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1.
Evolution of electrical conductivity and semiconductor to metal transition of iron oxides at extreme conditions 下载免费PDF全文
Yukai Zhuang 《中国物理 B》2022,31(8):89101-089101
Iron oxides are widely found as ores in Earth's crust and are also important constituents of its interiors. Their polymorphism, composition changes, and electronic structures play essential roles in controlling the structure and geodynamic properties of the solid Earth. While all-natural occurring iron oxides are semiconductors or insulators at ambient pressure, they start to metalize under pressure. Here in this work, we review the electronic conductivity and metallization of iron oxides under high-pressure conditions found in Earth's lower mantle. We summarize that the metallization of iron oxides is generally controlled by the pressure-induced bandgap closure near the Fermi level. After metallization, they possess much higher electrical and thermal conductivity, which will facilitate the thermal convection, support a more stable and thicker D$\prime\prime$ layer, and formulate Earth's magnetic field, all of which will constrain the large-scale dynamos of the mantle and core. 相似文献
2.
In many perovskite oxides, ferroelectricity is intimately related to octahedral rotation patterns, which can suppress or enhance polar distortions. Using first-principles density functional theory, we investigate the relation between octahedral rotation patterns and polar instability. Based on the rotation patterns commonly observed in perovskite oxides, we present a workflow that allows to systematically and efficiently search for the unstable polar phonon modes and identify metastable polar structures. We apply the workflow to investigate rotation-pattern-dependent polar phases of CaSnO3 and find metastable polar structures by changing rotation patterns. Further investigation of the polar R3c structures shows sizable polarization comparable to the conventional ferroelectrics. We discuss substrate materials having the potential to stabilize the polar structure. Our work provides an efficient way to identify new polar phases by changing the octahedral rotation patterns, which will be useful to design new functional materials in the thin-film/substrate configuration utilizing interfacial coupling. 相似文献
3.
4.
The development of selective electrocatalysts for the chlorine evolution reaction (CER) is majorly restrained by a scaling relation between the OCl and OOH adsorbates, rendering that active CER catalysts are also reasonably active in the competing oxygen evolution reaction (OER). While theory predicts that the OCl versus OOH scaling relation can be circumvented as soon as the elementary reaction steps in the CER comprise the Cl rather than the OCl adsorbate, it was demonstrated recently that PtN4 sites embedded in a carbon nanotube follow this theoretical prediction. Advanced experimental analyses illustrate that the PtN4 sites also reveal a different reaction kinetics compared to the industrial benchmark of dimensionally stable anodes (DSA). A reverse Volmer–Heyrovsky mechanism was identified, in which the rate-determining Volmer step for small overpotentials is followed by the kinetically limiting Heyrovsky step for larger overpotentials. Since the PtN4 sites excel DSA in terms of activity and chlorine selectivity, we suggest the Cl intermediate as well as the reverse Volmer–Heyrovsky mechanism as the design criteria for the development of next-generation electrode materials beyond DSA. 相似文献
5.
The activity of NiO/Co3O4 for the hydrogen evolution reaction (HER) during water splitting was increased by depositing these metal oxides on siloxene multi-sheets. The improvement in active sites due to siloxene was used to increase the catalytic activity. The hierarchical structure of the composite with the synergistic effect of metal oxides helped enhance the catalytic activity to show a low overpotential of 110 mV at 10 mA/cm2 in 1 M KOH and stability at 10 mA/cm2 over 20 h without an obvious change in voltage. The as-prepared catalyst can be a promising electrocatalyst for the HER owing to the low cost of transition metal oxides, the abundance of silicon on Earth, and the simplicity of the synthesis process. 相似文献
6.
采用共沉淀法成功地合成了不同Mg掺杂量的Ce1-xMgxO2(x=0.05、0.10、0.15、0.20)固溶体催化材料,并运用透射电子显微镜(TEM)、X射线衍射(XRD)、氮气吸附-脱附测试、拉曼光谱、X射线光电子能谱(XPS)、CO2程序升温脱附(CO2-TPD)等技术对这些材料进行了表征。结果发现,通过调控CeO2晶格中Mg的含量,可以调控所制备的Ce1-xMgxO2催化材料的粒径、比表面积、表面缺陷等。其中Ce0.90Mg0.10O2展现了最佳的表面性质,具有最小的平均粒径(约5.8 nm),最大的比表面积(约136 m2·g-1)以及最高的表面氧含量(31.98%)。将Ce1-xMgxO2催化材料涂覆在堇青石蜂窝陶瓷上制成整体催化剂,考察其对CO2和CH3OH直接合成碳酸二甲酯的催化性能。在140℃、2.4 MPa、反应2 h的条件下,Ce0.90Mg0.10O2整体催化剂上碳酸二甲酯的收率高达20.21%,催化效果明显优于CeO2和其余的Ce1-xMgxO2(x=0.05、0.15、0.20)催化材料。 相似文献
7.
Erbo Cheng Shoushuang Huang Dayong Chen Ruting Huang Qing Wang Zhangjun Hu Yong Jiang Zhen Li Bing Zhao Zhiwen Chen 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(7):969-978
Metal oxides have a large storage capacity when employed as anode materials for lithium‐ion batteries (LIBs). However, they often suffer from poor capacity retention due to their low electrical conductivity and huge volume variation during the charge–discharge process. To overcome these limitations, fabrication of metal oxides/carbon hybrids with hollow structures can be expected to further improve their electrochemical properties. Herein, ZnO‐Co3O4 nanocomposites embedded in N‐doped carbon (ZnO‐Co3O4@N‐C) nanocages with hollow dodecahedral shapes have been prepared successfully by the simple carbonizing and oxidizing of metal–organic frameworks (MOFs). Benefiting from the advantages of the structural features, i.e. the conductive N‐doped carbon coating, the porous structure of the nanocages and the synergistic effects of different components, the as‐prepared ZnO‐Co3O4@N‐C not only avoids particle aggregation and nanostructure cracking but also facilitates the transport of ions and electrons. As a result, the resultant ZnO‐Co3O4@N‐C shows a discharge capacity of 2373 mAh g?1 at the first cycle and exhibits a retention capacity of 1305 mAh g?1 even after 300 cycles at 0.1 A g?1. In addition, a reversible capacity of 948 mAh g?1 is obtained at a current density of 2 A g?1, which delivers an excellent high‐rate cycle ability. 相似文献
8.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(2):236-239
The crystal structure of Ce0.8Gd0.1Ho0.1O1.9 (cerium gadolinium holmium oxide) has been determined from powder X‐ray diffraction data. This is a promising material for application as a solid electrolyte for intermediate‐temperature solid oxide fuel cells (IT‐SOFCs). Nanoparticles were prepared using a novel sodium alginate sol‐gel method, where the sodium ion was exchanged with ions of interest and, after washing, the gel was calcined at 723 K in air. The crystallographic features of Gd and Ho co‐doped cerium oxide were investigated around the desired operating temperatures of IT‐SOFCs, i.e. 573 ≤ T ≤ 1023 K. We find that the crystal structure is a stable fluorite structure with the space group Fmm in the entire temperature range. In addition, the trend in lattice parameters shows that there is a monotonic increase with increasing temperature. 相似文献
9.
Ram Singh Prakash Biswas Prateek K. Jha 《International journal of quantum chemistry》2020,120(14):e26239
Extensive density functional theory calculations are performed to analyze the structure and activity of Cu and Cu Zn/Cu ZnO clusters containing up to 10 Cu/Zn atoms. The minimum-energy structures of Cu Zn and Cu ZnO clusters are found by doping minimum-energy pure Cu clusters with Zn atom(s) and ZnO molecule(s), respectively, followed by energy minimization of the resultant clusters. Odd-even alteration in properties that determine cluster stability/activity is observed with cluster size, which may be attributed to the presence/absence of unpaired electrons. The difference in behavior between Zn/ZnO doping can be interpreted in terms of charge transfer between atoms. Charge transfers from Zn to Cu in the Cu Zn clusters and from Cu and Zn atoms to O atom in Cu-ZnO clusters, which implies that the Cu atom acts as an electron acceptor in the Cu Zn clusters but not in the Cu ZnO clusters. Finally, the adsorption energies of glycerol and hydrogen on Cu Zn/Cu ZnO clusters are computed in the context of the use of Cu Zn/Cu ZnO catalysts in glycerol hydrogenolysis. Glycerol adsorption is generally found to be more energetically favorable than hydrogen adsorption. Dual-site glycerol adsorption is also observed in some of the planar clusters. Fundamental insights obtained in this study can be useful in the design of Cu Zn/Cu ZnO catalysts. 相似文献
10.
Marisa C. Oliveira Renan A. P. Ribeiro Elson Longo Mauricio R. D. Bomio Sergio R. de Lázaro 《International journal of quantum chemistry》2020,120(22):e26368
The structural, electronic, and vibrational properties of two leading representatives of the Zn-based spinel oxides class, normal ZnX2O4 (X = Al, Ga, In) and inverse Zn2MO4 (M = Si, Ge, Sn) crystals, were investigated. In particular, density functional theory (DFT) was combined with different exchange-correlation functionals: B3LYP, HSE06, PBE0, and PBESol. Our calculations showed good agreement with the available experimental data, showing a mean percentage error close to 3% for structural parameters. For the electronic structure, the obtained HSE06 band-gap values overcome previous theoretical results, exhibiting a mean percentage error smaller than 10.0%. In particular, the vibrational properties identify the significant differences between normal and inverse spinel configurations, offering compelling evidence of a structure-property relationship for the investigated materials. Therefore, the combined results confirm that the range-separated HSE06 hybrid functional performs the best in spinel oxides. Despite some points that cannot be directly compared to experimental results, we expect that future experimental work can confirm our predictions, thus opening a new avenue for understanding the structural, electronic, and vibrational properties in spinel oxides. 相似文献