Recent advances in single atom catalysts for the electrochemical carbon dioxide reduction reaction

The electrochemical carbon dioxide reduction reaction (CO₂RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO₂RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO₂RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C₁ products and formation of C₂₊ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO₂RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO₂RR are raised and possible solutions are provided.

The electrochemical carbon dioxide reduction reaction (CO₂RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels.     

A dual-electrode approach for highly selective detection of glucose based on diffusion layer theory: experiments and simulation

A dual-electrode configuration for the highly selective detection of glucose in the diffusion layer of the substrate electrode is presented. In this approach, a glassy carbon electrode (GCE, substrate) modified with a conductive layer of glucose oxidase/Nafion/graphite (GNG) was used to create an interference-free region in its diffusion layer by electrochemical depletion of interfering electroactive species. A Pt microelectrode (tip, 5 microm in radius) was located in the diffusion layer of the GNG-modified GCE (GNG-G) with the help of scanning electrochemical microscopy. Consequently, the tip of the electrode could sense glucose selectively by detecting the amount of hydrogen peroxide (H2O2) formed from the oxidization of glucose on the glucose oxidase layer. The influences of parameters, including tip-substrate distance, substrate potential, and electrolyzing time, on the interference-removing efficiency of this dual-electrode approach have been investigated systematically. When the electrolyzing time was 30 s, the tip-substrate distance was 1.8 a (9.0 microm) (where a is the radius of the tip electrode), the potentials of the tip and substrate electrodes were 0.7 V and 0.4 V, respectively, and a mixture of ascorbic acid (0.3 mM), uric acid (0.3 mM), and 4-acetaminophen (0.3 mM) had no influence on the glucose detection. In addition, the current-time responses of the tip electrode at different tip-substrate distances in a solution containing interfering species were numerically simulated. The results from the simulation are in good agreement with the experimental data. This research provides a concept of detection in the diffusion layer of a substrate electrode, as an interference-free region, for developing novel microelectrochemical devices.     

Reactivity of monolayer-protected gold nanoclusters at dye-sensitized liquid/liquid interfaces

Hexanethiolate monolayer-protected gold nanoclusters (MPCs) were used as redox quenchers at the polarizable water/1,2-dichloroethane (DCE) interface. Photocurrent responses originating from the heterogeneous quenching of photoexcited water soluble porphyrin complexes by MPCs dissolved in the DCE phase were observed. As MPCs can function as both electron acceptors and donors, the photocurrent results from the superposition of two simultaneous processes, which correspond to the oxidation and reduction of MPCs. The magnitude of the net photocurrent is essentially determined by the balance of the kinetics of these two processes, which can be controlled by tuning the Galvani potential difference between the two phases. We show that, within the available potential window, the apparent electron-transfer rate constants follow classical Butler-Volmer dependence on the applied potential difference.     

Oxidation resistant germanium nanowires: bulk synthesis, long chain alkanethiol functionalization, and Langmuir-Blodgett assembly

A simple method is developed to synthesize gram quantities of uniform Ge nanowires (GeNWs) by chemical vapor deposition on preformed, monodispersed seed particles loaded onto a high surface area silica support. Various chemical functionalization schemes are investigated to passivate the GeNW surfaces using alkanethiols and alkyl Grignard reactions. The stability of functionalization against oxidation of germanium for various alkyl chain lengths is elucidated by X-ray photoelectron spectroscopy. Among all schemes tested, long chain alkanethiols (> or = C12) are found to impart the most stable GeNW passivation against oxidation upon extended exposure to ambient air. Further, the chemically functionalized oxidation-resistant nanowires are soluble in organic solvents and can be readily assembled into close-packed Langmuir-Blodgett films potentially useful for future high performance electronic devices.     

退火条件对LDPE空间电荷特性的影响研究

使用冷却速率不同的3种退火方法制备了不同微观形态的LDPE薄膜,对薄膜试品进行了显微观测,并运用傅立叶红外分析对3种试品的结晶度进行了比较,同时使用PEA空间电荷测量技术对不同电场下这3种试品的空间电荷分布进行了观测,并基于结晶度和微观形态对LDPE空间电荷特性做了讨论.研究结果表明施加电场撤压后,高速冷却试品比低速冷却试品和正常冷却试品积聚更多的空间电荷,而随着撤压时间的增加,低速冷却试品中积聚的空间电荷衰减得最快.     

2,2''''-二苯基二硫的间接电解氧化合成

以KJ—NaI为间接电解质，丙酮为溶剂，用间接电解氧化的方法对硫酚进行偶联，高产率地得到了偶联产物2，2’-二苯基二硫(Ph2S2)．     

β-SiC非线性导电特性影响因素及机理的研究

研究了-βSiC非线性导电特性的影响因素及其机理,提出了利用-βSiC作为电机线棒防电晕材料的新方法.在-βSiC微粉合成的过程中,向其中掺杂V、Al等非4价金属,与-βSiC形成固溶体,可有效地改变β-SiC的非线性导电特性;-βSiC微粉表面吸附的Fe、Al、Mg、Ca、Ti、V等金属杂质,随其含量的提高,-βSiC电阻率下降;随表面胶态SiO2含量提高,-βSiC微粉电阻率提高,非线性系数增大;随晶体中x(C)/x(Si)的增大,-βSiC微粉电阻率降低,非线性系数减小.随着-βSiC微粉表面SiO2含量的增加,其防电晕涂层表面电阻率Sρ和起晕电压随之提高,最高可达55 kV,-βSiC完全可单独用作电机线棒的防电晕材料.