Theoretical Thermodynamic Efficiency Limit of Isothermal Solar Fuel Generation from H2O/CO2 Splitting in Membrane Reactors

Solar fuel generation from thermochemical H₂O or CO₂ splitting is a promising and attractive approach for harvesting fuel without CO₂ emissions. Yet, low conversion and high reaction temperature restrict its application. One method of increasing conversion at a lower temperature is to implement oxygen permeable membranes (OPM) into a membrane reactor configuration. This allows for the selective separation of generated oxygen and causes a forward shift in the equilibrium of H₂O or CO₂ splitting reactions. In this research, solar-driven fuel production via H₂O or CO₂ splitting with an OPM reactor is modeled in isothermal operation, with an emphasis on the calculation of the theoretical thermodynamic efficiency of the system. In addition to the energy required for the high temperature of the reaction, the energy required for maintaining low oxygen permeate pressure for oxygen removal has a large influence on the overall thermodynamic efficiency. The theoretical first-law thermodynamic efficiency is calculated using separation exergy, an electrochemical O₂ pump, and a vacuum pump, which shows a maximum efficiency of 63.8%, 61.7%, and 8.00% for H₂O splitting, respectively, and 63.6%, 61.5%, and 16.7% for CO₂ splitting, respectively, in a temperature range of 800 °C to 2000 °C. The theoretical second-law thermodynamic efficiency is 55.7% and 65.7% for both H₂O splitting and CO₂ splitting at 2000 °C. An efficient O₂ separation method is extremely crucial to achieve high thermodynamic efficiency, especially in the separation efficiency range of 0–20% and in relatively low reaction temperatures. This research is also applicable in other isothermal H₂O or CO₂ splitting systems (e.g., chemical cycling) due to similar thermodynamics.     

FEL光学速调管的升级性能分析

通过三维磁场的有限元计算,给出了自由电子激光（FEL）研究用光学速调管升级后的磁参数。国家同步辐射实验室合肥光源（HLS）电子储存环能量可以日常运行在200～800 MeV间,为了与电子储存环能量匹配,并在较高束电子能量下进行实验和得到较多的相干辐射光子,光学速调管从原来的对称结构升级成非对称结构,用于HLS储存环谐波产生FEL实验。给出了升级后非对称光学速调管的几组匹配磁参数,用于在HLS储存环注入能量和可以运行的最高能量下进行谐波FEL实验。初步计算表明,HLS 储存环电子束性能优越,能散很低,FEL实验用最高能散仅为2.05×10-4,相应FEL辐射的能散修正因子在0.96以上,可以忽略不计。     

晶体级联方式宽带三倍频方案的参数优化

 针对时间位相调制的宽带激光,采用分步离散傅里叶变换及四阶龙格－库塔算法进行数值模拟计算。讨论了采用KDP晶体级联方式时,入射基频光的光强、带宽以及晶体厚度对三倍频转换效率的影响。对采用一块РⅠ类二倍频晶体、一块Ⅱ类和一块Ⅰ类双混频晶体的级联宽带三倍频方式进行了晶体参数的优化。研究结果表明,使用两块级联的KDP晶体作为混频晶体,不仅能有效地提高带宽较宽条件下三倍频光的转换效率,还可以显著增大宽带三倍频的动态范围。经优化后,带宽1.11 nm时入射基频光强在3～8 GW/cm²范围内的三倍频转换效率可保持在60％～70％,比采用单倍频单混频方案时增大了30％～40％。     

Determination of arsenic in gold by flow injection inductively coupled plasma mass spectrometry with matrix removal by reductive precipitation

Arsenic was determined in gold by flow injection hydride generation inductively coupled plasma-mass spectrometry following a batch mode reductive precipitation removal of the interfering gold matrix. A solution of potassium iodide, L-ascorbic acid, and hydrochloric acid was used as the reluctant. The recovery of gold by precipitation and filtration was 99 ± 3%. The detection limit for arsenic in gold was 55 ng g⁻¹ in the solid. The concentration of arsenic that was determined in the Royal Canadian Mint gold sample FAU-10 was 29.7 μg g⁻¹ in the solid; this value was indistinguishable, with 95% confidence, from values determined at the Royal Canadian Mint by graphite furnace atomic absorption spectrometry and by inductively coupled plasma-mass spectrometry. The standard deviation for four replicate determinations of the arsenic in FAU-10 was 0.972 μg g⁻¹ in the solid.     

Determination of tin in steels by non-dispersive atomic fluorescence spectrometry coupled with flow-injection hydride generation in the presence of L-cysteine

Flow-injection hydride generation has been coupled with a non-dispersive atomic fluorescence spectrometer for the determination of trace concentrations of tin. The use of L-cysteine in stannane generation enhances the atomic fluorescence signal for tin. In addition, it appears that the flow-injection method allows the use of a wider range of acid concentrations, and hence interference from transition elements is also reduced. An absolute detection limit of 1.3 ng was achieved with a 0.5 ml sample. Ten determinations of a solution containing 100 ng ml⁻¹ of tin(H) generated a relative standard deviation of 1.8%. The linear dynamic range of the calibration curve extended over three orders of magnitude and sample throughput rate was 144 samples h⁻¹. Application of the proposed technique is demonstrated by the determination of tin in low alloy steel standard reference materials.     

Elliptic adaptive grid generation and area equidistribution

The derivation of elliptic adaptive grid control functions which satisfy the area equidistribution concept is presented. The resulting expressions are derived without approximation and are shown to provide explicit control over cell area distributions. A modification to the equidistribution concept which yields control functions that enable additional control of the near‐boundary grid resolution is also proposed. A computer code which incorporates these control functions has been developed and is applied to a series of complex fluid flows to demonstrate the validity and utility of the derived expressions. Copyright © 1999 John Wiley & Sons, Ltd.     

A Review of the System-Intrinsic Nonequilibrium Thermodynamics in Extended Space (MNEQT) with Applications

The review deals with a novel approach (MNEQT) to nonequilibrium thermodynamics (NEQT) that is based on the concept of internal equilibrium (IEQ) in an enlarged state space SZ involving internal variables as additional state variables. The IEQ macrostates are unique in SZ and have no memory just as EQ macrostates are in the EQ state space SX⊂SZ. The approach provides a clear strategy to identify the internal variables for any model through several examples. The MNEQT deals directly with system-intrinsic quantities, which are very useful as they fully describe irreversibility. Because of this, MNEQT solves a long-standing problem in NEQT of identifying a unique global temperature T of a system, thus fulfilling Planck’s dream of a global temperature for any system, even if it is not uniform such as when it is driven between two heat baths; T has the conventional interpretation of satisfying the Clausius statement that the exchange macroheatdeQflows from hot to cold, and other sensible criteria expected of a temperature. The concept of the generalized macroheat dQ=deQ+diQ converts the Clausius inequality dS≥deQ/T0 for a system in a medium at temperature T0 into the Clausius equalitydS≡dQ/T, which also covers macrostates with memory, and follows from the extensivity property. The equality also holds for a NEQ isolated system. The novel approach is extremely useful as it also works when no internal state variables are used to study nonunique macrostates in the EQ state space SX at the expense of explicit time dependence in the entropy that gives rise to memory effects. To show the usefulness of the novel approach, we give several examples such as irreversible Carnot cycle, friction and Brownian motion, the free expansion, etc.     

Parallel computation of incompressible flows with complex geometries

We present our numerical methods for the solution of large-scale incompressible flow applications with complex geometries. These methods include a stabilized finite element formulation of the Navier–Stokes equations, implementation of this formulation on parallel architectures such as the Thinking Machines CM-5 and the CRAY T3D, and automatic 3D mesh generation techniques based on Delaunay–Voronoi methods for the discretization of complex domains. All three of these methods are required for the numerical simulation of most engineering applications involving fluid flow. We apply these methods to the simulation of airflow past an automobile and fluid–particle interactions. The simulation of airflow past an automobile is of very large scale with a high level of detail and yielded many interesting airflow patterns which help in understanding the aerodynamic characteristics of such vehicles. © 1997 John Wiley & Sons, Ltd.     

Vibrational Spectroscopy of Surface Adsorbates by Sum Frequency Generation (SFG)

The vibrational spectroscopy by way of vibrational sum-frequency generation (VSFG) has been made of formic acid adsorbed on MgO(001) surface and of n-alkyltrichlorosilanes chemisorbed on quartz plates. It was revealed that the species on the MgO surface was formate ion (HCOO⁺) with CH bonds standing vertical to the surface and that the different adsorption sites showed up on repeated cycles of adsorption-desorption processes. The results of chemisorbed films indicated that the g-t and/or g-t-g′ conformational scquences of n-alkyl chains occurred more frequently by the length of alkyl chain and that the surface hydroxyls, which are the sites of chemisorption, are ripped off by pre-exposure of substrate to oxygen plasma.     

基于PPLN波导中倍频与差频效应的全光波长转换

对准相位匹配的铌酸锂光波导中基于倍频与差频级联二阶非线性效应的全光波长转换进行了研究.在建立理论模型的基础上,分别对单脉冲以及序列光脉冲的波长转换过程进行了数值模拟,并对转换过程中的走离现象以及脉冲延迟进行了分析.模拟结果表明信号光与抽运光脉冲非同步输入的情况下可以克服走离效应的影响,得到更好的转换效率.另外,在抽运时钟脉冲的驱动下,输入的40 Gb/s的NRZ信号光可以转换为RZ转换光,且波形较好.