Insight into room-temperature catalytic oxidation of NO by CrO2(110): A DFT study

The first-principles DFT calculations together with microkinetic analysis reveal the complex catalytic mechanism of low-content NO oxidation on CrO₂(110) at room temperature. It quantitatively makes clear that CrO₂(110) can exhibit considerable activity with the Mars-van-Krevelen mechanism preferred, and the nitrate species serves as the key poisoning species.     

Catalytic activity of nanocrystalline ZnM2O4 (M = Fe,Co) prepared via simple and facile synthesis of thermal decomposition of mixed metal complexes of Schiff bases generated from α-ketobutyric acid and diaminoguanidine

Metal complexes ([ML₂], where M = Fe, Co, or Zn; HL = 2-[(6-ethyl-5-oxo-4,5-dihydro-2H-[1,2,4]triazin-3-ylidene)-hydrazono]-butyric acid, C₉H₁₃N₅O₃) of a Schiff base derived from α-ketobutyric acid (α-KBA) and diaminoguanidine (Damgu) were synthesized and characterized using elemental, spectral, and thermal studies. The metal complexes exhibited similar decomposition behavior, with a highly exothermic final decomposition step resulting in the formation of metal oxides. Isomorphism among the complexes was revealed using a powder X-ray diffraction (PXRD) technique. Solid solution precursors ([Zn_1/3M_2/3(L)₂], where M = Fe, Co) were synthesized and characterized using various physico-chemical techniques. A thermal decomposition technique was used to prepare spinel-type zinc cobaltite (ZnCo₂O₄) and zinc ferrite (ZnFe₂O₄) nanocrystalline particles with the synthesized single source precursors. Structural studies using PXRD ascertained the predominant crystal phase to be spinel. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed a mean nanoparticle size of 18 ± 2 nm. Magnetic measurements revealed a weak magnetic behavior in the synthesized spinels. In the aqueous phase, the spinels exhibited catalytic activity, reducing 4-nitrophenol (4-NP) in the presence of NaBH₄ at room temperature. Additionally, the study demonstrated that the catalyst can be recovered and reused for five cycles with a more than 85% conversion efficiency.     

Prospects for the combination of mechanochemistry and flow applied to catalytic transformations

The urge of developing modern alternatives regarding industrial production has led to the creation of novel techniques that help overcome critical disadvantages from traditional batch mechanochemistry. One promising strategy includes the merging of flow processes with mechanochemistry. Two technologies are herein highlighted: twin-screw extrusion (TSE) and Impact (induction) in Continuous flow HEated Mechanochemistry (I-CHEM) allowing not only the industrial production of polymers but also active pharmaceutical ingredients, synthesis of (nano)materials, and the obtention of high-added value products from biomass and wastes valorization.     

Extraordinary transport behavior of gases in isothermally annealed poly(4‐methyl‐1‐pentene) membranes

Poly(4‐methyl‐1‐pentene) (PMP) membranes were modified through isothermal annealing to investigate the change of their crystalline structure and rigid and mobile amorphous fractions (RAF and MAF), assuming a three‐phase model, affected the gas transport behavior. The crystalline structure was characterized by wide‐angle X‐ray diffraction (WAXD) and small‐angle X‐ray scattering (SAXS) techniques, and the free volume properties were analyzed by positron annihilation lifetime spectroscopy. Compared with the pristine membrane, the annealed membranes show higher crystallinity; the crystals undergo partial structural change from form III to form I. The lamellar crystal thickness, rigid amorphous fraction thickness, and long period in the lamellar stacks increase with crystallinity. The annealed PMP membranes exhibit higher permeability due to the increase in larger size free volumes in MAF and higher selectivity due to the increase in smaller size free volumes in RAF, respectively. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2368–2376     

Effect of negative electric field on spin-dependent tunneling in double barrier semiconductor heterostructures

The effect of negative electric field on spin-dependent tunneling in double barrier heterostructures of III–V semiconductor is theoretically investigated. The transfer matrix approach is used by considering Dresselhaus and induced-Rashba effect to calculate the barrier transparency and polarization efficiency. Cent percent polarization efficiency can be achieved for the negative electric field by increasing the width of the potential barrier. The separation between spin-up and spin-down resonances are evaluated. The separation between spin resonances and tunneling lifetime of electrons are observed for various negative electric fields as well as for various barrier widths. The linear variation of spin separation and tunneling lifetime of electrons are observed as a function of negative electric field.     

FLTD三电极场畸变气体开关寿命特性

针对设计的一种场畸变气体开关,研究中间电极材料分别为不锈钢和黄铜条件下的烧蚀特性,结合开关寿命期间静态与触发特性的变化规律,获得决定开关寿命的关键因素,为三电极场畸变气体开关的性能优化提供理论支撑。研究结果表明,采用不锈钢和黄铜作为中间电极的烧蚀区域以及表面粗糙度均随着放电次数增加而增大,黄铜电极烧蚀较为严重且表面有明显的烧蚀圆斑,不锈钢电极则具有更高的表面粗糙度,阴阳极表面烧蚀存在明显差异,随着放电次数的增加,击穿点向电极边缘区域集中,影响开关的沿面绝缘特性,是导致开关寿命终结的主要原因。     

CaLuBO4∶Tb^3+荧光粉的制备及发光性质

采用高温固相反应法合成了不同Tb^3+掺杂浓度的CaLuBO4∶xTb^3+荧光粉,研究了样品的晶体结构和发光性质。在紫外光激发下,样品的发射光谱由Tb3+离子的5D3→7FJ(J=6,5,4)和5D4→7FJ′(J′=6,5,4,3)特征发射组成,其中位于545 nm和554 nm附近的5D4→7F5跃迁发射强度最大。荧光粉的激发光谱是由位于紫外区的Tb3+的4f-5d和f-f跃迁构成的。研究了Tb3+浓度对样品发光性质的影响。测量并分析了CaLuBO4∶xTb^3+荧光粉的5D3能级和5D4能级荧光寿命。结果表明,CaLuBO4∶xTb^3+是一种适于紫外激发的新型黄绿光荧光粉。     

Synthesis and stability evaluation of hierarchical silicoaluminophosphates with different structural frameworks in the methanol to olefins process

Silicoaluminophosphates (SAPOs) with different pore structures were synthesized through the implementation of polyethylene glycol (PEG) as a mesopores impregnation agent. Using PEGs with different molecular weights (MWs) and concentrations in the synthesis precursor, several samples were synthesized and characterized. Applying a PEG capping agent to the precursors led to the formation of tuned mesopores within the microporous matrix of the SAPO. The effects of the PEG molecular weight and PEG/Al molar ratio were investigated to maximize the efficiency of the catalyst in the methanol-to-olefin (MTO) process. Using PEG with a MW of 6000 resulted in the formation of both Zeolite Rho and chabazite structural frameworks (i.e., DNL-6 and SAPO-34). Pure SAPO-34 samples were successfully prepared using PEG with a MW of 4000. Our results showed that the PEG concentrations affect the porosity and acidity of the synthesized materials. Furthermore, the SAPO-34 sample synthesized with PEG (MW of 4000) and a PEG/Al molar ratio of 0.0125 showed a superior catalytic stability in the MTO reaction owing to the tuned bi-modal porosity and tailored acidity pattern. Finally, through reactivation experiments, it was found that the catalyst is stable even after several regeneration cycles.     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.     

介孔钯-硼合金纳米颗粒的制备和甲醇氧化电催化性能北大核心CSCD

合金化可以调节贵金属纳米材料的物理化学性质,从而显著提升它们的电催化性能。尽管合金化在过去的20多年里已取得诸多成果,但是如何充分发挥纳米合金的组分优势仍需深入的探究。本研究通过一步溶液相合成法实现了类金属硼(B)合金化的钯基介孔纳米催化剂材料的合成,同时探究了B原子的组分优势和介孔形貌的结构优势在碱性介质中电化学甲醇氧化反应(MOR)的协同作用。最优PdCuB介孔纳米催化剂表现出优异的电化学MOR活性和稳定性。机理研究表明,优异的催化活性源于B原子在Pd基介孔纳米催化剂中的积极协同作用;该协同作用通过电子效应(改变Pd的表面电子结构从而减弱CO基中间体的吸附)和双功能效应(促进OH_(2)的吸附从而氧化CO基中间体)在动力学上加速了有毒CO基中间体的去除(提高甲醇氧化的决速步骤)。同时,B原子的间隙插入和介孔结构抑制了物理奥斯特瓦尔德(Ostwald)熟化过程,显著增加了催化剂的稳定性。