铁基载氧体的污泥化学链气化过程中氮迁移热力学模拟与实验研究

基于吉布斯自由能最小化原理,采用HSC Chemistry 6.0软件,对污泥化学链气化过程中NO_x前驱物（NH₃和HCN）与Fe₂O₃载氧体的氧化还原行为进行了热力学模拟。基于污泥热解实验中NO_x前驱物的含量,计算载氧体与污泥的摩尔比（OC/SS）对NH₃、HCN以及NH₃和HCN混合气氧化过程的影响。热力学模拟结果表明：Fe₂O₃能显著促进NO_x前驱物的氧化和裂解,主要生成N₂,几乎无NO_x生成;当NH₃、HCN以及混合气（NH₃和HCN）分别作为还原剂时,其最优OC/SS分别为0.02、0.04和0.05;由于HCN还原性强于NH₃,其氧化速率较快。基于Fe₂O₃/Al₂O₃混合物（FeAl）载氧体,实验对比了污泥化学链气化与污泥热解过程中NO_x前驱物的释放特性,发现Fe₂O₃能显著降低烟气中NO_x前驱物的产率,NH₃和HCN产率分别下降32%和62%。实验结果与热力学模拟结果一致。     

纳米Fe2O3/硬脂酸/十八醇纳米复合相变蓄热材料的性能研究

针对有机相变材料热导率低的问题,将高热导率的纳米Fe₂O₃添加到硬脂酸/十八醇二元有机复合蓄热相变材料中,制备纳米复合蓄热相变材料。从分散剂的种类、分散剂与纳米材料的添加量以及超声时间4个方面研究其对纳米复合相变蓄热材料的稳定性及热物性的影响。结果表明,阴离子表面活性剂的分散效果优于阳离子和非离子表面活性剂。复合相变材料中添加质量分数为0.8%,十二烷基苯磺酸钠(SDBS)和质量分数为0.4%Fe₂O₃的体系,超声时间为80 min时,纳米Fe₂O₃在相变材料中的分散效果最好。添加纳米Fe₂O₃后复合蓄热相变材料的相变潜热及相变温度有所下降,热导率提高34.9%。300次热循环复合相变材料的相变温度波动区间不超过0.41℃,相变潜热波动区间不超过4.0%,热稳定性良好。     

Fe3+交联的预包覆Fe3O4纳米粒子改性rGO自支撑膜的储锂性能

本工作采用Fe³⁺对含有氧化石墨烯(graphene oxide,GO)预包覆Fe₃O₄的GO自支撑膜进行改性处理制备Fe³⁺诱导交联的预包覆Fe₃O₄纳米粒子复合热还原型氧化石墨烯自支撑膜(Fe³⁺@Fe₃O₄/r GO)。采用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)等测试手段表征材料组成、结构与形貌,并研究Fe³⁺@Fe₃O₄/r GO自支撑膜作为锂离子电池负极的储锂性能。结果表明球状Fe₃O₄纳米颗粒被GO片层紧密包裹,且经过Fe³⁺诱导交联的Fe³⁺@Fe₃O₄/r GO自支撑膜稳定性显著提高;电化学结果表明,在电流密度为100 m A/g恒...     

双金属NiFe/γ-Al2O3催化月桂酸甲酯脱氧的研究

采用浸渍法制备Ni10/γ-Al₂O₃、Ni₅-Fe₅/γ-Al₂O₃和Fe₁₀/γ-Al₂O₃催化剂,研究各催化剂对月桂酸甲酯的加氢脱氧(HDO)性能。通过H₂程序升温还原(H₂-TPR)、X射线衍射(XRD)和H₂程序升温脱附(H₂-TPD)对制得的催化剂和前驱体进行表征,证实双金属催化剂中形成NiFe合金且其有助于提高催化性能,阐明Ni与Fe之间的相互协同作用。Fe物种对Ni催化剂的月桂酸甲酯加氢性能和产物选择性具有显著影响,在低反应温度下表现出明显优于单金属催化剂的催化性能。在反应温度为340℃时,Ni₅-Fe₅/γ-Al₂O₃催化剂的月桂酸甲酯转化率为86.79%,烷烃化合物选择性达90%以上。     

Fe3O4纳米颗粒对玉米秸秆光发酵产氢的影响

以HAU-M1光合菌群作为发酵细菌,以玉米秸秆为发酵底物,研究Fe₃O₄纳米颗粒对光发酵产氢过程的影响。结果表明:粒径60 nm的Fe₃O₄纳米颗粒浓度为100 mg/L时,比产氢量达到(46.68±1.00)mL/g VSS,与对照组的(35.07±0.56)mL/g VSS相比提升(33.11±0.01)%,此时的能量转化率也提高33.10%。产氢动力学分析结果也表明Fe₃O₄纳米颗粒对反应体系有明显的影响,粒径60 nm的Fe₃O₄纳米颗粒浓度为100 mg/L时,最大产氢潜能和最大产氢速率分别为46.97 mL/g VSS和1.06 mL/(g VSS·h)。适宜的Fe₃O₄纳米颗粒的粒径和浓度能显著促进光发酵产氢能力,而浓度过高则会产生抑制作用。     

铁基和硅基材料对有机垃圾厌氧发酵产沼气的促进作用研究

制备并考察3种功能材料（Fe₂O₃、Silicalite-1和Fe₂O₃@Silicalite-1）的3种投加量（50、100和150 mg）对有机垃圾（鸡粪）的厌氧发酵产气影响。结果表明：各功能材料组的日沼气产量和甲烷含量相比于空白组均得到有效提高,其中Fe₂O₃组分别提高31.07%和10.34%;Silicalite-1组分别提高23.98%和12.07%;Fe₂O₃@Silicalite-1组的产气效果最佳,其最高累计产气量和甲烷含量分别提高41.39%和17.24%。由此可见,将纳米Fe₂O₃分散负载在多孔材料（Silicalite-1）上可作为一种有效的厌氧发酵催化剂,该材料可避免传统方法中纳米颗粒的团聚造成的自身性能失活,从而通过厌氧发酵技术耦合复合材料实现有机垃圾处理工艺的能源效益和环境效益。     

The preparation of Fe3O4/nanocellulose aerogel nanocomposite as anodes for lithium-ion batteries and electrochemical performance

纤维素因其环境友好、价格低廉等优点受到研究者的广泛关注,近年来作为碳材料广泛应用于电化学研究中。采用碳化后的纳米纤维素气凝胶为载体,六水合氯化铁为铁源,通过溶液热法合成了四氧化三铁/纳米纤维素气凝胶复合材料。通过XRD和SEM对产物进行了结构表征和微观形貌分析,并将其作为锂离子电池的负极材料,测试了一系列电化学性能,并与纯Fe₃O₄纳米颗粒的进行对比。结果表明,碳化后的纳米纤维素气凝胶保持着疏松多孔的三维网络结构,尺寸均一的Fe₃O₄纳米粒子均匀的分布于其中。该复合材料表现出优异的循环稳定性,在100 mA/g的电流密度下,首次放电比容量为1064 mA·h/g,100次循环后仍稳定在847 mA·h/g。相比于纯Fe₃O₄纳米颗粒,材料的电化学性能得到大幅度提高。本文有助于推动纤维素基碳材料在电化学领域中的进一步应用,为复合电极材料的发展提供一定的实验依据。     

Electrochemical thermal stability of the LiFePO4/LiNi0.8Co0.15Al0.05O2 blend cathode material for lithium ion batteries

为了改善LiNi_0.8Co_0.15Al_0.05O₂正极材料的电化学热稳定性能,加入LiFePO₄共混制成了LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂锂离子电池用混合正极材料。使用X射线衍射（XRD）和扫描电子显微镜（SEM）表征了结构和形貌,测试了电化学性能。结果显示,简单球磨的混合LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂正极材料中,纳米LiFePO₄粒子包覆在LiNi_0.8Co_0.15Al_0.05O₂粒子表面提高了混合正极材料在充放电过程中的电化学稳定性和结构稳定性。LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂混合正极材料在50 ℃下循环100周容量保持率为82.0%,明显地优于单一LiNi_0.8Co_0.15Al_0.05O₂材料的72.9%。     

Preparation of LiNi0.80Co0.15Al0.05O2 cathode material via Li-rich method

本文采用共沉淀法制备球形Ni_0.80Co_0.15Al_0.05(OH)_2.05前驱体,经预氧化后,采用富锂配比在氧气和空气气氛下烧结合成LiNi_0.80Co_0.15Al_0.05O₂正极材料.用X射线衍射,扫描电镜和恒电流充放电测试等方法对该材料的结构,形貌及电化学性能进行表征.结果表明:当锂配比为1.15时,氧气和空气中烧结合成的LiNi_0.80Co_0.15Al_0.05O₂正极材料的形貌,结构和电化学性能相当.富锂配比方法可在空气气氛下制备出电化学性能优异的LiNi_0.80Co_0.15Al_0.05O₂正极材料.0.1 C放电克比容量在200 mA·h/g以上,首次效率在87%左右;1 C放电克比容量在168 mA·h/g以上;800周循环容量保持率在80%以上.     

Thermal properties of a modified MOF-stearic acid composite phase change materials

以ZIF-67作为金属有机框架（MOF）,通过原位沉淀法生长在膨胀石墨片上对膨胀石墨进行改性,经过煅烧后形成Co₃O₄/EG分级多孔混合结构。为了优化硬脂酸的充放热性能,将Co₃O₄/EG与硬脂酸通过熔融共混和真空吸附法复合,制备出具有优异充放热性能的SA/Co₃O₄/EG复合相变材料。表征SA/Co₃O₄/EG复合相变材料的微结构、物相、相变焓值、相变温度和充放热时间等热物理性能,分析添加物Co₃O₄/EG的微结构对硬脂酸相变储热材料微结构和热性能产生的影响。添加物Co₃O₄/EG对SA/Co₃O₄/EG复合相变材料的相变温度影响较小,相变温度与Co₃O₄/EG添加量没有依赖关系。而复合储热材料的相变潜热随Co₃O₄/EG量的增加而减少,但与理论计算相差较少。Co₃O₄/EG分级多孔结构可以阻止Co₃O₄的团聚并提供高比表面积和孔体积吸附硬脂酸,多孔隙结构Co₃O₄和高热导率膨胀石墨（EG）的协同作用可以增加硬脂酸相变储热材料的热传递,缩短充放热时间,提高充放热效率。     

Porous nickel MCFC cathode coated by potentiostatically deposited cobalt oxide: II. Structural and morphological behavior in molten carbonate

Cobalt oxide was deposited on porous nickel by an electrodeposition technique as precursor of a novel MCFC cathode. The behavior of this cathode in molten (Li_0.52Na_0.48)₂CO₃ eutectics at 650 °C under an atmosphere of CO₂:air (30:70) was studied before and after 50 h of exposure by different techniques. Before the exposure, the deposit of cobalt corresponded to a Co₃O₄ thin layer of. This crystalline structure was identified by XRD and Raman spectroscopy. After its exposure in the eutectic melt a loss of cobalt was observed by XRD, Raman spectroscopy, XPS, EDS and ICP-AES. The change in the Co₃O₄ structure into lithium–cobalt–nickel oxide (LiCo_1−yNi_yO₂) was observed by Raman spectroscopy. The SEM micrographs for Co₃O₄-coated porous nickel showed different angular shapes with respect to porous Ni. The nickel solubility for the coated porous nickel, measured by ICP-AES, decreased with respect to uncoated nickel. The Co₃O₄-coated porous nickel cathode showed, after its immersion in the molten carbonate melt, a similar porosity but a higher pore size. LiCo_1−yNi_yO₂-coated NiO offers interesting features which combine the properties of nickel, lithium and cobalt in molten carbonate. This could be a promising novel MCFC cathode material.     

Facile controlled synthesis of hierarchically structured mesoporous Li4Ti5O12/C/rGO composites as high-performance anode of lithium-ion batteries

In this paper, a facile strategy is proposed to controllably synthesize mesoporous Li₄Ti₅O₁₂/C nanocomposite embedded in graphene matrix as lithium-ion battery anode via the co-assembly of Li₄Ti₅O₁₂ (LTO) precursor, GO, and phenolic resin. The obtained composites, which consists of a LTO core, a phenolic-resin-based carbon shell, and a porous frame constructed by rGO, can be denoted as LTO/C/rGO and presents a hierarchical structure. Owing to the advantages of the hierarchical structure, including a high surface area and a high electric conductivity, the mesoporous LTO/C/rGO composite exhibits a greatly improved rate capability as the anode material in contrast to the conventional LTO electrode.     

铜基底上无黏结剂Co3V2O8多孔纳米片阵列的制备以及锂离子电池性能研究

直接在铜基底上生长具有不同金属离子的多孔过渡金属氧化物,成为有前途的锂离子电池电极材料的候选。本文提出了一种简便可行的低温水热沉积方法在铜基底上制备前驱物阵列。前驱物经过煅烧处理得到具有多孔特性Co₃V₂O₈纳米片阵列,多孔纳米片阵列用作锂离子电池负极材料显示出了长期循环稳定性和高倍率性能。在1.0 A/g电流密度下,电池经过240次循环后显示出1 010 mA∙h/g的容量;在3.0 A/g的电流密度下,电池循环600次后显示出552 mA∙h/g的可逆容量。     

Multiphoton semiconductor photocatalysis

A composite catalyst consisting of Nb₂O₅ and platinized TiO₂ particles is found to initiate up-hill chemical reactions via a low-energy multiphoton process involving step-wise transition of electrons across the traps in Nb₂O₅ to the conduction band of Nb₂O₅ and then to the conduction band of TiO₂.     

Electrochemical performance of Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag composite cathodes in intermediate temperature solid oxide fuel cells

The electrochemical performances of Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag composite cathodes have been investigated in intermediate temperature solid oxide fuel cells. The Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag cathodes prepared by ball milling followed by firing at 920 °C show the maximum performance (power density: 0.15 W cm⁻² at 800 °C) at 3 wt.% Ag. On the other hand, the Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag composite cathodes with 0.1 mg cm⁻² (0.5 wt.%) Ag that were prepared by an impregnation of Ag into Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ followed by firing at 700 °C (but the electrolyte–Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ assembly was prepared first by firing at 1100 °C) exhibit much better performance (power density: 0.27 W cm⁻² at 800 °C) than the composite cathodes prepared by ball milling, despite a much smaller amount of Ag due to a better dispersion and an enhanced adhesion. AC impedance analysis indicates that the Ag catalysts dispersed in the porous Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ cathode reduce the ohmic and the polarization resistances due to an increased electronic conductivity and enhanced electrocatalytic activity.     

适合于太阳能热发电的锰铁锂复合金属氧化物储热特性与热化学反应机理

提出在锰基氧化物中添加Fe₂0₃和Li₂0,构建锰铁锂三元复合金属氧化物,降低热化学储热反应温度,更好地满足新一代太阳能热发电系统需求。实验发现,与Mn₂O₃相比,新生成的Li₂FeMn₃O₈复合氧化物的还原反应初始温度由773℃降低至622℃;还原反应活化能从797.10 kJ/mol降低至132.44kJ/mol;氧化反应由难以进行,变为从590℃开始进行;氧化放热量增至209.40 kJ/kg;经过105次循环后仍保持良好的循环反应稳定性。