MoO_3/石墨烯/碳纳米管复合阴极在MFCs中的应用

采用简单的水热合成法制备了氧化钼(MoO_3)/石墨烯(GNS)/碳纳米管(CNT)复合材料。用扫描电子显微镜(SEM)和X射线衍射仪(XRD)表征了材料的形貌和结构。用循环伏安(CV)和线性扫描(LSV)测试了材料的氧还原催化性能,结果发现,复合材料的氧还原电流和起始电位均大大优于单一的MoO_3,表现出较好的催化性能。含有3mg·cm~(-2) MoO_3/GNS/CNT复合材料作为阴极催化剂的MFC最大功率密度为510 m W·m~(-2),达到商业铂碳的83%。因此,廉价的MoO_3/GNS/CNT复合材料作为MFC阴极氧还原催化剂具有巨大的应用潜力。     

α-MoC/石墨烯复合材料的氧还原性能及其在微生物燃料电池中的应用

用改良Hummers法和碳热还原法分别制备了石墨烯和碳化钼。用扫描电子显微镜和XRD表征了材料的形貌和结构。用循环伏安和线性扫描测试了材料的氧还原催化性能,结果发现,复合材料的氧还原峰电流和起峰电位均大大优于单一材料,表现出较好的催化性能。含有12mg/cm~2α-MoC碳化钼/石墨烯复合材料作为阴极催化剂的MFCs最大功率密度为417.6m W/m~2,达到商业铂碳的68.2%。因此,廉价的α-MoC/石墨烯复合材料作为MFCs阴极氧还原催化剂具有巨大的应用潜力。     

MoO3/g-C3N4复合材料的制备及光催化性能

以三聚氰胺和四水合钼酸铵为前驱体,采用水热法制备了MoO₃/g-C₃N₄复合光催化剂。利用X-射线衍射仪（XRD）、红外光谱仪（FT-IR）、扫描电子显微镜（SEM）、X射线光电子能谱仪（XPS）及紫外-可见漫反射仪（DRS）等对制备的样品进行了表征。表征结果显示,棒状的三氧化钼负载在层状C₃N₄表面,复合材料的光吸收能力有一定的增强。材料可见光催化降解亚甲基蓝（MB）溶液的实验表明,三氧化钼和g-C₃N₄所复合产生的异质结具有较好的吸收光强度及催化降解性能,尤其是5%（质量分数）MoO₃/g-C₃N₄复合材料光催化降解率最好,达到95.7%,高于纯三氧化钼和g-C₃N₄。自由基与空穴捕获实验表明,·O₂^-是光催化反应中的主要活性物种。MoO₃/g-C₃N₄复合材料在4个循环周期内表现出了优异的稳定性。     

V2O5-MoO3/TiO2 催化剂的NOx选择性催化还原及SO2氧化活性

采用浸渍法以TiO₂为载体制备V₂O₅-MoO₃/TiO₂ 选择性催化还原催化剂,研究V₂O₅和MoO₃负载量对于催化剂选择性催化还原反应及SO₂氧化活性的影响,并考察氧含量、氨氮物质的量比和反应空速对3%V₂O₅-6%MoO₃/TiO₂催化剂选择性催化还原脱硝活性的影响。结果表明,随着催化剂中V₂O₅负载质量分数增加,V₂O₅-MoO₃/TiO₂ 催化剂的选择性催化还原活性和SO₂氧化活性均呈上升趋势。MoO₃的负载对催化剂的SO₂氧化活性有明显抑制作用。MoO₃负载质量分数超过9%,制备的催化剂既保持较高的低温选择性催化还原活性,又使选择性催化还原反应中的SO₂转化率小于1%。     

氧化锰基电催化材料的设计合成及其铝空气电池应用

电催化剂作为铝空气电池阴极的核心部分,其催化性能的优劣直接影响铝空气电池的产业化进程。本文采用尿素高温处理法将商业的Vulcan-72XC碳材料进行掺氮改性处理制备了N/VC₂。在此基础上,进一步负载不同的锰氧化物得到三种Mn₃O₄@N/VC₂、MnO@N/VC₂和MnO₂@N/VC₂复合材料。其中,MnO₂@N/VC₂具有最优的氧还原反应(ORR)催化性能,起始电位高达0.872 V。作为铝空气电池阴极催化剂,在大电流密度下放电功率密度可达到136 mW·cm^-2。本文通过对比分析不同氧化锰基复合材料的电催化性能,研究了碳载体和锰氧化物之间的交互作用。结果表明,多孔结构和丰富缺陷位点的协同作用是提高材料催化活性的主要原因。该工作为锰基氧化物催化剂的研发提供理论依据。     

MoS2/Y分子筛微生物电解池阴极材料制备及其电化学性能

采用水热法合成了一系列不同比例的MoS₂/Y分子筛复合物,并将其制成碳基复合电解池阴极。线性扫描伏安法（LSV）测试表明,当MoS₂和Y分子筛质量比为5∶2、碳纸负载量为1.5mg/cm²时,阴极催化析氢性能最佳。通过SEM、TEM、XRD、XPS和BET对复合材料进行表征,SEM测试表明MoS₂/Y分子筛为片状和八面体相互交织叠加的云状形貌。BET测试表明其具有排列规整的微孔-介孔多级孔道结构,利于加速H⁺还原和H₂扩散。本文还考察了以MoS₂/Y分子筛作为微生物电解池（MEC）阴极的析氢性能。在MEC运行5个周期的产氢实验中,MoS₂/Y分子筛所产生的平均最大电流密度、氢气产率和产氢量等都高于Pt电极,且具有长期稳定性。因此,MoS₂/Y分子筛是一种适于实际应用的析氢催化剂。     

微生物燃料电池MnO2/S-AC泡沫镍空气阴极的制备及其性能

利用超级电容器活性炭(S-AC)直接还原KMnO₄制备出复合比例分别为1:3、1:1和3:1的MnO₂/S-AC复合催化剂, 进而负载于泡沫镍上制得MnO₂/S-AC泡沫镍空气阴极。通过X射线衍射(XRD)、扫描电镜(SEM)、能量散射X 射线谱(EDX)和比表面积(BET)及孔分布测试对所制复合催化剂表征可知, 随复合比例的增加, 在S-AC表面的MnO₂由纳米薄片聚集成粒径为300～500 nm的颗粒, MnO₂/S-AC的内部及外部表面积都有所减少。基于线性扫描伏安曲线、功率密度曲线和极化曲线分析微生物燃料电池(MFC)的阴极性能和产电性能。复合比例为1:3时, MFC最大功率密度达到321.2 mW·m^-2, 比阴极负载S-AC时提高了约20%, 这与其较高的比表面积和MnO₂良好的催化活性相关。MnO₂/S-AC复合催化剂控制在一定的质量比时, 可以有效提高阴极性能及MFC的产电效果, 有助于空气阴极MFC的的放大和工程应用。     

MoO2/g-C3N4催化剂的制备及其氧化脱除模拟油中的硫化物

采用高温煅烧MoO₂和g-C₃N₄混合物制备了不同MoO₂含量的MoO₂/g-C₃N₄催化剂。采用X射线粉末衍射（XRD）、傅里叶红外光谱（FTIR）、扫描电镜（SEM）和N₂吸附脱附对催化剂的结构和性能进行了表征。以MoO₂/g-C₃N₄作为催化剂,H₂O₂为氧化剂,离子液体为萃取剂研究了反应体系的氧化脱硫性能。这项研究中考察了不同煅烧温度下制得的催化剂、负载量、氧化剂使用量、催化剂加入量、反应温度、萃取剂使用量、反应时间、硫化物类型等不同反应参数对脱硫率的影响。结果表明,在H₂O₂的使用量为0.2mL,MoO₂/g-C₃N₄加入量为0.03g,1-乙基-3-甲基咪唑硫酸乙酯离子液体1.0mL,反应温度为70℃,反应时间60min的最佳工艺条件下,24%-MoO₂/g-C₃N₄催化剂脱硫率可以达到94.8%,催化剂循环使用5次后活性没有明显下降。此外,研究了MoO₂/g-C₃N₄在离子液体中的催化氧化反应机理。     

氢氛还原法制备氧化铁/膨润土 复合材料及其表征研究

以膨润土和硝酸铁为原料,采用氢氛还原法制备Fe₃O₄/膨润土复合材料,并采用X射线衍射（XRD）、扫描电子显微镜（SEM）和电子能谱（EDS）做表征分析。通过实验得到最佳的工艺条件：n（OH^-）∶n（Fe³⁺）=1∶1、铁土比为10 mmol/g、还原温度为200 ℃、还原时间为30 min。制备的Fe₃O₄/膨润土具有良好的类Fenton催化性能、稳定性与磁分离性能。制备过程中铁元素化合物能够有效固载在膨润土上,并在氢气还原作用下转化为Fe3O4,所得Fe3O4/膨润土是结构分散、孔隙明显、物化形态优良的催化复合材料。     

甲醇氧化制甲醛铁钼催化剂表面结构与活性

利用共沉淀法在不同搅拌速度下制备了相同Mo/Fe原子比的甲醇氧化制甲醛催化剂,采用SEM、XRD和拉曼光谱等对催化剂进行表征,在固定床微反上评价催化剂活性和选择性。结果表明,搅拌速度增大,催化剂比表面积增大,催化活性增强,甲醛收率由600 r·min^-1时的73.8%增加到10000 r·min^-1时的95.7%（280℃）。此外,催化剂由片状的MoO₃和颗粒状的Fe₂（MoO₄）₃两部分组成,游离的片状MoO₃无明显催化活性,只有与Fe₂（MoO₄）₃结合时才具有催化活性。     

Ferroelectric solid solution Li1 − xTa1 − xWxO3 as potential photocatalysts in microbial fuel cells: Effect of the W content

Microbial fuel cells (MFCs) are bio-electrochemical systems that can directly convert the chemical energy contained in an effluent into bioelectricity by the action of microorganisms. The performance of these devices is heavily impacted by the choice of the material that forms the cathode. This work focuses on the assessment of ferroelectric and photocatalytic materials as a new class of non-precious catalysts for MFC cathode construction. A series of cathodes based on mixed oxide solid solution of LiTaO₃ with WO₃ formulated as Li_1-xTa_1-xW_xO₃ (x=0, 0.10, 0.20 and 0.25), were prepared and investigated in MFCs. The catalyst phases were synthesized, identified and characterized by DRX, PSD, MET and UV-Vis absorption spectroscopy. The cathodes were tested as photoelectrocatalysts in the presence and in the absence of visible light in devices fed with industrial wastewater. The results revealed that the catalytic activity of the cathodes strongly depends on the ratio of substitution of W⁶⁺ in the LiTaO₃ matrix. The maximum power densities generated by the MFC working with this series of cathodes increased from 60.45 mW·m^-3 for x=0.00 (LiTaO₃) to 107.2 mW·m^-3 for x=0.10, showing that insertion of W⁶⁺ in the tantalate matrix can improve the photocatalytic activity of this material. Moreover, MFCs operating under optimal conditions were capable of reducing the load of chemical oxygen demand by 79% (COD_initial=1030 mg·L^-1).     

Photodegradation catalyst screening by combinatorial methodology

In this work, a combinatorial methodology was developed for photodegradation catalyst screening. A fluorescence imaging detection system was designed for high throughput analysis, 1,6-hexamethylenediamine was used as the probe molecule for catalyst testing. The photodegradation activity of catalysts was evaluated by 1,6-hexamethylenediamine consumption during the photodegradation reaction. The methodology could provide reliable results. We found that pure TiO₂, ZrO₂, Nb₂O₅, MoO₃, and WO₃ did not show much activity for 1,6-hexamethylenediamine photodegradation under visible light. TiO₂ catalysts doped with different metal ions were tested. When TiO₂ was doped with Ta₂O₅, Nb₂O₅, V₂O₅, MoO₃, or WO₃, higher activity for photodegradation was observed. The doping of La³⁺, Ba²⁺, and Br⁻ to TiO₂ did not improve the catalytic activities. When doping TiO₂ with Mn²⁺, Cl⁻, Al³⁺, Cu²⁺, Fe³⁺, Na⁺, Mg²⁺, Li⁺, F⁻, Co²⁺, or K⁺, catalytic activity was lower than that of pure TiO₂. After elaborate catalysts screening, we discovered new catalysts, such as 50–70% TiO₂/0–20% WO₃/20–40% VO_2.5 and 20–30% TiO₂/30–50% MoO₃/40–60% VO_2.5 as well as 30% WO₃/20% ZrO₂/50% NbO_2.5 (synthesized from ZrCl₄, NbCl₅, and (NH₄)₅H₅[H₂(WO₄)₆]·H₂O in ethanol solution or suspension) and 60–70% WO₃/Nb₂O₅ (synthesized from WCl₆ and NbCl₅ in ethanol solution). We observed that the catalytic activity is sensitive to preparation methods and catalyst specific surface areas. When P123 (HO(CH₂CH₂O)₂₀(CH₂CH(CH₃)O)₇₀(CH₂CH₂O)₂₀H, designated EO₂₀PO₇₀EO₂₀) was used as template to synthesize mesoporous materials, the mesoporous catalysts showed higher activity than regular catalytic materials.     

PEMFC用Pt纳米线阴极催化剂的制备及在电堆中的应用

采用无模板法制备了用于质子交换膜燃料电池（PEMFC）的碳载铂纳米线（Pt NWs/C）阴极催化剂,使用透射电镜（TEM）和X射线衍射图谱技术（XRD）对催化剂的微观结构和形貌进行了表征。研究结果表明,制备的铂催化剂具有纳米线的结构,平均截面直径为（4.0±0.2）nm,线长为15～25 nm。利用循环伏安（CV）法和线性伏安扫描法（LSV）表征催化剂的电化学活性和氧还原反应（ORR）特性,结果表明制备的Pt NWs/C催化剂电化学特性良好。利用Pt NWs/C和Pt/C作为阴极催化剂制备膜电极（MEA）,并进行测试,最大功率密度分别为705.6 mW·cm^-2和674.4 mW·cm^-2。然后以Pt NWs/C和Pt/C为阴极催化剂组装了18片和20片的电堆,并进行性能测试,电堆的最大功率密度分别为409.2 mW·cm^-2和702.7 mW·cm^-2,单电池电压差异系数（C_v）分别为16.1%和4.36%,这表明Pt NWs/C作为阴极催化剂在放大后的膜电极组件（MEA）里表现出较好的催化活性,但与商业催化剂相比其性能与均一性还有待提高。该研究可为Pt NWs/C催化剂放大制备提供依据,同时可为后续的基于Pt NWs/C的电堆的耐久性测试和车载应用奠定基础。     

Catalytic performance of a novel ceramic-supported vanadium oxide catalyst for NO reduction with NH3

A novel TiO₂/Al₂O₃/cordierite honeycomb-supported V₂O₅–MoO₃–WO₃ monolithic catalyst was studied for the selective reduction of NO with NH₃. The effects of reaction temperature, space velocity, NH₃/NO ratio and oxygen content on SCR activity were evaluated. Two other V₂O₅–MoO₃–WO₃ monolithic catalysts supported on Al₂O₃/cordierite honeycomb or TiO₂/cordierite honeycomb support, two types of pellet catalysts supported on TiO₂/Al₂O₃ or Al₂O₃, as well as three types of pellet catalysts V₂O₅–MoO₃–WO₃–Al₂O₃ and V₂O₅–MoO₃–WO₃–TiO₂ were tested for comparison. The experiment results show that this catalyst has a higher catalytic activity for SCR with comparison to others. The results of characterization show, the preparation method of this catalyst can give rise to a higher BET surface area and pore volume, which is strongly related with the highly active performance of this catalyst. At the same time, the function of the combined carrier of TiO₂/Al₂O₃ cannot be excluded.     

The effect of dopants on the activity of MoO3/ZSM-5 catalysts for the dehydroaromatisation of methane

The effect of a number of dopants – Co²⁺, Fe³⁺, Al³⁺, Ga³⁺ and P^(V) – on the catalytic activity of MoO₃/ZSM-5 dehydroaromatisation catalysts has been investigated. Promotional effects were observed with Fe³⁺, Al³⁺ and Ga³⁺, whereas P^(V) added in the form of phosphomolybdic acid decreased the benzene formation rate. Doping with Co²⁺ was not observed to produce any promotional effects, aside from an initial high conversion and burst of hydrogen which was short-lived. In the case of iron, although the benzene formation rate was close to that for the non-doped parent catalyst in the early stages, benzene formation was enhanced at longer times on stream and the addition of iron was observed to enhance methane conversion, principally through enhanced coke formation. The addition of gallium was found to produce an enhancement of benzene production in the early stages of reaction, but its principal effect was the reduction of hydrogen producing side reactions associated with the formation of coke. In comparing the effects of metal ion addition, it is notable that the impregnation solutions of Fe³⁺, Al³⁺ and Ga³⁺ are acidic. Possible effects of these dopants such as zeolite dealumination, modification of catalyst acidity and the formation of mixed molybdenum containing phases or re-dispersion of the MoO₃ phase can be advanced as potential explanations for the observed effects.     

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.     

还原温度对Mo基催化剂物相及其加氢脱氧性能的影响

以碳纳米管(CNTs)为载体,通过控制催化剂合成的还原温度制备了一系列负载型Mo基催化剂。采用XRD、TEM、N₂物理吸附、XPS以及NH₃/H₂-TPD等技术对催化剂进行了表征,并研究了Mo基催化剂对硬脂酸催化加氢脱氧性能的影响。结果表明:随着还原温度的升高,催化剂表面的Mo物种逐渐被还原,还原过程为:MoO₃→MoO₂→Mo→Mo₂C。还原温度为450℃和550℃时,催化剂的活性相为MoO₂;还原温度为600℃时,催化剂的活性相为MoO₂/Mo/β-Mo₂C的混合相;还原温度为650℃和700℃时,催化剂的活性相全部转化为β-Mo₂C。与活性相MoO₂催化剂相比,β-Mo₂C催化剂具有更高的加氢脱氧活性。此外,还原温度为600℃的MoO₂/Mo/β-Mo₂C混合相催化剂因具有较大的比表面积、较多的酸中心数量和较强的H₂吸附能力,使得该催化剂在硬脂酸加氢脱氧反应中表现出最优越的催化活性。     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 1. Surface area of alumina

This is the first report of a group study on the preparation of a MoO₃/Al₂O₃ catalyst to find predominant preparation parameters for better and reproducible catalyst preparations. Variously prepared MoO₃/Al₂O₃ catalysts possessing 13 wt% MoO₃ were subjected to multiprong characterizations and catalytic tests. It was found that the surface area of the support was the most predominant preparation parameter for the dispersion of Mo oxide species; the dispersion increased as the surface area of the support increased. The formation of crystalline MoO₃ was observed at a surface Mo concentration higher than 3.2 Mo nm⁻². With sulfided MoO₃/Al₂O₃, it was established that the dispersion of Mo sulfide species increased with increasing surface area of the support and was in proportion to that of Mo oxide precursor species. The hydrodesulfurization activity of sulfided MoO₃/Al₂O₃ was proportional to the NO adsorption capacity. It is suggested that a homogeneous distribution of Mo oxide species is attained by an equilibrium adsorption technique. However, it was revealed that the surface area of the catalyst and Mo distribution were considerably modified by preparation parameters, such as drying processes, other than the surface area.