo/Al2O3 catalysts exhibited high selectivity for higher alcohols, reaching 73.9 % and 71.3 % for C2+OH in the alcohol products, respectively. CO conversion of KFeMo/Al2O3 catalyst can reach 84.9 % with excellent stability in the reaction. Moreover, the possible pathways of the reaction were obtained by in-situ DRIFT characterization.

Self-Inhibition Phenomena in Cu3Pt Oxidation by CO2.

This study investigates the oxidation behavior of Cu3Pt(100) in CO2 using a combination of ambient-pressure X-ray photoelectron spectroscopy, mass spectroscopy, and density functional theory modeling. Our in situ measurements reveal the simultaneous oxidation and reduction of Cu2O due to the opposing effects of atomic oxygen and CO generated from dissociative CO2 adsorption, leading to a dynamic equilibrium state of simultaneously occurring redox reactions. Complementary atomistic calculations elucidate the inhibitory effects of subsurface Pt enrichment and the counteracting roles of CO2 and CO in surface oxidation and reduction. These results provide mechanistic insights into the dissociative pathway of CO2 molecules and dynamic evolution of surface composition and reactivity of Cu-based alloy catalysts in CO2-rich environments, with broader implications for tuning gas-surface reactions by manipulating gas reactants or solid surface composition.

Surface Chemical Effects on Fischer–Tropsch Iron Oxide Catalysts Caused by Alkali Ion (Li, Na, K, Cs) Doping

Among the alkali metals, potassium is known to significantly shift selectivity toward value-added, heavier alkanes and olefins in iron-based Fischer–Tropsch synthesis catalysts. The aim of the present contribution is to shed light on the mechanism of action of alkaline promoters through a systematic study of the structure–reactivity relationships of a series of Fe oxide FTS catalysts promoted with Group I (Li, Na, K, Cs) alkali elements. Reactivity data are compared to structural data based on in situ, synchrotron-based XRD and XPS, as well as temperature-programmed studies (TPR-H2, TPC-CO, TPD-CO2, and TPD-H). It has been observed that the alkali elements induced higher carburization rates, higher basicities, and lower adsorbed hydrogen coverages. Catalyst stability followed the trend Na-Fe > unpromoted > Li-Fe > K-Fe > Cs-Fe, being consistent with the ability of the alkali (Na) to prevent active site loss by catalyst reoxidation. Potassium was the most active in promoting high α hydrocarbon formation. It is active enough to promote CO dissociative adsorption (and the formation of FeCx active phases) and decrease the surface coverage of H-adsorbed species, but it is not so active as to cause premature catalyst deactivation by the formation of a carbon layer resulting in the blocking active sites.

16O2 – 18O2 interface exchange study between gas phase and the BaFeO3–δ oxide

Studies of oxygen surface exchange kinetics for BaFeO3–δ oxide were performed using the oxygen isotope exchange method with pulsed supply of an isotopically enriched mixture (PIE) at the partial oxygen pressure 21.3 kPa in the temperature range of 350–600 °С. Oxygen surface exchange kinetics was considered in the framework of two-step model including two consecutive steps: dissociative adsorption of oxygen and incorporation of oxygen adatoms into the crystal lattice of the oxide. The rates of oxygen heterogeneous exchange (rH), as well as the rates of dissociative adsorption (ra) and oxygen incorporation (ri), have been calculated. The process of oxygen dissociative adsorption at the surface of BaFeO3–δ oxide was found to be the rate-determining step of the surface exchange. The appropriate models describing the oxygen exchange kinetics and possible mechanisms occurring in the system “gaseous oxygen – BaFeO3–δ oxide” were discussed.

Tailoring rGO[sbnd]Cu-Cu2O as a three-dimensional catalytic system in boosting of methanol electro-oxidation reaction

Tailoring a reduced graphene oxide-Cu-Cu2O (rGOCu-Cu2O) as a three-dimensional (3D) integrated catalytic system via an in-situ potential-controlled electrodeposition approach is a feasible pathway to boost methanol oxidation reaction (MOR) for direct methanol fuel cell. The enhancement in catalytic functionality and performances is due to the synergistic interaction between the in-situ electroreduced graphene oxide (rGO) and copper metal ions over it. The sequential and synergistic effect of the co-deposition potential, optimized time, and probable corrosion-promotion effect (formation of a galvanic cell between rGO and copper due to entrapped dissolved oxygen) is believed to be responsible for the structural growth of as-developed 3D catalytic systems. The MOR results suggest that the composite material deposited at the higher cathodic deposition potential (-1.2 V vs SCE), i.e., rGOCu (c) featured the remarkable lowest onset oxidation potential (i.e., +0.37 V), peak potential (i.e., +0.73 V), peak current density (135.76 mAcm−2), potentiostatic durability at +0.6 V after 3.5 h (∼65.85 mAcm−2) and outstanding cyclic stability (∼97.7 % current retention after 500 cycles), which is superior to the other modified composite electrodes. The enhanced performances are due to the effective dissociative adsorption of methanol from the available active catalytic site's and the presence of hydroxyl groups which has probably improved the oxidation of adsorbed intermediates from the surface. Further, Fourier-transform infrared (FT-IR) experiments revealed that formate as an active intermediate is being generated on all three rGOCu-Cu2O modified electrodes and follows the non-CO reaction pathway for direct oxidation of methanol.

Dissociative Oxygen Adsorption and Incorporation in Co3O4-Dispersed BaZr0.9Sc0.1O2.95 for PCFC Cathode.

The development of air electrodes with superior surface oxygen exchange properties at intermediate temperatures is crucial for improving the efficiency of protonic ceramic fuel cells. This study evaluated the surface exchange properties of Co3O4 dispersed protonic conductors, BaZr0.9Sc0.1O2.95. Although Co3O4 is widely acknowledged as superior dissociative adsorption catalysts, there is still ambiguity regarding the enhancement mechanisms of their surface exchange properties by Co3O4, as well as their optimal composition to achieve high catalytic activity. To overcome these difficulties, this study elucidated the effect of the chemical states and composition of composites on their surface exchange properties by evaluating their chemical states and surface exchange reaction rates with several compositions prepared at different temperature conditions using a vibrating-sample magnetometer and the pulse isotope exchange technique. For samples annealed at a high temperature, it became evident that the surface exchange activity became the most active by adding only 1 vol % Co3O4 and indicated an abrupt decline above this composition despite an increase in the volume of the catalysts. This was attributed to the combined effect of the high dissociative adsorption activity of the Co-containing solid solutions formed at a high temperature and a decrease in oxygen vacancies due to hole compensation. For samples annealed at intermediate temperature, their chemical states remained unchanged from those of the original milled powders, and their surface exchange properties monotonically improved with an increase in the volume of Co3O4. Based on the results, different chemical states of composites derived from different preparation conditions lead to completely different activation behavior of the surface exchange reaction.

Transition-Metal-Doped CeO2 for the Reverse Water-Gas Shift Reaction: An Experimental and Theoretical Study on CO2 Adsorption and Surface Vacancy Effects.

Transition metal-doped ceria (M-CeO2) catalysts (M = Fe, Co, Ni and Cu) with multiple loadings were experimentally investigated for reverse water gas shift (RWGS) reaction. Density functional theory (DFT) calculations were performed to benchmark the properties that impact catalytic activity of CO2 reduction. Temperature-programmed desorption (TPD) was conducted to study the CO2 binding strength on doped CeO2 surfaces; the trend of the energy along increasing metal loading agrees with the DFT calculations. Notably, CO2 dissociative adsorption energy and oxygen vacancy (OV) formation energy are key descriptors obtained from both DFT and experiments, which can be used to evaluate catalytic performance. Results show the effectiveness of transition metal doping in enhancing CO2 adsorption and reducibility of the surfaces, with Fe showing particularly promising results, i.e., CO2 conversion higher than 56% at 600 °C and 100% selectivity to CO. Cu exhibits 100% selectivity to CO but low CO2 conversion, while Co and Ni showed notable ability of methanation, particularly at high loadings. This study finds that an effective CeO2 based RWGS catalyst corresponds to OV sites that have low OV formation energies for surface reduction, and moderate CO2 adsorption energies for strong interaction with the surface to promote C-O bond scission.

Tuning the local electronic structure of Co15V-ZIF through bimetallic synergies as a bifunctional electrocatalyst for overall water splitting

Co-based bimetallic zeolite imidazolate frameworks (ZIFs) have been shown as promising electrocatalysts for the oxygen evolution reaction, but their electronic structure’s influence on the catalytic performance for overall water splitting still needs further investigation. In this study, Co15V-ZIF, structured as two-dimensional (2D) nanosheet arrays, are grown on nickel foam using one-step co-precipitation strategy. Owing to the synergistic effects of vanadium (V) and cobalt (Co) reasonably regulating the electronic structure, the synthesized bimetallic ZIFs demonstrate superior catalytic performance, which required the overpotentials of only 227 and 68 mV to achieve a current density of 10 mA cm−2 in 1 M KOH for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. Furthermore, the water electrolyzer assembled with bimetallic ZIF as cathode and anode exhibits the capability to achieve 10 mA cm−2 at a low cell voltage of 1.57 V. In situ Raman spectroscopy reveals that the introduction of V facilitates the formation of V-CoOOH, the real active site for OER, at lower applied potentials. Besides, it induces a local acidic environment on V-Co(OH)2, the real active sites, thereby enhancing the HER performance of the sample. Density Functional Theory (DFT) calculations further show that the synergistic effects of V and Co induce electron redistribution, thereby improving electrical conductivity, reducing the energy barrier for water dissociation and hydrogen adsorption, which promotes the formation of H3O+ and triggering H3O+-induced water reduction in alkaline media. This work provides new insight into tailoring electronic structures to rationally design highly efficient ZIF electrocatalysts.

DFT study of adsorption and potential detection of carbonyl fluoride on B-doped aluminum nitride nanosheets

Carbonyl fluoride (COF2) is a decomposition product that can be used to find failures in gas-insulated switchgear equipment. In this study, we applied Density Functional Theory (DFT) calculations to examine the suitability of pristine and boron-doped aluminum nitride nanosheets (AlNNS) for COF2 adsorption and sensing applications. Our investigation suggested a dissociative COF2 adsorption on pristine AlNNS, resulting in important adsorption energy (–2.19 eV), the releasing of a fluorine atom from the molecule and formation of new C–N, O–Al and F–Al bonds. Two preferential chemisorption geometries were achieved on the B-doped N-vacancy monolayer (B-vN-AlNNS), with adsorption energies of –1.04 and –3.44 eV. In the first geometry, only an O–B bond was formed, whereas in the another one similar interactions as in COF2/AlNNS took place. Furthermore, we analyzed the evolution of electronic properties in order to evaluate the performance of these nanosheets for COF2 detection purposes. Our results showed significant modifications in both energy gap and work function only after COF2 adsorption on B-vN-AlNNS. Finally, charge transfer analysis revealed electron exchange from the studied surfaces to the gas molecule. These findings suggest that B-doped AlNNS exhibits good performance for COF2 detection, and could encourage further experimental research to develop efficient sensing materials.

Effect of doping with iron and cations deficiency in the high conductive electrolyte La0.8Sr0.2Ga0.8Mg0.2O3–δ on oxygen exchange kinetics

The oxygen isotope exchange method was used to investigate the kinetics of the interaction between gaseous oxygen and LaGaO3-based oxides in a temperature range of 650 to 850 °C, with an oxygen pressure of 10 mbar. The stable isotopes of 18O/16O were used as labelled ions. The temperature dependencies of the heterogeneous oxygen exchange rate (rH), the oxygen dissociative adsorption rate (ra), the oxygen incorporation rate (ri), and the oxygen diffusion coefficient (D) were determined. A comparative analysis of the rH and D values for La0.8Sr0.2Ga0.8Mg0.2O3–δ was carried out with a view to identifying any similarities or differences when compared with the literature data on oxides with similar compositions. The effect of FeGa′ doping and the creation of an A-sublattice deficiency on the kinetic characteristics were investigated using the (La0.8Sr0.2)0.98Ga0.7Fe0.1Mg0.2O3–δ oxide as a case example. Correlations between the rate-determining step of oxygen exchange and the modification of the oxide composition were identified.

Plasma-catalytic dry reforming of CH4: Effects of plasma-generated species on the surface chemistry

By means of steady-state experiments and a global model, we studied the effects of plasma-generated reactive species on the surface chemistry and coking in plasma-catalytic CH4/CO2 reforming at reduced pressure (8–40 kPa). We used a hybrid ZDPlasKin-CHEMKIN model to predict the species densities over time. The detailed plasma-catalytic mechanism consists of the plasma discharge scheme, a gas-phase chemistry set and a surface mechanism. Our experimental results show that the coupling of Ni/SiO2 catalyst with plasma is more effective in CH4/CO2 activation and conversion than unpacked DBD plasma, with syngas being the main products. The highest total conversion of 16 % was achieved at 8000 V and 473 K, with corresponding CO and H2 yields of 15 % and 12 %, respectively. The reactants conversion and product selectivity are well captured by the kinetic model. Our simulation results suggest that vibrational species and radicals can accelerate the dissociative adsorption and Eley-Rideal (E-R) reactions. Path flux analysis shows that E-R reactions dominate the surface reaction pathways, which differs from thermal catalysis, indicating that the coupling of non-equilibrium plasma and catalysis can effectively shift the formation and consumption pathways of important adsorbates. For instance, our model suggests that HCOO(s) is primarily generated through the E-R reaction CO2(v) + H(s) → HCOO(s), while the hydrogenation reaction HCOO(s) + H → HCOOH(s) is the main source of HCOOH(s). Carbon deposition on the catalyst surface is primarily formed through the stepwise dehydrogenation of CH4, while the E-R reactions enhanced by plasma-generated H and O atoms dominate the consumption of carbon deposition. This work provides new insights into the effects of reactive species on the surface chemistry in plasma-catalytic CH4/CO2 reforming.

Water adsorption on ferroelectric PbTiO3 (0 0 1) surface: A density functional theory study

In this work, combining the density functional theory (DFT) calculations and the ab initio molecular dynamics (AIMD) simulations, the water adsorption behavior, including the molecular and the dissociative adsorption on the negatively polarized (0 0 1) surface of ferroelectric PbTiO3 was comprehensively studied. Our theoretical results show that the dissociative adsorption of water is more energetically favorable than the molecular adsorption on the pristine PbTiO3 (0 0 1) surface. It has been also found that introducing surface oxygen vacancies (OV) can enhance the thermodynamic stability of dissociative adsorption of water molecule. The AIMD simulations demonstrate that water molecule can spontaneously dissociate into hydrogen atoms (H) and hydroxyl groups (OH) on the pristine PbTiO3 (0 0 1) surface at room temperature. Moreover, the surface OV can effectively facilitate the dissociative adsorption of water molecules, leading to a high surface coverage of OH group, thus giving rise to a high reactivity for water splitting on defective PbTiO3 (0 0 1) surface with OV. Our results not only comprehensively understand the reason for the photocatalytic water oxidation activity of single domain PbTiO3, but also shed light on the development of high performance ferroelectric photocatalysts for water splitting.