用溶剂化金属原子浸渍法制备的高分散负载型催化剂Pd－Cu／C的结构与性质

应用溶剂化金属原子浸渍（ＳＭＡＩ）法制备了三种金属含量比不同的Ｐｄ－Ｃｕ／Ｃ双金属催化剂。经ＸＲＤ和ＴＥＭ测定结果表明，催化剂中Ｐｄ和Ｃｕ已形成合金，合金颗粒平均直径小于５ｎｍ。ＸＰＳ和Ａｕｇｅｒ谱说明Ｐｄ和Ｃｕ均以零价态存在。在亚异丙基丙酮（ＣＨ＿３）＿２Ｃ＝ＣＨＣＯＣＨ＿３加氢反应中，随着催化剂中Ｃｕ比例增加，催化活性增大，而生成六碳酮的选择性基本不变。     

Preparation and investigation of Pd doped Cu catalysts for selective hydrogenation of acetylene

A series of PdCu bimetallic catalysts with low Cu and Pd loadings and different Cu: Pd atomic ratios were prepared by conventionally sequential impregnation (CSI) and modified sequential impregnation (MSI) of Cu and Pd for selective hydrogenation of acetylene. Characterization indicates that the supported copper (II) nitrate in the PdCu bimetallic catalysts prepared by MSI can be directly reduced to Cu metal particles due to the hydrogen spillover from Pd to Cu(NO₃)₂ crystals. In addition, for the catalysts prepared by MSI, Pd atoms can form PdCu alloy on the surface of metal particles, however, for the catalysts prepared by CSI, Pd tends to migrate and exist below the surface layer of Cu. Reaction results indicate that compared with CSI, the MSI method enables samples to possess preferable stability as well as comparable reaction activity. This should be due to the MSI method in favor of the formation of PdCu alloy on the surface of metal particles. Moreover, even Pd loading is super low, <0.045 wt-% in this study, by through adjusting Cu loading to an appropriate value, attractive reactivity and selectivity still can be achieved.     

Pd-Cu/凹凸棒石黏土催化剂催化CO氧化性能

以凹凸棒石黏土(APT)作载体,采用浸渍法制备双金属催化剂Pd-Cu/APT、单金属催化剂Pd/APT和Cu/APT,在连续流动微反装置上考察催化剂的CO催化氧化活性,采用N_2物理吸附/脱附、X射线粉末衍射和程序升温还原/脱附等手段对催化剂进行表征。结果表明,Pd-Cu/APT催化剂中Cu主要以CuCl形式存在,Pd高度分散与Cu之间产生了明显的相互作用,使Cu物种的还原温度大幅降低;经水蒸汽预处理增强了Pd-Cu/APT催化剂表面酸性,促进了催化活性的提高。在CO体积分数为0.5%、水蒸汽体积分数3.3%、空速6 000h^(-1)和常温反应条件下,CO转化率可达90%以上。     

Pd-Cu/γ-Al_2O_3双金属催化剂脱除水中硝酸盐

采用分步浸渍法和共浸渍法制备系列Pd负载质量分数为1%的Pd-Cu/γ-Al2O3双金属催化剂,以氢气为还原剂研究其对水中硝酸盐催化脱除的性能。结果表明,催化剂中Cu与Pd物质的量比以及Cu、Pd的浸渍顺序对催化剂性能有重要影响,硝酸根转化率随着Cu与Pd物质的量比的增大而增大;硝酸根转化活性以Cu与Pd物质的量比为5∶1、先浸渍Pd再浸渍Cu所得催化剂较优;从氨氮选择性方面看,以先浸渍Cu后浸渍Pd制备的催化剂选择性较低,在Cu与Pd物质的量比为1∶1、先浸渍Cu再浸渍Pd所得催化剂较优。     

Catalytic performance and characterization of Pt-Ni bimetallic catalysts for oxidative steam reforming of methane

Effects of methane oxygen mixture addition to steam reforming of methane and subsequent removal of the methane oxygen mixture from the oxidative steam reforming of methane on catalytic performance were investigated using monometallic Ni and Pt catalysts and two Pt-Ni bimetallic catalysts. Hysteresis with respect to the addition and removal of the methane oxygen mixture was observed clearly on a Pt-Ni bimetallic catalyst prepared by co-impregnation method and the Ni catalyst. In contrast, no hysteresis was observed for a Pt-Ni catalyst that was prepared by sequential impregnation method. Combined with characterization results obtained using EXAFS analysis and FTIR of CO adsorption, Pt-Ni catalyst was prepared by sequential impregnation is formed Pt-Ni alloy particles, where Pt atoms are segregated on the surface, enhances the reducibility of Ni drastically and this is related to the behavior without hysteresis.     

Catalytic reduction of nitrate on Pt-Cu and Pd-Cu on active carbon using continuous reactor: The effect of copper nanoparticles

The increasing pollution of natural sources of drinking water encourages the development of new emerging technologies and processes for water remediation. This work deals with the study of catalytic reduction of contaminated waters containing nitrates (60 ppm) in a continuous reactor working at room temperature and atmospheric pressure and using hydrogen as reducing agent. Optimal proportions of Pt-Cu and Pd-Cu in bimetallic catalysts on activated carbon, obtained by wetness impregnation, have been found. Besides, novel catalysts obtained from copper nanoparticles doped with Pd or Pt and supported on activated carbon, have also been studied. For all catalysts the Pt-Cu pair seems to be more selective in the transformation of the nitrates ions to nitrogen compared to Pd-Cu pair. Furthermore, considering the noble metal amount, the bimetallic nanosphere catalysts are more active (between 20 and 50) than the impregnated ones. The catalysts have been characterized by hydrogen chemisorption, BET, X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis. During the reaction, a considerable amount of the noble metal in its oxidised form has been detected. Based on this result an additional step to the generally accepted reaction mechanism of the nitrate reduction has been proposed.     

FTIR study of the oxidation reaction of CO with O2 over bimetallic Pd–Rh/SiO2 catalysts in an oxidized state

CO species adsorbed on the surface of oxidized bimetallic Rh–Pd catalysts, prepared by coimpregnation and sequential impregnation methods, were analyzed in situ by IR spectroscopy, during the reaction of CO with O₂ in an oxidizing atmosphere. The results show that the two methods of impregnation lead to the existence of oxidized Rh on the surface of the bimetallic catalyst, however, in the case of the sequential impregnation method, the Pd surface is more reduced than in the case of catalysts prepared by coimpregnation. The simultaneous presence of reduced Pd and oxidized Rh that occurs in the catalysts prepared by sequential impregnation allows the existence of a synergistic effect similar to that proposed in the literature for the Pt–Rh system. The lower degree of oxidation of the Pd in the catalysts prepared by sequential impregnation, is mainly due to the fact that the Pd in these catalysts comes from the organic precursor palladium acetylacetonate, while in the catalysts prepared by coimpregnation, the Pd comes from the precursor PdCl₂. This revised version was published online in July 2006 with corrections to the Cover Date.     

Bimetallic catalysts for the hydrogenation of aromatic nitro compounds

The catalytic activity of bimetallic Pd-Ni, Pd-Cu, and Pd-Ag catalysts in the reaction of nitrobenzene hydrogenation was studied. It was found that the rate of hydrogenation on the bimetallic catalysts was higher than that on palladium metal (palladium black), and it depended on catalyst preparation pro cedures. The catalytic activity of the bimetallic systems increased in the order Pd-Cu< Pd-Ag ? Pd-Ni.     

Catalytic performance and QXAFS analysis of Ni catalysts modified with Pd for oxidative steam reforming of methane

Pd–Ni bimetallic catalysts prepared by co-impregnation and sequential impregnation methods were compared in the catalytic performance in oxidative steam reforming of methane. The sequential impregnation was more effective to the suppression of hot spot formation. According to the structural analysis by in situ quick-scanning X-ray absorption fine structure (QXAFS) during the temperature programmed reduction, the sequential impregnation method gave the bimetallic particles with higher Pd surface composition because of the low possibility of the Pd–Ni bond formation. Higher surface composition of Pd with higher reducibility than Ni is connected to the enhancement of the catalyst reducibility and the suppression of the hot spot formation.     

The synergic effects of highly selective bimetallic Pt-Pd/SAPO-41 catalysts for the n-hexadecane hydroisomerization

The hydroisomerization of n-hexadecane over Pt-Pd bimetallic catalysts is an effective way to produce clean fuel oil. This work reports a useful preparation method of bimetallic bifunctional catalysts by a co-impregnation or sequential impregnation process. Furthermore, monometallic catalysts with loading either Pt or Pd are also prepared for comparison. The effects of the metal species and impregnation order on the characteristics and catalytic performance of the catalysts are investigated. The catalytic test results indicate that the maximum iso-hexadecane yield over different catalysts increases as follows: Pt/silicoaluminophosphate SAPO-41iso-hexadecane yield of 89.4% when the n-hexadecane conversion is 96.3%. Additionally, the Pt-Pd/SAPO-41 catalyst also presents the highest catalytic activity and best stability even after 150 h long-term tests.     

Enhancement of oxygen reduction activity by sequential impregnation of Pt and Pd on carbon support

Two Pd-based PtPd bimetallic catalysts (mole ratio of Pt to Pd=1: 18) were prepared by co-impregnation (Pt-Pd/C) and sequential impregnation of Pt on Pd/C [Pt(Pd/C)] for the application to oxygen reduction reaction (ORR). The prepared bimetallic catalysts had lower ORR activities than Pt/C, while they showed largely enhanced activity compared to Pd/C. In particular, the extent of enhancement was found to be dependent on the surface composition. The observed mass and specific activities of Pt(Pd/C) were more than two times higher than those of Pt-Pd/C. The superior activity of Pt(Pd/C) observed from the performed studies was attributed to its Pt-rich surface.     

Pd–Ag/SiO2 and Pd–Cu/SiO2 cogelled xerogel catalysts for selective hydrodechlorination of 1,2-dichloroethane into ethylene

While 1,2-dichloroethane hydrodechlorination over pure palladium mainly produces ethane, increasing silver or copper content in bimetallic catalysts results in an increase in ethylene selectivity. The specific consumption rate of 1,2-dichloroethane decreases when silver or copper loading increases. The turnover frequency, that is, the number of catalytic cycle per active site (palladium atom and its surrounding silver or copper atoms) and per second, seems to be independent of surface composition of alloy particles and 1,2-dichloroethane hydrodechlorination is insensitive to the atom's nature (silver or copper).     

Ni-Cu/γ-Al2O3催化剂的制备及其脱氢反应研究

采用共沉淀法、浸渍法和共沉淀-浸渍法制备了3种不同的Ni-Cu/γ-Al2O3双金属催化剂,并利用微型连续管式反应器,考察了3种Ni-Cu/γ-Al2O3催化剂对氢能载体甲基环己烷(MCH)气相脱氢的催化性能。采用XRD、SEM、BET、BJH等手段对所制备的催化剂进行表征。结果表明,使用共沉淀-浸渍法制备的Ni-Cu/γ-Al2O3催化剂优于其他两种〔3种催化剂中Ni和Cu负载量均为26%且n(Ni)∶n(Cu)=8∶1〕。在反应温度673K,反应压力0.6 MPa,MCH与N2体积流量比为19∶27,混合进样体积空速240 h-1条件下,MCH脱氢转化率达到98.5%,产物甲苯的选择性接近100%。与铂等贵金属催化剂以及单金属镍催化剂相比,镍铜双金属催化剂在该反应中具有更好的应用前景。     

SMSI effect in the butadiene hydrogenation on Pd-Cu bimetallic catalysts

Niobla Pd-Cu supported bimetallic catalysts have been studied In the 1,3-butadlene hydrogenation. On catalysts reduced at 573K, the addition of copper to palladium decreased the hydrogen adsorption capacity and the turnover frequency but Increased the trans/cis 2-butene ratio. These results are ascribed to a bimetallic formation. After reduction at 773K. the hydrogen chemlsorptlon and turnover frequency are drastically reduced due to SMSI effect. The 1,3-butadlene hydrogenation seems to be a structure sensitive reaction.     

Adsorption and reduction of nitrate in water on hydrotalcite-supported Pd-Cu catalyst

The hydrotalcite-supported Pd-Cu catalysts were successfully prepared by the impregnation or coprecipitation method, and their adsorption and catalytic reduction activity for nitrate in water were evaluated. The catalysts were characterized by X-ray diffraction (XRD) and surface area (BET) analysis. The results demonstrated that hydrotalcite-supported Pd-Cu catalysts could significantly adsorb nitrate ions, and then, effectively catalytically reduce them. The excellent adsorption ability for nitrate resulted from the regenerated layer structure of calcined hydrotalcite catalyst in nitrate aqueous solution. Nitrate was forced into the interlayer space and adsorbed on the external surface. The adsorption kinetics and the adsorption isotherm could be well described by pseudo-second-order model and the Langmuir model, respectively. The comparison of catalytic reduction with the adsorption for nitrate indicated that catalytic hydrogenation activity for nitrate increased with increasing adsorption capacity; nitrate reduction on hydrotalcite-supported Pd-Cu catalysts was a consecutive and dynamic adsorption and catalytic hydrogenation process. In addition, the catalyst obtained by coprecipitation method, with intact regeneration of hydrotalcite structure and a high dispersion of active metals, hold higher adsorption and catalytic activity than that prepared by co-impregnation method.     

Novel mesoporous aluminosilicate supported palladium-rhodium catalysts for diesel upgrading: I. Preparation and characterisation

Bimetallic PdRh (with Pd/Rh mole ratio = 2/1) catalysts supported on a mesoporous aluminosilicate have been prepared and three methods of metal incorporation in the support have been compared: direct incorporation into the synthesis gel, impregnation and ion-exchange. Physico-chemical characterisations (nitrogen adsorption–desorption, hydrogen chemisorption, transmission electron microscopy, X-ray photoelectron and extended X-ray absorption fine structure spectroscopies), as well as simulated coking and regeneration tests are described. The dispersion, metal particle size and the formation of bimetallic particles within the material depend on the method of metal incorporation. Direct incorporation and ion-exchange methods lead to co-existence of PdRh intermetallic aggregates and segregated Pd; on the other hand, the impregnation method leads to the formation of very small and well dispersed PdRh alloy particles, with Pd preferentially located on the alloy particle surface.     

三氟三氯乙烷加氢脱氯Pd-Cu催化剂失活分析

以活性炭为催化剂载体,采用浸渍法制备Pd、Cu、Pd-Cu三种催化剂,将催化剂应用于三氟三氯乙烷(CFC-113)加氢脱氯制三氟氯乙烯(CTFE)的反应,考察Cu的引入对Pd催化剂性能的影响。对反应前后及再生的Pd-Cu催化剂进行X射线衍射(XRD)、X射线光电子能谱(XPS)、氮气吸附-脱附(BET)、氢气程序升温还原(H₂-TPR)、热重(TG)、氨气程序升温脱附(NH₃-TPD)等表征分析。研究表明,Pd催化剂具有较高的加氢脱氯性能,其主要产物为三氟乙烷,Cu的加入有利于提高CTFE的选择性。这应与Cu、Pd之间存在相互作用并形成合金,抑制了Pd的脱氯性能有关。反应后的催化剂存在表面结焦、反应过程中吸附Cl以及金属Cu价态变化和迁移等现象,其中表面高沸物的形成、卤元素吸附导致的金属迁移和Cu-Pd相互作用的改变是Pd-Cu催化剂失活的主要原因。     

微乳法制备Pd-Cu双金属催化剂

选择Cu为助剂,采用微乳法分别优选具有较好稳定性的Cu和Pd微乳液体系,并将Cu和Pd依次负载于Al_2O_3载体上,经干燥、活化和还原制备了Pd-Cu/Al_2O_3催化剂。采用原位IR、CO化学吸附和HRTEM等对催化剂进行表征,结果表明,与常规溶液负载法制备的Pd-Ag/Al_2O_3催化剂相比,采用微乳法降低了催化剂表面酸性,提高了活性组分Pd分散度,Pd粒径分布更为均匀。在750 mL加氢反应器中,采用C_2后加氢原料对催化剂性能进行评价,结果表明,与常规溶液负载法相比,微乳法制备的催化剂在反应温度低4℃条件下,乙炔转化率相当,选择性高9.9个百分点,绿油生成量较低。微乳法制备Pd-Cu双金属催化剂具有良好的工业应用前景。     

沉积-沉淀法制备Pd-Cu/凹凸棒土催化剂及其常温潮湿环境下CO催化氧化性能

采用沉积-沉淀法制备Pd-Cu/凹凸棒土(PC/APT)催化剂,以CO氧化为探针反应,在连续流动微反装置上考察其常温潮湿环境下CO催化氧化性能。作为对比,同时采用常规浸渍法制备催化剂。通过N2物理吸附-脱附、XRD、FT-IR和TPR等对催化剂结构和性质进行表征。结果表明,与浸渍法制备的催化剂不同,采用沉积-沉淀法制备的PC/APT催化剂上Cu物种分别以Cu_2Cl(OH)_3和CuO形式存在,其中,Cu_2Cl(OH)_3物种与Pd物种间相互作用较强,催化剂还原性能显著提高,表现出良好的CO催化氧化活性。在空速6 000 h~(-1)、CO体积分数0.5%和水蒸汽体积分数3.3%条件下,采用沉积-沉淀法制备的PC/APT催化剂上CO转化率大于84%的时间不低于160 min。     

Characterization of supported Pd-Cu bimetallic catalysts by SEM, EDXS, AES and catalytic selectivity measurements

Pd-Cu/γ-Al₂O₃ bimetallic catalysts were prepared according to different impregnation sequences of γ-Al₂O₃ and characterized by XRD, SEM, EDXS and AES. The catalysts were tested for the selective hydrogenation of aqueous nitrate solutions to nitrogen. The reaction selectivity was found to be dependent on the catalyst preparation procedures, which affect the spatial distribution of metallic copper and palladium phases. A catalyst prepared by impregnating γ -Al₂O₃ with copper followed by palladium gives higher selectivity to nitrogen than a catalyst prepared by impregnating the support with palladium followed by copper. The AES examination shows that in the catalyst exhibiting a higher nitrogen production yield, a reaction zone for the liquid-phase nitrate reduction is located in the interior of particles and covered by a layer of Pd atoms. This revised version was published online in July 2006 with corrections to the Cover Date.