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甲烷热裂解制氢并生成高附加值的纳米碳材料,被认为是极具发展前景的氢气生产途径,但高性能催化剂的研发仍存在诸多挑战.我们选择多种载体(TS-1、 IM-5、 Y、介孔SiO2、 γ-Al2O3、 CNTs),采用浸渍法制备Ni-Cu负载催化剂,通过低温N2吸附-脱附、 XRD、 SEM和H2-TPR等系列表征方法对样品进行分析,考察不同载体对催化剂甲烷裂解制氢和纳米碳材料的影响.实验结果发现,分子筛载体独特的孔道结构有利于金属颗粒的分散,能有效避免反应中界面效应导致的催化剂失活,可提高催化剂反应活性并延长反应寿命,也显著提高了其碳产率.其中以IM-5分子筛为载体的催化剂表现最佳,在反应温度为700℃时, NiCu/IM-5催化剂甲烷转化率高达80%,氢气选择性达100%,反应400 min后活性未见明显降低. NiCu/IM-5催化剂碳产率高达1 446 gC/gcat,是NiCu/SiO2催化剂的5.7倍, NiCu/γ-Al 相似文献
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对流化床中甲烷裂解制氢与催化剂再生过程进行了研究。选用25Ni/CuAl2O3和75Ni/CuAl2O3两种催化剂,分别在500℃和650℃进行甲烷裂解制氢与催化剂再生,反应与再生过程的温度与时间保持相同,催化剂再生时采用空气进行再生,气体流量均为370mL/min(STP)。实验结果表明,镍质量分数较低时催化剂表现出较好的稳定性,温度增加催化剂的稳定性降低。甲烷转化率随操作周期呈下降趋势,在500℃制氢与再生操作达到第五周期时,甲烷转化率趋于稳定。对切换时间的影响研究表明,切换时间存在一个最佳值,即切换5min时甲烷裂解制氢效率最高。对生成碳产品进行了XRD和TEM表征,并对实验结果进行了讨论。 相似文献
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构建低碳绿色能源体系是全世界追求的目标.氢气具有能量密度高、零碳排放的优势,是理想的清洁能源.目前市场上95%以上的氢气来自于与化石燃料相关的工艺,如煤气化、甲烷蒸汽重整等方法,在制氢过程中不可避免地会排放大量的温室气体.电解水制氢具有产氢纯度高、工艺简单、转换效率高等优点,还可直接与可再生能源(如太阳能、风能等)耦合,是一种很有前景的绿色制氢技术.碱性电解水,由于廉价的非贵金属基材料(如Fe、Co、Ni、Cu等)可以在电解槽中很好地工作,展现出了良好的应用前景.为了进一步提高非贵金属电催化剂分解水的催化活性,科研人员从增加活性位点数量和提高单个活性位点的本征活性两方面着手,发展新的高效电催化剂.独特的纳米结构设计能够增加催化剂的活性位点数量,进而提高催化剂的催化活性,但催化性能的提高程度有限.增加单个活性位点的本征活性是从本质上提高催化剂活性的另一种有效策略.其中,异质原子修饰是提高催化剂本征活性最有效的方法之一,它可以通过调节催化剂的物理化学性质来提高催化剂的本征活性,包括诱导相变、提高电导率、调整电子密度和建立双催化位点等.本文基于电解水析氢反应(HER)和析氧反应(OER)在碱... 相似文献
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CO2甲烷化反应是一个复杂的多相催化过程,在反应过程中会产生各种各样的中间体,其反应路径目前还存在许多争议和矛盾。深入系统地研究CO2甲烷化反应中催化剂表面中间体的演变过程,可以进一步从机理的角度优化催化剂的设计方案,提高催化性能。本工作主要基于原位红外光谱表征技术,总结梳理了最近关于CO2甲烷化反应路径研究的相关工作,着重探讨了负载型催化剂的活性金属、载体、助剂、合成方法等因素对CO2甲烷化反应路径的影响以及由此对催化剂性能所产生的积极效果。同时针对现阶段所面临的争论点,即反应气CO2与H2的活化位点、催化剂的活性位点以及未来可行的研究方法进行了详细论述。 相似文献
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采用化学湿法共沉淀制备了Cu和不同稀土(RE=La,Ce,Nd,Y)改性的甲烷分解制氢Ni-Al催化剂,并对催化剂进行了BET,XRD,TPR,SEM,TEM等技术表征和催化制氢性能评价.研究结果表明,稀土是比铜更理想的改性剂,稀土改性对催化剂具有良好热稳定作用,并提高催化制氢高温活性,La改性效果最佳;稀土改性催化剂具有较高的制氢稳定性能,700℃下连续制氢12 h后未出现失活.稀土改性可促进纳米碳管形成,大幅改善纳米碳形貌,并对固态碳有较强的抑制作用. 相似文献
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以柠檬酸法制备的Fe-MgO、Co-MgO和Ni-MgO为催化剂,CH4为碳源气,H2为还原气,在873、973和1073 K制备出碳纳米管,通过TEM和拉曼光谱表征,讨论了催化剂、制备温度、反应时间等因素对碳纳米管形貌、产率和内部结构的影响.结果表明:不同的催化剂在相同的温度下制备的碳纳米管的形态和内部结构有很大的差异.其中Fe-MgO催化剂制备的碳纳米管管径粗,且大小不均匀,而Ni-MgO催化剂制备的碳纳米管管径较细、较均匀.碳纳米管的产率随着裂解温度的变化而改变.Fe-MgO催化剂制备碳纳米管的产率随制备温度的升高而提高,而Ni-MgO催化剂制备碳纳米管的产率随制备温度的升高而降低.Fe-MgO催化剂制备碳纳米管,在1073K甚至更高的制备温度才能达到其最高产率.Co-MgO催化剂制备碳纳米管的产率在973 K左右产率较高,而用Ni-MgO催化剂制备碳纳米管,则在873 K甚至更低的制备温度就能达到最高产率.反应时间与碳纳米管的产率不成正比,有一最佳反应时间,如Ni-MgO催化剂的最佳反应时间为2 h. 相似文献
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采用非晶态多核配合的方法合成了La1-xCuxMnO3(x=0、0.05、0.1、0.2、0.3、0.4、0.5)系列催化剂, 并用X射线衍射(XRD)、透射电镜(TEM)、比表面测定仪(BET)等手段对催化剂的微观结构进行了表征. 研究了Cu掺杂对钙钛矿结构及其对CO催化氧化发光性能及催化氧化CO、CH4性能的影响规律. 结果表明, 当x≤0.1 时, Cu掺杂仍可形成单相的钙钛矿结构; 当x>0.1时, 过量掺杂的Cu以CuO杂相存在. Cu掺杂可改善La1-xCuxMnO3催化剂对CO和CH4的催化氧化活性. 经700 ℃焙烧3 h制备的La0.9Cu0.1MnO3催化剂具有最高CO催化氧化活性(T100%=170 ℃), 该结果与CO催化氧化发光结果一致.而La0.95Cu0.05MnO3催化剂对CH4的催化氧化活性最高(T95%=705 ℃). 相似文献
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富氧条件下具有FAU和BEA两种拓扑结构的CoH-FBZ选择催化CH4还原NO,显示出较CoH Y和CoH Beta机械混合催化剂更好的催化活性。应用吸附和程序升温脱附(TPD)方法研究了NO和NO+O2与催化剂表面间的相互作用。结果表明,载体的拓扑结构直接影响N、O物种在催化剂表面的稳定性。NO与O2在CoH-FBZ表面形成的吸附态 NOy及NO在CoH-FBZ表面形成的吸附态相对更稳定。CoH-FBZ的NO+O2-TPD脱附曲线在630K和660K形成两个NO2脱附峰,表明在CoH-FBZ表面形成了新的 NOy吸附中心,即可能有新的Co位产生,该新Co位与沸石催化剂CoH-FBZ中新强酸位协同作用,使CoH-FBZ表现出新的CH4-SCR催化特性。 相似文献
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Fourier‐transform infrared spectroscopy has been employed to investigate the adsorption and photo‐oxidation of CH4 over powdered TiO2. The interaction between the CH4 and TiO2 surface is weak. It is found that no CH4 molecules are adsorbed on the surface at 35 °C in a vacuum. Under UV irradiation, CH4 decomposes to form CO(a), CO2(g), H20(a), and HCOO(a) in the presence of O2. The photoreaction rate is retarded and only small amounts of CO(a) and HCOO(a) are formed in the absence of O2. It is observed that the oxygen atoms of O2 are incorporated into these photoproducts as 18O2 is used. The major 18O‐containing products are C18O(a), C18O2(g), H2 18O(a), HC16O18O(a), and HC18O18O(a) after 180 min UV irradiation. However, the extent of 18O incorporating into the adsorbed formate is dependent on UV irradiation time. In the early stage of UV irradiation HC16O16O(a) is the major formate form indicating the involvement of TiO2 lattice oxygens for its formation, but HC18O18O(a) becomes the major one after 180 min indicating the involvement of 18O2. Formate on TiO2 further photodecomposes to CO2(g), but not to CO(a). CO(a) formation is directly from CH4 photodecomposition with the participation of TiO2 lattice oxygens and O2. 相似文献
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在B3LYP/6-311 + G(2d, 2p)水平上计算了MgO + CH_4 → Mg+CH_3OH反应的 单态势能曲线。结果发现MgO和CH_4发生相互作用,首先形成两种类型的分子-分子 复合物(MgOCH_4和OMgCH_4);分子-分子复合物OMgCH_4能发生进一步转化,即 MgO插入到CH_4的C-H键中,产生中间体HOMgCH_3,此中间体在本反应中是能量上最 稳定的构型;它还有可能进一步发生反应,产生原子-分子复合物MgCH_3OH,但其 活化能太高,为299.8kJ·mol~(-1),是整个反应的速率控制步骤;最后一步是 MgCH_3OH放出CH_3OH分子,整个反应放热146.1 kJ·mol~(-1)。 相似文献
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Computational fluid dynamics (CFD) modeling of the complex processes that occur within the burner of a gas turbine engine has become a critical step in the design process. However, due to computer limitations, it is very difficult to completely couple the fluid mechanics solver with the full combustion chemistry. Therefore, simplified chemistry models are required, and the topic of this research was to provide reduced chemistry models for CH4/O2 gas turbine flow fields to be integrated into CFD codes for the simulation of flow fields of natural gas-fueled burners. The reduction procedure for the CH4/O2 model utilized a response modeling technique wherein the full mechanism was solved over a range of temperatures, pressures, and mixture ratios to establish the response of a particular variable, namely the chemical reaction time. The conditions covered were between 1000 and 2500 K for temperature, 0.1 and 2 for equivalence ratio in air, and 0.1 and 50 atm for pressure. The kinetic time models in the form of ignition time correlations are given in Arrhenius-type formulas as functions of equivaience ratio, temperature, and pressure; or fuel-to-air ratio, temperature, and pressure. A single ignition time model was obtained for the entire range of conditions, and separate models for the low-temperature and high-temperature regions as well as for fuel-lean and rich cases were also derived. Predictions using the reduced model were verified using results from the full mechanism and empirical correlations from experiments. The models are intended for (but not limited to) use in CFD codes for flow field simulations of gas turbine combustors in which initial conditions and degree of mixedness of the fuel and air are key factors in achieving stable and robust combustion processes and acceptable emission levels. The chemical time model was utilized successfully in CFD simulations of a generic gas turbine combustor with four different cases with various levels of fuel-air premixing. 相似文献
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On the Knowledge of the New Ionic Ozonides P(CH3)4O3 and As(CH3)4O3 P(CH3)4O3 and As(CH3)4O3 were prepared via ion exchange in liquid ammonia and characterized by X-ray-powder, IR, MS and DTA techniques. P(CH3)4O3 and As(CH3)4O3 are isotypic and have a wurtzite-like arrangement of ions with rotationally disordered O3?. (Powder data: P63mc; P(CH3)4O3: a = 687.8(2), c = 964.6(3) pm; As(CH3)4O3: a = 708.6(1), c = 991.0(3) pm). As(CH3)4O3 shows a displacive phase transition at ?135°C. The low temperature phase is orthorhombic (a = 715.8(7), b = 1 209(1), c = 943.3(1) pm). 相似文献
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Three-Dimensional ab initio Potential Energy Surface and Predicted Spectra for the CH4-Ne Complex
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We present a new three-dimensional potential energy surface (PES) for CH\begin{document}$ _4 $\end{document} -Ne complex. The electronic structure computations were carried out using the coupled-cluster method with singles, doubles, and perturbative triples [CCSD(T)], the augmented correlation-consistent aug-cc-pVXZ (X = T, Q) basis sets were employed with bond functions placed at the mid-point on the intermolecular axis, and the energies obtained were then extrapolated to the complete basis set limit. Analytic intermolecular PES is obtained by least-squares fitting to the Morse/Long-Range (MLR) potential function form. These fits to 664 points have root-mean-square deviations of 0.042 cm\begin{document}$ ^{-1} $\end{document} . The bound rovibrational levels are calculated for the first time, and the predicted infrared spectra are in good agreement with the experimental values. The microwave spectra for CH\begin{document}$ _4 $\end{document} -Ne dimer have also been predicted for the first time. The analytic PES can be used for modeling the dynamical behavior in CH\begin{document}$ _4 $\end{document} -(Ne)\begin{document}$ _N $\end{document} clusters, and it will be useful for future studies of the collision-induced-absorption for the CH\begin{document}$ _4 $\end{document} -Ne dimer. 相似文献