“反饰”修辞格生成和理解的心理机制研究

"反饰"修辞格,是通过语表形式上体现的反义关系来说明同一件事物内在的两个相反的特征。本文通过认知心理学"基于心理模型的语用推理"范式中的"自主-依存"和"显性-隐性"两个分析框架,研究反饰生成和理解的心理机制。反饰生成和理解的过程都需要言者与听者彼此构建相同的心理模型。

Catalytic cracking of light diesel over Au/ZSM-5 catalyst for increasing propylene production

The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were prepared by a modified deposition‐precipitation method by changing the preparation procedure and the amount of gold loading and were characterized by X‐ray diffraction, N2 adsorp‐tion‐desorption, temperature‐programmed desorption of NH3, transmission electron microscopy and inductively coupled plasma spectrometer. It was found that a small amount of gold had a posi‐tive effect on the catalytic cracking of light diesel oil and increased propylene production at a rela‐tively low temperature. The maintenance of the ZSM‐5 MFI structure, pore size distribution and the density of weak and strong acid sites of the Au/ZSM‐5 catalysts depended on the preparation pa‐rameters and the Au loading. Simultaneous enhancement of the micro‐activity and propylene pro‐duction relies on a synergy between the pore size distribution and the relative intensity of the weak and strong acid sites. A significant improvement in the micro‐activity index with an increase of 4.5 units and in the propylene selectivity with an increase of 23.2 units was obtained over the Au/ZSM‐5 catalyst with an actual Au loading of 0.17 wt%.

Influence of phosphoric anions on oxygen reduction reaction activity of platinum, and strategies to inhibit phosphoric anion adsorption

Nation-membrane-based proton exchange fuel cells （PEMFCs） typically operate at below 100 ℃. However, H3PO4-doped polybenzimidazole （PBI）-based PEMFCs can operate at 100-200 ℃. This is advantageous because of accelerated reaction rates and enhanced tolerance to poisons such as CO and S02, which can arise from reformed gas or the atmosphere. However, the strong adsorption of phosphoric anions on the Pt surface dramatically decreases the electrocatalytic activity. This study exploits the ＂third-body effect＂, in which a small amount of organic molecules are pre-adsorbed on the Pt surface to inhibit the adsorption of phosphoric anions. Pre-adsorbate species inhibit the ad- sorption of phosphoric anions, but can also partially occlude active sites. Thus, the optimum pre-adsorbate coverage is studied by correlating the oxygen reduction reaction （ORR） activity of Pt with pre-adsorbate coverage on the Pt surface. The influence of the pre-adsorbate molecule length is investigated using the organic amines, butylamine, octylamine, and dodecylamine, in both 0.1 mol/L HCI04 and 0.1 mol/L H3P04. Such amines readily bond to the Pt surface. In aqueous HCI04 electrolyte, the ORR activity of Pt decreases monotonically with increasing pre-adsorbate coverage. In aqueous H3P04 electrolyte, the ORR activity of Pt initially increases and then decreases with in- creasing pre-adsorbate coverage. The maximum ORR activity in H3P04 occurs at a pre-adsorbate coverage of around 20%. The effect of molecular length of the pre-adsorbate is negligible, but its coverage strongly affects the degree to which phosphoric anion adsorption is inhibited. Butylamine adsorbs to Pt at partial active sites, which decreases the electrochemically active surface area. Ad- sorbed butylamine may also modify the electronic structure of the Pt surface. The ORR activity in the phosphoric acid electrolyte remains relatively low, even when using the pre-adsorbate modified Pt/C catalysts. Further development of the catalyst and electrolyte is required before the commercialization of H3PO4-PBl-based PEMFCs can be realized.

Roles of heteroatoms in electrocatalysts for alkaline water splitting:A review focusing on the reaction mechanism

Alkaline water splitting is a promising technology for“green hydrogen”generation.To improve its efficiency,highly robust catalysts are required to reduce the overpotential for low electrical power consumption.Heteroatom modification is one of the most effective strategies for boosting catalytic performance,as it can regulate the physicochemical properties of host catalysts to improve their intrinsic activity.Herein,aiming to provide an overview of the impact of heteroatoms on catalytic activity at the atomic level,we present a review of the key role of heteroatoms in enhancing reaction kinetics based on the reaction pathways of the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in alkaline media.In particular,the introduction of heteroatoms can directly and indirectly optimize the interactions between the active sites and intermediates,thus improving the intrinsic activity.To clearly illustrate this influence in detail,we have summarized a series of representative heteroatom-modified electrocatalysts and discussed the important roles of heteroatoms in the OER and HER reaction pathways.Finally,some challenges and perspectives for heteroatom-modified electrodes are discussed.We hope that this review will be helpful for the development of efficient and low-cost electrocatalysts for water electrolysis and other energy conversion applications.

Controlling atomic phosphorous-mounting surfaces of ultrafine W_(2)C nanoislands monodispersed on the carbon frameworks for enhanced hydrogen evolution

Controllably mounting foreign atoms on the surfaces of earth-abundant electrocatalysts strongly improve their surface electronic properties for optimizing the catalytic performance of surficial sites to an unusual level,and provides a good platform to gain deep insights into catalytic reactions.The present work describes,employing ultrafine W2C nanoislands(average size:2.3 nm)monodispersed on the N,P dual-doped carbon frameworks as a model system,how to regulate the atomic phosphorous-mounting effect on the surfaces of W_(2)C to derive an active and stable P-mounting W_(2)C(WCP)catalyst for both acidic and alkaline hydrogen evolution reaction(HER).Since in situ phosphorus substitution into carbon sites of preformed W_(2)C nanoislands gradually proceeds from surfaces to solids,so that using a proper amount of phosphorus sources can readily control the surface mounting level to avoid the mass P-doping into the bulk.By this way,the activity per active site of WCP catalyst with robust stability can be optimized to 0.07 and 0.56 H_(2 )s^(-1) at-200 mV overpotential in acid and base,respectively,which reach up to the several-fold of pure-phase W_(2)C(0.01 and 0.05 H_(2) s^(-1)).Theoretical investigations suggest that compared with solid P doping,the P mounting on W_(2)C surface can more remarkably enhance its metallicity and decrease the hydrogen release barrier.This finding disclosed a key correlation between surface foreign atom-mounting and catalytic activity,and suggested a logical extension to other earth-abundant catalysts for various catalytic reactions.

A New Approach on Modification Reactions of Atherton-Todd, Betti, Mannich and Doebner with Arsine, Stibine and Bismuthine in Organometallic Chemistry

A new approach modification reactions Atherton-Todd, Betty, Mannich and Doebner reactions with of arsine, stibine and bismuthine have been proposed in organometallic chemistry of these elements. These new reactions can be used for the synthesis of drugs and biologically active organic compound of arsenic, antimony and bismuth. A possible new mechanism of the reaction is proposed.

Preparation and Electrochemical Application of Praseodymium Modified TiO2-NTs/SnO2-Sb Anode by Cyclic Voltammetry Method

A Pr-doped TiO2-NTs/SnO2-Sb electrode was prepared by a simple method, cyclic voltarnmetry （CV）. The methyl orange （MO）aqueous solution was selected as a simulated wastewater. The ordered microstructural TiO2-NTs substrate was synthesized by an electrochemical method to obtain large specific surface area and high space utilization. The phase structure, electrode surface morphology and electrochemical properties of electrodes were characterized by XRD, SEM and electrochemical technology, respectively. The results showed that praseo- dymium oxide was successfully doped into the SnOz-Sb film by CV method. Due to the doped Pr, the oxygen evo- lution potential increased from 2.25 V to 2.40 V. The degradation of MO was investigated by UV-vis. The Ct/C0（φ） was studied as a function to obtain the optimal parameters, such as the amount of doped Pr, current density and initial dye concentration. In addition, the degradation process followed pseudo-first-order reaction kinetics and the rate constant was 0.099 3 min-1. The result indicated that the introduction of Pr reduced the formation of oxygen vacancies or enhanced the formation of adsorbed hydroxyl radical groups on the surface, thus leading to better activity and stability.

Preparation of copper nanoparticles modified with [BMIm]BF_4 ionic liquid

Copper nanoparticles was prepared by ascorbic acid reducing CuC12 solution modified with [ BMIm ] BF4 ionic liquid. The size of copper nanoparticles was obviously affected by the concentration of Cu2＋ . The diameter of nanoparticles was smaller than 10 nm when the Cu2＋ concentration was smaller than 2× 10.2 moL/L. The pH and temperature of reductive reaction had no obvious effect on the size of copper nanoparticles.

Atomic-scale Pt clusters decorated on porousα-Ni(OH)_2 nanowires as highly efficient electrocatalyst for hydrogen evolution reaction

The synthesis of atomic-scale metal catalysts is a promising but very challenging project. In this work, we successfully fabricated a hybrid catalyst of PL/Ni（OH）2 with atomic-scale Pt clusters uniformly decorated on porous Ni（OH）2 nanowires （NWs） via a facile room-temperature synthesis strategy. The as-obtained Ptc/Ni（OH）2 catalyst exhibits highly efficient hydrogen evolution reaction （HER） performance under basic conditions. In 0.1moll-1 KOH, the Ptc/Ni（OH）2 has an onset overpotential of -0 mV vs. RHE, and a significantly low overpotential of 32 mV at a current density of 10mAcm-2, lower than that of the com- mercial 20% Pt/C （58 mV）. The mass current density data illustrated that the PL/Ni（OH）2 reached a high current den- sity of 6.34Amg^-1i at an overpotential of 50 mV, which was approximately 28 times higher than that of the commercial Pt/C （0.223Amg^-1i） at the same overpotential, proving the high-efficiency electrocatalytic activity of the as-obtained Ptc/Ni（OH）2 for HER under alkaline conditions.

A new insight into electrochemical detection of eugenol by hierarchical sheaf-like mesoporous NiCo2O4

NiCo2O4 nanosheets with sheaf-like nanostructure morphologies have been synthesized by a facile one-step hydrothermal reaction followed by annealing treatment. Impressively, the NiCo2O4 nanosheets exhibit rapid detection of eugenol. The linear range of detection is from 1-500μM, and the limit of detection is 5.4 μM. The NiCo2O4 modified electrode demonstrated high sensitivity, good repeatability and reproducibility, and long-term stability （7% decrease in response over 30 days）. Based on this work, an electrochemical reaction mechanism for eugenol oxidation was proposed, and in addition, the NiCo2O4 modified electrode was successfully employed for the analysis of eugenol in medicative balm samples. Recovery values for eugenol in medicative balm samples were in the range 98.7%-105.5%.

Histone modifications in DNA damage response

DNA damage is a relatively common event in eukaryotic cell and may lead to genetic mutation and even cancer. DNA damage induces cellular responses that enable the cell either to repair the damaged DNA or cope with the damage in an appropriate way. Histone proteins are also the fundamental building blocks of eukaryotic chromatin besides DNA, and many types of post-translational modifications often occur on tails of histones. Although the function of these modifications has remained elusive, there is ever-growing studies suggest that histone modifications play vital roles in several chromatin-based processes, such as DNA damage response. In this review, we will discuss the main histone modifications, and their functions in DNA damage response.

Intrinsically inert hyperbranched interlayer for enhanced stability of organic solar cells

Device stability becomes one of the most crucial issues for the commercialization of organic solar cells(OSCs) after high power conversion efficiencies have been achieved. Besides the intrinsic stability of photoactive materials, the chemical/catalytic reaction between interfacial materials and photoactive materials is another critical factor that determines the stability of OSC devices. Herein, we design and synthesize a reaction-inert rylene diimide-embedded hyperbranched polymer named as PDIEIE, which effectively reduces the work function of indium tin oxide electrode from 4.62 to 3.65 eV. Meanwhile, PDIEIE shows negligible chemical reaction with high-performance photoactive materials and no catalytic effect under strong ultraviolet illumination, resulting in much better photo-stability of OSCs with PDIEIE cathode interlayer(CIL), relative to the traditional CILs, including most-widely used metal oxides and polyethyleneimine derivatives.