Oxygen Mobility Research Articles

Impact of calcium and copper co-doping on the oxygen transport of layered nickelates: a case study of Pr1.6Ca0.4Ni1–yCuyO4+δ and a comparative analysis

This study aims at investigating oxygen content and diffusion in the Pr1.6Ca0.4Ni1‑yCuyO4+δ (y = 0.0–0.4) series. Single-phased materials were obtained via nitrate combustion using glycerol as a fuel. The materials exhibit an orthorhombic structure, which correlates well with the absolute oxygen content in the samples in the range of 4.15–3.97. The oxygen mobility in the samples was investigated by a temperature-programmed isotope exchange of oxygen (TPIE) with C18O2 in a flow reactor. The obtained curves, comprising few extrema, were fitted using a mathematical model that includes two or three distinct oxygen forms, each characterized by a specific diffusion coefficient value. The oxygen tracer diffusion coefficient values and the contribution of fast oxygen forms tend to decrease with increasing Cu content (except for Pr1.6Ca0.4Ni0.8Cu0.2O4+δ), which can be explained by the variation of highly mobile interstitial oxygen content since the effective activation energy values remains the same within the calculation error. Comparative analysis shows that this behavior is similar to the trends observed and discussed for Ca- and Cu-doped La and Nd nickelates. Nevertheless, the highest D* value for Ofast was demonstrated for the Pr1.6Ca0.4Ni0.8Cu0.2O4+δ sample (9.4·10–8 cm2/s at 700 °C), which correlates well with superior electrochemical properties of the electrodes on its basis.

Polyoxometalates‐Mediated Selectivity in Pt Single‐Atoms on Ceria for Environmental Catalysis

AbstractOptimizing the reactivity and selectivity of single‐atom catalysts (SACs) remains a crucial yet challenging issue in heterogeneous catalysis. This study demonstrates selective catalysis facilitated by a polyoxometalates‐mediated electronic interaction (PMEI) in a Pt single‐atom catalyst supported on CeO2 modified with Keggin‐type phosphotungstate acid (HPW), labeled as Pt1/CeO2‐HPW. The PMEI effect originates from the unique arrangement of isolated Pt atoms and HPW clusters on the CeO2 support. Electrons are transferred from the ceria support to the electrophilic tungsten in HPW clusters, and subsequently, Pt atoms donate electrons to the now electron‐deficient ceria. This phenomenon enhances the positive charge of Pt atoms, moderating O2 activation and limiting lattice oxygen mobility compared to the conventional Pt1/CeO2 catalyst. The resulting electronic structure of Pt combined with the strong and local acidic environment of HPW on Pt1/CeO2‐HPW leads to improved efficiency and N2 selectivity in the degradation of NH3 and NO, as well as increased CO2 yield when inputting volatile organic compounds. This study sheds the light on the design of SACs with balanced reactivity and selectivity for environmental catalysis.

Enhancement of CO2 adsorption and oxygen transfer properties on γ-Al2O3 support through surface modification with MgO-ZrO2 for coke suppression over Ni catalyst in CO2 reforming of methane

This work focuses on employing commercial γ-Al2O3 for surface modification with MgO-ZrO2 mixed oxide to enhance the potential of CO2 adsorption and oxygen mobility. This enhancement facilitates its application as a support in catalysts for CO2 utilization such as CO2 reforming of methane (CRM). To achieve this perspective, γ-Al2O3 was modified with 10 wt.% of various MgO and ZrO2 contents (MgO:ZrO2= 10:0, 9:1,7:3, 5:5, 3:7, 1:9 and 0:10) using the impregnation method. All samples including unmodified γ-Al2O3 (Al) were characterized. Due to the increase in basicity and oxygen transfer around the surface, the improvement of the CO2 adsorption was observed on γ-Al2O3 modified with 9 wt.% MgO-1 wt.% ZrO2 (9Mg1ZrAl) and 10 wt.% MgO (10MgAl), respectively. An application of these two superior samples as a support of 10 wt.% Ni (10Ni) catalysts for CRM was investigated and compared with an unmodified γ-Al2O3. Characterization results suggest the formation of NiO-MgO solid solution at the surface due to the decrease in metal-support interaction and the increase in metal dispersion. The Ni catalysts with the surface-modified support show higher CO2 activity that raises carbon deposition resistance. The greatest coke prevention was observed on 10Ni/9Mg1ZrAl that lowers the coke deposition by 42% compared to 10Ni/Al. It indicates that the composition of this modification allowed very low ZrO2 portion to merge with MgO and MgO to form solid solution with NiO. This enables the 10Ni/9Mg1ZrAl catalyst to generate labile oxygens which can be conveyed to the Ni metal sites on the catalyst.

Efficient catalytic oxidation of xylose to formic acid with the oxygen vacancies of CeO2 promoted the vanadium catalysts anchored on biochar

The catalytic oxidation of carbohydrates for the preparation of formic acid (FA) is an prominent route for high-value utilisation of biomass. Reforming xylose, a biomass derivative, into FA with high efficiency is essential for the advancement of non-homogeneous V-type catalysts. Here, we present the self-assembly of V and Ce onto a cellulose pulp for the synthesis of oxygen vacancy (Ov)-rich non-homogeneous-bimetallic catalysts (5Ce-VOx/BC-600). Under the optimised conditions, 71.46 % FA was obtained, which far exceeded the catalytic performance of the single-metal catalyst. Furthermore, the 5Ce-VOx/BC-600 catalyst showed excellent stability and reusability. Kinetic studies revealed that glyceric and glycolic acids served as the pivotal intermediates, undergoing subsequent deacidification and oxidation processes to yield FA and CO2. The analysis of the catalytic mechanism indicated that the incorporation of Ce enhanced the quantity of acidic sites and the concentration of Ov in the 5Ce-VOx/BC-600 catalyst, which promoted substrate adsorption and O2 activation. Meanwhile, the catalyst showed high lattice oxygen (OL) mobility and assisted the redox cycle of V5+/V4+ to oxidise xylose to FA. Significantly, the synergistic effect of Ce, V species and Ov enhances the OL mobility of the catalysts, thus promoting the efficient oxidation of xylose. The catalytic system was further extended to the oxidation of other biomass derivatives to FA, demonstrating excellent catalytic performance.

Synthesis and carbon monoxide purification performance of ZSM-5 molecular sieve Co-doped Mn/V catalytic material

Trackless, rubber-tired, diesel-powered vehicles are widely used in the mining industry. In recent years, the use of high-performance catalysts to remove carbon monoxide (CO) from diesel vehicle exhaust has attracted much attention. In this paper, a series of manganese-vanadium doped ZSM-5 molecular sieve catalysts were prepared by an impregnation method. The structures of the catalysts were characterized and experiments were conducted to evaluate their performance. The CO catalytic oxidation performance experiments revealed that Mn0.6-V0.4-ZSM-5 had the best performance, with a conversion rate of 97.5 % at 300 °C. The catalyst was also tested for water resistance and stability. Kinetic measurements were performed and the fitted activation energy was 22.68 kJ/mol. Characterization studies revealed that the surface defects formed by Mn and V doping provided a large number of active sites and oxygen vacancies for CO oxidation, increased the number of adsorbed oxygen species on the surface, and enhanced the redox capacity through the interaction of Mn4+ and V5+ to improve the catalytic oxidation performance of the catalyst. The adsorption configurations, adsorption energy (Ebin), and formation energy of oxygen vacancies of CO at different adsorption sites and different active fractions were calculated with density functional theory. The Ebin of CO on Mn2V2O7, the active fraction of Mn0.6-V0.4-ZSM-5, was −1.29 eV, which was the most stable adsorption configuration. This configuration had good oxygen mobility, and was conducive to CO catalysis, confirming the characterization and performance experiments.

Non-metallic cation and anion co-doped perovskite oxide ceramic membranes for high-efficiency oxygen permeation at low temperatures

Insufficient structural stability and limited lattice oxygen mobility at low temperatures seriously limit the application of perovskite-type oxides in mixed ionic-electronic conducting oxygen-permeable membranes. Engineering the crystal structure and oxygen vacancies by ion doping is an effective strategy to enhance both structural stability and lattice oxygen mobility. Different from conventional metal ion doping, we report that the co-doping of the classical SrCoO3-δ by the non-metallic cation P5+ and the anion Cl- stabilizes the cubic perovskite structure and allows low temperature oxygen permeation due to improved lattice oxygen mobility. In detail, P doped at the Co site transforms the crystal structure from the hexagonal phase to the cubic phase, and Cl doped at the oxygen site weakens the metal-oxygen bond, which significantly enhances the lattice oxygen mobility. Optimal doping concentrations were found to be SrCo0.95P0.05O3-δCl0.05 (SCP5Cl5). Furthermore, by constructing an asymmetric membrane with a sandwich structure, the oxygen permeation flux of the SCP5Cl5 ceramic membrane was up to 1.10 mL min-1 cm-2 at 873 K, which provides an effective strategy for developing oxygen-permeable membranes with high permeation flux at low temperatures.

Selective catalytic reduction of NO with NH3 over HZSM-5/CeO2 hybrid catalysts: Relationship between acid structure and reaction mechanism

CeO2 is active in the NH3 selective catalytic reduction of NO (NH3-SCR) reaction due to its excellent redox properties. However, the low surface acidity of CeO2 limits its NH3-SCR activity. In this study, highly active HZSM-5-modified HZSM-5/CeO2 (Z/Ce) mixed oxide catalysts were prepared by a simple physical milling method. The HZSM-5 modification stimulated many thermally stable Brønsted-acid structures and high oxygen mobility on the surface of the Z/Ce catalysts, promoting the acid cycling pathways driven by redox macrocycles, and accelerating NO removal. The NO conversion of 25Z/Ce at 200–400 °C is about 34.8 %-62.3 % higher than that of CeO2. A series of physicochemical and in situ interfacial reactions were analyzed to explore the medium- and high-temperature reaction mechanism on the CeO2 surface. The Eley-Rideal reaction mechanism on the Lewis-acid structure with NO(g) as the reactant is deduced. When HZSM-5 modified CeO2, more NO was activated to NO2(g) on the surface of the Z/Ce catalyst at medium and high temperatures (300 °C). This significantly enhanced the Eley-Rideal reaction mechanism with NO2(g) as the main reactant on the Brønsted-acid structure as well as the occurrence of the “Fast-SCR” reaction. This work provides a simple method to improve the performance of CeO2 in the NH3-SCR reaction and elucidates the reaction mechanism.

Modulating charge transfer and constructing synergistic bimetallic active sites for CO-SCR reactions in inverse spinel

The selective catalytic reduction of NO by CO (CO-SCR) are frequently catalyzed by spinel due to its exceptional stability and redox capabilities. In this research, a ternary metal-based inverse spinel catalyst Cu0.67Mn0.33Fe2O4 was synthesized utilizing the glycerol self-templating technique. Some Fe3+ (Fe3+Td) sites are transferred to vacant octahedral sites through the occupancy of tetrahedral sites by Mn species. Mn3+ (Mn3+Td) sites synergistically interact with Cu2+ and Fe3+ ions on the octahedral sites to promote charge transfer, producing numerous oxygen-defective and highly mobile oxygen species and constructing Cu+-Ov-Fe2+ active sites on the surface. Various characterizations demonstrated that Cu+-Ov-Fe2+ has greater catalytic activity, resistance to alkali metals, and water toxicity than the Cu2+-Ov-Fe2+ active site of CuFe2O4. In situ DRIFTS further revealed the reaction mechanism of the ternary metal-based inverse spinel catalyst, and this study provides novel perspectives on the development of Cu-based catalysts for CO-SCR.

Ultra-efficient Ru and Nb Co-Modified CeO2 Catalysts for Catalytic Oxidation of 1,2-Dichloroethane.

The oxidation of chlorinated volatile organic compounds on CeO2 is hindered by its high susceptibility to chlorine poisoning, resulting in a reduced efficiency and stability. In this study, Ru- and Nb-co-modified CeO2 catalysts were designed to achieve excellent activity, stability, and CO2 selectivity in the catalytic oxidation of 1,2-dichloroethane (EDC). The formation of Nb-O-Ce bonds was observed to enhance the surface acidic sites, thereby improving HCl selectivity and reducing the production of chlorinated byproducts. Meanwhile, it inhibits the formation of Ru-O-Ce and promotes the generation of highly dispersed RuO2 particles on the surface, enhancing the redox properties and mobility of the surface oxygen, thus increasing CO2 selectivity. In situ diffuse reflectance infrared Fourier transform spectroscopy results revealed that chlorine species preferentially attach to Nb species rather than to oxygen vacancies on the Ru/Nb/CeO2 catalyst. This allows more alkane groups to oxidize to formate on the oxygen vacancies, reducing byproduct concentration. Additionally, the oxidation of alkane groups to carboxylic acids is initiated on the Nb species, completing a comprehensive oxidation process under the synergistic effect of RuO2.

Low temperature sintering flue gas NH3-SCR denitrification mechanism of embedded 7Mn3Ce/AC catalyst

Friction of catalyst in practical application and transportation leads to the metal oxides shedding, thus diminishing the lifetime. In order to inhibit the active component fallout, a series of embedded catalysts were prepared by activated carbon (AC) fabrication from coal as based, which were designed to remove NOx from sinter flue gas. Research results demonstrated that the denitrification activity of 7Mn3Ce/AC catalyst reached 81.3 % at 180 °C, and still maintained stable NO conversion after 44 h. MnO2 and CeO2 were added in catalyst could increase the Oα proportion, leading to an improvement the mobility of oxygen. Moreover, the formation of oxygen vacancies by Oβ in cerium oxide was facilitated by a high relative ratio of Ce3+, and Mn4+ favorable redox properties promoted the reduction of NO to N2, which advantaged the denitrification process. Furthermore, abundant Lewis acid and Brønsted acid sites were instrumental in the accumulation of NH3 on the catalyst surface. The reaction pathway of 7Mn3Ce/AC catalyst followed the E-R and L-H mechanisms.

Mg bulk and surface modification on Ni/Y2Ti2O7 catalyst for dry reforming of methane

Dry reforming of methane (DRM) can simultaneously convert two greenhouse gases, CH4 and CO2, into high value-added synthetic gas, which can effectively alleviate the energy crisis and optimize the human ecological environment. In this work, the effect of Mg addition method on the activity of the Y2Ti2O7 pyrochlore supported Ni catalysts was investigated in DRM. The H2-TPR and XPS results showed that Mg modification enhanced the interaction between Ni and Y2Ti2O7 pyrochlore support. Thus, much smaller Ni grains with better thermal stability could be achieved on the Mg doped Ni/Y2Ti2O7 catalyst, as evidenced by the XRD, H2-TPD and TEM results. CO2-assistant CH4-TPSR demonstrated that Mg surface modification can facilitate the reaction between the activated CO2∗ and the H∗ produced by CH4 dissociation. Mg incorporation increased the basic site of the Ni/Y2Ti2O7 catalyst, as evidenced by CO2-TPD-MS results, which was conducive to the adsorption and activation of CO2 to promote the removal of coke deposition. Consequently, Ni/Y1·5Mg0·5Ti2O7 and Ni–MgO/Y2Ti2O7 catalysts exhibit higher stability and more potent coke resistance than the unmodified Ni/Y2Ti2O7 sample. It is concluded that higher Ni0 dispersion and more mobile active oxygen species are the main reasons for the improvement of activity and coke resistance of the Ni/Y2Ti2O7 catalysts. In addition, in situ DRIFTS results confirmed that CO2 activation of all catalysts followed the formate intermediate species path.

Enhancing Thermochemical Energy Storage Performance of Perovskite with Sodium Ion Incorporation

Perovskite materials are promising for thermochemical energy storage due to their ability to undergo redox cycling over a wide temperature range. Although BaCoO3 exhibits excellent air cycling properties, its heat storage capacity in air remains suboptimal. This study introduces Na into the lattice structure to enhance oxygen vacancy formation and mobility. DFT+U simulations of the surface structure of Na-doped BaCoO3−δ indicate that incorporating Na improves surface stability and facilitates the formation of surface oxygen vacancies. NaxBa1−xCoO3−δ compounds were synthesized using a modified sol–gel method, and their properties were investigated. The experimental results demonstrate that Na doping significantly enhances the redox activity of the material. The heat storage capacity increased by above 50%, with the Na0.0625Ba0.9375CoO3−δ solid solution achieving a heat storage density of up to 341.7 kJ/kg. XPS analysis reveals that Na doping increases the concentration of surface defect oxygen, leading to more active oxygen release sites at high temperatures. This enhancement in redox activity aligns with DFT predictions. During high-temperature cycling, the distribution of Na within the material becomes more uniform, and no performance degradation is observed after 300 cycles. Even after 450 cycles, Na0.0625Ba0.9375CoO3−δ retains over 96% of its initial redox activity, significantly outperforming fresh BaCoO3−δ. These findings elucidate the mechanism by which Na doping enhances the thermochemical heat storage performance of BaCoO3−δ and provide new insights for the design of perovskite-based materials.

Low temperature atomic layer deposition of PbO2 for electrochemical applications

A low temperature atomic layer deposition (ALD) process for PbO2was developed using bis(1-dimethylamino-2-methyl-2-propanolate)lead(II), Pb(DMAMP)2, and O3as the reactants, with a high growth rate of 2.6 Å/cycle. PbO2readily reduces under low oxygen partial pressures at moderate temperatures making it challenging to deposit ALD PbO2from Pb2+precursors. However, thin films deposited with this process showed small crystalline grains of α-PbO2and β-PbO2, without signs of reduced PbOxphases. The ALD PbO2thin films show the high electrical conductivity characteristic of bulk PbO2. In situ measurements of ALD PbO2film conductivity during growth suggest a reaction mechanism by which sub-surface oxygen mobility contributes to the growth of resistive PbO or PbOxduring the Pb(DMAMP)2surface reaction step, which is only fully oxidized from Pb2+to Pb4+during the O3reaction step. These films were electrochemically reduced to PbSO4in H2SO4and then reoxidized to PbO2, demonstrating their suitability for use as an electrode material for fundamental battery research and other electrochemical applications.

A novel homological approach for the comprehensive study of nonstoichiometric oxide with exceptional oxygen mobility

Actual work devoted to the development of a novel homological approach for describing the kinetic properties of grossly nonstoichiometric oxides ABO3-δ with perovskite structure. The approach consists in considering such oxides having different oxygen stoichiometry 3-δ as chemical homologues involved in the same oxygen exchange reaction and forming a continuous series in δ. The proposed approach is considered using the oxide with exceptional oxygen mobility Ba0·5Sr0·5Co0·8Fe0·2O3-δ (BSCF). The kinetic properties of BSCF were studied by new method of the oxygen partial pressure relaxation. The equilibrium properties of BSCF were reported earlier and obtained by original technique of the quasi-equilibrium oxygen release. The power law dependence of the kinetic parameters on the equilibrium oxygen partial pressure is considered as the consequence of linear free energy relationship similar to the Brønsted-Evans-Polanyi relation.

CO2 utilization and on-purpose ethylene production: a chemical looping approach

CO2-assisted ethane dehydrogenation (CO2-ODHE) is a promising carbon atom economy process for upgrading CO2 to CO in tandem with C2H6 to C2H4 conversion. Iron oxide-based materials are selective for on purpose ethylene production through CO2-ODHE. The feed admission mode was found to play an important role on catalytic performance. Alternating C2H6 (reduction step) and CO2 (oxidation step) feedstock to a fixed bed reactor (chemical looping concept, CO2-ODHE-CL) attained constant ethane and CO2 conversion per step at 600oC, equal to ~17.6%, while C2H4 selectivity during the reduction step was ~75%. The lattice oxygen mobility is a descriptor for the materials used during the CO2-ODHE-CL, since low mobility resulted in an increased C-H bond scission selectivity, i.e., C2H4 production, during the reduction step. Temperature programmed 18O2 isotope exchange experiments, along with temperature programmed H2 – reduction, were employed to exemplify the latter statement, investigating the lattice oxygen reactivity of the examined materials and the mechanism through which the lattice oxygen is reacting. X-ray techniques (X-ray Diffraction, X-ray Raman Scattering Spectrometry, X-ray Absorption Spectrometry) along with structural modeling demonstrated that the formation of a spinel like arrangement between Mg and Fe, stabilized lattice oxygen and thus minimized the undesired C-C bond scission during the C2H6 step of CO2-ODHE-CL.

Efficient low-temperature CO removal from high-humidity sintering flue gas by combination Cu and OMS-2

The non-precious metal manganese-based catalysts currently show insufficient CO catalytic oxidation performance in actual sintering flue gas conditions, with increased water vapor levels causing catalyst deactivation. This study utilized a high-performance manganese dioxide octahedral molecular sieve (OMS-2). The effect of metal doping on the catalytic CO oxidation performance was investigated in preparing OMS-2 using the co-precipitation method. The experiments showed that Cu doping increased CO conversion efficiency more than other metals (Co, Ag, Zn, and Fe), with optimal performance achieved at a 1.91 wt% doping level. Besides, Cu doping significantly enhanced water resistance of the catalyst, enabling effective CO removal in high-humidity conditions. The study observed that Cu ions infiltrated the catalyst framework by substituting some of the Mn ions, creating additional active sites in the form of oxygen vacancies and improving surface oxygen mobility, thereby enhancing the performance of CO catalytic oxidation. Furthermore, Cu doping demonstrated selective absorption of water vapor, with CuxO in the catalyst, effectively adsorbing water vapor and protecting the initial active sites, thereby mitigating water vapor-induced poisoning. Even in 15 vol% H2O at 150 °C, 1.91%Cu-OMS-2 maintained total catalytic activity. Therefore, the co-precipitation method-prepared 1.91%Cu-OMS-2 catalyst holds excellent potential for CO removal in sintering flue gas and shows promise for practical applications.

Polyoxometalates-Mediated Selectivity in Pt Single-Atoms on Ceria for Environmental Catalysis.

Optimizing the reactivity and selectivity of single-atom catalysts (SACs) remains a crucial yet challenging issue in heterogeneous catalysis. This study demonstrates selective catalysis facilitated by a polyoxometalates-mediated electronic interaction (PMEI) in a Pt single-atom catalyst supported on CeO2 modified with Keggin-type phosphotungstate acid (HPW), labeled as Pt1/CeO2-HPW. The PMEI effect originates from the unique arrangement of isolated Pt atoms and HPW clusters on CeO2 surface. Electrons are transferred from ceria support to the electrophilic tungsten in HPW clusters, and subsequently, Pt atoms donate electrons to the now electron-deficient ceria. This phenomenon enhances the positive charge of Pt atoms, moderating O2 activation and limiting lattice oxygen mobility compared to the conventional Pt1/CeO2 catalyst. The resulting electronic structure of Pt combined with the strong and local acidic environment of HPW on Pt1/CeO2-HPW leads to improved degradation of NH3, N2 selectivity in the NO conversion, and CO2 yield when inputting volatile organic compounds. This study sheds the light on the design of SACs with balanced reactivity and selectivity for environmental catalysis applications.

Improved biohydrogen production using Ni/ZrxCeyO2 loaded on foam reactor through steam gasification of sewage sludge

The pervasive generation of sewage sludge (SES) and deficiencies in its disposal methods have resulted in several significant environmental and human health challenges. This study explored the catalytic effect of nickel (Ni)-based CeO2, ZrO2, Zr0.8Ce0.2O2, Zr0.4Ce0.6O2, and γ-Al2O3 supports in fixed beds and foam reactors in the steam gasification of SES. A comparison of the hydrogen selectivity and gas yield of the synthesized catalysts confirmed that the metal composite support, especially Zr0.8Ce0.2O2, had a positive effect on the catalytic activity and stability. This can be attributed to the enhanced oxygen vacancies and oxygen mobility, resistance to coke deposition, uniform morphology, improved dispersion, and increased number of Ni sites on the Zr0.8Ce0.2O2 support. Furthermore, foam reactors offer unique advantages in improving hydrogen production. This study provides an advanced strategy for SES valorization that fulfills the requirements of an economically and environmentally sustainable technology.

Revealing the promotional effect of Zr and phosphate Co-decorated on δ-MnO2 catalysts for highly efficient catalytic elimination of chlorinated VOCs: An experimental and theoretical study

The development of advanced catalysts for catalytic oxidation of CVOCs still presents challenges in terms of low activity, chlorination poisoning and the formation of toxic byproducts. In this study, a series of nP-MnxZry catalysts with exceptional catalytic oxidation activity were developed for the removal of CVOCs in industry. Among them, 15P‐MZ exhibited the optimal catalytic activity and stability for CB degradation, achieving a T90 of 180 ℃. Notably, the CB oxidation rate of 15P‐MZ was found to be 5.76 times higher than that of MnO2 at 155 °C. Structure and properties analysis combining with DFT calculations revealed that the dual modification strategy involved Zr doping and phosphate loading induced the formation of high concentration of oxygen vacancy over 15P‐MZ, which enhanced oxygen mobility, facilitating the breakage of the aromatic ring. Meanwhile, this strategy introduced more Brønsted acid sites, promoting the dissociation of Cl in the form of HCl, thereby inhibiting the formation of polychlorinated byproducts. Moreover, the activation effect of phosphate on the dissociation of H2O further promoted the Cl dissociation, thereby regenerating more active sites and improving catalytic activity and stability in humid environment, making it more promising for industrial applications.

In situ observation of reversible phase transitions in Gd-doped ceria driven by electron beam irradiation

Ceria-based oxides are widely utilized in diverse energy-related applications, with attractive functionalities arising from a defective structure due to the formation of mobile oxygen vacancies (VO⋅⋅\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{O}^{\\cdot \\cdot }$$\\end{document}). Notwithstanding its significance, behaviors of the defective structure and VO⋅⋅\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{O}^{\\cdot \\cdot }$$\\end{document} in response to external stimuli remain incompletely explored. Taking the Gd-doped ceria (Ce0.88Gd0.12O2-δ) as a model system and leveraging state-of-the-art transmission electron microscopy techniques, reversible phase transitions associated with massive VO⋅⋅\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{O}^{\\cdot \\cdot }$$\\end{document} rearrangement are stimulated and visualized in situ with sub-Å resolution. Electron dose rate is identified as a pivotal factor in modulating the phase transition, and both the VO⋅⋅\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{O}^{\\cdot \\cdot }$$\\end{document} concentration and the orientation of the newly formed phase can be altered via electron beam. Our results provide indispensable insights for understanding and refining the microscopic pathways of phase transition as well as defect engineering, and could be applied to other similar functional oxides.