Comparison of reduction behavior of Fe2O3, ZnO and ZnFe2O4 by TPR technique

Advanced integrated gasification combined cycle (IGCC) power generation systems require the development of high-temperature,regenerable,desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels.As a sort of effective desufurizer,such as Fe2O3,ZnO and ZnFe2O4,it will endure strong reducing atmosphere in desulfurization process.The reduced degree of desufurizer can have an effect on its desulfurization reactivity.In this paper,Fe2O3,ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH.After aging,washing and drying,the solids were calcined at 800℃.The reduction behaviors of sample were characterized by temperature-programmed reduction (TPR).It is found that there are two reduction peaks for Fe203 in TPR,and whereas no reduction peaks for ZnO are found.The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3.ZnFe2O4 is easier to be reduced than Fe2O3.The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.     

Sm掺杂对Fe2O3催化剂NH3-SCR反应活性及抗水抗硫性作用

氮氧化物(NO_x)是主要的环境污染物之一,会造成酸雨、光化学烟雾和温室效应等环境问题.氨选择性催化还原(NH₃-SCR)技术是目前控制NO_x排放的最有效技术.其中,Fe₂O₃催化剂因其良好的抗硫性和低廉的成本而受到广泛关注,有望用作NO_x消除催化剂,但是它的低温还原性差、脱硝效率低等缺点限制了其应用.近期研究表明,钐掺杂金属氧化物可以调节其表面酸碱性及氧化还原性,可有效提高氧化物催化剂的脱硝效率和抗水抗硫性能.因此,将铁、钐二者优势结合,为合成一种低温、高效、环境友好型脱硝催化剂提供了可能.本文通过柠檬酸辅助的溶胶凝胶法合成了一系列钐均匀掺杂入Fe₂O₃纳米颗粒的复合氧化物脱硝催化剂,采用X射线光电子能谱(XPS),氢气程序升温还原(H2-TPR),氨气程序升温脱附(NH₃-TPD)以及原位漫反射红外光谱(in situ DRIFTS)等方法研究了钐的掺杂对铁基催化剂脱硝效率和抗水抗硫性的影响,旨在揭示催化剂表面物理化学性质和催化活性之间的关系.通过活性测试发现,钐的掺杂可以使Fe_0.94Sm_0.06O_x催化剂在175?325℃时实现>95%的脱硝效率和>93%的N2选择性.动力学测试研究表明,当基于催化剂的比表面积计算时,Fe_0.94Sm_0.06O_x催化剂的脱硝效率是纯Fe₂O₃催化剂的11倍;基于质量计算时则为37倍.此外,250℃时抗水抗硫测试结果显示,Fe_0.94Sm_0.06O_x催化剂可以在通入200×10^-6SO₂+5 vol%H₂O,空速为90000 h^-1时脱硝效率保持83%达168小时,并且在切断H₂O和SO₂后,该催化剂的脱硝效率可以很快完全恢复.XPS和H2-TPR结果表明,钐的掺杂使Fe_0.94Sm_0.06O_x催化剂的表面产生了大量的表面吸附氧,从而促进了NO的氧化以及快速NH₃-SCR反应的进行.NH₃-TPD与原位DRIFTS结果表明,钐的掺杂增强了催化剂的表面酸性,有效地提高了NH₃的吸附和活化能力,进而提高了催化剂的脱硝效率.另外,钐的掺杂还可以促使NH₄HSO₄在Fe_0.94Sm_0.06O_x催化剂表面较低温度下的分解,从而使催化剂具有很好的抗水抗硫性能.     

并流淤浆混合法制备铜基甲醇合成催化剂及助剂Al2O3的作用研究

采用并流淤浆混合法制备了一系列具有不同铜锌铝比的铜基甲醇合成催化剂CuO/ZnO/Al2O3，测试了其催化性能(甲醇收率和CO转化率)及物相结构，并对该制备方法进行评价。Cu∶Zn∶Al摩尔比为4∶5∶1 的铜基催化剂显示了最好的催化活性。通过对催化剂前驱物煅烧过程进行DTA分析及对前驱物进行XRD分析表明， 催化剂前驱物的物相与Al2O3的量有关。当Al2O3的量较低时，前驱物的物相以(Cu0.3 Zn0.7)5(CO3)2(OH)6为主；当Al2O3的量较高时，前驱物中物相(Cu0.3Zn0.7)5(CO3)2(OH)6的量下降，而物相Cu2CO3(OH)2的量增加。物相(Cu0.3 Zn0.7)5(CO3)2(OH)6对终态催化剂的活性是十分有利的 。     

Cu2O/ZnO的形貌可控制备及光催化性能

以CuSO₄和ZnCl₂为原料, 采用温和的液相还原法制备得到Cu₂O/ZnO微米结构高效光催化剂. 研究了不同[Cu²⁺]/[Zn²⁺]比条件下所得Cu₂O/ZnO复合物的形貌和光催化活性. 通过5.5 h的光照, Cu₂O/ZnO光催化剂对甲基橙染料的降解率为(77.5±0.1)%. 将多形貌Cu₂O/ZnO复合物作为阳极, 铂片作为对电极, 中间注入甲基橙溶液, 组装“三明治”结构拟电池, 研究了复合物的光降解机制.     

结构助剂SiO2、Al2O3对铁基催化剂浆态床F-T合成性能的影响

采用连续共沉淀与喷雾干燥成型技术相结合的方法制备了微球状Fe/Cu/K/SiO2和Fe/Cu/K/Al2O3催化剂，研究SiO2和Al2O3作为结构助剂对铁基催化剂吸附行为、炭化行为及F-T合成反应性能的影响。表征结果表明,与Al2O3相比较，SiO2抑制了H2的吸附，但促进了CO的吸附，有利于催化剂的炭化。催化剂在260℃、1.5MPa、H2/CO=0.67和2000h-1下的浆态床F-T合成反应评价表明，Fe/Cu/K/SiO2催化剂具有较高的F-T合成活性、高的水煤气变换反应（WGS）活性，且其烃产物选择性明显向高炭数方向偏移，而Fe/Cu/K/Al2O3催化剂则表现出较低的F-T合成活性、低的水煤气变换反应（WGS）活性和高的轻质烃选择性。但Fe/Cu/K/Al2O3催化剂比Fe/Cu/K/SiO2催化剂具有更好的运行稳定性。     

Ce0.45Zr0.45Y0.07La0.03O1.95/La-Ba-Al2O3质量比对整体式铁基催化剂上稀薄甲烷燃烧的影响

采用共沉淀法和胶溶法分别制备了高性能的储氧材料Ce0.45Zr0.45Y0.07La0.03O1.95(OSM)和耐高温高比表面的La-Ba-Al2O3,并以它们为载体,制备了一系列整体式铁基催化剂.考察了该系列催化剂对甲烷稀薄燃烧的催化性能.并用低温N2吸附-脱附,储氧量(OSC)测试,X射线衍射(XRD)和H2程序升温还原(H2-TPR)等测试手段考察了不同Ce0.45Zr0.45Y0.07La0.03O1.95/La-Ba-Al2O3质量比对催化剂特性的影响.活性测试结果表明,当Ce0.45Zr0.45Y0.07La0.03O1.95/La-Ba-Al2O3质量比为1:1时新鲜和老化催化剂的活性均最好,新鲜催化剂可在50000h-1的高空速条件下使含量为1%(体积分数)的甲烷在446℃起燃,553℃完全转化;低温氮气吸附-脱附测试结果和H2-TPR表明,不同的Ce0.45Zr0.45Y0.07La0.03O1.95/La-Ba-Al2O3质量比使催化剂表现出不同的织构性能和还原性能;XRD测试结果表明,OSM以均一固溶体存在,Fe高度分散在载体上.综合以上表征手段得出:合适的Ce0.45Zr0.45Y0.07La0.03O1.95/La-Ba-Al2O3质量比导致催化剂具有优异的稀薄甲烷催化燃烧活性和热稳定性.     

掺杂铬对NiFe2O4的磁性和结构稳定性影响

利用物理特性测试仪对共沉淀法制备的Cr3+掺杂NiFe2O4的磁性能进行测试,发现掺杂Cr3+并经350、 600℃焙烧的NiFe2O4样品,饱和磁化强度Ms和剩磁Mr随掺杂量的增加而下降,矫顽磁场强度Hc随掺杂量的增加而增加.XRD平均晶粒测试结果显示,样品的平均晶粒大小随掺杂量的增加而减小.在共沉淀过程掺杂的Cr3+经600℃热处理后已进入NiFe2O4晶格.晶格中的Cr3+对NiFe2O4分解CO2的H2/CO2循环反应性能产生很大影响,纯NiFe2O4循环反应15次失活,而掺4%Cr3+的NiFe2O4循环反应50次仍然具有活性.     

Study on Au/Al2O3 catalysts for low-temperature CO oxidation in situ FT-IR

Au/Al2O3 catalyst was prepared by a modified anion impregnation method and investigated with respect to its initial activity and stability for low-temperature CO oxidation. The activity changes of the catalyst were examined after separate treatment in CO+O2 or CO2+O2. Furthermore, in situ FT-IR studies were performed to investigate the species on the surface when CO or CO+O2 or CO2+O2 was selected separately as adsorption gas. The results showed that Au/Al2O3 catalyst exhibited very high initial activity, but the catalytic activity was found to decrease gradually during CO oxidation with time on stream. And also, the activity of the catalyst declined after treatment in CO+O2 or CO2+O2. The formation and accumulation of carbonate-like species during CO oxidation or treatment in CO+O2 or CO2+O2 might be mainly responsible for the activity decrease, which was reversible.     

Au/Mn2O3/Al2O3催化剂的制备及其deNOx活性

由于燃煤烟气、汽车尾气的过度排放 ,大气中ＮＯｘ(其中ＮＯ占 90 %以上 )浓度已呈上升趋势。ＮＯ在阳光作用下 ,易形成光化学烟雾 ,危害人体的呼吸系统。ＮＯ还是破坏大气臭氧层和形成酸雨的前驱气体之一 ,破坏生态环境。催化分解和催化还原法是消除ＮＯ(ｄｅＮＯｘ)的主要方法。但由于实际环境中ＮＯ往往与某一种或几种还原性气体 (如ＣＯ、低碳烃 )共存 ,所以催化还原法是人们公认的有应用前景的ｄｅＮＯｘ 方法[1 ] 。近十几年来 ,国内外研究较多的ｄｅＮＯｘ 催化剂是Ｃｕ ＺＳＭ 5 ,其催化活性除受原料气中氧含量的影响外 ,很大程度上…     

Fe2O3-TiO2磁性复合材料的制备及可见光催化性能

以FeCl₃和Ti(C₄H₉O)₄为前驱体, 通过复合溶胶法制备了Fe₂O₃-TiO₂磁性复合光催化剂, 并用 XPS, XRD, SEM, EDS及BET进行了表征. 对亚甲基蓝的降解实验证明, Fe₂O₃的引入将复合材料的光响应范围扩展至可见光区, 且掺杂的Fe₂O₃摩尔分数为1.0%时, 样品可见光催化性能最高. 磁强计的测试结果显示, 复合光催化剂具有一定的磁性, 可在反应结束后利用磁场从体系分离, 使催化剂得到回收再利用.     

Tl2Ba2Ca2Cu3O10的化学键性质和同质异能位移研究

Tl2Ba2Ca2Cu3O10 was reported to be a superconductor with a highest transition temperature of 125 K among the homologous series of Tl2Ba2Can-1CunO2n+4. The direct information on the Cu ion site at the atomic level is important for elucidating the superconductivity mechanism. The local bond properties of Tl2Ba2Ca2Cu3O10 were studied using the average band-gap model. The calculated results show that the covalency of Cu(1)-O bond is 0.561, and the average covalency of Cu(2)-O is 0.296. M(o)ssbauer isomer shifts of 57Fe in Tl2Ba2Ca2Cu3O10 were calculated using the chemical surrounding factor, defined by covalency and electronic polarizability. It is verified that for lower doping, Fe substitute the Cu at the Cu (1) site in forms of Fe3+ and Fe4+; for higher doping, Fe3+ and Fe4+ ion occupies Cu(1) and Cu(2) site respectively.The studies show that the determination of the correspondence between spectrum components and actual copper sites occupied by M(o)ssbauer nucleus was made easier with the aid of the calculation results of the chemical bond parameters.     

On the reversible O2 binding of the Fe-porphyrin complex

Electronic mechanism of the reversible O(2) binding by heme was studied by using Density Functional Theory calculations. The ground state of oxyheme was calculated to be open singlet state [Fe(S =1/2) + O(2)(S = 1/2)]. The potential energy surface for singlet state is associative, while that for triplet state is dissociative. Because the ground state of the O(2)+ deoxyheme system is triplet in the dissociation limit [Fe(S = 2) + O(2)(S = 1)], the O(2) binding process requires relativistic spin-orbit interaction to accomplish the intersystem crossing from triplet to singlet states. Owing to the singlet-triplet crossing, the activation energies for both O(2) binding and dissociation become moderate, and hence reversible. We also found that the deviation of the Fe atom from the porphyrin plane is also important reaction coordinate for O(2) binding. The potential surface is associative/dissociative when the Fe atom locates in-plane/out-of-plane.     

K2O-Fe2O3系催化剂的穆斯堡尔谱研究

利用穆斯堡尔谱在K2 O Fe2 O3催化剂中检出了α Fe2 O3(大晶粒及微晶 )、KFeO2 、K1 XFe11O17、α FeOOH和γ FeOOH等物相 ,它们的相对含量取决于催化剂的含钾量及煅烧温度 ,相对含量的改变导致样品的穆斯堡尔谱图出现了复杂的变化 .与XRD相比 ,穆斯堡尔谱可对钾与氧化铁的相互作用进行更有效的表征 ,穆斯堡尔谱和TPR研究都表明钾可延缓催化剂中Fe(III)的被还原 .     

H2O在Fe3O4 (111)表面吸附的结构及热力学研究

使用密度泛函理论（GGA/PBE）对H₂O在Fe_tet1-和Fe_oct2-终结Fe₃O₄ (111)表面的吸附行为进行了研究。对于Fe_tet1-终结表面,在1/5 ML覆盖度下,带有氢键的H₂O分子以及异裂解离的结构具有最高的稳定性,而类似水合氢离子的OH₃⁺-OH结构出现在2/5 ML覆盖度下,其次为带有氢键的水的聚合体。这些结果与实验中观测到的现象一致。对于Fe_oct2-终结表面,在1/6 ML覆盖度下,分子态H₂O的吸附是有利的,而在1/3 ML覆盖度下多种吸附形式共存。H₂O吸附在Fe_tet1-终结表面比吸附在Fe_oct2-终结表面热力学上更有利。此外,通过计算局域态密度（LDOS）对吸附机理进行了分析。     

Al含量对Pt-S2O82-/ZrO2-Al2O3型固体超强酸催化剂异构化性能的影响

通过向S₂O₈^2-/ZrO₂催化剂中同时引入适量的Pt和Al₂O₃, 制备出了具有较高催化性能和高稳定性的Pt-S₂O₈^2-/ZrO₂-Al₂O₃型固体超强酸催化剂. 以正戊烷异构化反应为探针, 考察了Al含量对催化剂的异构化性能的影响, 并采用XRD, BET, FTIR, TPR, TG-DTA, NH₃-TPD和ICP手段对催化剂进行了表征. 结果表明, Al能够延迟ZrO₂的晶化温度, 抑制硫的分解; Al能够增加催化剂的比表面积, 增强硫氧键的结合, 提高催化剂的还原性能, 增加催化剂的酸强度和酸总量. 当Al₂O₃质量分数为2.5%时, Pt-S₂O₈^2-/ZrO₂-Al₂O₃固体超强酸催化剂的催化活性最高, 正戊烷异构化收率可达60.02%, 选择性在98.2％以上.     

助剂对低温水煤气变换反应Au/αFe2O3催化剂性能的影响

采用共沉淀法制备了系列Au/αFe2O3 MOxM=Zr、Al、Mg、Ca、Ba)催化剂，通过N2物理吸附、XRD、H2-TPR和CO2-TPD-MS等手段对催化剂的物化性质进行表征，考察了富氢下低温水煤气变换（WGS）反应中助剂对Au/αFe2O3催化剂性能的影响。结果表明，助剂ZrO2能有效提高Au/α Fe2O3催化剂在富氢气氛下低温WGS反应活性和稳定性，反应温度150℃时CO转化率可达88.45%，且催化剂具有较高的稳定性。研究发现，添加ZrO2助剂能抑制载体晶粒的生长，降低载体晶粒度，提高催化剂的比表面积，改善催化剂的还原性能和表面酸碱度，从而提高催化剂的催化活性和稳定性。     

焙烧温度对低温水煤气变换Au/Fe2O3催化剂性能的影响

采用改性沉积-沉淀法制备了系列低温水煤气变换Au/Fe2O3催化剂,发现经300℃焙烧的样品具有较好的催化活性和稳定性.并运用N2物理吸附、原位X射线粉末衍射(in situ XRD)、程序升温还原(H2-TPR)和X射线光电子能谱(XPS)等技术,探讨焙烧温度对催化剂性能的影响机制,同时对样品的失活原因进行了分析.结果表明,催化剂性能与焙烧温度引起的金和载体氧化铁的相互作用以及载体还原性质的变化密切相关.XPS表征结果说明,尽管反应后在催化剂表面有碳酸盐或类碳酸盐物种生成,但半定量分析表明这些物种的形成不是催化剂失活的主要原因;根据在低温水煤气变换反应过程中Au/Fe2O3催化剂的比表面积明显下降,载体的结晶度也明显提高,推断Au/Fe2O3催化剂载体的结构性质的变化才是其失活的主要原因.     

富表面氧空位Fe2O3/ZnO催化剂在光催化合成氨中的应用

光催化合成氨是一种绿色节能的合成氨技术,设计制造丰富的表面氧空位和异质结构是促进氮分子活化和抑制电子-空穴复合的重要方法。我们以乙二醇作为还原剂,采用溶剂热法制备合成了Fe2O3/ZnO光催化剂,利用X射线衍射(XRD)、透射电镜(TEM)、电子顺磁共振(EPR)、紫外-可见漫反射(UV-Vis DRS)、荧光光谱(PL)及光电流(PC)对Fe2O3/ZnO催化剂进行表征,并考察了Fe2O3/ZnO催化剂在常温、常压下的光催化合成氨的性能。4%Fe2O3/ZnO催化剂在无牺牲剂下用于光催化合成氨,有较好的光催化效率和稳定性,其合成氨效率达到2059μmol·L-1·g-1·h-1。其高催化效率归因于:可见光区域吸收的提高、氮分子在表面氧空位与Fe3+活性中心上的协同活化及光生电子与空穴的高分离效率。     

Simultaneous Tuning Band Gaps of Cu2O and TiO2 to Form S-Scheme Hetero-Photocatalyst

Photocatalytic Z or S scheme merits higher redox potentials and faster charge separation. However, heterostructure photocatalysts with band gaps of bulk materials often have a type I band structure leading to poor photocatalytic activity. In view of this, we report simultaneous tuning of band gaps of Cu₂O and TiO₂, where quantum dot Cu₂O nanoparticles were formed on doped TiO₂ with Ti³⁺. The reduced size of Cu₂O made its conduction band more negative, whereas the introduction of Ti³⁺ made the absorption edge red shift to the visible light region. The as-formed heterostructure enabled an S-Scheme mechanism with remarkable activity and stability for visible light photodegradation of 4-chlorophenol (4-CP). The as-obtained photocatalysts’ activity demonstrated ca. 510-fold increase as compared to individual ones and a mechanical blend. The as-obtained photocatalysts maintained over 80 % for 5 cycles and 2 months exposure to O₂ did not decrease the degradation rate. ESR characterization and scavenger experiments proved the S-Scheme mechanism.     

氧化铟掺杂对ZnFe2O4半导体气敏性能的影响

用化学共沉淀法在ＺｎＦｅ２Ｏ４中掺入Ｉｎ２Ｏ３．Ｘ射线衍射分析证实，Ｉｎ２Ｏ３与ＺｎＦｅ２Ｏ３之间没有新相生成，晶格常数有微小变化．掺入Ｉｎ２Ｏ３降低了ＺｎＦｅ２Ｏ４的电导，改变了该系列材料的导电机制，提高了材料对乙醇的敏感性和选择性，而且缩短了材料的响应时间