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1.
Single-wall carbon nanotubes (SWNTs) with high surface area were synthesized over nanoporous Co-Mo/MgO by a chemical vapor deposition (CVD) method. The SWNTs were used as catalyst support for selective hydrogenation of syngas to hydrocarbons. Here an extensive study of Fischer-Tropsch synthesis (FTS) on CNT-supported cobalt catalysts with different amounts of cobalt loading up to 40 wt% is reported. The catalysts were characterized by different methods including N2 adsorption-desorption, X-ray diffraction, hydrogen chemisorption, inductively coupled plasma (ICP) and temperature-programmed reduction. Enhancement of the reducibility of Co3O4 to CoO, CoO to Coo and small cobalt oxide particles, dispersion of the cobalt, and activity and selectivity of FTS were investigated and compared with a conventional support. The CNT supported catalysts achieve a high dispersion and high loading of the active metal, cobalt in particular, so that the bulk formation of cobalt metal, which tends to occur in conventional support, can be avoided. The results showed that the specific activity of CNT supported catalysts increase significantly (there is a two fold increase in CO Conversion per gram of the active metal) with respect to the conventional supported catalyst.  相似文献   

2.
Single-wall carbon nanotubes (SWNTs) with high surface area were synthesized over nanoporous Co-Mo/MgO by a chemical vapor deposition (CVD) method. The SWNTs were used as catalyst support for selective hydrogenation of syngas to hydrocarbons. Here an extensive study of Fischer-Tropsch synthesis (FTS) on CNT-supported cobalt catalysts with different amounts of cobalt loading up to 40 wt% is reported. The catalysts were characterized by different methods including N2 adsorption-desorption, X-ray diffraction, hydrogen chemisorption, inductively coupled plasma (ICP) and temperature-programmed reduction. Enhancement of the reducibility of Co3O4 to CoO, CoO to Coo and small cobalt oxide particles, dispersion of the cobalt, and activity and selectivity of FTS were investigated and compared with a conventional support. The CNT supported catalysts achieve a high dispersion and high loading of the active metal, cobalt in particular, so that the bulk formation of cobalt metal, which tends to occur in conventional support, can be avoided. The results showed that the specific activity of CNT supported catalysts increase significantly (there is a two fold increase in CO Conversion per gram of the active metal) with respect to the conventional supported catalyst.  相似文献   

3.
SiO(2) supported cobalt (Co) catalyst could be partially reduced and anchored by unreduced Co ions during a carbon monoxide (CO) chemical vapor deposition (CVD) process. This resulted in the formation of sub-nanometre metallic Co clusters catalyzing the growth of single-walled carbon nanotubes (SWNTs) with a narrow diameter distribution.  相似文献   

4.
Atomically dispersed and nitrogen coordinated single metal sites (M-N-C, M=Fe, Co, Ni, Mn) are the popular platinum group-metal (PGM)-free catalysts for many electrochemical reactions. Traditional wet-chemistry catalyst synthesis often requires complex procedures with unsatisfied reproducibility and scalability. Here, we report a facile chemical vapor deposition (CVD) strategy to synthesize the promising M-N-C catalysts. The deposition of gaseous 2-methylimidazole onto M-doped ZnO substrates, followed by an in situ thermal activation, effectively generated single metal sites well dispersed into porous carbon. In particular, an optimal CVD-derived Fe-N-C catalyst exclusively contains atomically dispersed FeN4 sites with increased Fe loading relative to other catalysts from wet-chemistry synthesis. The catalyst exhibited outstanding oxygen-reduction activity in acidic electrolytes, which was further studied in proton-exchange membrane fuel cells with encouraging performance.  相似文献   

5.
以Co和Ni为催化剂活性组分、活性炭为载体,通过饱和浸渍法制得非贵金属催化剂,采用XRD、SEM和TPD对催化剂性能进行表征,考察了该催化剂用于富氢气中CO选择性氧化活性及H2O或/和CO2对催化性能的影响。研究结果表明,催化剂以NiO和高分散的Co3O4为主要物相,催化剂吸附O2的能力随着金属氧化物负载量的增加而增加,且催化剂对O2分子的吸附能力明显强于CO2分子。金属氧化物负载量为35%的催化剂表现出较高的CO选择性氧化活性和选择性,在低于473K时O2氧化选择性达50%以上,此时可将CO浓度降到40×10-6以下,达到燃料电池对氢燃料气的要求。同时,催化剂表现出较强的抗水蒸气和CO2的能力。  相似文献   

6.
We have studied the compatibility of various catalysts for ethylene and ethanol chemical vapor deposition (CVD) syntheses of single-walled carbon nanotubes (SWNTs) on Si substrates. A strong selectivity between the catalyst elemental species and carbon source was found; SWNT yield for Fe (Co) catalysts was much higher for ethylene (ethanol) CVD than for ethanol (ethylene) CVD. This strong and completely opposite selectivity implies significantly different SWNT growth mechanisms for ethanol and ethylene CVD on Si substrates.  相似文献   

7.
An extensive study of Fischer-Tropsch (FT) synthesis on cobalt nano particles supported on γ-alumina and carbon nanotubes (CNTs) catalysts is reported.20 wt% of cobalt is loaded on the supports by impregnation method.The deactivation of the two catalysts was studied at 220 C,2 MPa and 2.7 L/h feed flow rate using a fixed bed micro-reactor.The calcined fresh and used catalysts were characterized extensively and different sources of catalyst deactivation were identified.Formation of cobalt-support mixed oxides in the form of xCoO yAl2O3 and cobalt aluminates formation were the main sources of the Co/γ-Al2O3 catalyst deactivation.However sintering and cluster growth of cobalt nano particles are the main sources of the Co/CNTs catalyst deactivation.In the case of the Co/γ-Al2O3 catalyst,after 720 h on stream of continuous FT synthesis the average cobalt nano particles diameter increased from 15.9 to 18.4 nm,whereas,under the same reaction conditions the average cobalt nano particles diameter of the Co/CNTs increased from 11.2 to 17.8 nm.Although,the initial FT activity of the Co/CNTs was 26% higher than that of the Co/γ-Al2O3,the FT activity over the Co/CNTs after 720 h on stream decreased by 49% and that over the Co/γ-Al2O3 by 32%.For the Co/γ-Al2O3 catalyst 6.7% of total activity loss and for the Co/CNTs catalyst 11.6% of total activity loss cannot be recovered after regeneration of the catalyst at the same conditions of the first regeneration step.It is concluded that using CNTs as cobalt catalyst support is beneficial in carbon utilization as compared to γ-Al2O3 support,but the Co/CNTs catalyst is more susceptible for deactivation.  相似文献   

8.
We report a simple and efficient chemical vapor deposition (CVD) process that can grow oriented and long single-walled carbon nanotubes (SWNTs) using a cobalt ultrathin film ( approximately 1 nm) as the catalyst and ethanol as carbon feedstock. In the process, millimeter- to centimeter-long, oriented and high-quality SWNTs can grow horizontally on various flat substrate surfaces, traverse slits as large as hundreds of micrometers wide, or grow over vertical barriers as high as 20 microm. Such observations demonstrate that the carbon nanotubes are suspended in the gas flow during the growth. The trace amount of self-contained water (0.2-5 wt %) in ethanol may act as a mild oxidizer to clean the nanotubes and to elongate the lifetime of the catalysts, but no yield improvement was observed at the CVD temperature of 850 degrees C. We found that tilting the substrates supporting the Co ultrathin film catalysts can grow more, longer carbon nanotubes. A mechanism is discussed for the growth of long SWNTs.  相似文献   

9.
以对苯二甲酸(H2BDC)为配体、乙酸钴为Co源、水作溶剂,通过共沉淀法合成了金属有机框架材料(Co-BDC MOFs);以其为前驱体分别在乙炔和氩气氛下采用化学气相沉积法制备了核壳结构Co@C催化剂。结合XRD、氮吸附、SEM、TEM、XPS、TGA和Raman光谱等手段对Co@C催化剂的结构和组成进行了表征,考察了该催化剂在费托合成反应中的活性及稳定性。结果表明,炭化气氛对炭层结构的石墨化程度有较大影响,而对金属Co核的物相结构和粒径影响较小;乙炔气氛有助于形成多孔的石墨炭壳,从而促进烃链的生长,Co@C-C2H2催化剂上的C5+烃产物选择性高达82.66%,反应过程中催化剂物相由单相金属Co转变为金属Co与Co2C的混合相,且无失活现象发生,表明Co2C具有较高的费托反应催化活性。  相似文献   

10.
 分别采用硝酸钴、醋酸钴、硫酸钴和氯化钴为前驱体制备了Co/SiO2催化剂,用XRD,TPR,SEM和H2-TPD等实验技术考察了钴盐前驱体对催化剂结构和二氧化碳重整甲烷反应性能的影响,重点考察了硝酸钴和醋酸钴的作用.结果表明,由醋酸钴制备的Co/SiO2催化剂有最佳的催化活性和稳定性,它在钴物种的存在状态、金属-载体相互作用、钴金属晶粒度及抗烧结、抗积炭能力等方面,均与由硝酸钴制备的Co/SiO2催化剂存在显著的差别.Co/SiO2催化剂的反应活性和稳定性分别与其金属分散度和抗烧结、抗积炭能力密切相关.  相似文献   

11.
Regular tricobalt tetraoxide (Co(3)O(4)) nanocubes with tunable sizes have been synthesized by a simple magnetic field assisted hydrothermal reaction. In contrast to other traditional methods, no surfactant is added to the reaction system, the morphology of the product is controlled by the application of an external magnetic field and the size distribution of the product is tuned by simply modifying the ratio of distilled water to ethanol in the solvent. The growth process of Co(3)O(4) nanocubes is investigated and discussed in detail. It is found that the differences in polarity and dielectric constant between distilled water and ethanol and thus the difference of cobalt coordination ions concentration in the different solvents are the major factors that determine the final size distribution of Co(3)O(4) nanocubes. Magnetic properties of Co(3)O(4) nanocubes synthesized under (MF) and not under (ZF) an external magnetic field are then investigated. It is believed that during their growth, the alignment of spins in the Co(3)O(4) particles and thus the magnetic and crystal lattices of Co(3)O(4) are influenced by the external magnetic field. Spins in MF arrange in a less-ordered manner and cannot be totally compensated by each other, therefore makes them have a stronger tendency to align into an ordered figuration, which leads to a relatively larger magnetization and higher Néel temperature (T(N)) of MF comparing to sample ZF.  相似文献   

12.
采用CO气体对NO进行选择性催化还原(CO-SCR)是一种有前景的脱硝技术.目前已报道的CO-SCR催化剂的脱硝特性主要是在无氧条件下开展的研究,考虑到实际应用情况,探究一种在有氧环境中具有较高脱硝效率的催化剂是很有必要的.作为一种新型功能性材料的金属有机骨架是脱硝催化剂的优良载体,其中ZIFs系列具有优良的性能.引入Cu对ZIF-67衍生的Co3O4/C进行改性,通过浸渍法在载体上负载铜后,热解氧化获得一系列CuOx/Co3O4/C催化剂.利用ICP、 SEM、 XRD、 TEM、 TGA、 XPS、 BET和H2-TPR等技术对催化剂的物理化学性质进行表征,结果表明,由于Cu的引入增加了表面的氧空位,改善了氧化还原能力,进而提高了催化剂脱硝活性.在制备的一系列催化剂中, 8.0 CuOx/Co3O4/C在300℃时即可达到约95%NO转化率,并且其N2选择性也达到9...  相似文献   

13.
通过催化剂将CO转化为无毒气体仍然是目前减少CO污染的主要手段.随着纳米技术的快速发展,纳米催化剂因其在催化反应中呈现出的独特结构效应(如形貌效应、尺寸效应等)而受到人们的广泛关注.已有大量研究表明,纳米Co3O4作为一种非贵金属氧化物催化剂具有强烈的催化形貌效应,展现出优异的CO低温催化活性.因此,通过合理的设计来调控催化剂粒子的形貌,从而进一步改善催化剂的性能已成为近年来催化剂领域的重要研究方向.对于Co3O4纳米催化剂的可控制备,水热法具有反应温和、操作简便和产品形貌易控等特点.早期的研究主要围绕于Co3O4形貌的可控合成以及不同形貌Co3O4催化剂对其催化活性产生的影响,较少有对其形貌形成机制的报道.特别是在水热反应中,系统研究各反应参数对催化剂各异形貌的形成影响鲜有报道.
  本文在前人的研究基础上,重点研究了水热反应过程中各主要反应参数对产品形貌控制的影响,绘制了一副不同形貌Co3O4材料的合成过程图,并研究了Co3O4纳米催化剂催化CO氧化的形貌效应.通过水热法先成功合成了三种不同形貌(纳米棒、纳米片和纳米立方)的碱式碳酸钴纳米粒子,然后将其焙烧得到了Co3O4纳米粒子.采用扫描电子显微镜(SEM),透射电子显微镜(TEM), X射线粉末衍射仪(XRD),程序升温还原(H2-TPR和CO-TPR),氮气吸附-脱附比表面积测试(BET),氧气程序升温脱附(O2-TPD), X射线光电子能谱(XPS)等表征手段研究了不同反应参数对纳米碱式碳酸钴前驱体形貌形成的作用和各异形貌Co3O4纳米粒子在催化CO氧化反应中催化性能的差异及原因.
  结果表明, Co3O4较好地继承了碱式碳酸钴的形貌,在较低温度条件下(≤140°C),钴源(CoCl2或Co(NO3)2)是影响前驱体形貌的关键因素,反应时间只对粒子的尺寸产生较大影响.低温下, CoCl2作为钴源易诱导生产纳米棒状碱式碳酸钴,而Co(NO3)2则有利于纳米片状生成.当温度高于140°C后,无论何种钴源,最终均制得纳米立方体.表面活性剂CTAB对前驱体的均一性和粒子的分散性产生重要影响,加入CTAB后得到的产品尺寸更均一,形貌更加规整.对比于其他两种形貌的样品, Co3O4纳米片显示出更好的CO催化氧化活性.
   XPS结果表明,各形貌Co3O4纳米材料的表面组成存在明显差异,活性物种Co3+含量的不同是影响催化活性差异的重要原因. Co3O4纳米片具有更多的Co3+活性位,立方纳米Co3O4表面吸附氧含量较高, Co3O4纳米棒则暴露出相对更多的Co2+.因此,在三种形貌催化剂上CO氧化反应中, Co3O4纳米片表现出最优的催化活性,纳米立方次之,而纳米棒最差. H2-TPR, CO-TPR和O2-TPD等结果也表明, Co3O4纳米片拥有更强的还原性能和脱附氧能力,其次是纳米立方Co3O4.这与XPS结果一致,证实了不同形貌Co3O4纳米催化剂上暴露活性位的数量和表面氧物种的不同是造成彼此间催化CO氧化活性差异的重要原因.此外,通过稳定性测试发现Co3O4纳米片具有较高的催化稳定性,在水蒸气存在的情况下Co3O4纳米片逐渐失活,但随后在干燥条件下其催化活性又逐渐得到恢复.  相似文献   

14.
将锌钴双掺杂的金属有机框架(MOFs)纳米颗粒(ZnCo-ZIF)与聚丙烯腈(PAN)混溶形成前驱体溶液, 通过静电纺丝与高温热化学反应, 获得了一种多孔碳纳米纤维负载的钴单原子催化剂(A-Co@PCFs). 高温热解时, 聚丙烯腈分解碳化形成碳纳米纤维主体, MOFs纳米颗粒结构坍塌伴随锌组分的挥发, 在纤维表面形成了丰富的多级孔结构. 由于碳纳米纤维和孔道结构的双重限域作用, 使钴组分不能聚集成钴纳米颗粒, 而是形成高度分散的钴单原子. 电化学测试结果表明, 该钴单原子催化剂可将CO2电还原为CO, 在-0.66 V(vs. RHE)下, CO的法拉第效率可达94%. 并且经过60 h的耐久性测试, 其催化性能没有明显的性能衰减, 显示出较高的稳定性. A-Co@PCFs的高活性与高稳定性可归因于材料的多孔结构和高度分散的钴原子, 这也使其具有代替贵金属催化剂的可能性.  相似文献   

15.
Mesoporous high surface area MCM-41 and SBA-15 type silica materials with fibrous morphology were synthesized and used as support materials for the ALCVD (atomic layer chemical vapor deposition) preparation of Co/MCM-41 and Co/SBA-15 catalysts. Co/MCM-41 and Co/SBA-15 catalysts were prepared by deposition of Co2(CO)8 from the gas phase onto the surfaces of preheated support materials in a fluidized bed reactor. For both silica materials, two different kinds of preparation methods, direct deposition and a pulse deposition method, were used. Pure silica supports as well as supported cobalt catalysts were characterized by various spectroscopic (IR) and analytical (X-ray diffraction, Brunauer-Emmett-Teller, elemental analysis) methods. MCM-41 and SBA-15 fibers showed considerable ability to adsorb Co2(CO)8 from the gas phase. For MCM-41 and SBA-15 silicas, cobalt loadings of 13.7 and 12.1 wt % were obtained using the direct deposition method. The cobalt loadings increased to 23.0 and 20.7 wt % for MCM-41 and SBA-15 silicas, respectively, when the pulse deposition method was used. The reduction behavior of silica-supported cobalt catalysts was found to depend on the catalyst preparation method and on the mesoporous structure of the support material. Almost identical reduction properties of SBA-15-supported catalysts prepared by different deposition methods are explained by the structural properties of the mesoporous support and, in particular, by the chemical structure of the inner surfaces and walls of the mesopores. Pulse O2/H2 chemisorption experiments showed catalytically promising redox properties and surface stability of the prepared MCM-41- and SBA-15-supported cobalt catalysts.  相似文献   

16.
"A series of 15%Co/Al2O3 catalysts were prepared by incipient wetness impregnation under various calcination conditions (90-500 oC), and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy experiments (XPS), temperature programmed reduction, and catalytic measurements of hydrogenation of carbon monoxide to long-chained hydrocarbons leading to clean fuels (Fischer-Tropsch synthesis). The results of XPS show the presence of incompletely decomposed cobalt nitrate for catalysts calcined at 90-200 oC, and the presence of Co3O4 for catalysts calcined at 200-500 oC. For the four alumina-supported nano cobalt catalysts with different thermal treatment (200-500 oC), XRD and XPS results illustrated that there were mainly nano Co3O4 crystalite phases of 9-10 nm and the size of cobalt nano-particles did almost not change with the different temperature of thermal treatment. This was different from that of silica-supported cobalt catalysts. The supported cobalt catalyst (CoAp340 sample) calcinated at 340 oC presented a better activity for Fischer Tropsch synthesis to clean fuels, at mild conditions like atmospheric pressure (100 kPa), 1800 mL/g/h and 190 oC; rather than high pressure (2 MPa or more)."  相似文献   

17.
The effects of the addition of manganese to a series of TiO(2)-supported cobalt Fischer-Tropsch (FT) catalysts prepared by different methods were studied by a combination of X-ray diffraction (XRD), temperature-programmed reduction (TPR), transmission electron microscopy (TEM), and in situ X-ray absorption fine structure (XAFS) spectroscopy at the Co and Mn K-edges. After calcination, the catalysts were generally composed of large Co(3)O(4) clusters in the range 15-35 nm and a MnO(2)-type phase, which existed either dispersed on the TiO(2) surface or covering the Co(3)O(4) particles. Manganese was also found to coexist with the Co(3)O(4) in the form of Co(3-x)Mn(x)O(4) solutions, as revealed by XRD and XAFS. Characterization of the catalysts after H(2) reduction at 350 degrees C by XAFS and TEM showed mostly the formation of very small Co(0) particles (around 2-6 nm), indicating that the cobalt phase tends to redisperse during the reduction process from Co(3)O(4) to Co(0). The presence of manganese was found to hamper the cobalt reducibility, with this effect being more severe when Co(3-x)Mn(x)O(4) solutions were initially present in the catalyst precursors. Moreover, the presence of manganese generally led to the formation of larger cobalt agglomerates ( approximately 8-15 nm) upon reduction, probably as a consequence of the decrease in cobalt reducibility. The XAFS results revealed that all reduced catalysts contained manganese entirely in a Mn(2+) state, and two well-distinguished compounds could be identified: (1) a highly dispersed Ti(2)MnO(4)-type phase located at the TiO(2) surface and (2) a less dispersed MnO phase being in the proximity of the cobalt particles. Furthermore, the MnO was also found to exist partially mixed with a CoO phase in the form of rock-salt Mn(1-x)Co(x)O-type solid solutions. The existence of the later solutions was further confirmed by scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) for a Mn-rich sample. Finally, the cobalt active site composition in the catalysts after reduction at 300 and 350 degrees C was linked to the catalytic performances obtained under reaction conditions of 220 degrees C, 1 bar, and H(2)/CO = 2. The catalysts with larger Co(0) particles ( approximately >5 nm) and lower Co reduction extents displayed a higher intrinsic hydrogenation activity and a longer catalyst lifetime. Interestingly, the MnO and Mn(1-x)Co(x)O species effectively promoted these larger Co(0) particles by increasing the C(5+) selectivity and decreasing the CH(4) production, while they did not significantly influence the selectivity of the catalysts containing very small Co(0) particles.  相似文献   

18.
Catalytic methane decomposition into hydrogen and carbon nanofibers and the oxidations of carbon nanofibers with CO2, H2O and O2 were overviewed. Supported Ni catalysts (Ni/SiO2, Ni/TiO2 and Ni/carbon nanofiber) were effective for the methane decomposition. The activity and life of the supported Ni catalysts for methane decomposition strongly depended on the particle size of Ni metal on the catalysts. The modification of the catalysts with Pd enhanced the catalytic activity and life for methane decomposition. In particular, the supported Ni catalysts modified with Pd showed high turnover number of hydrogen formation at temperatures higher than 973 K with a high one-pass methane conversion (>70%). However, sooner or later, every catalyst completely lost their catalytic activities due to the carbon layer formation on active metal surfaces. In order to utilize a large quantity of the carbon nanofibers formed during methane decomposition as a chemical feedstock or a powdered fuel for heat generation, they were oxidized with CO2, H2O and O2 into CO, synthesis gas and CO2, respectively. In every case, the conversion of carbon was greater than 95%. These oxidations of carbon nanofibers recovered or enhanced the initial activities of the supported Ni catalysts for methane decomposition.  相似文献   

19.
张丽娟  王自军  刘源 《分子催化》2012,26(3):204-210
采用共沉淀法制备了Co3O4/Ce0.8Pr0.2O2催化剂,并将其用于乙醇水蒸气重整制氢反应,考察了Co3O4负载量以及Pr掺杂对催化剂性能的影响.采用X射线衍射、程序升温还原、热重分析和透射电子显微镜对催化剂的结构和表面性质进行表征.结果表明,催化剂中部分Co进入到载体的晶格中,使载体发生畸变产生更多的氧空位;载体中Pr掺杂有利于生成更多的氧空位,提高了催化剂的抗积碳性能,同时Pr掺杂可以增强Co3O4与载体之间的相互作用,提高金属Co的抗烧结性能;15%Co3O4/Ce0.8Pr0.2O2催化剂具有最好的催化活性,在反应温度为400℃,空速80 000 mL/(g.h),n(H2O)∶n(EtOH)=3的条件下可将乙醇完全转化;10 h稳定性测试结果表明该催化剂具有较好的稳定性.  相似文献   

20.
《Chemical physics letters》2002,350(1-2):109-114
Single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) were synthesized on silicon substrate by the control of catalyst size, hydrocarbon species, and carbon flux through chemical vapor deposition (CVD). Catalysts for SWNTs and MWNTs could be obtained by an agglomeration of sputtered Co–Mo and pure Co thin films, respectively. The addition of Mo in the Co catalyst provides an effective nucleation site for SWNT and the low carbon flux by using methane gas in CVD reaction makes it possible to grow a single-walled structure.  相似文献   

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