微波诱导Fe3O4/AC催化氧化降解邻苯二甲酸二甲酯

为了有效地提高活性炭在微波场中的催化活性和分离性,采用化学共沉淀法制备了磁性四氧化三铁/活性炭（Fe₃O₄/AC）催化剂,并结合微波辐射技术用于催化氧化降解水中邻苯二甲酸二甲酯（DMP）。利用BET、扫描电镜/能谱（SEM/EDS）、X射线衍射（XRD）、X射线光电子能谱（XPS）、红外光谱（FTIR）和振动样品磁强计（VSM）等手段对催化剂的微观结构、形貌和磁性能进行了表征。研究了不同反应体系对DMP的降解率及反应动力学的影响,探讨了催化剂用量、微波辐射功率和溶液初始pH等因素对微波诱导Fe₃O₄/AC催化氧化降解DMP的影响,考察了催化剂的重复使用性能。结果表明,所制备的铁氧化物主要以Fe₃O₄为主,并已成功负载于活性炭上。Fe₃O₄/AC具有超顺磁性,饱和磁化强度为21.2emu/g,可通过外加磁场作用快速地从溶液中分离出来。微波诱导催化反应体系对DMP的降解率大于单独吸附或单纯微波辐射反应体系,且反应速率均符合一级反应动力学。催化剂用量越多,降解率越高;微波辐射功率的增加可以提高降解效率;溶液初始pH对DMP的降解率影响非常显著,随着pH的增大,降解率明显提高。Fe₃O₄/AC具备良好的催化活性及稳定性,循环使用5次后DMP的降解率仍保持在83.5%。通过气相色谱-质谱联用仪（GC-MS）分析,推断DMP在微波诱导Fe₃O₄/AC催化体系中的降解主要包括水解、异构化、羟基化、甲酸甲酯基的脱落和苯环三取代及苯环开环等5个途径。     

铁氧化物在流化床温度和CO气氛下的形态迁移及其对NO催化还原

利用小型固定床实验台实验研究了铁氧化物在典型流化床温度和CO还原性气氛下的形态迁移及其生成物对NO的催化还原作用,采用分级还原结合X射线衍射（XRD）表征分析,确定铁氧化物与CO和NO反应后生成物的价态及各种铁氧化物对NO的还原机制。结果表明,Fe₂O₃在实验条件下可依次被CO还原为Fe₃O₄、FeO和单质铁,反应过程中随着还原度的增加,还原速率逐级下降,从Fe₂O₃还原到Fe₃O₄的速率最高,FeO还原到Fe速率最低,在实验温度范围内,床温升高有利于提高Fe₂O₃到Fe₃O₄的还原速率和还原度。不同形态的铁氧化物对NO的催化还原特性不同,Fe₂O₃及其部分还原后生成的Fe₃O₄都不能直接与NO反应,Fe₂O₃对CO催化还原NO的效果很弱,而Fe₃O₄对CO还原NO的反应却有很强的催化作用,而进一步还原生成FeO与单质铁还可直接与NO反应。     

磁性纳米钌催化剂制备及其催化甲苯氢化反应性能

采用共沉淀法制备Fe₃O₄粒子,用SiO₂对Fe₃O₄纳米粒子进行表面包覆,用改性聚乙烯吡咯烷酮对所得磁性粒子进行表面修饰,制备磁性纳米粒子负载钌催化剂Ru/PVP-DB-171/SiO₂/Fe₃O₄。红外光谱、X射线衍射、扫描电子显微镜及透射电子显微镜分析表明,所得粒子结构是面心尖晶石结构,Fe₃O₄为核,无定形SiO₂为壳,纳米钌吸附在磁性载体表面。该粒子具有高分散性,可用磁分离实现固液分离。以甲苯液相催化加氢反应为模型,评价磁性负载钌催化剂的催化性能,计算出甲苯氢化的活化能为16.6 kJ·mol^-1,在433 K和4.0 MPa条件下,反应转换数达30 262 mol·(mol-Ru）^-1,Ru催化剂可循环使用8次,添加助剂的种类和数量影响催化剂活性。     

氧化石墨烯负载纳米Fe3O4类芬顿处理制药废水

采用改进Hummer法制备了氧化石墨烯(GO)负载纳米Fe₃O₄磁性催化剂(Fe₃O₄/GO),对其进行了X射线衍射仪、扫描电子显微镜和能量-色散光谱表征,并将其应用于多相类芬顿处理高浓化学原料药生产废水。结果表明,Fe₃O₄颗粒成功负载在GO表面,且没有出现明显的团聚现象。当废水的pH为3,双氧水(H₂O₂的质量分数30%)投加量10 mL/L,催化剂投加量2 g/L,反应120 min后COD去除率达78%,UV254去除率高达81%。三维荧光光(3D-EEM)分析可知,芳香类和富里酸类物质在催化降解过程中得到有效去除。     

载体对Pt催化甲基环己烷脱氢性能的影响

采用浸渍法制备了Al₂O₃、SiO₂、Y₂O₃及活性炭负载的0.2%(质量分数,下同)Pt催化剂。氮气吸附脱附、H₂-TPR、CO脉冲吸附对催化剂表征的结果表明,活性炭载体上活性组分的分散度最高,催化甲基环己烷(MCH)脱氢反应的结果表明,活性炭负载的Pt催化剂具有最高的催化活性。     

Fe3O4/MWCNTs湿式催化降解PVA废水

通过共沉淀法将Fe₃O₄负载到多壁碳纳米管中,制备Fe₃O₄/MWCNTs纳米材料。通过X射线衍射仪(XRD)、透射电子显微镜(TEM)、X射线能谱仪(EDS)、N₂物理吸附仪和傅里叶红外光谱仪(FTIR)对样品的结构、形貌和表面性能进行了表征。结果表明,Fe₃O₄成功负载到MWCNTs表面,并且表现出良好的分散性和均一性。在等号pH=2.5、催化剂添加量为1.5 g/L、反应温度为275℃、氧气压力为1.0 MPa条件下,将Fe₃O₄/MWCNTs纳米材料作为催化剂,采用湿式氧化法降解质量浓度为2%的PVA废水,反应120 min后,降解率为93.6%,黏均分子量降低了99.0%,溶液中的大分子酚、醛和酮类等物质被氧化为相对分子质量较小的酸类物质等,实现了对PVA废水的降解。     

SiO2负载钴系催化剂的环己烯环氧化性能

采用沉积沉淀法制备不同负载量的SiO₂（硅胶）负载钴氧化物催化剂,采用X射线衍射（XRD）、X射线光电子能谱（XPS）、透射电镜（TEM）、N₂吸脱附等手段对催化剂进行表征,结果表明钴系氧化物为Co₃O₄,并且钴氧化物均匀地负载在SiO₂（硅胶）载体上,其活性组分的粒子大小集中分布在2～10nm。将制备的催化剂应用于环己烯环氧化反应,以环己烯、分子氧为原料,异丁醛为催化助剂,N,N-二甲基甲酰胺（DMF）为反应溶剂,在高压釜中进行。同时将SiO₂负载钴氧化物催化剂与不同载体上制备的钴系催化剂进行比较,发现催化剂用量0.20g、环己烯2.00g、异丁醛3.50g、反应温度50℃、反应时间5h、氧气压力4MPa时,环己烯的转化率和环氧环己烷的选择性分别可达到66.56%和71.03%。     

稻壳白炭黑负载Fe2O3的气相芬顿反应NO预氧化

以稻壳为硅源,采用直接煅烧法制备白炭黑,以其为载体,采用共浸渍法制备Fe₂O₃/SiO₂催化剂;并采用同样方法以商用二氧化硅为载体制备Fe₂O₃/C-SiO₂催化剂,将二者用于催化H₂O₂预氧化NO的实验。探究不同工况（负载量、催化温度、H₂O₂汽化温度、H₂O₂流量和水汽浓度）对NO预氧化的影响,并对催化剂进行表征,分析其物理化学性质对催化性能的影响。结果表明,在负载量为50%、催化温度为140℃、H₂O₂汽化温度为120℃、H₂O₂流量为2.5mL/h时,达到最佳工况,NO氧化度能达到73%;在相同实验条件下Fe₂O₃/SiO₂催化剂的预氧化效果要比Fe₂O₃/C-SiO₂催化剂高20%左右。TPR结果表明载体可以降低活性组分的还原温度,减少活性组分的团聚;催化剂的晶相结构稳定,机械强度及热稳定性良好;ESR和XPS结果显示Fe₂O₃/SiO₂催化剂的催化性能优于Fe₂O₃/C-SiO₂催化剂,能够更好地催化分解H₂O₂产生·OH。     

钙钛矿型复合氧化物对甲烷的部分氧化及在混合太阳能氧化还原过程的应用

利用固相法合成了3种钙钛矿型复合氧化物Fe₂O₃-CaTi_xM_1-xO₃,研究了其结构、晶型和氧化还原活性。在固定床反应器中考察了该氧化物对两步法甲烷催化氧化制合成气及水分解制氢的活性及选择性。X射线衍射结果表明3种钙钛型复合氧化物均由正交晶系钙钛矿相和赤铁矿相组成。3种钙钛矿复合氧化物对甲烷的氧化活性顺序为Fe₂O₃-CaTi_0.85Ni_0.15O₃ >Fe₂O₃-CaTi_0.85Co_0.15O₃ >Fe₂O₃-CaTi_0.85Fe_0.15O₃。固定床反应结果表明,以Fe₂O₃-CaTi_0.85Ni_0.15O₃为氧载体催化剂,CH₄转化率可达96%,CO和H₂产率达71%,同时水分解反应的转化率为40%。利用Aspen Plus^®对Fe₂O₃-CaTi_0.85Ni_0.15O₃在混合太阳能氧化还原过程的效率及合成油和H₂产率进行了模拟。模拟计算结果证明基于复合氧化物的混合太阳能氧化还原过程可以有效提高CH₄利用率。     

超顺磁催化剂H3PW12O40/Fe3O4@SiO2的制备、结构表征及在汽油烷基化脱硫中的应用

采用改进Stöber法制备超顺磁Fe₃O₄@SiO₂复合粒子作为催化剂载体,再通过浸渍法将H₃PW₁₂O₄₀（HPW）负载在Fe₃O₄@SiO₂载体上,制备了一系列超顺磁负载型催化剂HPW/Fe₃O₄@SiO₂。并使用X射线衍射（XRD）、傅里叶红外（FT-IR）、氨的程序升温脱附（NH₃-TPD）、扫描电镜（SEM）、N₂吸附-脱附和振动样品强磁计（VSM）对催化剂进行表征。结果表明,HPW固定并均匀分散在Fe₃O₄@SiO₂载体上,40% HPW/Fe₃O₄@SiO₂催化剂具有较高的饱和磁强度 （30.1 emu·g^-1）和较大的比表面积 （303.6 m²·g^-1）,并可用外加磁场进行分离。采用40% HPW/Fe₃O₄@SiO₂催化噻吩与1-辛烯组成的模拟汽油的烷基化脱硫反应,在160℃下反应2 h,噻吩转化率达到85.5%,有较好的催化脱硫性能,且可以多次循环利用。     

生物质活性炭负载零价铁纳米晶簇直接催化还原NO

采用等体积浸渍法制备以生物质活性炭为载体的纳米铁基催化剂，利用TG、SEM、XPS、Raman等分析仪器对催化剂进行表征，探讨了活性炭负载零价铁和铁氧化物在无氧条件下脱硝的机理。结果表明：在750℃热还原条件下制得的铁基催化剂具备较高的活性，其活性中心是分散均匀的零价铁纳米晶簇。在280℃无氧条件下对NO的脱除效率达100%，且避免了活性炭载体的损耗。研究发现，催化剂快速失活是由于零价Fe被氧化为Fe₃O₄，因而降低了脱硝剂的活性。直接对失活催化剂进行热还原可以完全恢复活性，但这种方法会消耗炭载体；利用CO作为还原剂进行制备与再生，可以有效提高纳米晶簇的分散性，延长脱硝寿命并减少炭载体的损失，为零价Fe催化剂在实际应用中提供了可能性。     

The high catalytic activity and strong stability of 3%Fe/AC catalysts for catalytic wet peroxide oxidation of m-cresol: The role of surface functional groups and FeOx particles

FeO supported on activated carbon (AC) has been shown to be an ideal catalyst for catalytic wet peroxide oxidation (CWPO) due to its high CWPO reaction activity and stability. Although there have been some studies on the mechanism of Fe/AC catalysis in CWPO, the specific contribution of each component (surface oxygen groups and FeO_x on AC) inside an Fe/AC catalyst and their corresponding reaction mechanism remain unclear, and the reaction stability of CWPO catalysts has rarely been discussed. Then the optimal CWPO catalyst in our laboratory, 3%Fe/AC, was selected. (1) By removing certain components on the AC through heat treatment, its contribution to the reaction and the corresponding reaction mechanism were investigated. With the aid of temperature-programmed desorption–mass spectrometry (TPD–MS) and the CWPO reaction, the normalized catalytic contributions of components were shown to be: 37.3% (carboxylic groups), 5.3% (anhydride), 19.3% (ether/hydroxyl), -71.4% (carbonyl groups) and 100% (FeO_x), respectively. DFT calculation and EPR analysis confirmed that carboxylic groups and Fe₂O₃ are able to activate the H₂O₂ to generate ·OH. (2) The catalysts at were characterized at different reaction times (0 h, 450 h, 900 h, 1350 h, and 1800 h) by TPD–MS and Mössbauer spectroscopy. Results suggested that the number of carboxylic goups gradually increased and the size of paramagnetic Fe₂O₃ particle crystallites gradually increased as the reactions progressed. The occurrence of strong interactions between metal oxides and AC was also confirmed. Due to these effects, the strong stability of 3%Fe/AC was further improved. Therefore, the reasons for the high activity and strong stability of 3%Fe/AC in CWPO were clearly shown. We believe that this work provides an idea of the removal of cresols from wastewater into the introduction to show the potential applications of CWPO.     

Catalytic decomposition of N2O over monolithic supported noble metal-transition metal oxides

The decomposition of nitrous oxide to nitrogen and oxygen using a series of monolithic (ceria-alumina washcoated cordierite) supported transition metal (Cu, Fe, Co, Ni, Mn) and noble metal (Ir, Rh) oxide catalysts has been studied using gas chromatography. The effect of combining a transition metal with a noble metal has also been investigated. A synergetic effect was observed between transition metal and noble metal oxides in the presence of a small amount of water for some of the catalysts. The synergy between Fe-Ir and Ni-Ir was also verified under dry conditions. X-ray photoelectron spectroscopic measurements on these catalysts indicate that Fe, Rh and Ir are present predominantly as Fe₂O_3, RhO₂ and IrO₂, while significant amounts of Co and Ni ions may migrate inside the support to form cobalt and nickel aluminate. Only the Fe-Ir catalyst showed a significant interaction between the noble metal and the transition metal. The effect of water, oxygen and carbon monoxide on the catalytic behaviour of the five most active catalysts (Ni-Ir, Ni-Rh, Fe-Ir, Co-Ir, Ir) has also been investigated. Oxygen and water were found to inhibit the catalytic activity, although the extent of oxygen inhibition is limited, presumably due to the presence of ceria in the monolith washcoat support. Conversely, carbon monoxide greatly enhances catalytic activity.     

Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 samples impregnated with Cu(II)-phthalocyanine

A number of supported metal oxide catalysts were screened for their catalytic performance for the oxidation of carbon black (CB; a model diesel soot) using NO₂ as the main oxidant. It was found that contact between the carbon and catalyst was a key factor in determining the rate of oxidation by NO₂. Oxides with low melting points, such as Re₂O₇, MoO₃ and V₂O₅ showed higher activities than did Fe₃O₄ and Co₃O₄. The activities of MoO₃ and V₂O₅ on various supporting materials were also examined. MoO₃/SiO₂ was the most active catalyst among the supported MoO₃ examined, whereas, V₂O₅/MCM-41 showed the highest activity among the supported V₂O₅. Different performances of the supported MoO₃ catalysts were explained by the interaction of MoO₃ with the supports: a strong MoO₃/support interaction may result in a poor mobility of MoO₃ and a poor activity for oxidation of carbon by NO₂. The high activity of V₂O₅/MCM-41 was associated with its catalysis of the oxidation of SO₂ by NO₂ to form SO₃, which substantially promotes oxidation of carbon by NO₂. Addition of transition metal oxides or sulfates to supported MoO₃ and V₂O₅ was also investigated. Combining MoO₃ or V₂O₅ with CuO on SiO₂, adding VOSO₄ to MoO₃/SiO₂ or MoO₃/Al₂O₃ and adding TiOSO₄ or CuSO₄ to V₂O₅/Al₂O₃ improved the catalytic performance.     

La2O3/AC催化剂在CO同时还原SO2和NO反应中的性能

以改性活性炭为载体,采用等体积浸渍法制备了La₂O₃/AC催化剂。采用XRD和BET手段对催化剂进行表征,使用微型固定床反应器考察催化剂的脱硫脱硝活性。结果表明,La₂O₃/AC催化剂对CO同时还原SO₂和NO具有良好活性,负载质量分数10%的La₂O₃/AC催化剂活性较好,SO₂和NO转化率达到90%的反应温度最低,分别为335 ℃和325 ℃;载体与活性组分之间存在协同作用,引入活性炭载体能够降低反应温度并提高催化活性。     

Molecular structure and reactivity of the Group V metal oxides

The physical, electronic and reactivity properties of bulk and supported Group V metal oxides (V, Nb, Ta and Db) were compared at the molecular level. Dubnium is a very short-lived element, 60 s, whose properties have not been extensively studied, but can be predicted from knowledge of the other members of the Group V metal oxides. Bulk V₂O₅ possesses platelet morphology with the active surface sites only located at the edges: primarily surface redox sites and some surface acidic sites. Bulk Nb₂O₅ and Ta₂O₅, as well as to be expected for bulk Db₂O₅, possess isotropic morphologies and the active surface sites relatively homogeneously dispersed over their surfaces: only surface acidic sites. However, the bifunctional bulk V₂O₅ was found to exhibit a much higher specific acidic catalytic activity than the acidic bulk Nb₂O₅ and Ta₂O₅, the latter being almost identical in their specific acidic catalytic activity. The bulk properties of the Group V metal oxides were essentially transferred to the analogous supported Group V metal oxides, where the active Group V metal oxides were present as a two-dimensional monolayer on various oxide supports (e.g., Al₂O₃, TiO₂, ZrO₂ as well as Nb₂O₅ and Ta₂O₅). For supported vanadia catalysts, the active surface sites were essentially redox sites, with the exception of supported V₂O₅/Al₂O₃ that also contained strong acidic sites. For supported niobia and tantala catalysts, as well as to be expected for supported dubnia catalysts, the active surface sites were exclusively acidic sites. However, the TOF_redox for the supported vanadia catalysts and the TOF_acidic for the supported niobia and tantala catalysts varied over several orders of magnitude as a function of the specific oxide support with the electronegativity of the oxide support cation. However, the TOF_redox varied inversely to that of the TOF_acidic variation because of the opposite requirements of these active surface sites. Surface redox sites are enhanced by reduction and surface acidic sites are enhanced by stabilization (lack of reduction). The current fundamental understanding of the Group V metal oxides allows for the molecular engineering of their metal oxide applied catalytic materials.     

不同金属氧化物对重质生物油再裂解的比较性研究

通过TG-FTIR、GC/MS和XRD等分析手段,研究了Fe₂O₃、Al₂O₃、CaO和TiO₂四种金属氧化物催化下重质生物油的热解特性及产物差异。结果表明：应用上述四种催化剂的再裂解实验均促进了重质生物油的脱氧,其中CaO催化下脱氧效果最好,Al₂O₃能够有效降低反应温度,Fe₂O₃有效促进了重质生物油成炭前的解聚、固相产物质量降幅达21.23%,TiO₂对CO₂的生成有最明显的抑制效果、同时可以降低反应结束温度;在低温下,除CaO外的三种催化剂均对有效产物的生成有促进作用,但对不同种类的物质各有侧重,而CaO则会使反应所需温度升高且对愈创木酚的富集有很强的选择性;在中温下,CaO和TiO₂表现出较好的催化效果。上述催化热解过程有效促进了酚类的富集,效果最好的是Al₂O₃,酚类相对含量增幅达31.10%。除Fe₂O₃外的三种金属氧化物均降低了生物炭的有序度,添加CaO制备的生物炭具有最无序的炭结构和最高的固相产率。     

Fischer–Tropsch synthesis. Conversion of alcohols over iron oxide and iron carbide catalysts

Both iron oxide (Fe₂O₃) and iron carbide catalysts are active for the dehydration of tertiary alcohols; the oxide catalyst is not reduced nor is the bulk carbide oxidized by the steam generated during the dehydration reaction. Secondary alcohols are selectively converted to ketones plus hydrogen by both the iron oxide and carbide catalyst. Fe₂O₃ is reduced to Fe₃O₄ during the conversion of secondary alcohols. Both iron carbide and oxide catalysts dehydrogenate a primary alcohol (C_n) to an aldehyde which undergoes a secondary ketonization reaction to produce a symmetrical ketone with 2n−1 carbons. These results plus those of our earlier ¹⁴C-tracer studies suggest that dehydration of alcohols to produce olefins makes a minor, if any, contribution during Fischer–Tropsch synthesis with an iron catalyst at low and intermediate pressure conditions.