Aligned Co3O4–CoOOH heterostructure nanosheet arrays grown on carbon paper with oxygen vacancies for enhanced and robust oxygen evolution

Developing efficient and stable non-noble metal oxygen evolution reaction (OER) electrocatalysts for sustainable overall water-splitting is extremely desirable but still a great challenge. Herein, we developed a facile strategy to fabricate Co₃O₄–CoOOH heterostructure nanosheet arrays with oxygen vacancies grown on carbon paper (Co₃O₄–CoOOH/CP). Benefiting from the unique 3D architecture, large surface area, synergistic effects between Co₃O₄, CoOOH and oxygen vacancies, the obtained self-supporting Co₃O₄–CoOOH/CP presents excellent electrocatalytic OER activity (low overpotentials of 245 and 390 mV at 10 and 100 mA cm⁻²) and robust long-term stability in alkaline condition. The present strategy provides the opportunities for the future rational design and discovery of high-performance non-noble metal based electrocatalysts for advanced water oxidation and beyond.     

Synthesis,characterization, and visible-light photocatalytic activity of transition metals doped ZTO nanoparticles

Transition metals doping has been proved to be a feasible way for tuning the physical properties on the surface and bulk of nanomaterials and also for the good performance in decontamination of emerging pollutants. In this context, doped samples of zinc tin oxide or zinc stannate nanoparticles (ZTO NPs) by several transition metals were synthesized in order to enhance the optical absorbance with the aims of reducing the band gap and therefore ameliorated their photocatalytic activity. They were characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy, Raman spectroscopy and photoluminescence. The XRD patterns and the microscopic observations showed the formation of spherical nanoparticles with an average size of about 30 nm and highly pure ZTO phase with an inverse spinel structure. The Raman spectra were dominated by bands relatives to the F2g (2) and A1g symmetries modes of inverse spinel structure. The band gap Eg is estimated to be 3.75 eV for the undoped sample, and 3.67, 3.64, 3.78 and 3.21 eV, for 2% Fe, 2% Mg, 2% Gd, and 2% Mn doped ZTO samples, respectively.Furthermore, the undoped ZTO NPs have the intrinsic problem of recombination of photogenerated charge carriers. We have shown that the reduction of the band gap and oxygen vacancies resulting from the doping effect could be a useful tool for trapping and avoid the recombination of electrons coming from photosensitized rhodamine B (RhB) under visible light irradiation. Owing to the structural advantages and low band gap, 2% Mn doped ZTO NPs, with the kinetic rate constants k of 0.024 min⁻¹, show enhanced performance for the elimination of RhB in aqueous solution compared to undoped and other doped ZTO NPs.     

Carbon-based TiO2-x heterostructure nanocomposites for enhanced photocatalytic degradation of dye molecules

Application of brown titanium dioxide (TiO_2-x) and its modified composite forms in the photocatalytic decomposition of organic pollutants in the environment is a promising way to provide solutions for environmental redemption. Herein, we report the synthesis of effective and stable TiO_2-x nanoparticles with g-C₃N₄, RGO, and multiwalled carbon nanotubes (CNTs) using a simple hydrothermal method. Among all the as-synthesized samples, excellent photocatalytic degradation activity was observed for RGO-TiO_2-x nanocomposite with high rate constants of 0.075 min^?1_, 0.083 min^?1 and 0.093 min^?1 for methylene blue, rhodamine-B, and rosebengal dyes under UV–Visible light irradiation, respectively. The altered bandgap (1.8 eV) and the large surface area of RGO-TiO_2-x nanocomposite impacts on both absorption of visible light and efficiency of photogenerated charge electron (e^?)/hole (h⁺) pair separation. This resulted in enhanced photocatalytic property of carbon-based TiO_2-x nanocomposites. A systematic study on the influence of different carbon nanostructures on the photocatalytic activity of brown TiO_2-x is carried out.     

Investigation on external stimuli engendered magnetic ordering in polycrystalline CaCu3Ti4O12 quadruple perovskite

The consequences of high energy mechanical milling, microwave-assisted heating and rapid thermal cooling on magnetic ordering in polycrystalline CaCu₃Ti₄O₁₂ cubic perovskite have been investigated by means of X-ray powder diffractometry (300?K), dc magnetization in field – cooled and zero – field cooled modes (H = 100?Oe and 1000?Oe, T?=?5–300?K) (M – T curves) and M – H loop characteristics (T?=?5?K and 300?K, H_max = 70?kOe). The M – T curves of unmilled and 16?h milled samples show pure antiferromagnetic and weak ferromagnetic ordering, respectively, 1?h and 6?h milled samples demonstrate the coexistence of both the phases while microwave-assisted and quenched samples exhibit classic antiferromagnetic transition and a low temperature paramagnetic–like contribution with different weights, well supported by the M – H loop characteristics. The observed transformations in the magnetic ordering are attributed to the ball-milling induced stress which curtails hybridization of empty Ti-3d orbitals with Cu-3d and O-2p orbitals and secondary phase formation. Oxygen vacancies associated with bound magnetic polarons originate ferromagnetism in the milled samples while unpaired electrons inhabited at the empty sites are the cause of paramagnetic centers. The low-temperature Curie – tail in M – T curve for quenched and microwave assisted samples is attributed to Ti³⁺ cations.     

PMN-PT陶瓷中的氧缺位及其消除

研究了组成中Pb含量的变化对组成为Pbx(Mg1/3Nb2/3)0.65Ti0.35O3的铌镁酸铅-钛酸铅(PMN-PT)陶瓷压电性能的影响,发现化学计量比组成(x=1)的Pbx(Mg1/3Nb2/3)0.65Ti0.35O3陶瓷经常出现压电性能的大幅度退化现象,而A位适量缺Pb能稳定地获得高性能的Pbx(Mg1/3Nb2/3)0.65Ti0.35O3陶瓷。XPS元素价态分析的结果表明,化学计量比的Pbx(Mg1/3Nb2/3)0.65Ti0.35O3陶瓷中含有较多的氧缺位,氧缺位的产生源于MgNb2O6(MN)合成过程中的气氛差异,A位适量缺Pb能有效地消除这种氧缺位而稳定地获得正常的压电性能,其机理被认为是氧缺位与铅缺位的复合。     

Quantum chemical SINDO1 study of vanadium pentoxide

An improved set of parameters for vanadium in the semiempirical quantum chemical SCF MO method SINDO1 is presented. It is shown that both the geometries and heats of formation of a number of vanadium-containing compounds calculated by this method are in good agreement with available experimental data. Model clusters of increasing size are used for the study of geometric and energetic properties of vanadium pentoxide. Both hydrogen atom and proton adsorption on the (010) surface of vanadium pentoxide and a subsequent formation of different oxygen vacancies have been investigated. Based on these computational results the reactivities of V₂O₅-surface oxygen atoms for adsorption are discussed.     

Highly dispersed CeO2–x nanoparticles with rich oxygen vacancies enhance photocatalytic performance of g-C3N4 toward methyl orange degradation under visible light irradiation

CeO₂/g-C₃N₄ photocatalysts have attracted tremendous attention in the photocatalytic degradation of organic pollutants. The design and construction of highly active CeO₂/g-C₃N₄ photocatalysts without harsh conditions are still challenging. Herein, highly dispersed CeO_2–x nanoparticles with rich oxygen vacancies were successfully precipitated on the surface of g-C₃N₄ under mild conditions. The fabricated CeO_2–x/g-C₃N₄ exhibits remarkable activity and stability for photocatalytic degradation of MO pollutant. The optimal rate constant of MO degradation over CeO_2–x/g-C₃N₄ is about 0.031 min^?1, which is three times higher than that of g-C₃N₄. A negligible activity decrease is observed after three cycling runs. The enhanced catalytic performance can be ascribed to the excellent dispersion of CeO_2–x with rich oxygen vacancies that benefit O₂ adsorption and visible light absorption. In addition, the proper band alignment between CeO_2–x and g-C₃N₄ is conducive to the highly efficient separation of photogenerated electron–hole pairs.     

低CO2选择性的合成气制轻烯烃双功能催化剂

为开发高活性、高收率的合成气制低碳烯烃（STO）双功能催化剂，通过共沉淀法制备非化学计量尖晶石Zn-Cr-Al氧化物，对其织构性质、晶体结构、形貌特征以及表面电荷性质等进行研究。结果表明添加过量锌能够促进晶体粒径减小，表面氧空位增多。其中Zn/(Cr+Al)摩尔比为1.25时锌含量较为适宜，将其与SAPO-34沸石分子筛结合为双功能催化剂用于STO性能研究。在进气n(H2):n(CO)=2:1，3000 mL/(gcat·h)，3.2 MPa，400 ℃反应条件下，实现46.9% CO转化率，C2-4烯烃收率高达15.9%，高于大部分已有文献报道（8~14%），特别是副产物CO2选择性仅29.2%，低于普遍报道的40~50% CO2选择性。并且催化剂运行100 h后活性良好，稳定的催化性能使其具有工业应用价值。     

The influence of oxygen vacancies on piezoelectricity in samarium-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 ceramics

A study of 0.71Pb(Mg_1/3Nb_2/3)O₃-0.29PbTiO₃ shows that, when it is doped with 2.5% Sm on the A-site, in addition to an almost threefold increase in piezoelectric charge coefficient and dielectric permittivity, there is a 2 order of magnitude reduction in conductivity, attributed to a decrease in oxygen vacancy concentration. An analysis of the nonlinearity of permittivity with respect to field amplitude shows that both the reversible and irreversible contributions increase significantly with Sm-doping, with simple models showing that these changes are consistent with a reduction in the concentration of dipolar defects that can inhibit both polarization rotation and domain wall translation. Contrary to the argument that doping increases heterogeneity, there is little change in the diffuseness of the peak in permittivity as a function temperature, whilst there is a 15% increase in spontaneous polarization with Sm addition. Through comparison of the Rayleigh law parameters with those published for other piezoelectric materials, it is concluded that a significant contribution to the observed increase in piezoelectric performance due to Sm-doping of PMN-PT is similar in origin to that seen in soft, donor-doped PZT and other conventional piezoelectric ceramics.