固体氧化物电解池直接电解CO2的研究进展

固体氧化物电解池是一种高效、环境友好型的能量转换器件,可以直接将电能转化为化学能. 本文介绍了近年来作者课题组在固体氧化物电解池直接用于CO₂还原的研究进展,并以阴极材料为主着重讨论了金属陶瓷电极和混合导电型钙钛矿氧化物电极的研究工作,最后展望了未来固体氧化物电解池直接电解CO₂的研究思路和方向.     

氧离子传导型固体氧化物电解池燃料电极的研究进展

固体氧化物电解池可高效地电解H₂O/CO₂制备燃料,越来越受到人们的重视. 本文对近年来在燃料电极（阴极）材料方面的研究进展进行了全面综述,指出各种阴极材料的优缺点及发展趋势,强调亟待解决的关键科学与技术问题.     

克服高温二氧化碳电解产生的碳沉积问题（英文）

固体氧化物电解池(SOEC)中的高温二氧化碳电还原(HT-CO₂RR)具有对产物CO选择性近乎100%、能量效率高且产率可达到工业标准等特点.该技术能够将可再生能源、二氧化碳和水转化成高能量化合物,是实现碳中和的有效途径,具有较强的应用前景.但这种二氧化碳利用方法容易受电解过程中的积碳影响,严重损害电解池的能量效率和运行寿命.近年来,研究者们努力分析积碳问题,并通过改变反应条件来抑制积碳生成,或尝试设计无积碳产生的电极材料.然而,这些抑制积碳的策略同时牺牲了催化活性和能量效率.因此,未来研究需要兼顾催化电极的性能、电解池的能量效率和稳定性.本文概述了关于减少HT-CO₂RR中积碳的研究进展,讨论可能加速其大规模实际应用的未来研究方向,并阐述了SOEC的HT-CO₂RR中积碳的形成机制.HT-CO₂RR中积碳的形成是由于CO发生了歧化反应:2CO(g)■C+CO₂(g),也被称为Boudouard反应.该反应涉及两个基本步骤:(1)表面CO^*解离为C     

高温固体氧化物电解制氢技术发展现状与展望

固体氧化物电解池是一种先进的能量转换装置,具有高效、简单、灵活、环境友好等特点,是目前国际能源领域的研究热点. 本文对高温固体氧化物电解制氢技术的基本原理、关键材料、系统组成、发展历程及国内外研究现状等进行了总结和分析,小结了该技术发展面临的主要挑战,简述了清华大学在高温固体氧化物电解领域近期的研究进展,并对其未来应用前景进行了展望.     

固态氧化物电解池中碳-分子电化学转化为可再生燃料

近年来,随着社会环保意识的迅速提高以及对可再生能源利用能力的大幅增强,以燃料电池和电解池为代表的电化学技术已经逐渐在能源的存储、转化和利用方面发挥着不可或缺的独特作用.其中,固态氧化物电解池经过多年的发展,在装置成本和工作效率上取得了长足的进步,在储能转化方面具有重要的潜力.与此同时,伴随着《巴黎协定》签订以来各国的“碳中和”路线图逐渐出台,利用相对廉价易得的可再生电能,将二氧化碳(CO₂)和甲烷(CH₄)等碳-(C1)分子电解转化为高附加值的可再生燃料(如水煤气、乙烯等),对于碳中和目标的实现具有重要的意义.因此,C1分子电化学转化的研究成为了当下重点关注的研究领域,许多重要的研究成果和技术进步在过去几年中不断涌现.固态氧化物电解池作为一种代表性的C1分子电解和转化平台,也日渐引起相关领域研究人员的关注和兴趣.与传统的C1分子催化转化方法相比,基于固态氧化物电解池的电解转化技术具有两个重要优点:高能量转换效率与体系抗中毒能力.这两个特性作为体系稳健性的基石,保障了C1分子转化为可再生燃料的反应过程的长期可持续性.本文首先简要回顾了固态氧化物电解池的前沿技术与发展,并从电解池系统分类、反应体系的特征和反应体系发展的前景与挑战这三个方面,简要介绍了近年来基于固态氧化物电解池体系的C1分子电化学转化的代表性工作.CO₂与CH₄作为廉价易得的C1分子的代表,其转化因其反应分子惰性及反应过程不可控性而广受研究者关注,本文重点关注了在固态氧化物电解池中CO₂,CO₂/H₂O和CH₄三个体系的电化学反应过程和近期研究进展,希望可为相关研究人员未来设计更合适的催化剂和构建更优的电解池结构提供有益的参考.本文还针对目前固态氧化物电解池体系在C1分子转化领域所面临的挑战,提出了未来的一些可能的研究方向,以期助力研究者在不远的将来实现C1分子电解生产可再生燃料的实用化.     

镍高度分散在铁基钙钛矿用于高温固体氧化物电解池阴极的CO2电催化还原研究(英文)

利用太阳能、风能等可再生清洁电能将CO₂催化转化为高附加值化学品或燃料,在CO₂转化和可再生电能存储方面表现出极具潜力的应用前景.高温固体氧化物电解池(SOEC)可将CO₂电催化还原为CO,具有能量效率高、成本低等优点.目前,钙钛矿氧化物已被广泛应用于SOEC电解CO₂的阴极材料,但存在电极催化活性低等问题,因而限制其规模化发展和应用.通常采用浸渍、原位溶出或掺杂等策略引入大量活性中心以提升钙钛矿氧化物电极性能.然而,这些策略仍然面临一些挑战,如浸渍法易引入大颗粒物种而堵塞气体传输通道,原位溶出法能耗较大且析出量较少,掺杂法调控活性幅度有限.因此,发展新型简便方法以合理构建具有高度分散活性位点的阴极材料,可有效拓展电化学三相反应界面,进而加快SOEC高温电解CO₂的电极动力学速率.本文采用机械研磨法将1.0%NiO高度分散于La_0.8Sr_0.2Fe0_3-δ-Ce_0.8Sm_0.2     

在RuO2|Pd|YSZ|PddeNOx电解池中O2-传导的速控步骤

研究了500～750℃富氧条件下RuO₂|M|YSZ|Pd(M=Ag,Pd,Pt,Au)固体电解质电解池在0～4V直流电压下对NO的分解性质.600℃下,O^2-在Pd|YSZ阴极界面处的传导是O^2-在RuO₂|Pd|YSZ|Pd固体电解质电解池中传导过程的速控步骤.反应温度越低,RuO₂|Pd|YSZ|Pd电解池上NO电催化分解相对于氧分解的选择性因子α越大.600℃下O^2-在M|YSZ阴极界面处的传导阻力按Ag2|Ag|YSZ|Pd电解池上分解率为15.3%,NO选择性因子达到13.4.     

大气压下甲烷火花放电制乙炔和合成气

用大气压下火花放电方法和发射光谱原位诊断技术, 对CH₄直接转化制乙炔和间接转化制合成气进行了研究, 并与介质阻挡放电进行了比较。结果表明, 火花放电具有能量效率高的突出优点, 能够高效地将CH₄活化成C原子、H原子和C₂等活泼物种。当CH₄单独进料时, 能得到以C₂H₂为主的烃类产物。当CH₄与CO₂和O₂共进料时, 能得到H₂/CO比值可调的合成气产物。在用火花放电转化CH₄和CO₂制合成气时, 添加O₂能够避免反应器的结炭问题, 反应温度只需225 ℃, 与常规催化法相比具有明显的低温优势。     

高温共电解H2O/CO2制备清洁燃料

高温共电解(high temperature co-electrolysis,HTCE)H2O和CO2技术是一种很有前景的清洁燃料制备和CO2减排新技术。该技术可利用可再生能源或核能提供的电能和高温热,通过高温固体氧化物电解池(solid oxide electrolysis cell,SOEC)将H2O和CO2共电解生产合成气(H2+CO),再将制备的合成气用于生产各种液态碳氢燃料。本文详细介绍了利用高温固体氧化物电解池共电解H2O和CO2制备合成燃料的基本原理、发展历程和目前世界各国的研究进展,对该技术的优势和特点进行了分析,并对该技术在关键材料、反应机理等方面存在的问题进行了总结和讨论,最后对其在新能源技术领域的应用前景作了展望。     

绿色路径C-N偶联合成尿素的最新研究进展（英文）

化学品的工业合成通常在高能耗的条件下进行,加剧了能源危机和环境问题.在可再生电力或/和太阳能的驱动下,可以降低反应的能量屏障,从而在更温和的条件下实现化学品的高效绿色合成.二氧化碳和氮作为主要的小分子,可通过电催化合成各种含碳和氮的燃料,在缓解环境问题的同时降低能源枯竭的压力,达到高效储能的目的.本文综合评述了N₂和CO₂电化学转化的最新研究进展,重点关注了反应条件的改进、反应路线的调整及催化机理的研究.最后,对C-N电催化耦合目前面临的挑战和未来发展进行了展望.为进一步开发N₂和CO₂的电化学转化提供了指导.     

A method for molecular correlation energy calculations. Application to the determination of dissociation energies of diatomic and polyatomic molecules

A simple and economical method for molecular correlation energy calculations is developed. In this method, the internal part of the correlation energy is calculated by means of a CI in a minimal basis set and the non-internal part (semi-internal and all-external) is evaluated using an original atoms-in-molecule method. It is successfully applied to the determination of dissociation energies of some diatomic (H₂, NH, C₂, CN, N₂, CO, NO, O₂, F₂) and polyatomic (H₂O, N₂O, CO₂, N₃H, CH₂N₂, CH₂CO, C₂N₂) molecules. The results are compared to those obtained using very elaborate variational methods.Aspirant du Fonds National Belge de la Recherche Scientifique.     

Partitioning of atomization energy

The present work provides a technique for partitioning the atomization energy of a molecule into diatomic contributions. The method is largely based on the redistribution of the kinetic energy term in Mayer's energy partitioning and uses free‐atom energies as a reference. The comparison of Mayer's original method, the alternative Ichikawa–Yoshida approach, and the new atomization energy partitioning (AEP) shows that the new approach has advantages in describing trends in diatomic energies in molecules with triple bonds, as well as for hydrogen bonds. The proposed AEP is a viable alternative to Mayer's energy partitioning method. © 2007 Wiley Periodicals, Inc. Int. J. Quantum Chem, 2008     

Interaction energy contours of molecules as probed by a test atom

Potential energy contour curves for some simple molecules interacting with a test atom (a Li atom in the ground state) are calculated by theab initio method. Relative hardness of the repulsive molecular surface is found to be anisotropic. This indicates that the outer boundary surface of a molecule changes its form depending on the extent of applied external forces. The attractive nature of the molecular surface is demonstrated to be local. Surroundings of electronegative atoms having nonbonded electron pairs are found to be attractieve to the test atom having both electron-donating and electron-accepting abilities.     

A representation of the polarization term in the interaction energy between a molecule and a point-like charge

The interaction energy of a molecule M with a point-like charge q can be partitioned into simpler contributions, two of which can be expressed in terms of the charge distribution _M of the sole M. The first term, qV(r), represents the interaction of q with the undistorted charge _M ⁰ of M while the second q ² P(r) gives the additional contributions due to the polarization of _M ⁰ under the influence of the charge q placed at the point r. In this paper we investigate the possibility of getting an inexpensive and sufficiently accurate analytical representation of P(r) over the whole space outside the van der Waals volume of M.     

Synthesis of Imines via Reactions of Benzyl Alcohol with Amines Using Half‐Sandwich (η6‐p‐cymene) Ruthenium(II) Complexes Stabilised by 2‐aminofluorene Derivatives

A new class of half‐sandwich (η⁶‐p‐cymene) ruthenium(II) complexes supported by 2‐aminofluorene derivatives [Ru(η⁶‐p‐cymene)(Cl)(L)] ( L  = 2‐(((9H‐fluoren‐2‐yl)imino)methyl)phenol ( L ¹ ), 2‐(((9H‐fluoren‐2‐yl)imino)methyl)‐3‐methoxyphenol ( L ² ), 1‐(((9H‐fluoren‐2‐yl)imino)methyl)naphthalene‐2‐ol ( L ³ ) and N‐((1H‐pyrrol‐2‐yl)methylene)‐9H‐fluorene‐2‐amine ( L ⁴ )) were synthesized. All compounds were fully characterized by analytical and spectroscopic techniques (IR, UV–Vis, NMR) and also by mass spectrometry. The solid state molecular structures of the complexes [Ru(η⁶‐p‐cymene)(Cl)(L²)], [Ru(η⁶‐p‐cymene)(Cl)(L³)] and [Ru(η⁶‐p‐cymene)(Cl)(L⁴)] revealed that the 2‐aminofluorene and p‐cymene moieties coordinate to ruthenium(II) in a three‐legged piano‐stool geometry. The synthesized complexes were used as catalysts for the dehydrogenative coupling of benzyl alcohol with a range of amines (aliphatic, aromatic and heterocyclic). The reactions were carried out under thermal heating, ultrasound and microwave assistance, using solvent or solvent free conditions, and the catalytic performance was optimized regarding the solvent, the type of base, the catalyst loading and the temperature. Moderately high to very high isolated yields were obtained using [Ru(η⁶‐p‐cymene)(Cl)(L⁴)] at 1 mol%. In general, microwave irradiation produced better yields than the other two techniques irrespective of the nature of the substituents.     

能源转换演示装置的设计

针对高中化学教材中提到的新能源问题,探索设计了可将太阳能转化为电能,电能转化为化学能,化学能转化为电能,电能转化为热能的能源转换演示装置。通过该实验的演示,可以让学生直观地感受到几种能量之间的转化过程,可供教学参考和借鉴。     

Influence of multivalent ions on power production from mixing salt and fresh water with a reverse electrodialysis system

Reverse electrodialysis is a membrane-based technique for production of sustainable electricity from controlled mixing of a diluted electrolyte solution (e.g., river water) and a concentrated electrolyte solution (e.g., sea water). Reverse electrodialysis has been investigated with pure sodium chloride solutions. In practice, however, in most cases also other ions are present in both feed solutions. In the present paper, the effect of multivalent ions on the performance of a reverse electrodialysis stack was investigated. Results show that, besides a higher stack resistance in presence of multivalent ions, especially the presence of multivalent ions in the dilute solution has a lowering effect on the stack voltage. This can be explained by an observed transport of these ions from the diluted electrolyte solution to the concentrated electrolyte solution. In order to prevent or hamper this transport against the activity gradient, monovalent-selective membranes can be used. This shows indeed better results with respect to the stack voltage. Therefore, it would be beneficial to use monovalent-selective membranes in reverse electrodialysis, especially in the case of a relatively high content of multivalent ions in the dilute (i.e., in the first stages of the installation where the sodium chloride content in the dilute is still relatively low).     

Electron impact ionization of amines using crossed electron-molecular beams

Ionization energy functions of triethyl amine, tri-n-propyl amine, N,N-dimethyl-benzenamine and N,N-diethyl-benzenamine, and appearance energy functions of major products of dissociative ionization have been measured using a high sensitivity crossed electron beam-molecular beam apparatus incorporating a quadrupole mass spectrometer and an on-line laboratory computer. The data obtained is useful in understanding the role of dopants in gas laser plasmas.     

Efficient calculation of two-dimensional adiabatic and free energy maps: Application to the isomerization of the C13C14 and C15N16 bonds in the retinal of bacteriorhodopsin

Accurate calculation of potential energy and free-energy profiles along reaction coordinates of biological processes such as enzymatic reactions or conformational changes is fundamental to the obtention of theoretical insight into protein function. We describe here the practical implementation of the Automatic Map Refinement Procedure (AMRP) and two-dimensional Weighted Histogram Analysis Method (WHAM) for efficient computation of adiabatic potential energy and free-energy maps, respectively. Methods for efficiently sampling configuration space with high-energy barriers and for removing hysteresis in the case of periodic reaction coordinates are presented. The application of these techniques to the isomerization of the C13C14 and C15N16 bonds in the retinal of bacteriorhodopsin is described. In dark-adapted bacteriorhodopsin (bR), the retinal moiety exists in two conformers, all-trans and (13,15)cis, with the latter making ≃67% of the population. This experimental free energy difference is reproduced here to within k_BT. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1644–1658, 1999     

太阳能光解水制氢的研究进展

本文概述了利用光催化技术催化分解水制氢的反应机理和研究进展。结合作者的最近研究,重点描述了TiO2及过渡金属氧化物,层状金属氧化物以及某些能利用可见光的光催化材料的结构和光催化特性,阐述了核课题的意义和今后的研究方向。