Thermochemistry of Pd–In,Pd–Sn and Pd–Zn alloy systems

The standard enthalpy of formation of several Pd–M alloys (M = In, Sn and Zn) has been measured using a high temperature direct drop calorimeter. The reliability of the calorimetric results has been determined and supported by using different analytical techniques: light optical microscopy, scanning electron microscopy equipped with electron probe microanalysis (EPMA with EDS detector) and X-ray powder diffraction analysis. The values of Δ_fH (kJ/mol atoms) for the following phases were obtained for the formation in the solid state at 300 K: PdIn (49 at.%In): ?69.0 ± 1.0; Pd₂In₃ ?57.0 ± 1.0; Pd₃In₇: ?43.0 ± 1.0; PdSn₂: ?50.0 ± 1.0; Pd₂Zn₉ (77 at.%Zn): ?33.7 ± 1.0; Pd₂Zn₉ (78 at.%Zn): ?34.0 ± 1.0; Pd₂Zn₉ (80 at.%Zn): ?35.0 ± 1.0. The results show exothermic values which increase from the Pd–Zn to the Pd–Sn and Pd–In systems; the data obtained have been discussed in comparison with those available in literature.     

Pd Close Coupled Catalyst

Europe III standards require significantly higher emissions reduction, especially for hydrocarbon (HC). For a typical vehicle, a large portion (up to 80 %) of the HC emissions occurs during cold start. A variety of technologies are under development to reduce cold start HC emissions, including close coupled catalysts1; electrically heated catalysts2 and hydrocarbon absorbers3. Among them, the close coupled catalyst gradually dominated the technologies4. A high performance close coupled cat…     

Synthesis and characterization of Sibunit-supported Pd–Ga,Pd–Zn,and Pd–Ag catalysts for liquid-phase acetylene hydrogenation

Pd/Sibunit and Pd–M/Sibunit (M = Ga, Zn, or Ag) catalysts have been synthesized, and their catalytic properties in liquid-phase acetylene hydrogenation have been investigated. Doping of the palladium catalyst with a metal M leads to the formation of the Pd₂Ga, PdZn, or Pd_0.46Ag_0.54 bimetallic compound. The bimetallic particles are much smaller (1.6–2.0 nm) than the monometallic palladium particles (4.0 nm). Doping with zinc raises the ethylene selectivity by 25% without affecting the activity of the catalyst. Specific features of the effect of each of the dopants on palladium are reported.     

纳米Pd粉的热稳定性研究

采用化学液相合成法制备了纳米Pd,热稳定性研究表明,温度在773～523K内,样品的平均粒径d与退火温度T之间服从Arrhenius关系,且平均粒径与退火时间t之间满足经验公式d=ktn。纳米Pd的热稳定范围T≤250℃。计算得到纳米Pd颗粒生长的表观激活能为0.15eV,远比纳米复合材料的生长激活能小（约为1eV）。故纳米Pd颗粒-极易长大,热稳定范围非常窄。     

Catalytic conversion of cellulose into polyols using carbon-nanotube-supported monometallic Pd and bimetallic Pd–Fe catalysts

A series of carbon nanotube (CNT)-supported monometallic Pd and bimetallic Pd–Fe catalysts were synthesized and employed for catalytic hydrogenolysis of cellulose into polyols, including hexitol, ethylene glycol (EG), 1,2-propanediol (1,2-PG), and glycerol (Gly). The physicochemical properties of the catalysts were characterized by nitrogen physical adsorption measurements, X-ray diffraction analysis, transmission electron microscopy, and X-ray photoelectron spectroscopy. The total yield of hexitol, EG, 1,2-PG, and Gly in hydrolytic hydrogenation of cellulose was 37, 55, and 53% for Pd/CNTs, Pd–Fe/CNTs (Pd:Fe = 1:1), and Pd–Fe/CNTs (Pd:Fe = 1:2), respectively. Addition of Fe to Pd significantly modified the physicochemical properties of the nanoparticles and their catalytic performance, especially regarding hexitol selectivity. The promoting effect of Fe, especially for hexitol selectivity, compared with the monometallic catalyst is due to the fact that incorporation of Fe may stabilize Pd⁰ nanoparticles and lead to downshift of the d-band center of Pd metal nanoparticles by charge transfer from Fe to Pd. Recycling experimental results showed that leaching of Fe resulted in a significant decrease in the hexitol yield obtained using the Pd–Fe/CNTs after the first recycle, further demonstrating that Fe element plays a promoting role for hexitol formation.     

CO在Pd平板与Pd38团簇表面上的催化氧化机理研究

采用密度泛函理论(DFT)计算模拟Pd平板和Pd_(38)团簇上的CO催化氧化过程,分析了CO在Pd催化剂表面上的氧化反应机理。结果表明,在Pd_(38)团簇模型上CO催化氧化的决速步骤是O_2的解离,反应能垒为0.65 eV,而在Pd平板模型上的决速步骤是CO的氧化,其反应能垒为0.87 eV。对比决速步骤的活化能发现,CO在Pd_(38)团簇上的氧化反应更易进行,说明CO氧化更易在小颗粒催化剂表面上进行,即Pd催化剂的活性与活性组分颗粒大小相关,活性组分颗粒越小,暴露的活性位点越多,其催化活性也越高。     

甲醇水蒸气重整制氢Pd/ZnO催化剂还原过程中Pd与ZnO的相互作用

 采用程序升温还原、程序升温脱附、程序升温电导及X射线衍射研究了并流共沉淀法制备的15.9%Pd/ZnO催化剂还原过程中结构和物种的变化及电荷的传递,考察了还原温度对该催化剂催化甲醇水蒸气重整制氢的影响. 结果表明,还原过程中Pd与ZnO间存在明显的相互作用,导致氢溢流,溢流氢促进了ZnO还原并使ZnO与Pd形成活性中心PdZn合金. 催化剂的还原历程为 PdO/ZnO → Pd/ZnO → PdZnO1-x/ZnO → 无定形PdZn合金/ZnO → 晶型PdZn合金/ZnO. 并流共沉淀法制备的Pd/ZnO催化剂Pd分散度高, PdZn合金形成温度低. 在523～573 K还原后,催化剂的PdZn合金粒径为5～14 nm, 此时催化剂对甲醇的转化率及二氧化碳选择性均达到最大值.     

Pd/C催化剂用于CO2电化学还原生成CO:Pd载量的影响

CO₂电化学还原反应可以将CO₂转化为燃料并同时实现再生能源的有效存储. 目前纳米结构的多相催化剂已经广泛应用于此反应,其中碳负载钯纳米粒子（Pd/C）表现出优异的CO₂电化学还原性能. 本工作研究了钯载量对于Pd/C催化剂结构以及其催化CO₂还原生成CO反应活性和选择性的影响. 不同载量的Pd/C催化剂通过液相还原方法制备,钯纳米粒子均匀地分散在碳载体上,载量并没有明显改变对纳米粒子的粒径. 在优选的电解质（0.1 mol·L^-1 KHCO₃）中,CO法拉第效率与载量呈现火山型曲线关系,-0.89 V时载量为20wt%的Pd/C催化剂达到最高的CO法拉第效率(91.2%). 生成CO的几何电流密度随着钯载量的增加而增加,但CO转换频率具有相反的趋势,载量为2.5wt%的Pd/C催化剂具有最高的转换频率. 这种载量对CO₂电化学还原反应活性和选择性的影响主要由活性位的数量、反应动力学、中间物种的稳定性以及反应物、中间物种和产物的传质过程等共同决定.     

甲烷低温氧化Pd催化剂的研究进展

环保意识和污染物排放标准的提高,使天然气汽车尾气减排成为了亟待解决的问题.催化氧化被认为是消除稀燃天然气汽车尾气中强温室效应气体甲烷最为有效的途径之一,而Pd催化剂被认为是甲烷低温氧化的首选催化剂.通过对Pd催化剂制备中的前驱体、载体、助剂、制备方法各制备要素综述,总结了各要素对催化剂低温氧化活性、稳定性和抗硫中毒性能的影响,并系统介绍了Pd催化剂制备的最新发展.基于对当前研究的认识,提出了开发低成本高性能催化剂的措施.     

水蒸汽在Pd表面吸附的热力学

用密度泛函方法和相对论有效原子实势分别对PdOH2、PdOH 及PdO 的几何构型进行了优化, 得到PdOH2分子为Cs构型, Pd 与H2O 分子不在同一平面, RPdO=0.2283 nm; PdOH 分子为2A'态, RPdO=0.1965 nm, ROH=0.0968 nm, ∠PdOH=110.186°; PdO分子基态为3Π, RPdO=0.1858 nm. 根据电子-振动近似理论计算了不同温度下金属Pd与H2O、OH及游离态O原子反应的生成热力学函数, 导出了反应平衡压力随温度的变化关系, 分析认为水蒸汽引起Pd合金膜中毒是由于H2O分子的离解产物OH和O原子吸附在膜表面所致.     

全Pd催化剂质子交换膜燃料电池

用改良的浸渍法合成了多种不同合金度的碳载PdCu纳米粒子, 考察其对氧还原和氢氧化反应的催化行为, 并择优应用到质子交换膜燃料电池(PEMFC)中. 研究发现, 阳极采用Pd₈₀Cu₂₀/C催化剂, 阴极采用Pd₉₀Cu₁₀/C催化剂组装的单电池在65℃下最大功率密度接近204 mW/cm².     

Pd催化甲醇裂解制氢的反应机理

基于密度泛函理论(DFT), 研究了甲醇在Pd(111)面上首先发生O—H键断裂的反应历程(CH3OH(s)→CH3O(s)+H(s)→CH2O(s)+2H(s)→CHO(s)+3H(s)→CO(s)+4H(s)). 优化了裂解过程中各反应物、中间体、过渡态和产物的几何构型, 获得了反应路径上各物种的吸附能及各基元反应的活化能数据. 另外, 对甲醇发生C—O键断裂生成CH3(s)和OH(s)的分解过程也进行了模拟计算. 计算结果表明, O—H键的断裂(活化能为103.1 kJ·mol-1)比C—O键的断裂(活化能为249.3 kJ·mol-1)更容易; 甲醇在Pd(111)面上裂解的主要反应历程是: 甲醇首先发生O—H键的断裂, 生成甲氧基中间体(CH3O(s)), 然后甲氧基中间体再逐步脱氢生成CO(s)和H(s). 甲醇发生O—H键断裂的活化能为103.1 kJ·mol-1, 甲氧基上脱氢的活化能为106.7 kJ·mol-1, 两者均有可能是整个裂解反应的速控步骤.     

Pd8簇催化氢化乙炔的反应机理

采用密度泛函理论(DFT)中的B3PW91方法研究了过渡金属Pd₈簇催化氢化乙炔的反应机理. 研究表明: H₂进入Pd₈簇后解离成H原子, 并且只有当H原子吸附在Pd₈簇表面上时, 催化氢化反应才能发生. 过渡金属Pd₈簇催化氢化乙炔的反应机理的研究证实该催化反应从两种反应物出发经过两条不同的反应途径完成催化氢化反应, 两种反应物分别为吸附在Pd₈簇上的乙炔(Pd₈(2H)－CH＝CH)和其同分异构体亚乙烯基吸附物(Pd₈(2H)－C＝CH₂). 两条途径均为多步连续的加氢反应, 不同之处在于从Pd₈(2H)－CH＝CH出发的为单一路径, 解离后的H原子分步依次加成到吸附在Pd₈簇上的乙炔中的C原子上, 直到反应完成生成乙烷. 而从Pd₈(2H)－C＝CH₂出发的路径较为复杂, 分别经过两个不同的过渡态和中间体生成次乙基中间体, 该过程相对应的反应位垒相差约12.552 kJ·mol^-1, 说明这两个过渡态同时存在, 无先后次序. 然后继续加成H原子直到生成乙烷完成反应. 同时, 两条路径分别形成一系列具有应用价值的C₂有机化合物中间体, 其中一些中间体通过分子内质子转移相互转化, 使得原本独立的两条反应路径联系在一起, 成为网状路径.     

Preparation of 103Pd seeds Part II. “Molecular Plating” of 103Pd onto copper rod

A method for ¹⁰³Pd molecular plating onto the surface of the copper rod is reported. The optimal composition of the plating bath was: palladium chloride 2 g/l, ammonium hydroxide (28%) 150 ml/l, sodium hypophosphite 12 g/l, and ammonium chloride 37 g/l. The whole procedure of ¹⁰³Pd molecular plating will last 50 minutes at 40 °C. This article provides valuable experience for the preparation of ¹⁰³Pd seeds.     

脉冲色谱H_2-0_2滴定法测定Pd/C催化剂中Pd的分散度

近来脉冲色谱H_2—O_2滴定法已用于负载型Pd催化剂分散度的测定。但对于Pd/C催化剂,由于同时存在溶解氢和溢出(Spillover)氢而使问题复杂化,至今未见该法用于Pd/C中Pd的分散度测定的报道。本文寻找出克服上述困难的方法,取得与X射线谱线宽化法基本吻合的结果。     

Calorimetric investigation of order–disorder transition in Cu0.6Pd0.4 and Cu0.85Pd0.15 alloys

Order–disorder phase transitions in Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys have been investigated using differential scanning calorimetry and drop calorimetry. The differential scanning calorimetry measurements show that the transition in both these alloys are reversible in nature and the enthalpy increment measurements reveal that these transitions are first order in nature. The transition temperature of first-order phase transition in Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys have been evaluated to be 884(±2) and 799(±2) K, respectively, from drop calorimetric measurements. The latent heat of first-order phase transition in Cu_0.6Pd_0.4 alloy were evaluated to be 31.2(±0.6) and 28.9(±0.5) J g^?1, by enthalpy increment and differential scanning calorimetry measurements, respectively. Similarly, the latent heat of first-order phase transition in Cu_0.85Pd_0.15 alloy were evaluated to be 23.1(±0.6) and 21.3(±0.5) J g^?1, by enthalpy increment and differential scanning calorimetry measurements, respectively. The solidus temperatures of Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys were found to be 1,457(±2) and 1,360 K, respectively.     

Pd／C催化剂用于苯胺氧化羰基化

研究了催化剂制备条件、助催化剂对负载型Ｐｄ／Ｃ催化剂性能的影响及氧分压、原料苯胺中硝基苯的加入对苯胺氧化羰基化反应的影响；用Ｘ光电子能谱（ＸＰＳ）、程序升温还原（ＴＰＲ）和现场红外（ＩＲ）表征钯催化剂；根据实验结果提出在Ｐｄ／Ｃ－ＮａＩ催化剂体系、醇介质中，苯胺氧化羰基化可能的反应机理．     

Pd催化剂在甲醇裂解中的应用研究进展

贵金属Pd是甲醇分解反应常用的催化剂，本文综述了不同载体负载的Pd催化剂的催化性能以及反应条件对其催化活性、选择性和稳定性的影响。并介绍了其中一些催化剂的制备方法，对催化反应动力学和催化机理进行了简要的概括。