RhNi/SBA-15纳米催化剂的制备及其催化水合肼分解制氢性能

通过浸渍还原法将RhNi纳米颗粒负载在SBA-15(介孔二氧化硅)上制备出不同金属比的RhNi/SBA-15催化剂,进一步考察催化剂的结构及其催化水合肼制氢的性能。结果表明：RhNi/SBA-15催化剂中形成RhNi双金属,Rh和Ni双金属之间的协同作用有效提升催化剂活性。所制RhNi/SBA-15催化剂中Rh和Ni物质的量之比为9:1,在反应温度为323 K,NaOH浓度为0.15 mol/L时,该催化剂具有较高的活性,转化频率(TOF)为2 569.6 h^-1,经过5次循环后仍保持良好的催化活性。     

纳米TiO_2的合成及纳米TiO_2/Pt修饰电极的电化学催化性能

采用溶胶-凝胶法合成纳米TiO2粉体,通过正交实验优化了纳米TiO2的合成工艺条件,用透射电镜及X-射线衍射技术对纳米TiO2样品进行表征;进而采用涂膜法制备纳米TiO2/Pt修饰电极,通过循环伏安法研究其在葡萄糖体系中的电化学催化性能。结果表明:在钛酸丁酯与乙醇体积比为2∶3、烘干温度为80℃、焙烧温度为500℃时,合成的纳米TiO2具有最佳电化学催化性能;合成的纳米TiO2为锐钛矿型,颗粒粒径分布在5~20nm之间;纳米TiO2/Pt修饰电极对葡萄糖具有显著的电化学催化活性。     

非晶态Ni-W-B合金的制备及催化硼氢化钠水解制氢

采用化学还原法合成了非晶态金属硼化物Ni-W-B合金,并用于硼氢化物水解制氢。通过X射线衍射分析(XRD)、扫描电子显微镜(SEM)、X射线能谱分析(EDX)证明,样品Ni-W-B为非晶态的、均匀的球形颗粒,平均粒径约60~70 nm。催化活性实验证明,Ni-W-B合金对Na BH4水解制氢有较好的催化活性;W的含量对催化活性有一定影响,其W与Ni的最佳摩尔比为0.1。影响因素实验证明,Na BH4水解制氢速率与体系温度及催化剂用量呈正比。使用寿命测试证明,经过10次水解循环之后催化剂活性没有明显降低,说明Ni-W-B催化剂有较好的稳定性。     

溶胶凝胶法制备nAl/CuO纳米复合材料

发展了碱性催化sol-gel方法,以尿素为碱性催化剂,基于三水合硝酸铜[Cu(NO_3)_2·3H_2O]和纳米铝粉制备了nAl/CuO纳米复合材料。使用红外光谱(FIIR)、X射线衍射(XRD)、差热分析(DSC)、扫描电子显微镜(SEM)表征了所得纳米复合材料的化学组成、形貌和能量释放特性。结果表明,弱碱性环境下sol-gel法制备的nAl/CuO体系具有典型的凝胶网络结构,nAl能在CuO凝胶中稳定、均匀分散,碱性sol-gel法有利于改善nAl/CuO的混合。DSC测试nAl/CuO纳米复合材料放热量为1 018 J/g,达到其理论热焓(4 077 J/g)的25%。     

溶胶凝胶法制备nAl/CuO纳米复合材料

发展了碱性催化sol-gel方法,以尿素为碱性催化剂,基于三水合硝酸铜[Cu(NO_3)_2·3H_2O]和纳米铝粉制备了nAl/CuO纳米复合材料。使用红外光谱(FIIR)、X射线衍射(XRD)、差热分析(DSC)、扫描电子显微镜(SEM)表征了所得纳米复合材料的化学组成、形貌和能量释放特性。结果表明,弱碱性环境下sol-gel法制备的nAl/CuO体系具有典型的凝胶网络结构,nAl能在CuO凝胶中稳定、均匀分散,碱性sol-gel法有利于改善nAl/CuO的混合。DSC测试nAl/CuO纳米复合材料放热量为1 018 J/g,达到其理论热焓(4 077 J/g)的25%。     

溶胶-凝胶法制备Ni/ZrO2对甲烷干重整的催化性能

采用溶胶凝胶法制备负载型催化剂Ni/ZrO_2,考察金属Ni负载量对甲烷干重整反应的催化性能的影响。利用XRD,N_2吸附,SEM和H_2-TPR等手段表征Ni/ZrO_2样品。与金属镍催化剂相比,金属镍掺杂的催化剂Ni/ZrO_2具有更高的催化活性,随着金属镍的掺杂量的增加先增大后减小,镍负载量为9%的催化剂Ni(9)/ZrO_2的催化性能最好,这归因于ZrO_2能够较好的分散金属镍粒子以及增大对CO_2的吸附能力,从而有利于抑制高温还原烧结和增加催化甲烷干重整反应活性位。     

水热法制备Ni/Nd2O3催化剂及其催化水合联氨制氢

采用水热合成法制备了Ni/Nd₂O₃催化剂，对其催化水合联氨制氢性能进行了考察，探讨了催化剂合成条件及催化体系中NaOH浓度对催化性能的影响，并采用XRD、XPS、TEM、TG对催化剂进行了分析表征。结果表明，当Ni/Nd=94∶6、水热条件为8h、120℃时，合成的Ni/Nd₂O₃催化剂在催化水合联氨制氢时表现出了最优的催化性能，其H₂选择性为95.9%。该催化剂中Ni的结晶度较高，Nd以Nd₂O₃的形式存在，具有促进颗粒分散、暴露活性位点、协助Ni、Nd电子转移等优点。与不加NaOH溶液的催化制氢体系相比，当NaOH的加入浓度为1.3mol/L时，催化剂催化水合联氨的制氢速率提高了约3.7倍。催化剂可维持良好的稳定性，循环使用5次后H₂选择性仍高达94.4%。     

Pt/TiO_2光催化制氢的初步研究

对无氧条件下Pt/TiO_2光催化重整甲醇制氢的基本步骤进行简化,在同一体系中进行了光催化剂的合成和光催化制氢的两步反应。基于正交设计法对该复杂体系进行了分析,得到Pt载量、甲醇/水体积、灯距、前反应时间这4种影响因素的3个不同水平对放氢速率的影响。确定了最佳实验条件为Pt载量0.5％(mol)、甲醇/水体积比5:1、灯距12 cm、前反应时间3h。分析结果表明,Pt载量对放氢速率的影响最大。实验获得的最高放氢速率为5.84 ml·h~(-1)·g~(-1)。     

Ni与Co催化乙醇制氢研究进展

乙醇制氢具有环保、清洁、可持续等优点,其关键在于选择合适的催化剂。相较于贵金属催化剂而言,Ni与Co基催化剂因其具有成本低且活性高的优点,近年来在乙醇催化制氢中逐渐成为研究热点。然而Ni与Co基催化剂在催化乙醇水蒸气重整制氢的过程中仍存在着稳定性较差、低温催化活性低和使用寿命较短等问题。本文介绍了乙醇制氢的机理,围绕载体的类型及催化剂活性纳米颗粒的合金化改性,综述了近年来Ni与Co基催化剂催化乙醇水蒸气重整制氢的研究现状,总结了提高催化剂性能的方法及措施,并展望了Ni与Co基催化剂未来的发展方向,为颗粒尺寸小且低温催化活性高、稳定性好的Ni与Co基催化剂的制备提供思路。     

Co/La2O3催化乙醇水蒸汽重整制氢反应的研究

采用浸渍、热分解、氢还原等步骤制备了一系列Co/La2O3,催化剂,并将其应用于乙醇水蒸汽重整制氢反应.采用固定床反应考察了温度和水醇比对催化剂性能的影响.用N2吸附、XRD、TPR等手段对催化剂进行了表征.结果表明:5%Co/La2O3,催化剂对乙醇水蒸汽重整制氢反应表现出最高的活性.在500℃、水醇比为3:1时,乙醇的转化率达可到64.8%,H2的产率和选择性分别为1.0 mol/mol和86.1%.另外,在反应温度低于450℃时,H2的选择性可达90%以上.     

纳米金属钴粒子的制备及对高氯酸铵热分解的影响

The monodispersed Co nanoparticles were successfully prepared by means of hydrogen plasma method in inert atmosphere. The particle size, specific surface area, crystal structure and morphology of the samples were characterized by transmission electron microscopy （TEM）, BET equation, X-ray diffraction （XRD）, and the corresponding selected area electron diffraction （SAED）. The catalytic effect of Co nanoparticles on the decomposition of ammonium perchlorate （AP） was investigated by differential thermal analyzer （DTA）. Compared with the thermal decomposition of pure AP, the addition of Co nanoparticles （2%-10%, by mass） decreases the decomposition temperature of AP by 145.01-155.72℃. Compared with Co3O4 nano-particles and microsized Co particles, the catalytic effect of Co nanoparticles for AP is stronger. Such effect is attributed to the large specific surface area and its interaction of Co with decomposition intermediate gases. The present work provides useful information for the application of Co nanoparficles in the AP-based propellant.     

Preparation,characterization and comparative electrochemical studies of MgMXMn2-XO4 (x=0, 0.5; M= Ni/Co)

In this study, the structural, electrical and electrochemical properties of the compounds MgM_xMn_2-xO₄ [M = Ni/Co: x = 0,0.5] were investigated by preparing the materials by the citric acid assisted simple, cost effective sol-gel method. X-ray Diffraction (XRD) confirmed that Ni/Co doping created a phase transition of MgMn₂O₄ from tetragonal spinel-structure with a space group of I4₁/amd to a cubic spinel structure with a space group of Fd-3m. HRTEM and SAED analysis showed the bare compound to be polycrystalline and doped compounds to be single crystalline in nature. SEM analysis showed the agglomerated submicron sized particles for all the three compounds. The electrical properties of the compounds have been investigated through AC impedance spectroscopy. The electrical conductivity of the bare compound MgMn₂O₄ was found to be 5.09 × 10⁻⁶ S/cm at 583 K. Cyclic Voltammetry (CV) and Galvanostatic Charge-Discharge (GCD) studies made by the three electrode system shows that all the samples under study could undergo reversible redox reactions in the aqueous magnesium nitrate solution. MgMn₂O₄ sample exhibited highest specific discharge capacity of 263 mAh/g at the current density of 30 mA/g.     

镍/铁二元金属催化降解水体中的莠去津和对氯苯酚

在一定反应条件下,考察了Ni/Fe二元金属对不同取代基上Cl原子的脱除特性。实验以莠去津和对氯苯酚(p-CP)为研究对象,在水溶液中进行了脱氯降解。结果表明,与金属Fe0相比,Ni/Fe对莠去津和p-CP均有明显的催化脱氯降解效果。单位比表面Ni/Fe对p-CP和莠去津的表观反应速率常数分别为:kSA=7.61×10-4(min-1.m-2)和k′SA=5.64×10-3(min-1.m-2),说明Ni/Fe对三氮苯环上Cl原子有更强的脱除特性。不同反应pH对Ni/Fe降解p-CP的影响比莠去津小,反应60 min,p-CP在pH=2.0、3.0、4.0和未调节pH条件下的脱氯效率分别为43%、44%、35%和28%;120 min分别为69%、62%、57%、48%。而莠去津在pH=4.0和未调节pH条件下几乎没有还原,主要是受氯化物本身性质的影响。另外,通过反应体系的电化学测试表明,在Ni/Fe催化还原莠去津和p-CP的过程中,反应中主要的还原剂是Fe0溶解产生并吸附在催化剂表面的H2。     

Structure of Pt–Co/Al2O3 and Pt–Co/NaY Bimetallic Catalysts: Characterization by In Situ EXAFS,TPR, XPS and by Activity in Co (Carbon Monoxide) Hydrogenation

Temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and in situ extended X-ray absorption fine structure (EXAFS) studies were performed to investigate Pt-Co/NaY and Pt-Co/Al₂O₃ bimetallic catalysts. The EXAFS experiments were carried out at the Pt L_III and Co K edges of the same sample. This particular approach allows a precise determination of the electronic and structural characteristics of the metallic part of the catalyst. For both systems in situ reduction under pure H₂ results in the formation of nanometer-scale metallic clusters. For both Co and Pt, nearest neighbors are Co atoms. The complete set of parameters implies the presence of two families of nanometer-scale metallic clusters: monometallic Co nanosized particles and Pt-Co bimetallic clusters, in which only Pt-Co bonds exist (no Pt-Pt bonds). TPR and XPS results indicating a reduction of Co²⁺ ions in Pt-Co/NaY to a greater extent than in Pt-Co/Al₂O₃ give evidence of a facilitated reduction. XRD also shows the presence of nanometer-scale particles with only a very small fraction of larger bimetallic particles. In subsequent mild oxidation of the reduced systems the Co nanoparticles are still present inside the supercage of NaY zeolite in bimetallic form and the oxidation of the metallic particles is slowed down. Catalytic behavior is in good agreement with the structure of the Pt-Co bimetallic system.     

Pd/Co Bimetallic Nanoparticles: Coelectrodeposition under Protection of PVP and Enhanced Electrocatalytic Activity for Ethanol Electrooxidation

A series of Pd–Co bimetallic nanostructures with Co compositions ranging from 0 to 13 at.% were fabricated on glassy carbon electrode by one step electrodeposition in the presence of polyvinylpyrrolidone (PVP). The roles of PVP and Co have been systematically investigated by using combined techniques such as scanning electron microscopy, energy dispersive spectrometry, cyclic voltammetry, X‐ray diffraction, and chronoamperograms. PVP was used as an additive to stabilize the Pd nanoparticles and inhibit agglomeration during their formation. The prepared Pd₁₀₀Co₁₀ bimetallic nanostructures exhibited great catalytic activity towards ethanol oxidation in alkaline, which implies that low Co doping can be a convenient way to enhance the electrocatalytic property of Pd. The present study shows that the Pd/Co bimetallic nanoparticulate can be a promising catalyst for portable applications in direct ethanol fuel cell in alkaline solution.     

催化裂化再生器中铂助燃剂催化活性的测定(Ⅰ)——在新助燃剂上CO氧化的反应动力学

研究了催化裂化再生条件下铂助燃剂上ＣＯ氧化反应动力学。在排除了反应管及稀释剂的催化氧化作用后，测定了铂含量为１０－６ｇ／ｇ的国产新助燃剂上的反应动力学数据，得出了在氧过量时一氧化碳和氧的反应级数分别为１和０．５。给出了６６０℃下的反应速度常数值及其置信区间。     

Antioxidant Activity of Hydrogen Water Mask Pack Composed of Gel-Type Emulsion and Hydrogen Generation Powder

In this study, hydrogen generation powder samples were prepared using zinc carbonate as a precursor, at a temperature varying from 400 to 700 °C in H₂ atmosphere, and were characterized in terms of antioxidant activity. The concentration of dissolved hydrogen obtained by the powder samples was measured using a dissolved hydrogen meter as a function of time. In addition, the antioxidant activity of the samples was evaluated based on the Oyaizu’s method, removal rate of ·OH radicals, and ferric reducing antioxidant power. Finally, the hydrogen mask pack was fabricated using the hydrogen generation powder sample and gel-type emulsion. In the clinical test on the mask pack, the effect of the mask on skin aging was characterized and compared to that of a commercial sample. The skin densities of the participants in the experimental group and the control group increased by 18.41% and 9.93% after 4 weeks, respectively. The improved skin density of the participants who used the hydrogen mask pack in the experimental group, might be attributed to the recovery effect of the hydrogen molecule in the mask pack on the denatured thick skin layer.     

Preparation and Catalytic Activity of Co/CNTs Nanocomposites via Microwave Irradiation

Co nanoparticles supported on carbon nanotubes (CNTs) were prepared by microwave‐assisted heating of the hydrazine reduction in ethylene glycol (EG). The Co/CNT nanocomposites prepared by the microwave‐irradiation method (MIM‐Co/CNTs) were characterized by XRD, SEM, EDS, and BET. It was found that MIM‐Co/CNTs had compact coating, high cobalt loading, and large BET surface area. The obtained products for the thermal decomposition of ammonium perchlorate (AP) were investigated by DTA. The catalytic activity of MIM‐Co/CNTs was better than that of pure Co nanoparticles and Co/CNT nanocomposites by water‐bath method (WBM‐Co/CNTs). The addition of 5 wt.‐% MIM‐Co/CNTs decreased the high decomposition temperature of AP by 174.05 °C and increased the total DTA heat release by 0.799 kJ g⁻¹.     

催化裂化再生器中铂助燃剂催化活性的测定(Ⅱ)——助燃剂的平衡活性及其模拟

研究了实际运转中铂助燃催化一氧化碳氧化的反应动力学。发现它与新助燃剂的反应级数相同。进而用动力学法测定了取自６个生产厂２２个样品的平衡活性，其平衡活性只有新助燃剂活性的９．３６％～１３．３６％。这个差异主要是由水热失活引起的。在８００℃下，用含氧的氮气将新助燃剂老化３ｈ，或用１００％水蒸气老化２ｈ，可以自实验室模拟老化到平衡活性的水平。     

CdS/TiO2复合纳米粒子的制备及其产氢性能研究

采用化学沉淀法制备了CdS包覆TiO2（CdS/TiO2）复合纳米粒子,利用XRD、TEM、SEM、UV-vis吸收光谱等对其进行了表征分析,并以可见光分解水制氢为探针反应考察了复合纳米粒子的活性。结果表明,CdS/TiO2 复合纳米粒子的颗粒大小约为40nm,TiO2 以锐钛矿型存在,CdS以六方相存在;复合纳米粒子的吸收光谱较TiO2 发生“红移”,大幅拓宽了对可见光区的吸收范围。光解水制氢实验表明,CdS/TiO2 复合纳米粒子具有良好的可见光释氢活性和光学稳定性。