Methane Steam Reforming on Supported Nickel Based Catalysts. Effect of Oxide ZrO₂, La₂O₃and Nickel Composition

The catalytic properties of Ni (4 and 10 wt%) supported on both La2O3 and ZrO2 were investigated for the methane steam reforming reaction between 475℃ and 700℃ at atmospheric pressure. The catalysts were prepared by the impregnation method and characterized by several techniques (atomic absorption, BET method, X-ray diffraction and TG-TPO). The catalytic activity of Ni/support systems strongly depends on both of the nature and physico-chemical properties of the support. No deactivation was observed in catalytic systems, whatever the reaction temperature indicating high stability of the catalyst.

Effects of the Supports on Activity of Supported Nickel Catalysts for Hydrogenation of m-Dinitrobenzene to m-Phenylenediamine

The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.

Study on the Reaction Mechanism for Carbon Dioxide Reforming of Methane over supported Nickel Catalyst

The adsorption and dissociation of methane and carbon dioxide for reforming on nickel catalyst were extensively investigated by TPSR and TPD experiments. It showed that the decomposition of methane results in the formation of at least three kinds of surface carbon species on supported nickel catalyst, while CO2 adsorbed on the catalyst weakly and only existed in one kind of adsorption state. Then the mechanism of interaction between the species dissociated from CH4 and CO2 during reforming was proposed.

Ethylene Polymerization with Palygorskite Supported Nickel-Diimine Catalyst

A nickel-diimine catalyst [N, N'-bis(2,6-diisopropylphenyl)-1,4-diaza-2,3-dimethyl-1, 3-butadiene nickel dibromide, DMN] was supported on palygorskite clay for ethylene slurry polymerization. The effect of supporting methods on the catalyst impregnation was studied and compared. Pretreatment of the support with methylalumi-noxane (MAO) followed by DMN impregnation gave higher catalyst loading and catalytic activity than the direct impregnation of DMN. Catalyst activity as high as 5.42×105g PE·molNi-1·h-1 was achieved at ethylene pressure of 6.87×105 Pa and polymerization temperature of 20℃. In particular, the morphological change of the support during MAO treatment was characterized and analyzed. It was found that nano-fiber clusters formed during the support pretreatment, which increased the surface area of the support and favored the impregnation of the catalyst. The investigation of polymerization behavior of supported catalyst revealed that the polymerization rate could be kept at a relatively high level for a long time, different from the homogeneous catalyst. By analyzing the SEM photographs of the polymer produced by the supported catalyst, the morphological evolution of polymer particles was preliminarily studied.

SILICA-SUPPORTED NICKEL AND ZIRCONIUM CATALYSTS FOR BRANCHED POLYETHYLENE

8-Aminoquinoline nickel dichloride and bis(cyclopentadienyl)zirconium dichloride (Cp_2ZrCl_2) were supportedsimultaneously on silica to produce branched polyethylene successfully by combined polymerization. The supportedpolymerization results showed that the molecular weight of polyethylene increased while the molecular weight distributionbecame wider and the molecular chains of oligomers remaning in the final solution became shorter as compared to theoligomers obtained in polymerization processes with pure 8-aminoquinoline nickel dichloride catalysis, as well as theCp_2ZrCl_2 and nickel combination system. With decreasing amount of Ni catalyst in the supported catalyst, the molecular chains of oligomers in the resulting solution became shorter, while α-olefin selectivity increased.

Effect of initial nickel particle size on stability of nickel catalysts for aqueous phase reforming

The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.

Influence of the synthesis method parameters used to prepare nickel-based catalysts on the catalytic performance for the glycerol steam reforming reaction

The influence of the synthesis method parameters used to prepare nickel-based catalysts on the catalytic performance for the glycerol steam reforming reaction was studied.A series of Al2O3-supported Ni catalysts were synthesized,with nickel loading of 8 wt%,using the incipient wetness,wet impregnation,and modified equilibrium deposition filtration methods.The catalysts＇ surface and bulk properties were determined by inductively coupled plasma（ICP）,N2 adsorption-desorption isotherms（BET）,X-ray diffraction（XRD）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,and temperature-programmed reduction（TPR）.Used catalysts were characterized by techniques such as elemental analysis and SEM in order to determine the level of carbon that was deposited and catalyst morphology.The results indicated that the synthesis method affected the textural,structural and surface properties of the catalysts,differentiating the dispersion and the kind of nickel species on alumina＇s surface.The formation of nickel aluminate phases was confirmed by the XRD and TPR analysis and the β-peak of the Ni/Al-edf catalyst was higher than in the other two catalysts,indicating that the nickel aluminate species of this catalyst were more reducible.Both Ni/Al-wet and Ni/Al-edf catalysts showed increasing CO2 selectivities and approximately constant CO selectivities for temperatures above 550℃,indicating that these catalysts successfully catalyze the water gas shift reaction.It was also confirmed that the Ni/Al-edf catalyst had the highest values for glycerol to gaseous products conversion,hydrogen yield,allyl alcohol,acetaldehyde,and acetic acid selectivities at 650℃ and the lowest carbon deposition of the catalysts tested.The correlation of the catalysts＇ structural properties,dispersion and reducibility with catalytic performance reveals that the EDF method can provide catalysts with higher specific surface area and active phase＇s dispersion,that are easier to reduce,more active and selective to hydrogen production,and more resistant to carbon deposition.

High activity of a Pt decorated Ni/C nanocatalyst for hydrogen oxidation

The Pt decorated Ni/C nanocatalysts were prepared for hydrogen oxidation reaction（HOR） in fuel cell.By regulating the contents of Pt and Ni in the catalyst,both the composition and the structure affected the electrochemical catalytic characteristics of the Pt-Ni/C catalysts.When the Pt mass content was 3.1% percent and that of Ni was 13.9% percent,the Pt-Ni/C-3 catalyst exhibited a larger electrochemically active surface area and a higher exchange current density toward HOR than those of pure supported platinum sample.Our study demonstrates a feasible approach for designing the more efficient catalysts with lower content of noble metal for HOR in fuel cell.

Methanation of carbon dioxide on Ni/ZrO_2-Al_2O_3 catalysts:Effects of ZrO_2 promoter and preparation method of novel ZrO_2-Al_2O_3 carrier

The novel nickel-based catalysts with a nickel content of 12 wt% were prepared with the zirconia-alumina composite as the supports. The new carriers, ZrO2 improved alumina, were synthesized by three methods, i.e., impregnation-precipitation, co-precipitation, and impregnation method. The catalytic properties of these catalysts were investigated in the methanation of carbon dioxide, and the samples were characterized by X-ray diffraction （XRD）, X-ray photoelectron spectroscope （XPS）, temperature-programmed reduction （TPR） and temperature-programmed desorption （TPD） techniques. The new catalysts showed higher catalytic activity and better stability than Ni/γ-Al2O3. Furthermore, as a support for new nickel catalyst, the ZrO2-Al2O3 composite prepared by the impregnation-precipitation method was more efficient than the other supports in the methanation of carbon dioxide. The highly dispersed zirconium oxide on the surface of γ-Al2O3 inhibited the formation of nickel aluminate-like phase, which was responsible for the better dispersion of Ni species and easier reduction of NiO species, leading to the enhanced catalytic performance of corresponding catalyst.

Effects of preparation conditions of Au/FeO_x /Al_2O_3 catalysts prepared by a modified two-step method on the stability for CO oxidation

Composite oxide FeO x /Al 2 O 3 -supported gold catalysts were prepared by a modified two-step method. The effects of preparation conditions on the initial catalytic activity and long-time stability were studied for CO oxidation. XRD, XPS and in situ FTIR were employed to investigate the state of FeO x and the species on the catalyst surface. The results showed that Au/FeO x /Al 2 O 3 catalysts prepared by this method exhibited high activity and high stability in a wide pH value range. Calcination pretreatment was proved to be beneficial to improving the activity and stability. The beneficial effects of FeO x acting as a structural promoter could be ascribed to the ability to supply active oxygen species. As the precursor of FeO x , Fe（NO 3 ） 3 is superior to FeCl 3 for obtaining higher stability.

Ethanol steam reforming over Ni-Cu/Al_2O_3-M_yO_z (M = Si, La, Mg,and Zn) catalysts

Ni-based catalysts doped with copper additives were studied on their role in ethanol steam reforming reaction. The effects of Cu content, support species involving Al2O3-SIO2, Al2O3-MgO, Al2O3-ZnO, and Al2O3-La2O3, on the catalytic performance were studied. Characterizations by TPR, XRD, NH3-TPD, XPS, and TGA indicated that catalysts 30Ni5Cu/Al2O3-MgO and 30Ni5Cu/Al2O3-ZnO have much higher H2 selectivity than 30Ni5Cu/Al2O3-SiO2, as well as good coke resistance. H2 selectivity for 30Ni5Cu/Al2O3-MgO catalyst was 73.3% at 450 ℃ and increased to 94.0% at 600℃, whereas for 30Ni5Cu/Al2O3-ZnO catalyst, the H2 selectivity was 63.6% at 450 ℃ and 95.2% at 600℃. TheseAl2O3-MgO and Al2O3-ZnO supported Ni-Cu bimetallic catalysts may have important applications in the production of hydrogen by ethanol steam reforming reactions.

Effect of boron addition on the MoO_3/CeO_2–Al_2O_3 catalyst in the sulfur-resistant methanation

The effect of boron on the performance of MoO_3/CeO_2–Al_2O_3 catalysts, which were prepared with impregnation method, was investigated. The catalysts were characterized with N_2 adsorption–desorption, XRD, H_2-TPR, and NH_3-TPD, and were tested in sulfur-resistant methanation. The results indicated that the MoO_3/CeO_2–Al_2O_3 catalysts modified by boron showed higher catalytic performance in sulfur-resistant methanation. The CO conversion increased from 47% to 62% with 0.5 wt% boron content. When the content of boron was under 0.5 wt%, the results suggested there was an increase in the amorphous form of MoO_3 caused by the generation of weak and intermediate acid sites, which had weakened the interaction between the active components and supports. While, the catalyst added 2.0 wt% boron showed the strong acid sites and the largest crystalline size resulting in the uneven distribution of ceria.

Modification of Ni/SiO_2 Catalysts by Means of a Novel Plasma Technology

Atmospheric high frequency cold plasma jet was applied to modify Ni/SiO2 catalysts. The catalysts prepared by two different methods with plasma jet were compared with conventional catalysts. BET, XRD, H2-TPD and high-resolution transmission electron microscopy （HRTEM） were used to characterize these catalysts. The results showed that the catalyst prepared with plasma jet had higher nickel dispersion, larger specific surface area and smaller nickel particle size, about 5 nanometres. Detailed analyses revealed that improved structure and characteristic of the plasma catalyst were benefited from the large amount of hydrogen atoms in the plasma jet, by which the catalyst reduction can be easily achieved in shorter period of time at lower temperature, thus avoiding sintering and conglomeration of the active particles and the support. The activity of catalysts was investigated in the methane reforming with CO2. It is shown that the conversions of CH4 and CO2, the yields of H2 and CO were all significantly increased for the plasma catalysts.

Monodisperse Nickel Nanoparticles Supported on SiO_(2) as an Effective Catalyst for the Hydrolysis of Ammonia-Borane

Monodisperse Ni nanoparticles(NPs)have been synthesized by the reduction of nickel(Ⅱ)acetylacetonate with the borane–tributylamine complex in a mixture of oleylamine and oleic acid.These Ni NPs are an active catalyst for the hydrolysis of the ammonia–borane(AB,H3N⋅BH3)complex under ambient conditions and their activities are dependent on the chemical nature of the oxide support that they were deposited on.Among various oxides(SiO_(2),Al_(2)O_(3),and CeO_(2))tested,SiO_(2)was found to enhance Ni NP catalytic activity due to the etching of the 3.2 nm Ni NPs giving Ni(Ⅱ)ions and the subsequent reduction of Ni(Ⅱ)that led to the formation of 1.6 nm Ni NPs on the SiO_(2)surface.The kinetics of the hydrolysis of AB catalyzed by Ni/SiO_(2)was shown to be dependent on catalyst and substrate concentration as well as temperature.The Ni/SiO_(2)catalyst has a turnover frequency(TOF)of 13.2 mol H_(2)⋅(mol Ni)^(–1)⋅min^(–1)—the best ever reported for the hydrolysis of AB using a nickel catalyst,an activation energy of 34 kJ/mol±2 kJ/mol and a total turnover number of 15,400 in the hydrolysis of AB.It is a promising candidate to replace noble metals for catalyzing AB hydrolysis and for hydrogen generation under ambient conditions.

Effects of supports and combined process on hydrogen purification over nickel supported catalysts

Hydrogen purification must be done to meet the different purposes of hydrogen utilization.In the present work,it is confirmed that the catalyst Ni/CeO2 has the highest activity for total methanation(Total MET) of CO and CO2,and is thus most suitable for hydrogen purification for ammonia synthesis.While,the catalyst Ni/ZrO2 appears the best one for selective methanation of CO(CO-SMET) in the H2-rich gas to produce clean fuel for proton exchange membrane fuel cell(PEMFC).In spite of this,the catalyst Ni/ZrO2 without adding chlorine ions as promoter is not yet capable of removing the CO in the reformate gas to below 10 ppm in a wide reaction temperature range by the way of CO-SMET.Adding chlorine ions as promoter is indeed not favorable for practical application due to its gradual loss in the catalytic reaction as proved in our previous work.Therefore,a step to decrease CO2 concentration(called as de-CO2 step) is suggested to be set prior to the CO-SMET step in this work.It is proved that such combination of de-CO2 step and CO-SMET step is efficient to achieve a deep removal of CO to below 10 ppm with a high selectivity more than 50% in a wide reaction temperature range of 220-280℃over the catalyst Ni/ZrO2 without adding chlorine ions as promoter.The combined process has potential for practical application,at least in the large-scale power plant of PEMFC.

Supporting of Nickel(Ⅱ) Acenaphthenediimine with Free Amino Group for Ethylene Polymerization

Bis （4-（4-amino-3, 5-diethylbenzyl）-2, 6-diethylphenylimino） acenaphthene] di- chloronickel （NiLCl2） was prepared and supported on SiO2 modified by methyl trichlorsilane（S-1） and on SiO2-MgCl2/TiCl4 （S-2） respectively. Two supported catalysts S-1 and S-2 used as catalysts for ethylene polymerization were studied and the influences of various polymerization conditions, including the polymerization temperature, cocatalysts, Al/Ni molar ratio on the catalytic activity, branching degree and branch length of PE were also investigated. The experimental results show that the supported catalysts exhibit higher catalytic activity for ethylene polymerization, the highest catalytic activity of S-1 using AlEt2Cl as cocatalyst at 50 ℃, reaching 5.8×10^5gPE/molNi·h, and needed lower Al/Ni molar ratio compared to homogeneous analogue.

A review on transition metal oxides based photocatalysts for degradation of synthetic organic pollutants

This review provides insight into the current research trend in transition metal oxides(TMOs)-based photocatalysis in removing the organic colouring matters from water.For easy understanding,the research progress has been presented in four generations according to the catalyst composition and mode of application,viz:single component TMOs(the firstgeneration),doped TMOs/binary TMOs/doped binary TMOs(the second-generation),inactive/active support-immobilized TMOs(the third-generation),and ternary/quaternary compositions(the fourth-generation).The first two generations represent suspended catalysts,the third generation is supported catalysts,and the fourth generation can be suspended or supported.The review provides an elaborated comparison between suspended and supported catalysts,their general/specific requirements,key factors controlling degradation,and the methodologies for performance evaluation.All the plausible fundamental and advanced dye degradation mechanisms involved in each generation of catalysts were demonstrated.The existing challenges in TMOs-based photocatalysis and how the researchers approach the hitch to resolve it effectively are discussed.Future research trends are also presented.

水热法制备Ni/CeO_(2)-Al_(2)O_(3)及催化乙炔选择性加氢

首先,采用水热法制备了不同CeO_(2)质量分数(x%)的xCeO_(2)-Al_(2)O_(3)载体;然后,采用初湿浸渍法制备了Ni质量分数为2%的Ni/xCeO_(2)-Al_(2)O_(3),以乙炔选择性加氢制乙烯反应为探针反应,结合XRD、SEM、H_(2)-TPR、BET、XPS、NH_(3)-TPD、TG评价了Ni/xCeO_(2)-Al_(2)O_(3)催化性能。结果表明,Ni/5CeO_(2)-Al_(2)O_(3)表现出最佳的催化性能,在280℃下,乙炔转化率为99.7%,乙烯选择性为94.9%。Ni/5CeO_(2)-Al_(2)O_(3)具有最大的比表面积(164.2 m^(2)/g)和孔径(7.2 nm),适当的氧空位含量〔9.2%,即Ce^(3+)峰面积/(Ce^(3+)峰面积+Ce^(4+)峰面积),下同〕。CeO_(2)的添加减弱了Ni/Al的强相互作用,减少了惰性NiAl2O4尖晶石相的生成,有效提升了催化剂的活性、选择性和稳定性。在30 h的反应时间内,乙炔转化率降至90.0%,原因在于反应过程中造成的炭沉积降低了Ni/5CeO_(2)-Al_(2)O_(3)的比表面积(151.5 m^(2)/g)和孔径(6.6 nm)。

不同配体修饰的UiO-66-X/ZnIn_(2)S_(4)(X=H、NH_(2)、(OH)_(2)、Br)负载型催化剂的光催化性能研究

通过水热法制备了不同配体修饰的UiO-66-X/ZnIn_(2)S_(4)(X=H、NH_(2)、(OH)_(2)、Br)负载型光催化剂,并采用傅里叶红外光谱仪、X射线衍射仪、扫描电子显微镜、紫外-可见漫反射光谱仪、光致发光光谱仪和电化学工作站对样品进行表征,分析了不同配体修饰方案对UiO-66-X/ZnIn_(2)S_(4)光催化性能的影响。以罗丹明B(RhB)和甲基橙(MO)溶液为目标污染物,探究不同修饰基团的电子效应对复合材料吸附性能和光催化性能的影响。结果表明:配体修饰后的ZU-(OH)_(2)/GF对阳离子染料RhB的吸附效率最好,在30 min时吸附效率为46.8%,反之,所有修饰后的复合材料对阴离子染料MO的吸附性能均低于未修饰的复合材料。在模拟太阳光照射下,所有复合材料经过配体修饰后的光催化性能都得到明显提升,其中ZU-(OH)_(2)/GF在150 min后对RhB的降解率高达99.0%。经过连续5次循环后,对RhB的去除率均保持在98%以上。这归因于配体修饰可以有效增强复合材料的光吸收性能,其中给电子基团还可以使复合材料活性中心的电子云密度增大,有效促进光生电子-空穴的分离和转移。