多孔阳极氧化铝膜的制备研究

在直流恒压下,在不同的酸性溶液中对铝片实施两步阳极氧化制备多孔氧化铝膜,在磷酸溶液中制得的模板孔径大,并且电解时间缩短,加快了制备模板的过程。同时利用阳极氧化初期电流密度的变化,分析了多孔氧化铝膜的形成机理。     

多孔氧化铁纳米盘的制备与表征

通过水热-高温处理两步法,合成了直径150～200 nm厚度40～80 nm的多孔α-Fe₂O₃纳米盘颗粒。并用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、氮气吸附-脱附仪和震动样品磁强计(VSM)对样品进行了表征。对颗粒生长的机理进行了初步研究,结果表明磷酸根离子对α-Fe₂O₃纳米颗粒(001)面的选择性吸附在盘状颗粒的生长过程中起着重要作用。合成的多孔纳米盘颗粒BET比表面积为27 m²·g^-1,孔径在2～100 nm的范围内分布,样品还具有明显的铁磁性,较其他结构的α-Fe₂O₃纳米颗粒具有较高的矫顽力。     

铝阳极氧化多孔膜层的界面电性能研究

采用电渗方法研究了经硫酸溶液氧化并利用逆向电解方法剥离后的铝阳极氧化多孔膜层的ζ电位与溶液ｐＨ的关系．结果表明：该多孔膜层在１．０×１０－２ｍｏｌ／ＬＫＣｌ溶液中的ｐＨ等电点（ｐＨＩＥＰ）＝９．２０,２．００＜ｐＨ＜９．２０,ζ＞０,多孔膜荷正电;９．２０＜ｐＨ＜１１．００,ζ＜０,多孔膜荷负电．     

还原剂对多孔阳极氧化铝纳米孔道结构的影响

多孔阳极氧化铝(PAA)和多孔阳极氧化钛纳米管(PATNT)的结构调控近年来倍受关注. 在形成机理尚不清楚的情况下, 对PAA和PATNT的结构调控很难避免盲目性. 为验证“氧气气泡模具”可以形成纳米孔道这个新观点, 本文采用化学方法对PAA的结构进行调控, 成功地引入了一种还原剂来吸收纳米孔道中的氧气气泡. 在添加还原剂的草酸溶液中得到了一种特殊的阳极氧化铝膜. 研究了还原剂的含量对磷酸溶液中形成PAA孔道结构的影响, 结果表明随着还原剂含量的增加, PAA的孔道直径逐渐减小, 有序性降低. 对比了添加还原剂前后阳极氧化过程的电压-时间曲线的差异, 结果表明, 在含有还原剂溶液中制备的阳极氧化铝膜的导电性明显提高. 在密封的条件下, 还原剂能吸收掉孔道中的氧气, 使气泡模具效应消失, 得到完全的致密型氧化膜. 这些实验事实充分证明PAA中有序孔道的形成是氧气气泡模具效应的结果.     

溶液组分对铝阳极氧化多孔膜界面电性能的影响

采用电渗法研究了电解质溶液组分对铝阳极氧化多孔膜层界面电性能的影响。结果表明，多孔膜分别经含Ｆ＾－，ＰＯ＾３－４，ＳｉＯ＾２－３或单宁酸溶液浸泡处理后，膜在０．０１ｍｏｌ／ＬＫＣｌ溶液中等电点由原来的ｐＨＩＥＰ＝９．２０分别移至ｐＨＩＥＰ＝３．４０，４．３０，３．３０display structure     

多孔氧化铝有序膜的制备研究

本文用阳极氧化法分别在硫酸和草酸电解液中成功制备出高度有序、具有纳米级孔洞的氧化铝有序阵列模板。采用饱和HgCl₂去除Al基体后,得到典型六方形结构的多孔Al₂O₃有序膜。通过改变氧化电压、氧化时间等条件使模板的孔径、孔深可调、膜厚度可控,并系统研究了对模板有序性、孔径、膜厚度等的影响因素,总结出制备Al₂O₃有序膜的最佳工艺。     

二次阳极氧化方法制备有序多孔氧化铝膜

通过二次阳极氧化方法制备多孔氧化铝膜与一次阳极氧化方法制备多孔氧化铝膜孔排布规律性的对比,结果发现,二次阳极氧化方法制取的多孔氧化铝膜孔排布规律性明显好于一次阳极氧化法制取的多孔膜.在几个微米范围内,孔呈理想的六角排布.去除一次阳极氧化膜后,二次阳极氧化得以在更良好的表面进行,制取的氧化铝膜孔规律性和有序度更高.有序区域的尺寸与晶粒内的亚晶大小有一定关系.     

特殊型纳米多孔阳极氧化铝模板的制备

多孔阳极氧化铝(PAA)模板具有六角有序排列的柱形孔,且孔径均匀可调,加之其良好的机械和热稳定性,在纳米材料领域得到了广泛研究和应用。近年来,人们通过改变铝阳极氧化条件制备出了多种特殊型纳米PAA模板,并利用这些模板结合物理或化学方法成功地合成了多种新型纳米功能材料。本文在简要介绍常规纳米PAA模板制备的基础上,较全面地综述了诸如孔道呈分叉形、锯齿形、骨形、倒圆锥形,孔洞呈菱形、三角形、正方形,孔道或孔壁结构呈周期性变化等特殊型纳米PAA模板的制备,揭示了电场强度和电解液种类、温度在PAA孔洞形貌尺寸调控方面的重要性,并展望了这类模板的发展方向及应用前景。     

阳极氧化水解法制备TiO2纳米膜

TiO2在光电化学电池领域已成为比较重要的半导体材料，自从1972年，Fuishima和Honda首次把TiO2电极用于光电解水以来，人们已经使用多种方法，如化学气相沉积、TiO2粉的烧结、RF射频溅射、等离子体喷涂或用胶体TiO2涂膜等各种方法，来制备单晶（金红石），多晶（金红石、锐钛矿     

无定形氧化铁层在纳米多孔BiVO4的光电化学分解水反应中的作用

通过"人工光合成"过程,将太阳能转化成氢能的形式加以存储和利用,是替代传统化石能源的清洁能源的制备有效途径.其中,光电化学分解水是氢能制备的最有潜力的路径之一.n型BiVO4由于具有丰富的储量、较窄的带隙以及合适的能带位置,被称为光电化学领域的研究热点.然而,未修饰的BiVO4光阳极性能并不理想,主要原因在于载流子复合严重、导电性差以及表面催化动力学低等性质的制约.科研工作者们针对这些方面已进行了非常多的研究,例如与电子传输层的复合、产氧电催化剂的担载以及异质结的构建等.其中表面动力学和电荷分离的同时提升是更理想的改善BiVO4光阳极性能的方法.我们在上述研究基础上,采用光化学沉积法在纳米多孔BiVO4电极表面担载无定形氧化铁层,将电极在1.23 V vs.RHE电位下的光电流提升至2.52 mA/cm2,是初始光电化学性能的3倍.采用间歇光照计时电流(i-t)测试,电化学交流阻抗谱(EIS),X射线光电子能谱(XPS),原位和非原位的X射线精细结构能谱(in-situ and ex-situ XAFS)等表征手段研究了无定形氧化铁层的成分和光电化学反应过程中的价态变化,从而分析出光电化学性能提升的原因.间歇光照i-t测试和EIS测试结果表明,无定形氧化铁沉积在BiVO4使电荷累积减少,复合率降低.XPS测试结果发现无定形氧化铁层存在少量的二价铁成分.通过原位XAFS测试发现,BiVO4/FeOx电极中Fe原子的价态在光照和施加外加偏压条件下会有价态的升高,而撤去光照和偏压后Fe原子的价态状态与最初非原位的测试结果重合.这样的结果证明了无定型氧化铁层在光电化学反应过程中由于二价铁成分的存在,能够很好的通过价态改变实现空穴的吸附和传输,即吸附空穴,被空穴氧化成三价或四价,同时结合自身电催化活性,促进表面分解水反应的进行.而水的氧化反应结束时,则伴随着二价铁离子的再生成.这种反应机理为开发更高效的电催化剂,匹配光电极使用,有着重大的指导意义.     

Formation and Morphological Evolution of Nanoporous Anodized Iron Oxide Films北大核心CSCD

The preparation of iron oxide films with nanoporous structure by anodization has attracted much attention for its potential applications. However, the formation mechanism of porous structure during anodization is still unclear. In this paper, the composition of anodic current during the formation of nanoporous anodized iron oxide film was analyzed in combination with the current density-potential response (I-V curve) and the derivation of Faraday爷s law. The results showed that the anodic current consisted of an ionic current (leading to the migration of ions to form oxide) and an electronic current (leading to the oxygen evolution), and the formation of the nanoporous anodized iron oxide film was correlated with the ratio of the two currents. Only when the potential was higher than a certain critical potential (20 V under the present experimental conditions), the ionic current to electronic current could maintain a proper ratio, and the precipitated oxygen promoted the formation of nanoporous structures. Otherwise, the anodized iron oxide film existed in the form of an irregular loose layer or a dense layer. However, at relatively high potential of anodization (e.g. 50 V in this experiment), the electronic current might accounted for a large proportion of the total current, which was not conducive to the increase of nanoporous anodized iron oxide film thickness. In addition, the dense film covered on the nanopore channels at the initial stage of anodization, as well as the cavities between segmented oxides, indicated the possible evolution of oxygen bubbles inside the oxide film. And the cations and anions achieved mass transfer around the oxygen bubbles, leading to the formation of the nanoporous anodized iron oxide film. Further, during the morphologic evolution of the anodized iron oxide film, the pore size of the surface increased with the time of anodization, which may be related to the dissolution of the oxide on the surface by prolonged erosion in the electrolyte and the continuous outward spillage of oxygen bubbles punched out the surface oxide. © 2021 Authors. All rights reserved.     

Highly Magnetic Nanoporous Carbon/Iron‐Oxide Hybrid Materials

The preparation of size‐controllable Fe₂O₃ nanoparticles grown in nanoporous carbon with tuneable pore diameters is reported. These hybrid materials exhibit strong non‐linear magnetic properties and a magnetic moment of approximately 229 emu g^?1, which is the highest value ever reported for nanoporous hybrids, and can be attributed to the nanosieve effect and the strong interaction between the nanoparticles and the carbon walls.     

硫铁矿烧渣制备氧化铁黄和氧化铁红

对利用硫铁矿烧渣制备氧化铁黄和氧化铁红进行了研究。考察了影响硫铁矿烧渣还原、酸溶、中和、氧化等过程的各种因素。结果表明,在适宜的条件下,利用烧渣可以制备出用做颜料的氧化铁黄和氧化铁红。     

Selective Formation of Spinel Iron Oxide in Thin Films by Complexing Agent-Assisted Sol-Gel Processing

The structure of iron oxide was controlled by regulating the hydrolytic polymerization of aquo iron complexes with organic polydentate ligands such as diols. Iron oxides were prepared by calcining the precursor polymers obtained from iron nitrate nonahydrate and diols. When the diols were 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol, α-Fe₂O₃ with corundum structure appeared exclusively or as the main crystalline phase, in spite of the amount of diol used and the calcination temperature. In the case of 1,2-decanediol and 1,2-dodecanediol, when five moles of the diols were used to one mole of iron nitrate and the calcination temperatures were below 400°C, ψ-Fe₂O₃ with spinel structure appeared as the main phase and, when less than five moles of the diols were used, α-Fe₂O₃ appeared exclusively or as the main phase, irrespective of the calcination temperature. This tendency was also observed in thin films. Thus, a transparent magnetic film composed of γ-Fe₂O₃ could be prepared by applying a benzene solution of the iron polymer, obtained with 5 equivalents of 1,2-decanediol, on quartz and calcining the gel film at 350°C.     

煅烧温度对阳极氧化WO3多孔薄膜的形貌及光电化学性能的影响

采用一步式阶跃电压加压方法,在NH4F/(NH4)2SO4电解质溶液中对W片进行阳极氧化处理制备了WO3多孔薄膜,通过后续热处理温度的控制,制备了性能规律性变化的WO3多孔纳米薄膜材料.用场发射扫描电镜(FE-SEM)、X射线衍射(XRD)分析等手段考察了热处理温度对氧化钨晶体结构和形貌影响的规律,在450°C以下的煅烧温度下,薄膜保持50-100nm孔径;通过对光电化学性质、光催化降解甲基橙动力学行为的研究,考察了不同热处理温度对WO3多孔薄膜光电转换性能影响的规律.研究表明,450°C煅烧处理后的WO3薄膜在500W氙灯光源照射及1.2V偏压下,光电流密度达到5.11mA·cm-2;340及400nm单色光辐射下光电转换效率(IPCE)值分别达到87.4%及22.1%.电化学交流阻抗谱显示,450°C煅烧处理后的WO3薄膜表现出最佳的导电率及最小的界面电荷转移电阻.实验结果证明,高结晶度的多孔结构是WO3薄膜具有高光电转换效率的主要因素,控制热处理温度是实现薄膜具有高孔隙率、完整结晶度、低电阻的重要手段.     

纳米介孔氧化铁的制备

纳米氧化铁的许多优异性能使其成为广泛的研究热点。本文介绍了纳米氧化铁的制备及其颗粒大小、形貌控制等方面的进展状况。综述了各种不同形态介孔氧化铁及含铁介孔纳米复合材料的研究进展,结合课题组的研究工作,重点评述了介孔氧化铁的制备进展,并对该领域的研究方向和需要解决的问题提出了自己的观点。     

Adsorption of Bismarck Brown by Iron Oxide Nanosphere and Its Modified Form

In the present study, adsorption of Bismarck Brown (BB) dye onto iron oxide nanospheres (IONs) and modified IONs by HCl from aqueous solution was investigated. The IONs was synthesized by solvothermal method and then modified by HCl. The high magnetic properties of both adsorbents lead to facial separation from aqueous solution by an external magnet. The results show that the modification of adsorbent cause higher adsorption capacity for removal of BB from aqueous solution. The prepared adsorbents were characterized by SEM, XRD, FTIR, and ATR-IR techniques. The adsorption kinetic and equilibrium data were fitted with different models. The results show that the equilibrium and kinetic data were best fitted with Langmuir–Freundlich isotherm and fractal-like pseudo-second-order kinetic model, respectively. The effects of pH and temperature have also been investigated.     

氧化铁磁性纳米粒子固定化酶*

纳米粒子作为酶固定化的载体,当其具有磁性时,制备的固定化酶易于从反应体系中分离和回收,操作简便;并且利用外部磁场可以控制磁性材料固定化酶的运动方式和方向,替代传统的机械搅拌方式,提高固定化酶的催化效率。在众多纳米材料中,氧化铁因其在磁性、催化等多方面的良好特性而倍受瞩目。本文对近年来各种氧化铁磁性纳米粒子固定化酶,尤其是固定化脂肪酶和蛋白酶的制备方法及其应用做了较为详细的阐述,对这些氧化铁磁性纳米粒子固定化酶的优缺点和发展前景进行了讨论。     

Micronization of Iron Oxide Particles Using Gas Antisolvent Process

Iron oxide particles were micronized by supercritical carbon dioxide (CO₂) as an antisolvent in a batch gas antisolvent (GAS) process. In the present study, the feasibility of GAS process to micronize the iron oxide particles using dimethyl sulfoxide (DMSO) as a solvent was investigated. In this direction, particle size and morphology changes were investigated with changing solution pressure (80–150 bar), temperature (308.15–328.15 K), and concentration (1.5–6 g/l). Based on the different experimental conditions, the particle size of the original iron oxide was decreased in the range of 17.25 to 4.23 µm, which shows a the success of the GAS process to reduce the particle size of the intact iron oxide particles. Simultaneously, morphology changes were observed starting from the irregular morphology for synthesized particles to more regular shapes that included fused and spherical-fused particles.