多组分钼铋系催化剂的还原机理

通过全反射X射线荧光光谱分析(TXRF)和X射线衍射法(XRD)分析新鲜催化剂（MB98）的元素组成,主要元素以Bi₂Mo₃O₁₂,Bi₂MoO₆,FeMoO₄,CoMoO₄,NiMoO₄,MoO₃Fe₂Mo₃O₁₂ 的形式存在。通过XRD、拉曼光谱(Raman)和光电子能谱法(XPS)分析多组分钼铋系催化剂的还原机理,测定不同还原程度催化剂中Mo,Bi,Fe,Co,Ni的主要物相结构和离子价态分布。XRD和Raman测试结果表明：催化剂还原过程分4步反应序贯进行;Fe₂Mo₃O₁₂和(Fe/Co/Ni)MoO₄中的晶格氧通过体相扩散向钼酸铋迁移;催化剂的储氧能力不仅与钼酸铋有关,还与Fe₂Mo₃O₁₂和(Fe/Co/Ni)MoO₄有关。XPS测试结果表明：还原生成的FeMoO₄,MoO₂和Bi主要分布于催化剂体相;在还原过程中,元素Mo,Bi首先在催化剂表面富集,然后向体相迁移;元素Fe,Co,Ni由体相向表面迁移。     

纳米四氧化三铁吸附水中汞离子的研究

以纳米Fe₃O₄颗粒作吸附剂,研究其用量、粒径、吸附温度以及pH值等因素对Hg²⁺吸附效果的影响,考察了纳米Fe₃O₄颗粒对水中Hg²⁺的吸附性能,并对吸附结果的重现性和吸附机理进行了研究。结果表明：纳米Fe₃O₄颗粒对水中Hg²⁺的吸附去除率随其用量的增加、粒径的减小而增大;对Hg²⁺吸附的最佳温度为19℃、最佳pH值为3.5,此pH值不需要经过酸或碱调节,便于控制;实验的重现性良好;纳米Fe₃O₄颗粒吸附水中Hg²⁺以物理吸附为主。纳米Fe₃O₄颗粒对Hg²⁺的吸附符合Freundlich吸附方程,显示了很强的纳米效应,是一种具有较好应用前景的Hg²⁺吸附剂。     

Fe2O3半导体中光生电荷分离和传输研究进展

 利用自然界丰富的太阳能光电催化分解水制氢是解决能源问题的理想方法之一,也是光催化领域最具挑战性的课题之一。Fe₂O₃半导体由于其禁带宽度窄,具有优异的可见光吸收性能,而且对环境友好、来源丰富、价格低廉,有望成为未来光催化领域的重要材料。但Fe₂O₃半导体中光生电子-空穴的复合速率很快,导致其光化学能转化效率很低。综述了近年Fe₂O₃半导体中光生电荷分离和传输的研究进展,从杂原子掺杂、半导体复合、Fe₂O₃半导体微观形貌控制3个方面分析了影响Fe₂O₃半导体光催化剂光电转化效率的因素,提出有效抑制光生电子-空穴的复合是提高Fe₂O₃半导体光电催化分解水活性的关键。论述了Fe₂O₃半导体光催化剂的构成原理、设计思想、目前效果以及存在问题,展望了Fe₂O₃半导体光催化剂研究的发展趋势。     

超顺磁性Fe3O4空心亚微球固定脂肪酶的研究

采用溶剂热法合成磁性亚微米球，并且利用扫描电镜、透射电镜、傅里叶红外光谱仪、X-射线衍射仪、振动样品磁强计等对合成样品进行了分析表征，结果表明所获样品为平均粒径为350nm的超顺磁性Fe₃O₄空心亚微球。对该样品进行了SiO₂包覆或氨基硅烷修饰，分别将Fe₃O₄空心亚微球、SiO₂包覆Fe₃O₄空心亚微球和氨基功能化Fe₃O₄空心亚微球作为固定化载体进行脂肪酶固定化。研究表明Fe₃O₄空心亚微球经SiO₂包覆或氨基功能化后对脂肪酶的固载量分别提高3.2和4.0倍，固定化酶比活力提高2.9和3.4倍。固定化的最优条件为pH6、25℃的条件下固定22h。     

低温合成TiO2/Fe3O4磁载光催化剂的光催化性能研究

采用化学共沉淀法合成的磁性纳米Fe₃O₄为磁核,以钛酸四丁酯为原料,通过溶胶-凝胶法,在较低温度下合成了TiO₂/Fe₃O₄磁性光催化剂。利用XRD、TEM、SEM-EDX等分析方法对合成催化剂的相组成、形貌、粒度、元素分布等进行了表征;研究了不同焙烧温度及TiO₂/Fe₃O₄比例对降解罗丹明B光催化活性及磁分离回收性能的影响。结果表明,在100、300和450 ℃焙烧温度下磁性光催化剂的催化活性依次降低,较低温度(100 ℃)制备的催化剂具备较高的催化活性;当TiO₂质量分数处于67.3%～73.0%时,催化剂既具有较高的光催化降解活性也具有较好的磁分离回收性能;光催化剂TiO₂/Fe₃O₄（100 ℃,TiO₂质量分数70%）在循环使用5次后,在降解75 min时仍能达到对罗丹明B 99%的脱色率和90%的回收率。     

微波烧结法制备Fe2O3掺杂0.55PNN-0.45PZT压电陶瓷及性能

 微波烧结是一种新型、高效的陶瓷烧结工艺,具有升温速度快、节能省时、改善微观结构以及降低烧结温度等特点.本文采用微波烧结工艺制备了Fe₂O₃掺杂的0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(简写为0.55PNN-0.45PZT)压电陶瓷,烧结温度为1200℃、保温时间为2h.利用X射线衍射(X-ray Diffraction,XRD)、扫描电子显微镜(Scanning Electron Microscope, SEM)、阻抗分析仪及铁电分析仪等测试表征方法,研究了Fe₂O₃掺杂对陶瓷的结构、介电以及压电性能的影响.结果表明,所有陶瓷样品均为钙钛矿结构,随着Fe₂O₃掺杂量的增加,压电和介电性能呈先增加后减小趋势.当Fe₂O₃掺杂量为0.8%(质量分数)时,陶瓷达到最优电学性能：压电常数(d₃₃)、平面机电耦合系数(k_p)、相对介电常数(ε_r)和介电损耗(tanδ)分别为d₃₃=520pC/N,k_p=0.51,ε_r=4768,tanδ=0.026.     

含环氧基团的磁性高分子复合微球

在Fe₃O₄ 磁流体的存在下,采用无皂乳液聚合法制备了磁性苯乙烯-甲基丙烯酸缩水甘油酯（GMA）-甲基丙烯酸-（β-羟乙酯）三元共聚物／Fe₃O₄复合微球,对所得磁性高分子微球的形貌及磁性能进行了表征,探讨了GMA、引发剂、亲水单体的含量及磁流体用量对磁性高分子微球形貌和性能的影响。结果表明,随单体中GMA含量增加磁性高分子微球的分散性变差,随磁流体和亲水性单体含量增加磁性高分子微球的粒径减小,引发剂的含量对其粒径影响不明显。磁性复合微球中Fe₃O₄的质量分数可达19.80%,微球具有超顺磁性,其饱和磁化强度可达12.62emu/g。     

纳米复合铁-硅氧化物的制备、性能及其应用

用溶胶-凝胶法制备了纳米γ-Fe₂O₃及γ-Fe₂O₃/SiO₂复合氧化物，以透视电镜(TEM)、热重 差热分析(TG-DTA)、Brunauer Emmett Teller (BET)分析和X射线衍射分析(XRD)对纳米粒子进行表征，以CH₄为模型反应，在固定床流动反应器中对复合氧化物进行催化活性评价，并制作了气敏元件。考察了γ-Fe₂O₃及γ-Fe₂O₃/SiO₂敏感元件对CO和其他还原性气体的灵敏度及焙烧温度对敏感度的影响，得到对CO检测的合适焙烧温度分别为500℃和600℃和最佳操作温度310℃。结果表明，γ-Fe₂O₃/SiO₂纳米复合氧化物中SiO₂对γ-Fe₂O₃的相变温度、加强热稳定性及提高气体灵敏度起到较大的作用。     

抗脱落铁基二氧化铅电极的研究

采用3步阳极氧化法在铁片表面依次生成铁氧化膜、β-PbO₂和α-PbO₂，制得结合牢固、抗脱落性能优良、具有 Fe/Fe_xO_y/β-PbO₂/α-PbO₂结构的铁基二氧化铅电极。采用XPS、XRD、交流阻抗和扫描电镜对铁氧化膜组成、β-PbO₂和α-PbO₂的晶型及电化学活性、电极切面结构进行了分析表征。借鉴漆膜性能标准测试方法，对铁基二氧化铅镀层的抗机械脱落性能进行了综合测试评价。研究发现，预先将铁基体放在4 mol/L KOH水溶液中，在温度80℃、阳极电流密度60mA/cm²条件下，使铁片表面预氧化生成一层棕红色的Fe₃O₄薄膜，然后再依次阳极氧化电镀β-PbO₂和α-PbO₂，能够获得抗机械脱落性好、电化学反应活性高的铁基二氧化铅电极。     

同多钨酸根柱撑镍铝水滑石的原位合成

采用原位沉积法在γ-Al₂O₃表面原位合成了对苯二甲酸阴离子柱撑的镍铝水滑石,并用同多钨酸根阴离子部分交换了镍铝水滑石中的对苯二甲酸阴离子。用XRD,BET, FT-IR和TG-DTA等测试方法对材料进行表征。结果表明,经过同多钨酸根阴离子的交换以后,垂直于水滑石层板方向的平行层板方向的晶格参数(c)值变小,平行层板方向的晶格参数(a)值不变,(003)、(006)、(009) 衍射峰处的层间距(d)值比为3∶2∶1;交换过程没有改变水滑石的结构,水滑石原位生长在γ-Al₂O₃表面及内孔,比表面积由γ-Al₂O₃载体的219m²/g增加到247m²/g,孔径分布则由原来的2～11nm变化为3～4nm。     

冷却速率对低碳钢线材表面氧化皮微观结构的影响

采用X射线衍射与Mossbauer谱分析相结合,研究了不同冷却速率下低碳钢表面形成氧化皮的微观结构;借助磁力显微镜的抬高模式测量氧化皮的磁畴图,获得了氧化皮内Fe₃O₄的分布形态及冷却速率对其变化的影响.结果表明：快速冷却时氧化皮中Fe₂O₃的含量减少;FeO与Fe₃O₄的比例增大;化学计量的FeO含量和Fe₃O₄的缺陷程度也随冷却速率的变化而变化.氧化皮的相组成和氧化皮内Fe₃O₄的分布形态是影响氧化皮性能的主要因素.     

Mechanism of the heterogeneous reaction of carbonyl sulfide with typical components of atmospheric aerosol

Carbonyl sulfide (COS) is one of the most abundantsulfur-containing species in the troposphere and lowerstratosphere. The atmospheric average concentration ofCOS is about 500 pptv with relatively little variation[1,2].In the stratosphere, where photochemical reactions occur,carbonyl sulfide can be oxidized into sulfur dioxide andfurther to sulfate aerosol[3—6]. The sulfate aerosol plays animportant role in heterogeneous chemical processes,ozone depletion and atmospheric radiation balance wh…     

Structure and 57Fe conversion electron Mössbauer spectroscopy study of Mn-Zn ferrite nanocrystal thin films by electroless plating in aqueous solution

Mn1-xZnxFe2O4thin films with various Zn contents and of different thickness were synthesized on glass substrates directly by electroless plating in aqueous solution at 90℃ without heat treatment. The Mn-Zn ferrite films have a single spinel phase structure and well-crystallized columnar grains growing per- pendicularly to the substrates. The results of conversion electron ^57Fe Mossbauer spectroscopy （CEMS） Indicate that the cation distribution of Mn1-xZnxFe204 ferrite nanocrystal thin films fabricated by electroless plating is different from the bulk materials＇ and a great quantity of Fe^3＋ ions are still present on A sites for x〉0.5. When the Zn content of the films increases, Fe^3＋ ions in the films transfer from A sites to B sites and the hyperfine magnetic field reduces, suggesting that Zn2. has strong chemical affinity towards the A sites. On the other side, with the increase of the thickness of the films, Fe3＋ ions, at B sites in the spinel structure, increase and the array of magnetic moments no longer lies in the thin film plane completely. At x = 0.5, Hc and Ms of Mn1-xZnxFe204thin films show a minimum of 3.7 kA/m and a maximum of 419.6 kA/m, respectively.     

Surface interactions of MoO3/ α-Fe2O3 system

α-Fe₂O₃ -supported molybdena catalysts have been prepared by heating a mixture of MoO₃ and α-Fe₂O₃. XRD, XPS, LRS, TG-DTA and Mössbauer spectroscopy were used to characterize the interactions between MoO₃ and α-Fe₂O₃. The dispersion capacity of MoO₃ on the surface of α-Fe₂O₃ determined by XRD and XPS was 0.8 mmol/100m² α-Fe₂O₃ in the samples calcined at 420 . For the sample with low MoO₃ loading, LRS and FT-IR results showed that Mo⁶⁺ ions were located in the tetrahedral vacant sites on the surface of α-Fe₂O₃, signed as Mo- . The amount of Mo-II species, formed by Mo6+ ions incorporated into the octahedral vacant sites, increased with the MoO₃ loading. Based on the assumption that the (001) plane of α-Fe₂O₃ is preferentially exposed, almost all the Mo⁶⁺ ions of the dispersed molybdena species existed at the surface octahedral sites for the sample with MoO₃ loading close or beyond the dispersion capacity, and formed the Mo-II species. In this case, the capping O^2- ions linking with the incorporated Mo⁶⁺ ions formed a surface epitaxial structure, which was in good agreement with the results predicted by the incorporation model proposed previously. XRD and Mössbauer spectroscopy of the MoO₃ α-Fe₂O₃ samples calcined at different temperatures showed that the calcination temperature could strongly influence the interaction extent: ( i) at 420 , MoO₃ dispersed on the surface of α-Fe₂O₃ and formed surface Mo species; (ii ) at 500 , MoO₃ reacted with the bulk of α-Fe₂O₃ and formed Fe₂(MoO₄)₃ compound.     

Corrosion behavior of ferritic ODS steel prepared by adding YH_2 nanoparticles in supercritical water at 600 °C

The corrosion behavior of the ferritic oxide dispersion strengthened(ODS)steel(14Cr-3Al-2W-0.1Ti)prepared by adding YH_2nanoparticles(NPs)was investigated in supercritical water(SCW)at 600°C for 1500 h.The mass gain of the ODS steel(215.5 mg/dm~2)was lower than that of SUS430 steel(357.2 mg/dm~2).A dual oxide layer generated on the surface of ODS steel after corrosion in SCW.The outer layer was composed of Fe_2O_3and Fe_3O_4,while the inner layer composed of the spinel-type FeCr_2O_4together with Al_2O_3.The generation of Y_2Ti_2O_7NPs in the ODS steel by adding YH_2NPs prohibits the formation of Y-Al-O particles and leaves more Al available to form a continuous protective oxide scale to improve the corrosion resistance.Moreover,the Y_2Ti_2O_7NPs act as efficient barriers to suppress the outward diffusion of metal atoms.This novel ODS steel shows potential applications in supercritical water.     

Corrosion behavior and mechanism of the automotive hot-dip galvanized steel with alkaline mud adhesion

The corrosion behavior and mechanism of hot-dip galvanized steel and interstitial-free (IF) substrate with alkaline mud adhesion were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and linear polarization. The results show that non-uniform corrosion occurs on the galvanized steel and IF substrate during 250 h with the mud adhesion. The corrosion products on the galvanized steel are very loose and porous, which are mainly ZnO, Zn₅(OH)₈C₁₂·H₂O and Zn(OH)₂, and Fe-Zn alloy layer with a lower corrosion rate is exposed on the galvanized steel surface; however, the corrosion products on IF substrate are considerably harder and denser, whose compositions of rust are mainly FeOOH and Fe₃O₄, and several pits appear on their surface. The results of continuous EIS and linear polarization measurements exhibit a corrosion mechanism, that is, under activation control, the charge transfer resistances present different tendencies between the galvanized steel and IF substrate; in addition, the evolution of linear polarization resistances is similar to that of charge transfer resistances. The higher contents of dissolved oxygen and Cl- ions in the mud play an important role in accelerating the corrosion.     

304不锈钢在闭塞区溶液中钝化膜组成和结构性能

采用X射线光电子能谱 (XPS)和交流阻抗法 (EIS)研究了 304不锈钢在闭塞区溶液中钝化膜的组成和性能。研究结果表明：在闭塞区溶液中 304不锈钢表面钝化膜的外层主要为CrO₃、CrCl₃、CrOOH、Fe₂O₃、γ-FeOOH、Fe(OH)₃、CrO^2-₄ 、Cr(OH)₃、NiCl₂ 、FeCl₂ 和FeCl₃；溅射 3min时膜内层主要为Cr₂O₃、CrO₂ 、FeCl₂ 、FeCl₃以及少量的FeO。Cl^-吸附在钝化膜表面，破坏了钝化膜的完整性，改变了钝化膜的结构性能。     

Molybdenite alkali fusion and leaching: reactions and mechanism

The production of MoO₃ from Sarcheshmeh molybdenite concentrate via a pyro-hydrometallurgical process was studied. The molybdenite concentrate and sodium carbonate were premixed and fused under air atmosphere. Then the fused products were leached in water and the dissolved molybdenum was recovered as ammonium molybdate. The ammonium molybdate was then calcined to produce molybdic oxide. At the fusion stage, the effect of the mass ratio of carbonate to sulfide on the reaction products and the solubility of the products was investigated. The results show that during the fusion, sodium molybdate and sodium sulfate are the final reaction products and sodium sulfide is detected as an intermediate reaction product. By melting at 850℃ with 5wt% excess carbonate, the maximum solubility of the products is obtained. The molybdenum is recovered from the solutions as ammonium molybdate.     

固体超强酸S2O2-8/Fe2O3-ZrO2-La2O3催化制备生物柴油

用沉淀—浸渍法制备固体超强酸S₂O^2-₈/Fe₂O₃-ZrO₂-La₂O₃催化剂，通过XRD和FTIR对其结构进行表征。将该催化剂用于催化制备生物柴油并考察了反应条件对生物柴油产率的影响。结果表明，当Fe、Zr和La的摩尔比为1∶0.42∶0.075时，催化剂活性最高。其催化制备生物柴油的最佳工艺条件为，催化剂用量为菜籽油质量的2%，醇和油的摩尔比为12∶1，反应温度为220℃，反应时间为10h，产率可达90.3%。催化剂重复使用5次反应时间达50h，产率仍达83%。GC-MS表征表明制得的生物柴油的纯度较高。     

Novel photocatalysis oxidation system UV/Fe^2＋/air to degrade 4-CP wastewater

This paper reported the degradation of 4-CP wastewater by a novel photocatalysis oxidation system-- UV/Fe^2＋/air system, in which air was used as a cheap oxidant that reacted with the excitation state of organics to form H2O2 under the UV light. The formed H2O2 reacted with the added ferrous ion to form Fenton reaction and led to the quick degradation of organic pollutants. It was found that 4-CP could be completely removed within 40 min. The degradation of 4-CP in the UV/Fe^2＋/air system was superior to the conventional UV/Fenton system （the initial concentration of H2O2 was 22 mg·L^-1）. UV/Fe^2＋/air is an effective and cheap method for treatment of the organics that can be excited by UV light.