First principles investigations of Fe,Co, Ni in model honeycomb carbon networks

The behaviors of ferromagnetic transition metals of the first period: Fe, Co and Ni are examined within density functional theory calculations in two dimensional carbon extended networks using model structure LiC₆. Around geometry optimized structures, the energy-volume equations of states considering non magnetic and spin polarized configurations established ferromagnetic ground states with magnetizations –reduced with respect to the metals’– of 2 μ_B for FeC₆ and 1 μ_B for CoC₆ while no magnetic solution could be identified for NiC₆. In the D_6h point group of the P6/mmm space group l_m decomposition of the d states results with increasing energy into doublet state E_1g with d(x²-y²) and d(xy); singlet state A_1g d(z²) and doublet state E_2g d(xz) and d(yz) lying on E_F and responsible of the onset of magnetic moments. This was mirrored via molecular orbital approach with a construct of Fe embedded between two extended carbon networks thus validating the model structure proposed for TC₆ compounds. The 100% polarization in one spin channel allows proposing potential uses in spintronics applications.     

Sonochemical conversion of CO2 into hydrocarbons: The Sabatier reaction at ambient conditions

In this study, we investigated an alternative method for the chemical CO₂ reduction reaction in which power ultrasound (488 kHz ultrasonic plate transducer) was applied to CO₂-saturated (up to 3%) pure water, NaCl and synthetic seawater solutions. Under ultrasonic conditions, the converted CO₂ products were found to be mainly CH₄, C₂H₄ and C₂H₆ including large amount of CO which was subsequently converted into CH₄. We have found that introducing molecular H₂ plays a crucial role in the CO₂ conversion process and that increasing hydrogen concentration increased the yields of hydrocarbons. However, it was observed that at higher hydrogen concentrations, the overall conversion decreased since hydrogen, a diatomic gas, is known to decrease cavitational activity in liquids. It was also found that 1.0 M NaCl solutions saturated with 2% CO₂ + 98% H₂ led to maximum hydrocarbon yields (close to 5%) and increasing the salt concentrations further decreased the yield of hydrocarbons due to the combined physical and chemical effects of ultrasound. It was shown that CO₂ present in a synthetic industrial flue gas (86.74% N₂, 13% CO₂, 0.2% O₂ and 600 ppm of CO) could be converted into hydrocarbons through this method by diluting the flue gas with hydrogen. Moreover, it was observed that in addition to pure water, synthetic seawater can also be used as an ultrasonicating media for the sonochemical process where the presence of NaCl improves the yields of hydrocarbons by ca. 40%. We have also shown that by using low frequency high-power ultrasound in the absence of catalysts, it is possible to carry out the conversion process at ambient conditions i.e., at room temperature and pressure. We are postulating that each cavitation bubble formed during ultrasonication act as a “micro-reactor” where the so-called Sabatier reaction -$C{O}_2+4H_2\stackrel{\mathit{Ultrasonication}}{\to }C{H}_4+2H_{2}O$ - takes place upon collapse of the bubble. We are naming this novel approach as the “Islam-Pollet-Hihn process”.     

In situ confinement of iron-based active sites within high porosity carbon frameworks with enhanced activity for rechargeable Zn–air battery

Non-noble bifunctional electrocatalysts with robust activity and stability toward oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are greatly significant but challenging for Zn-air batteries. Here, in situ confinement of FeN_x active sites in high porosity carbon framework (FeN_x/CMCC) derived from chelate of carboxymethylcellulose (CMC) and iron ions were synthesized. Particularly, construction of FeN_x within porous carbon framework accelerates the electron transfer and the sufficient utilization of active centers, and then expedites the reaction kinetics of ORR and OER. As expected, the optimized FeN_x/CMCC exhibits superior ORR activity with a larger half-wave potential of 0.869 V. The rechargeable Zn-air battery delivers a higher power density of 99.6 mW/cm² and a special capacity of 781.9 mA h/g_Zn at 10 mA/cm², together with excellent durability of over 335 h. Remarkably, the as-assembled solid-state battery exhibits a higher open circuit voltage (OCV) of 1.5 V, a special capacity of 709.7 mA h/g_Zn, as well as prolonged cycling stability (90 h). Moreover, the flexible solid-state battery displays negligible loss of electrochemical performance under various bending angles, illustrating its potential application in flexible electronic devices.     

Relationship of nanostructure and thermo-chemical response/thermal ablation of carbon aerogels

In this work, the interfacial mass balance relations combined with the non-parametric kinetic (NPK) analysis results were used for evaluating the thermo-chemical ablation process and oxidation mechanism of carbon aerogels with various porous structure. It was found that the two-parameter model of Nomen–Sempereis was able to describe the kinetics of the oxidation reaction and to reveal the structure-dependent contribution of two main processes with chemical and physical nature. The porosity of the carbon aerogel, rather than the other microstructural features, was realized more effective on the rate of ablation.     

Design of Functional Carbon Composite Materials for Energy Conversion and Storage

The carbon composite materials have been a research hotspot in the fields of catalysis, energy conversion and so on, because of their features of large structure and morphology variety, good chemical and electrochemical stability, and high electronic conductivity, large specific surface area and rich active sites. This paper summarizes some research progress of carbon composite materials, including assembly methodologies, their structure regulation, properties, and related applications. Moreover, the current challenges and the prospects of these materials are also discussed.     

对自由落体的诺维科夫时间与牛顿绝对时间关系讨论

文章首先将史瓦西黑洞场中自由下落质点的固有时(诺维科夫坐标时)公式,由自然单位制化成了国际单位制中的形式.然后,根据牛顿第二定律和万有引力定律,推导出了自由下落质点经历的绝对时间公式,进而证明了广义相对论中自由落体经历的固有时,恰好等于牛顿力学给出的绝对时间.最后,对自由下落质点在黑洞内外经历的时间进行了特例计算.     

Accurate correction of arbitrary spin fermion quantum tunneling from non-stationary Kerr-de Sitter black hole based on corrected Lorentz dispersion relation

According to a corrected dispersion relation proposed in the study on the string theory and quantum gravity theory, the Rarita-Schwinger equation was precisely modified, which resulted in the Rarita-Schwinger-Hamilton-Jacobi equation. Using this equation, the characteristics of arbitrary spin fermion quantum tunneling radiation from non-stationary Kerr-de Sitter black holes were determined. A number of accurately corrected physical quantities, such as surface gravity, chemical potential, tunneling probability, and Hawking temperature, which describe the properties of black holes, were derived. This research has enriched the research methods and enabled increased precision in black hole physics research.     

Wave-based analysis of dual acoustic black holes for anechoic termination of shock testing devices

Shock testing is an important issue for the survivability of an equipment under shock environment in aerospace and military industries. One of the problems faced in conventional shock testing devices is the need for redesigning of the geometry whenever the responses to different shock environments are tested. To circumvent the redesigning processes, a structure with two ‘acoustic black holes (ABHs)’ on both ends, referred to as the beam with dual ABHs, is proposed as a shock testing device. The beam with dual ABHs is capable of simulating diverse shock environments by controlling the applied force because it can be regarded as an infinite beam at high frequency range with the aid of the anechoic terminations by the ABHs. To systematically investigate the beam with dual ABHs, we develop a wave-based method that uses the reflection matrix of an ABH to perform free and forced vibration analyses. From the analyses on frequency response function and shock response spectrum of the beam with dual ABH, it is suggested that the beam with dual ABHs is feasible as a semi-permanent shock testing device.     

Methylthiouracil‐modified Carbon Paste Electrode as a New Voltammetric Sensor Based on a 1,4‐Michael Addition Reaction for Detection of Dopamine

A sensitive dopamine sensor was constructed based on the modified carbon paste electrode with methylthiouracil as a nucleophile in the 1,4‐Michael addition reaction. An ECE mechanism was suggested for dopamine oxidation at the modified electrode. Design of experiments was used in the optimization of variables. Under the optimum conditions, calibration graph was linear in the range of 0.20–15.0 µM with a detection limit of 73 nM. The relative standard deviations (n=5) for 0.50 µM of dopamine was 3.83 %. The selectivity of the sensor was also studied. The developed sensor was applied for analysis of pharmaceutical and biological samples.     

双电极法现场快速检测地下水和湖水中碳酸氢根和碳酸根

地下水和湖水中碳酸氢根( HCO-3)和碳酸根( CO2-3)含量是地球化学碳行为和碳循环的重要表征,但两种离子的浓度易受环境影响而改变,因此,地下水和湖水中HCO-3和CO2-3真实含量的测定一直是个难题。实验利用CO2的水解平衡,通过pH电极和二氧化碳电极联用,建立了HCO-3和CO2-3现场快速测定的新方法,解决了地下水和湖水中HCO-3和CO2-3真实含量的测定难题。研究结果表明,在pH=4.8±0.1的底液中, HCO-3和CO2-3的线性范围分别为0.027~570 mg/L和1.25×10-8~39.7 mg/L。共存的金属离子、强酸阴离子(K+、Na+、Mg2+、Cl-、SO2-4,100 mg/L)、弱酸阴离子和弱酸(HSO-3、NO-2、HOAc,50 mg/L)对测定干扰小于5%。实际水样加标实验回收率在95.2%~99.2%之间,相对标准偏差为2.6%~3.7%。与酸碱滴定法进行对比,本方法的准确性良好。但方法受温度影响,因此标准溶液与样品应在同一温度下测量。总体而言,双电极法灵敏、快速、经济且电极携带方便、操作简单、对环境要求不高,十分适合现场和室内一般自然水体的快速检测。本方法已成功应用于青海省地下水和青海湖湖水中HCO-3和CO2-3的现场测定。实验表明,海东地区地下水样品pH在6.4~7.4之间,HCO-3含量为234~4096 mg/L,CO2-3含量为0.16~1.89 mg/L；青海湖湖水样品pH≈8.7,HCO-3含量范围在1.36~1.86 g/L,CO2-3含量在32.3~43.9 mg/L,与文献结果吻合。