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1.
通过原位引入Mg一步法合成了Mg@MCM-41复合介孔材料,并将其作为载体制备了高性能Ni基CO_2甲烷化催化剂。通过BET、XRD、TEM、CO_2-TPD、TG等手段对催化剂进行了表征分析,着重比较了Mg/Si物质的量比对于催化剂特性的影响。结果表明,当Mg/Si物质的量比为0.05时能够在不破坏孔道结构的前提下显著增加催化剂上的碱性位,有效地提高了催化剂对CO_2的吸附和活化,从而促进CO_2甲烷化反应过程中反应物的转化。实验所制得的催化剂均具有较好的热稳定性和催化反应活性,其中,Ni/0.05Mg@MCM-41在CO_2甲烷化反应表现出最优的催化性能,在320℃,1 MPa的条件下,CO_2转化率和CH_4选择性分别高达84.3%和97.8%。  相似文献   

2.
在有序介孔TiO2中原位担载了高分散的Cu(OH)2,并将其应用于炔烃的氧化偶联(Glaser)多相催化反应,该催化剂表现出很高的催化活性.Cu(OH)2为催化剂的主要活性组分,TiO2的有序介孔和较大的比表面积有利于Cu(OH)2的分散以及反应物和产物的扩散,具有重要的应用前景.  相似文献   

3.
采用一锅合成法通过调变自组装过程中硫酸和盐酸的体积比,成功制备了系列介孔SO42-/ZrO2-SiO2固体酸材料(Zr/Si物质的量为1.1).XRD、UV-Vis DRS、HR-TEM等表征结果表明,所得材料均具有高度有序的二维介孔结构及四方相氧化锆的晶体结构.氮吸附和FT-IR表征结果进一步发现,通过改变硫酸/盐酸体积比可有效调变材料比表面积、孔容、孔径及表面L酸与B酸的相对强度.与纯硅介孔分子筛SBA-15不同,此系列SO42-/ZrO2-SiO2固体酸材料均在正戊烷的异构化反应中表现出较高的催化活性和稳定性.其原因在于,在合成过程中硫酸的加入不仅促使了酸基的形成,而且稳定了催化剂的晶体结构;盐酸的存在则保持了有序的介孔结构.由此可见,混酸合成体系有望制备出结构有序、酸性可调、催化性能优越的新型催化材料,并在众多酸催化反应中取得应用.  相似文献   

4.
Dimethyl carbonate (DMC) synthesis reaction by oxidative carbonylation of methanol has been studied using vapor phase flow reaction system in the presence of Cu-based catalysts. A series of Cu-based catalysts were prepared by the conventional impregnation method using activated carbon (AC) as support. The effect of various promoters and reaction conditions on the catalytic reactivities were intensively evaluated in terms of methanol conversion and DMC selectivity. The morphological analysis by X-ray diffraction and SEM was also conducted in order to characterize the emloyed catalysts. Regardless of catalyst compositions, the optimal reaction temperature for oxidative carbonylation of methanol was found to be around 120–130°C. The reaction rate was too slow below 100°C, while too much by-products was produced above 150°C. Among the various catalysts employed, CuCl2/NaOH/AC catalyst with the molar ratio of OH/Cu=0.5–1.0, has shown the best catalytic performance, which appears to have a strong relationship with the formation of intermediate species, Cu2(OH)3Cl.  相似文献   

5.
Mesoporous γ-Al2O3 nanofiber was prepared via a simple reverse precipitation route using Si-containing Al(OH)3 and HNO3 as raw materials. The resultant Si-containing mesoporous γ-Al2O3 nanofiber exhibited high surface area of 320 m2/g, large pore volume of 1.17 cm3/g and large pore size of 10.5 nm. The introduction of Si element remarkably enhanced the thermal stability of mesoporous γ-Al2O3. The as-prepared nanofiber could maintain relative high surface area(110 m2/g) and pore volume(0.73 cm3/g) up to 1100 ℃. The effects of various experimental conditions, such as pH value, reaction temperature and aging temperature on the structural properties of the mesoporous γ-Al2O3 were also investigated.  相似文献   

6.
主要考察了NO2对Cu/SAPO-34分子筛催化剂在整个温度范围内(100-500°C)NH3选择性催化还原(SCR)NO性能的影响.研究所使用样品为新鲜Cu/SAPO-34催化剂在750°C下水热处理4 h的稳定期样品.通过X射线衍射(XRD)和扫描电子显微镜(SEM)对样品的结构以及形貌进行表征,采用SCR活性评价、动力学实验以及原位漫反射傅里叶变换红外光谱(in situ-DRIFTS)表征催化剂的性能以及催化剂表面物种的变化.活性评价实验结果表明,NO2会抑制催化剂的低温(100-280°C)活性,但其存在会提高催化剂的高温(280°C以上)活性.与此同时,随着反应物中NO/NO2的摩尔比例减少,由于NH4NO3物种的分解,副产物(N2O)的浓度增大.动力学结果表明,Cu/SAPO-34催化剂上快速SCR反应的表观活化能(Ea=64.02 kJ?mol-1)比标准SCR反应的表观活化能(Ea=48.00 kJ?mol-1)更大.In situ-DRIFTS实验结果表明NO比NO2更容易在催化剂表面形成硝酸盐,并且NO2更容易与吸附在Br?nsted酸性位上的NH3物种反应生成NH4NO3.低温下,催化剂表面的NH4NO3物种会覆盖SCR反应的活性位,造成活性降低,但在高温时,形成的NH4NO3物种一部分会被NO还原为N2,而另一部分会直接热分解为N2O,造成催化剂的选择性降低.  相似文献   

7.
Rare earth metal sandwiched Keggin-type heteropolyoxometalates, K11[RE(PW11O39)2] (RE–PW11, RE = La, Ce, Pr, Nd, Sm, Eu, Dy and Y), were anchored onto aminosilylated mesoporous silica SBA-15 and the resulting RE–PW11/APTS/SBA-15 materials were characterized by ICP, FT-IR, XRD, N2 adsorption, 31P MAS NMR and TEM. The RE–PW11 clusters preserve their structure in the surface-modified mesopores. The catalytic activity of RE–PW11 clusters was tested on heterogeneous oxidation of cyclohexene by H2O2. The interaction between RE–PW11 and amino groups grafted on the channel surface of SBA-15 leads to strong immobilization of RE–PW11 due to the introduction of the rare earth metal centre, which is against the leaching during the reaction.  相似文献   

8.
采用一锅蒸发诱导自组装法(EISA)制备了一系列不同铈锆物质的量比的铈锆固溶体催化剂,用TGA研究了其热化学循环分解CO_2制CO的催化性能,并采用XRD、Raman光谱、H2-TPR、XPS、SEM和N_2吸附-脱附等手段对催化剂的物相结构、还原性能和表面化学性质进行了表征分析,用热重分析(TGA)研究了铈锆固溶体对热化学循环分解CO_2制CO的催化性能。结果表明,随着Ce/Zr物质的量比增加,铈锆固溶体催化剂的CO_2高温分解活性先增大后减小。Ce/Zr物质的量比为1的Ce_(0.5)Zr_(0.5)O_2催化剂由于具有较多的晶格缺陷和氧空穴,氧迁移能力强,催化活性高,而Ce/Zr物质的量比为3的Ce_(0.75)Zr_(0.25)O_2催化剂具有相对稳定的氧空穴数,循环稳定性好。循环反应后,所有的催化剂均出现了一定程度的烧结,且富锆固溶体发生了相分离,这可能会影响催化剂的性能。  相似文献   

9.
丁丁  王琪  金方  陈亚中  崔鹏  刘荣  沈浩 《应用化学》2016,33(4):466-472
以Si O2为载体,铜氨溶液为前驱体,采用蒸氨法在不同蒸氨压力下制备了系列铜负载量质量分数为20.0%的Cu/Si O2催化剂。采用X射线衍射(XRD)、H2-程序升温还(H2-TPR)、高分辨透射电子显微镜(HRTEM)、X射线诱导俄歇电子能谱(XAES)等技术手段对催化剂的物理化学性能进行了表征。考察了蒸氨速率对催化剂物化结构及其草酸二甲酯催化加氢制乙二醇的催化性能影响。在反应温度200℃、压力3.0 MPa、液时空速LHSV=0.4 h-1、氢气草酸二甲酯摩尔比80∶1的反应条件下测定了催化剂的活性。结果表明,在蒸氨压力为31.3 k Pa条件下制备的催化剂表现出了最佳活性和选择性,草酸二甲酯转化率达到了99.9%,乙二醇选择性达94.4%。H2-TPR、XRD、TEM、FTIR及XAES表征结果表明,较低蒸氨压力有利于铜氨离子快速分解负载在载体上,避免铜粒子聚集长大,还原后形成Cu2O和Cu0物种颗粒尺寸较小,分散比较均匀,催化活性,尤其是乙二醇的选择性更佳。  相似文献   

10.
The liquid-phase alkylation of phenol with 1-dodecene was carried out over WOx/ZrO2 solid acid catalysts. The catalysts were prepared by wet impregnation method using zirconium oxyhydroxide and ammonium metatungstate. Catalysts with different WO3 loading (5–30 wt.%) were prepared and calcined at 800 °C and catalyst with 15% WO3 was calcined from 700–850 °C. All the catalysts were characterized by surface area, XRD, and FTIR. The catalyst with 15% WO3 calcined at 800 °C (15 WZ-800) was found to be the most active in the reaction. The effect of temperature, molar ratio and catalyst weight on dodecene conversion and products selectivity was studied in detail. Under the optimized reaction conditions of 120 °C, phenol/1-dodecene molar ratio 2 and time 2 h, the catalyst 15 WZ-800 gave >99% dodecene conversion with 90% dodecylphenol selectivity. Comparison of the catalytic activity of 15 WZ-800 with sulfated zirconia calcined at 500 °C (SZ-500) and Hβ zeolite showed that activity of SZ-500 was lower than that of 15 WZ-800, while Hβ zeolite showed negligible activity. It is observed that the presence of water in the reaction mixture was detrimental to the catalytic activity of WOx/ZrO2. The catalyst 15 WZ-800 also found to be an efficient catalyst for alkylation of phenol with long-chain olefins like 1-octene and 1-decene.  相似文献   

11.
以氢氧化铜和拟薄水铝石为原料(Cu/Al物质的量比为1/2),采用固相法经过不同温度焙烧后获得了一系列Cu-Al氧化物催化剂.当焙烧温度由500 ℃提高到900 ℃时,催化剂的主要铜物种由CuO渐变为CuAl2O4,比表面积由75.0 m2/g降低至16.6 m2/g.在甲醇重整反应过程中,以CuAl2O4为主要成分且具有较高比表面积的催化剂表现了优异的催化性能.另外,以CuAl2O4为主要成分的催化剂不经过预还原处理时,在反应过程中同时存在活性铜的释放和烧结,其催化活性呈现先增加后降低的趋势.在本研究催化剂制备条件下,优选800 ℃焙烧的催化剂,其催化性能优于商业Cu-Zn-Al催化剂,且具有可再生性.当催化剂不经过预还原处理时,在水醇物质的量比为1、240 ℃、1.01×106 Pa、质量空速为1.75 h-1的条件下,甲醇起始转化率为55.2%;反应进行288.3 h时,甲醇转化率升高至79.3%;反应继续运行至1 000.5 h时,甲醇转化率降低至63.9%.  相似文献   

12.
以γ-Al2O3为原料采用原位合成法制备CuAl2O4催化材料,通过XRF、XRD、BET和H2-TPR等手段对催化材料进行表征,考察铜铝物质的量比对CuAl2O4催化材料结构、性质及其催化甲醇水蒸气重整制氢性能的影响。结果表明,不同铜铝物质的量比主要影响了铜物种的还原性能,从而影响了其催化甲醇水蒸气重整制氢的性能。当铜铝物质的量比为1:2时,CuAl2O4催化材料的催化性能较好,在反应温度为260℃,水醇物质的量比为1.2,甲醇气体空速为800 h-1时,甲醇转化率为100%,产氢速率为895 mL/(kg·s)。  相似文献   

13.
采用沉淀法合成了CeO_2载体,再经浸渍法负载活性组分得到CuO/CeO_2催化材料,探究了铈源(Ce(NO_3)_3·6H_2O、Ce Cl_3·6H_2O、Ce(NH_4)_2(NO_3)_6、Ce(SO_4)_2·4H_2O)对CuO/CeO_2催化性能的影响。通过采用XRD、SEM、N_2O滴定、BET和H_2-TPR等表征手段对催化材料的结构和性质研究发现,四种铈源合成的CuO/CeO_2催化材料在Cu比表面积、还原性能以及活性组分和载体间的相互作用方面存在着明显差别。其中,由Ce(NO_3)_3·6H_2O合成的CuO/CeO_2催化材料的Cu比表面积较大,CuO还原温度较低,CeO_2载体与CuO之间相互作用较强,在甲醇水蒸气重整反应过程中,表现出较佳的催化活性,在反应温度为553 K,水醇比n(H_2O)/n(MeOH)为1.2,甲醇水蒸气气体空速(GHSV)为1760 h~(-1)时,甲醇的转化率为100%,重整气中CO摩尔含量为0.84%。  相似文献   

14.
Transition metal copper substituted mesoporous silica (Cu-SBA-15) was synthesized using triblock copolymers surfactant as template agent under acidic condition. The result Cu-SBA-15 was characterized with XRD, ICP-AES, FT-IR and N2 adsorption–desorption measurements, which prove that Cu(II) was mainly incorporated into the framework of Cu-SBA-15. Its catalytic activity was studied for phenol hydroxylation using H2O2 (30%). The substituting element (Cu2+) is incorporated into the framework position forming a new type of active site which raises the phenol conversion to 62.4% and the diphenol (the mixture of catechol (CAT) and hydroquinone (HQ)) selectivity to 97%. The Cu-SBA-15 has very high selectivity for catechol (about 71% selectivity), which is completely different from that of the microporous titanium silicalite zeolites (47.1% phenol conversion and about 50% selectivity to CAT under same reaction conditions). The results obtained indicate that the selective oxidation of phenol with H2O2 by a radical substitution mechanism.  相似文献   

15.
以Pluronic P123作结构导向剂,采用Al (NO33-NaAlO2双水解法合成氧化铝,在成胶过程中加入正硅酸乙酯,制备硅质量分数分别为5%、10%、15%的SiO2-Al2O3载体,并通过共浸渍法制备出Co-Mo/SiO2-Al2O3润滑油加氢处理催化剂。通过XRD、N2吸附-脱附、Py-FTIR、NH3-TPD、H2-TPR、TEM和XRF等手段对载体及催化剂的性质进行表征。结果表明,硅质量分数为10%的SiO2-Al2O3具有优良的孔结构、较多的中强酸以及部分有序的介孔结构。以此为载体制备的Co-Mo/10% SiO2-Al2O3催化剂中,MoS2颗粒均匀地分散在载体上,具有更多的B酸性位和Ⅱ型CoMoS活性相。以减二线蜡油为原料油的固定床活性评价结果表明,生成油中主要组分为链烷烃与环烷烃;尤其Co-Mo/10% SiO2-Al2O3催化剂具有优良的加氢性能,在15 MPa、380℃、氢油比为1000、空速为0.6 h-1的反应条件下,其HDS和HDN数值均超过99%,产品中S含量小于10 μg/g,N含量小于2 μg/g,可以满足后续异构脱蜡等对原料的要求。  相似文献   

16.
The photocatalytic reduction of CO2 has attracted considerable attention owing to the dual suppression of environmental pollution and energy shortage. The technology uses solar energy to convert carbon dioxide into hydrocarbon fuel, which is of great significance for achieving the carbon cycle. The development of low-cost photocatalytic materials is critical to achieving efficient solar energy to fuels conversion. One of the most commonly employed photocatalysts is TiO2. However, it suffers from broad band gap as well as the recombination of photo-excited holes and electron. Hence, in this work, we report the photochemical reduction of CO2 using rod-like PCN-222(Cu)/TiO2 composites as photocatalyst through a simple hydrothermal method, in which TiO2 nanoparticles are anchored at the interface of the SiC rod PCN-222(Cu). Multiple characterization techniques were used to analyze the structure, morphology, and properties of the PCN-222(Cu)/TiO2 composite. A series of characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), Fourier-transform infrared spectroscopy, photo-electrochemical, and photoluminescence (PL) confirm the successful preparation of PCN-222(Cu)/TiO2 composites. SEM reveals that the TiO2 nanoparticles are uniformly distributed on the surface of the rod-shaped PCN-222(Cu)/TiO2. XRD results show that PCN-222(Cu) and PCN-222(Cu)/TiO2 composite photocatalysts with good crystal structure were successfully synthesized. According to the DRS results, the prepared PCN-222(Cu)/TiO2 composite samples exhibit characteristic absorption peaks of metalloporphyrins in the visible region. PL spectroscopy, transient photocurrent response, and electrochemical impedance spectroscopy further confirm that the rod-like PCN-222(Cu)/TiO2 samples have high electron-hole pair separation efficiency. By controlling the mass ratio of PCN-222(Cu) and TiO2, the photocatalytic CO2 reduction performance test shows that the 10% PCN-222(Cu)/TiO2 composite achieves optimal catalytic performance, yielding 13.24 μmol·g−1·h−1 CO and 1.73 μmol·g−1·h−1 CH4, respectively. All the rod-like PCN-222(Cu)/TiO2 composites exhibit better photocatalytic CO2 activity than that of TiO2 nanoparticles or PCN-222(Cu) under the illumination of xenon lamps, which is attributed to charge transport and electron-hole separation capabilities. After three test cycles, the catalytic activity of PCN-222(Cu)/TiO2 photocatalyst was virtually unchanged. The reduction yield of the catalyst increased for 8 h under continuous illumination, indicating that PCN-222(Cu)/TiO2 composites have acceptable stability. The estimation of the band gap curve and the Mote-Schottky curve test show that the lowest unoccupied molecular orbital position of PCN-222(Cu) is more negative than the TiO2 of the conduction band; hence, a possible photocatalytic reaction mechanism of the PCN-222(Cu)/TiO2 composite is proposed. This study provides a new strategy for the integration of metal-organic frameworks and oxide semiconductors to construct efficient photocatalytic systems.  相似文献   

17.
采用尿素水解法制备了Cu/SiO2催化剂, 探究其用于乙酸甲酯(MA)加氢制取乙醇的催化性能, 并通过N2物理吸附、X射线衍射(XRD)、程序升温还原(TPR)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等表征方法分析了催化剂的物理化学特性, 探究了铜负载量和还原温度等对催化剂结构的影响, 以及与催化活性之间的关系. 发现在铜负载量分别为10%、20%和30% (质量分数, w)的催化剂中, 铜负载量为20%的催化剂因具有较多且分散均匀的活性组分而表现出最佳的加氢效果. 接着在铜负载量为20%的催化剂上研究了还原温度(270, 350, 450 ℃)对催化性能的影响, 发现在350 ℃下还原的催化剂活性最高, 在最佳的反应条件下, 乙酸甲酯转化率达到97.8%, 乙醇选择性达到64.9% (理论最大值为66.6%), 主要归属于它具有较高的铜物种分散度, 最合适的Cu0/(Cu0+Cu+)摩尔比例, 同时实现了解离氢气和活化乙酸甲酯的功能.  相似文献   

18.
The effects of doping of Co3O4with MgO (0.4–6 mol%) and V2O5 (0.20–0.75 mol%) on its surface and catalytic properties were investigated using nitrogen adsorption at −196°C and decomposition of H2O2 at 30–50°C. Pure and doped samples were prepared by thermal decomposition in air at 500–900°C, of pure basic cobalt carbonate and basic carbonate treated with different proportions of magnesium nitrate and ammonium vanadate. The results revealed that, V2O5 doping followed by precalcination at 500–900°C did not much modify the specific surface area of the treated Co3O4 solid. Treatment of Co3O4 with MgO at 500–900°C resulted in a significant increase in the specific surface area of cobaltic oxide. The catalytic activity in H2O2 decomposition, of Co3O4 was found to suffer a considerable increase by treatment with MgO. The maximum increase in the catalytic reaction rate constant (k) measured at 40°C on Co3O4 due to doping with 3 mol% MgO attained 218, 590 and 275% for the catalysts precalcined at 500, 700 and 900°C, respectively. V2O5-doping of Co3O4 brought about a significant progressive decrease in its catalytic activity. The maximum decrease in the reaction rate constant measured at 40°C over the 0.75 mol% V2O5-doped Co3O4 solid attained 68 and 93% for the catalyst samples precalcined at 500 and 900°C, respectively. The doping process did not modify the activation energy of the catalyzed reaction but much modified the concentration of catalytically active constituents without changing their energetic nature. MgO-doping increased the concentration of CO3+–CO2+ ion pairs and created Mg2+–CO3+ ion pairs increasing thus the number of active constituents involved in the catalytic decomposition of H2O2. V2O5-doping exerted an opposite effect via decreasing the number of CO3+–CO2+ ion pairs besides the possible formation of cobalt vanadate.  相似文献   

19.
为了提高苯乙炔加氢反应中的苯乙烯选择性,本文采用"胶体-等体积浸渍"两步法制备了Pd-Cu/γ-Al2O3双金属催化剂.利用高分辨率透射电镜(HRTEM)、X射线光电子能谱(XPS)、CO脉冲化学吸附、N2物理吸附、电感耦合等离子体原子发射光谱(ICP-AES)等技术表征了Pd-Cu/γ-Al2O3的结构性质,考察了Cu/Pd摩尔比、Pd负载量以及金属引入顺序对Pd-Cu/γ-Al2O3催化苯乙炔选择性加氢性能的影响.结果表明,与Pd/γ-Al2O3单金属催化剂相比,Pd-Cu/γ-Al2O3的苯乙烯选择性大幅度提高,尤其是当Pd负载量为0.3%(w),且Cu/Pd摩尔比为0.6时,Pd-Cu/γ-Al2O3表现出优异的加氢选择性;在0.1 MPa和40°C下,当苯乙炔转化率为90%时,双金属催化剂的苯乙烯选择性可达95%;当转化率达到99%以上时,苯乙烯选择性仍保持在82%左右.分析表明,Pd-Cu/γ-Al2O3中形成了Pd-Cu合金,但是两种金属间不存在电子转移,Cu对Pd的几何效应才是导致Pd-Cu/γ-Al2O3苯乙烯选择性增加的主要原因.  相似文献   

20.
Surface modified titania dioxide composite nanoparticles prepared by hydrogen reduction reaction and a mesoporous TiO2 foam made from a surface modifier and a long chain organic surfactant were characterized by diffractive, spectroscopic and microscopic techniques and studied for their catalytic activity towards the decomposition of an industrial water pollutant, methyl orange. The surface deposition of ruthenium and silicon particles improved the photocatalytic activity of the composite particles resulting in a faster decomposition of the methyl orange compared to commercial TiO2 alone. Modification of TiO2 with RuO2 only offered a marginal benefit over TiO2 while the incorporation of RuO2 and SiO2 into TiO2 resulted in a marked increase in the rate constant and catalytic activity. These results are consistent with the enhanced surface properties of the composite materials resulting from the modification of TiO2 with RuO2 and SiO2. This surface enhancement effects appear synergetic to the charge separation process and hence the photocatalytic results are explained on the basis of a mechanism involving efficient charge transfer across the interfaces of the composites involving photogenerated electron–hole pairs. Results obtained in this study show that the percentage degradation after 1 h of illumination was 47.15% for TiO2 foam, 75.5 and 106.4%, respectively, for TiO2/RuO2 (SiO2 5%, w/w) and TiO2/RuO2(SiO2 10%, w/w) and 34.15% for commercial TiO2.  相似文献   

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