射频等离子制备石墨烯负载Co3O4催化剂及其析氧性能研究

氢能的引入能有效提升配电网的供电可靠性,而电解水制氢是实现低碳转型的关键技术,开发高效的电解水催化剂势在必行。过渡金属氧化物储量大、催化活性高,是具有广阔应用前景的析氧反应催化剂。本文通过射频等离子体处理制备石墨烯上负载Co₃O₄析氧催化剂,XRD、Raman和XPS测试结果显示,二维结构石墨烯的引入加速表面电子迁移,增大了反应面积。等离子体处理促进了纳米粒子在石墨烯上的负载,利用等离子体刻蚀作用在催化剂表面制造出大量碳结构缺陷和氧空位结构,改善了活性位点分布,有效调控Co₃O₄电子结构,提高析氧催化活性。电化学测试表明,本文中合成的Co₃O₄@rGO在电流密度为50 mA·cm^-2时的过电位为410 mV,动力学反应速率较快,表现出优于商业IrO₂的析氧催化活性。     

The Riemann–Hilbert analysis to the Pollaczek–Jacobi type orthogonal polynomials

In this paper, we study polynomials orthogonal with respect to a Pollaczek–Jacobi type weight The uniform asymptotic expansions for the monic orthogonal polynomials on the interval (0,1) and outside this interval are obtained. Moreover, near , the uniform asymptotic expansion involves Airy function as , and Bessel function of order α as in the neighborhood of , the uniform asymptotic expansion is associated with Bessel function of order β as . The recurrence coefficients and leading coefficient of the orthogonal polynomials are expressed in terms of a particular Painlevé III transcendent. We also obtain the limit of the kernel in the bulk of the spectrum. The double scaled logarithmic derivative of the Hankel determinant satisfies a σ‐form Painlevé III equation. The asymptotic analysis is based on the Deift and Zhou's steepest descent method.     

Ti含量对溶胶-凝胶法制备Ti、Ga共掺ZnO薄膜性能的影响

采用溶胶-凝胶旋涂法在玻璃衬底上沉积纳米结构Ti、Ga共掺ZnO薄膜(TGZO,Ga掺杂量为1.0;(原子分数,下同)),用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、分光光度计(UV-Vis)、四探针测试仪、霍尔效应测试仪研究了Ti含量对TGZO薄膜的物相组成、表面形貌、电学和光学性能的影响.结果表明:所有TGZO薄膜均表现出六方纤锌矿的多晶结构,并具有(002)择优取向生长,在380～780 nm波长范围内具有良好的透射率(>86;);随着Ti含量的增加,TGZO薄膜的晶粒尺寸和可见光平均透射率均先增加后减小,而光学带隙和电阻率先减小后增加;Ti掺杂量为1.0;时,具有最高的可见光透射率92.82;,最窄的光学带隙3.249 eV,以及最低电阻率2.544×10-3Ω·cm.     

Platinum Oxide Nanoparticles for Electrochemical Hydrogen Evolution: Influence of Platinum Valence State

Electrochemical hydrogen generation is a rising prospect for future renewable energy storage and conversion. Platinum remains a leading choice of catalyst, but because of its high cost and low natural abundance, it is critical to optimize its use. In the present study, platinum oxide nanoparticles of approximately 2 nm in diameter are deposited on carbon nitride (C3N4) nanosheets by thermal refluxing of C3N4 and PtCl₂ or PtCl₄ in water. These nanoparticles exhibit apparent electrocatalytic activity toward the hydrogen evolution reaction (HER) in acid. Interestingly, the HER activity increases with increasing Pt⁴⁺ concentration in the nanoparticles, and the optimized catalyst even outperforms commercial Pt/C, exhibiting an overpotential of only −7.7 mV to reach the current density of 10 mA cm⁻² and a Tafel slope of −26.3 mV dec⁻¹. The results from this study suggest that the future design of platinum oxide catalysts should strive to maximize the Pt⁴⁺ sites and minimize the formation of the less active Pt²⁺ species.     

On the Relative Twist Formula of l-adic Sheaves

We propose a conjecture on the relative twist formula of l-adic sheaves, which can be viewed as a generalization of Kato—Saito's conjecture. We verify this conjecture under some transversal assumptions. We also define a relative cohomological characteristic class and prove that its formation is compatible with proper push-forward. A conjectural relation is also given between the relative twist formula and the relative cohomological characteristic class.     

The Influencing Mechanism of Acidity on the Oxidation Peak Currents of Uric Acid and Ascorbic Acid at the PACPE by Cyclic Voltammetry

In this paper, a pre‐anodized carbon paste electrode (PACPE) is fabricated by a simple electrochemical pretreatment method, which can be used for the simultaneous determination of uric acid (UA) and ascorbic acid (AA). The influencing mechanism of the acidity on the size of oxidation peak current (i_p,a) of UA and AA is discussed in detail. According to the results, in different pH conditions, the intensity of hydrogen bonding between UA, AA and the surface of PACPE, the degree of reduction reaction at the auxiliary electrode, and the structural configurations of UA and AA with different species in reaction system have evident influence on the size of oxidation peak current. In pH 7.00 phosphate buffer solution, the calibration curves for UA and AA are obtained in the range of 5.0 x 10^‐7–5.0 x 10^‐5 mol/L and 3.0 x 10^‐5–5.0 x 10^‐3 mol/L, respectively. The detection limits for UA and AA are found to be 2.0 x 10^‐8 mol/L and 1.2 x 10^‐6 mol/L, respectively. This proposed method has been successfully applied to determine UA and AA in human urine simultaneously with satisfactory results.     

Design,Synthesis, and Herbicidal Evaluation of Novel Uracil Derivatives Containing 1,3,4‐Thiadiazolyl Moiety

Uracil derivatives, such as commercial herbicides butafenacil and benzfendizone, have been identified as inhibitors of protoporphyrinogen oxidase (Protox, EC 1.3.3.4), one of the most important action targets of herbicides. In order to search for novel Protox inhibitors with high efficacy, broad‐spectrum activity, and safety to crops, commercially herbicide butafenacil was used as lead compound for further optimization; a series of title compounds 8a , 8b , 8c , 8d , 8e , 8f , 8g , 8h , 8i , 8j , 8k , 8l , 8m , 8n were designed and synthesized by introducing 1,3,4‐thiadiazole moiety into the uracil skeleton. The preliminary bioassays (in vitro) indicated that most of the target compounds displayed better inhibition against Echinochloa crus‐galli than Brassica campestris. The greenhouse bioassay results indicated that most of the compounds tested exhibited good‐to‐excellent herbicidal activities against B. campestris, A. retroflexus, E. crusgalli, and D. sanguinalis in pre‐emergence treatment at a dose of 1500 g/ha, for example, compound 8d showed 100% inhibition against the four plants tested in pre‐emergence treatment at a dose of 1500 g/ha. So, these types of skeletons can be used as valuable lead compounds for the development of a pre‐emergent herbicide.     

Accurate Theoretical Study of LiS Radical and Its Singly Charged Cation and Anion in their Ground Electronic State

Potential energies of LiS(²Π), LiS^-(¹Σ⁺) and LiS⁺(³Σ^-) are calculated by using the multireference configuration interaction method including Davidson correction and the augmented correlation-consistent basis sets aug-cc-PV(X+d)Z (X=T, Q). Such obtained potential energies are subsequently extrapolated to the complete basis set limit. Both the core-valence correction and the relativistic effect are also considered. The analytical potential energy functions are then obtained by fitting such accurate energies utilizing a least-squares fitting procedure. By using such analytical potential energy functions, we obtain the accurate spectroscopic parameters, complete set of vibrational levels and classical turning points. The present results are compared well with the experimental and other theoretical work.     

分析力学初值问题的一种变分原理形式

明确了分析力学初值问题的控制方程，按照广义力和广义位移之间的对应关系，将 各控制方程卷乘上相应的虚量，代数相加，进而在 原空间中建立了分析力学初值问题的一种变分原理形式，即建立了分析力学初值问题的卷积 型变分原理和卷积型广义变分原理. 推导了分析力学初值问题卷积型变分原理和卷积型广义 变分原理的驻值条件. 在建立分析力学初值问题的一种变分原理形式的同时, 将变积方法推广为卷变积方法.