Determination of the standard enthalpies of formation of Pd2Ga and PdGa by high-temperature direct synthesis calorimetry
作者:S.V. Meschel、O.J. Kleppa
DOI:10.1016/s0040-6031(97)00019-1
日期:1997.5
Abstract The standardenthalpies of formation of PdGa and Pd 2 Ga have been determined by high-temperature direct synthesis calorimetry at (1473 ± 2) K. The following values of Δ f H 0 in kJ (mol of atoms) −1 are reported: PdGa (−71.6 ± 2.3); Pd 2 Ga (−64.4 ± 2.0). The results are compared with reported calorimetric data and with predicted values from the semi-empirical model of Miedema et al.
摘要 PdGa 和 Pd 2 Ga 的标准生成焓已通过高温直接合成量热法在 (1473 ± 2) K 下确定。 Δ f H 0 以 kJ(原子摩尔数) -1 为单位的以下值被报道:钯 (-71.6 ± 2.3); Pd 2 Ga (-64.4 ± 2.0)。将结果与报告的量热数据和 Miedema 等人的半经验模型的预测值进行比较。
Palladium–gallium intermetallic compounds for the selective hydrogenation of acetylenePart I: Preparation and structural investigation under reaction conditions
The intermetallic compounds PdGa and Pd3Ga7 are introduced as selective catalysts for the hydrogenation of acetylene. Single phase PdGa and Pd3Ga7 can readily be prepared by the appropriate thermal treatment of the stoichiometric mixtures of the corresponding elements. The initial low surface areas of the as-prepared materials can be increased by careful mechanical treatment without decomposition.
引入金属间化合物PdGa和Pd 3 Ga 7作为用于乙炔氢化的选择性催化剂。单相PdGa和Pd 3 Ga 7可以通过对相应元素的化学计量混合物进行适当的热处理而容易地制备。可以通过仔细的机械处理而不分解来增加所制备材料的初始低表面积。DSC / TG,原位粉末X射线衍射和原位对PdGa和Pd 3 Ga 7的详细研究在各种惰性或反应性气体气氛下进行热处理时,X射线吸收光谱显示出很高的热稳定性。直至约600 K的温度,晶体结构中的长程和短程有序保持不变。相变和分解都无法检测到。除了较高的热稳定性(在反应条件下保持活性部位隔离)外,在还原条件下未观察到氢或碳在金属间化合物中的结合。除了是有趣的模型系统之外,钯-镓金属间化合物还有望用作高选择性加氢催化剂。
The direct synthesis of hydrogen peroxide from H<sub>2</sub> and O<sub>2</sub> using Pd–Ga and Pd–In catalysts
作者:Sheng Wang、Richard J. Lewis、Dmitry E. Doronkin、David J. Morgan、Jan-Dierk Grunwaldt、Graham J. Hutchings、Silke Behrens
DOI:10.1039/c9cy02210d
日期:——
The direct synthesis of hydrogen peroxide is investigated using PdGa/TiO2 and PdIn/TiO2 catalysts prepared by an acid-washed sol-immobilisation procedure, which allows for enhanced catalytic selectivity.
A two-step synthesis for the preparation of single-phase and nanoparticulate GaPd and GaPd2 by coreduction of ionic metal-precursors with LiHBEt3 in THF without additional stabilizers is described. The coreduction leads initially to the formation of Pd nanop articles followed by a Pd-mediated reduction of Ga3+ on their surfaces, requiring an additional annealing step. The majority of the intermetallic particles have diameters of 3 and 7 nm for GaPd and GaPd2, respectively, and unexpected narrow size distributions as determined by disk centrifuge measurements. The nanoparticles have been characterized by XRD, TEM, and chemical analysis to ensure the formation of the intermetallic compounds. Unsupported nanoparticles possess high catalytic activity while maintaining the excellent selectivity of the ground bulk materials in the semihydrogenation of acetylene. The activity could be further increased by depositing the particles on alpha-Al2O3.
Etching of the intermetallic compounds PdGa and Pd3Ga7: An effective way to increase catalytic activity?
The structurally ordered intermetallic compounds PdGa and Pd3Ga7 constitute highly selective catalysts for the selective semi-hydrogenation of acetylene. The milling of as-synthesized samples, followed by etching with ammonia solution increased the activity of the catalysts by factor of 60. Chemically etched samples possess high activity and simultaneously keep their high selectivity. Chemical analysis confirms that the etching procedure is mostly specific to gallium species, thus less affecting the palladium. Detailed investigations reveal the influence of the chemical etching on the morphology and surface of the particles. As a result of the etching, nano-caverns are formed (SEM and BET), and the surface is enriched in palladium (XPS and EDX), while the bulk crystal structure is not affected (XRD). The mechanism and applicability of the etching procedure is discussed in view of the active-site isolation concept. (C) 2009 Elsevier Inc. All rights reserved.