Solubility of hydrogen in PdAg and PdAu binary alloys using density functional theory

The present work deals with the study of palladium-silver (PdAg) and palladium-gold (PdAu) binary alloys over a broad range of temperatures and alloy compositions using density functional theory (DFT) to find possible conditions where the solubility of hydrogen (H) is significantly higher than that of pure palladium (Pd). Several alloy structures, such as Pd(100-x)Ag(x) with x = 14.81, 25.93, 37.04, and 48.51, Pd(100-x)Aux with x = 14.81, 25.93, and 37.04, and Pd(100-x)Cu(x) with x = 25.93 and 48.51 were considered. The lattice constants of these structures were optimized using DFT, and relaxed structures were used for the estimation of binding energy. It was found that the solubility of H in PdAg is higher than pure Pd with a maximum at approximately 30% Ag at 456 K. Also, the solubility of PdAu alloys was higher than pure Pd with a maximum at about 20% Au with a solubility 12 times higher than that of pure Pd. It was found that for a 3.7% H concentration in a PdAg alloy, a cell expansion of 0.15-0.2% occurs, which if ignored may affect the individual binding energy of the O-site by approximately 3.56% and may affect the predicted solubility by approximately 11.8%.     

Reactivity of hydrogen with solid-state films of alkylamine- and tetraoctylammonium bromide-stabilized Pd, PdAg, and PdAu nanoparticles for sensing and catalysis applications

Hydrogen gas spontaneously adsorbs to Pd metal as atomic hydrogen and diffuses into the lattice to form PdHx. We previously showed that films of hexanethiolate-coated Pd monolayer-protected clusters (MPCs) do not readily react with H2 due to the strong chemical bonding of the thiolate to the Pd, which inhibits the reaction. Consequently, these films require ozone or heat treatment for reactivity to occur, which is inconvenient for sensing or catalysis applications. In this report, we describe the reactivity between H2 and solid-state films of alkylamine-coated Pd, PdAg (10:1), and PdAu (10:1) MPCs and films of tetraoctylammonium bromide (TOABr)-stabilized Pd and PdAg (10:1) nanoparticles as determined by changes in film conductivity. Our data show that Pd nanoparticles coated with these more weakly coordinated amine or ammonium groups readily react with H2 without any need for ozone or heat treatment. The conductivity of films of octylamine (C8NH2)- or dodecylamine (C12NH2)-coated Pd, PdAg, and PdAu MPCs increases irreversibly upon initial exposure to 100% H2 to varying degrees and with different reaction kinetics and then exhibits stable, reversible changes in the presence of H2 concentrations ranging from 9.6 to 0.08%. The behavior upon initial exposure to H2 (conditioning) and the direction and magnitude of the reversible conductivity changes depend on the alkyl chainlength and alloy composition. Films of TOABr-coated Pd and PdAg nanoparticles show stable, reversible increases in conductivity in the presence of H2 concentrations from 9.6 down to 0.11% without conditioning. Surface FTIR spectroscopy and atomic force microscopy (AFM) provide information about the organic monolayer and film morphology, respectively, following reactivity with H2. This work demonstrates a simple approach toward preparing films of chemically synthesized Pd-containing nanoparticles with controlled reactivity to H2 for sensing and catalysis applications.     

Achieving optimum selectivity in oxygen assisted alcohol cross-coupling on gold

Oxidative coupling of alcohols is of great practical importance due to the wide range of synthetic applications using esters. Controlling the selectivity toward production of specific esters in cross-coupling is a long-sought goal in designing efficient synthetic routes. We report a quantitative study of the factors that determine the esterification selectivity in the oxidative cross-coupling of alcohols mediated by oxygen-covered Au(111). The high reactivity of gold is attributed to the activity of atomic oxygen bound to Au particles in forming surface-bound alkoxy species. The relative surface concentrations of alkoxys and the ease of the β-H elimination play critical roles in determining the product distribution. For a given reactant composition the surface concentration of alkoxys is skewed toward the higher molecular weight alcohol in the mixture exposed to the surface. Vibrational spectroscopic studies reveal that the relative stabilities of alkoxys parallel the gas phase acidities of the corresponding alcohols, in agreement with other coinage metal surfaces. Further, the activation energies for β-H cleavage of alkoxys are found to follow the descending order: E(methoxy) > E(ethoxy) > E(butoxy). The combination of these factors optimizes cross-coupling in a reactant mixture containing an excess of the lower molecular weight alcohol. The excellent match of product distribution between our low-pressure, single-crystal study and that observed for atmospheric pressure, liquid-phase reactions over supported gold catalysts provides strong evidence that the mechanistic insights gained from fundamental surface science study can serve as guiding principles in controlling selectivity under realistic catalytic conditions.     

可持续固相合成高分散PdAg合金纳米颗粒用于电催化氢氧化和氢析出反应

固相研磨作为一种新型可持续的合成方法,近年来引起了人们广泛关注,为负载型金属合金纳米催化剂的制备提供了新思路.尽管有关合金催化剂研究取得了系列进展,但现有制备方法大多存在操作步骤复杂、形貌难以控制等问题,严重制约了合金催化剂的规模化应用.本文发展了一种可持续化策略,即于室温下在玛瑙研钵中直接研磨合成了一系列高分散在碳载体上的小尺寸PdAg合金纳米颗粒(PdAg/C).此法无需任何溶剂和有机试剂,保证了整个过程简单便捷、绿色环保,同时确保了PdAg合金纳米颗粒表面清洁无污染,利于样品的催化应用.利用TEM,XRD和XPS表征技术对系列PdAg/C样品的组成及形貌进行了深入探究.TEM结果表明,所得催化剂中金属颗粒尺寸较小(4.9±1.03 nm),且高度分散在碳载体表面.XRD结果表明,Pd9Ag1/C,Pd5Ag5/C和Pd1Ag9/C催化剂特征衍射峰位于对应的Pd/C和Ag/C衍射峰之间,且会随着Ag含量的不断增加逐渐向低角度偏移.XPS结果表明,三个催化剂中均存在Pd,Ag两种元素,且随着Ag含量的增加,它们的Pd 3d结合能逐渐正移;而随着Pd含量的不断增加,三样品的Ag 3d结合能逐渐负向偏移.由此可见,采用可持续固相合成法成功制得了碳负载的PdAg合金纳米颗粒.一系列对比实验表明,PdAg合金纳米颗粒的尺寸和分散度显著依赖于NaOH,而与碳载体的形貌、比表面积和类型无明显关系.将系列PdAg/C样品用于碱性电催化氢氧化(HOR)和析氢反应(HER)时,均展现出高的催化性能.其中,Pd9Ag1/C催化性能最佳,在HOR中,质量交换电流密度和面积交换电流密度分别为26.5 A gPd^–1和0.033 mA cmPd^–2;在HER中,电流密度为10 mA cm^–2时所需过电位仅为68 mV;此外,Pd9Ag1/C催化剂经过1000圈CV循环测试后,催化活性未显著衰减,对两个目标反应均展现出优异的电化学稳定性.PdAg/C高催化活性主要归因于两个方面:(1)PdAg合金纳米颗粒表面洁净、尺寸小且分散均匀,能提供大量可利用的活性位点;(2)Pd与Ag之间强的协同与合金效应使得催化剂具有最佳的本征活性.     

Template effects in vinyl acetate synthesis on PdAu surface alloys: a density functional theory study

Structure sensitivity is one of the key parameters that needs to be controlled to obtain atomistic design of catalysts. By means of density functional theory we have analyzed the synthesis of vinyl acetate from acetic acid, ethylene, and oxygen in several local configurations of Pd dimers on two gold surfaces (111) and (100). We have found that the most active configuration shows the best compromise between the sufficient adsorption of the reactants without poisoning the Pd template and a low barrier for the rate determining step.     

Equilibrium hydrogen pressures in vanadium alloys

The dissolution of hydrogen gas in vanadium-based alloys containing niobium, chromium and titanium was studied by measuring the equilibrium pressure, at various compositions, from 763 to 1125 K. Hydrogen followed Sieverts' law in all the alloys studied up to a hydrogen-to-metal atom ratio of 0.25. The values of the enthalpies of solution of hydrogen for these vanadium-based alloys ranged from −18.5 to −46.8 ± 1.5 kJ (mol H)⁻¹ and the standard entropies of solution of hydrogen ranged from −57.4 to −62.6 ± 5.5 J K⁻¹ (mol H)⁻¹. The present results agree extremely well with a previous low temperature study of these alloys which employed an isopiestic technique to measure indirectly the equilibrium hydrogen pressures.     

PdAu(100)和PdAu(111)双金属表面的密度泛函理论研究

采用密度泛函理论(Density Functional Theory DFT)研究Au(100)和Au(111)表面含有不同Pd构型时表面的形成能.结果表明,非连续Pd构型的形成能较连续Pd构型的低,在表面易形成,其中第二临位Pd对构型被证实是乙烯与醋酸结合生成醋酸乙烯反应中催化活性最高的构型.随后计算CO在不同表面Pd原子的顶位吸附能和Pd原子的d带中心,结果显示表面Pd原子与相邻金原子之间几乎没有电子传递,并且PdAu(111)表面的Pd原子d带中心随周围Au原子个数的增加而远离费米能级,伴随着CO在其上吸附能的减小,但是同样的趋势在PdAu(100)表面不存在.最后,通过计算,CO在金属表面的吸附机理为CO成键轨道5σ的电子传递给Pd原子的d带,而Pd原子的d带电子又反馈回CO的反键轨道2π*.     

Electrosorption of hydrogen into palladium-gold alloys

Hydrogen electrosorption into Pd-Au alloys has been studied in acidic solutions (1 M H₂SO₄) using cyclic voltammetry. Pd-Au electrodes with limited volume were prepared by electrochemical co-deposition. It was found that the maximum H/(Pd+Au) ratios decrease monotonically with increasing gold content and reach zero at ca. 70 at% Au. Similarly to the case of Pd limited volume electrodes, two peaks in the hydrogen region, corresponding to two types of sorbed hydrogen, are observed on voltammograms for Pd-rich alloys. The hydrogen capacity, H/(Pd+Au), measured electrochemically, depends on the sweep rate in the cyclic voltammetry experiments, which suggests that two different mechanisms for hydrogen desorption from the Pd-Au alloy are possible. After a strong decrease of Pd concentration at the electrode surface, caused by long cyclic polarization to sufficiently anodic potentials, the amount of absorbed hydrogen is still significant for alloys initially rich in Pd. The results obtained from CO adsorption experiments suggest that only Pd atoms are active in the hydrogen absorption/desorption process. Electronic Publication     

PdAg/MIL-101(Fe)催化NaBH4水解制氢

将PdAg纳米颗粒负载到MIL-101(Fe)上作为硼氢化钠水解制氢的催化剂。采用XRD、TEM、HRTEM、XPS、SEM和EDS等方法对催化剂PdAg/MIL-101(Fe)的结构进行了表征。PdAg/MIL-101(Fe)在硼氢化钠水解制氢中表现出较高的催化活性,在温和的条件下水解制氢最大速率为2.60 L·min^–1·g_cat.^–1。详细研究了反应温度、催化剂用量、氢氧化钠和硼氢化钠浓度对该催化反应的影响规律。结果发现,制氢速率很大程度上依赖于反应温度,随着反应温度的升高,制氢速率明显增加,制氢的表观活化能为54.89 kJ·mol^–1。该催化剂重用性能好,5次循环后仍能保持活性。     

Solution of hydrogen in palladium/copper alloys

The solution of hydrogen in $\text{Pd}\text{Cu}$ fcc substitutional alloys has been examined in the region of low hydrogen contents. Relative partial molar enthalpies of absorption at infinite dilution are found to be somewhat less exothermic for the alloys than for palladium but the change with X_Cu is small. Partial excess entropies of absorption decrease with X_Cu but not as markedly as for the other Pd/group IB alloys. Relative electrical resistance relationships for $\text{Pd}\text{Cu}$ alloys have been determined as a function of their hydrogen contents. Interstitial hydrogen increases the relative electrical resistance to a lesser extent with increase of X_Cu, but the absolute increase of resistance is nearly invariant with X_Cu.     

Thermodynamics of hydrogen solution and hydride formation in Pd-Mn alloys. 2. Ordered alloys

There are marked differences in H(2) solubilities between ordered and disordered Pd-Mn alloys with the largest difference found between the L1(2) and the disordered form of the Pd(3)Mn alloy. The thermodynamics of H(2) solution have been determined for the L1(2) form, the long-period superstructure (lps), and the disordered forms of the Pd(0.80)Mn(0.20) and Pd(0.75)Mn(0.25)(Pd(3)Mn) alloys. Relative partial molar enthalpies and entropies were determined mainly by reaction calorimetry over the range of H contents accessible from p(H)()2 approximately 10 Pa to approximately 0.3 MPa (303 K). The enthalpies for absorption of H(2) are more exothermic over most of the range of H contents for the L1(2) forms of the Pd(3)Mn and Pd(0.80)Mn(0.20) alloys than for their other forms. The reaction enthalpies are constant across a relatively wide range of H contents for the L1(2) form of the Pd(0.80)Mn(0.20) and Pd(3)Mn alloys indicating that there are two-phase coexistence regions (303 K). The H-H attractive interaction, which leads to hydride formation, is much greater for the L1(2) than for the other forms of the Pd(3)Mn alloy and for Pd itself. It has been found that the H-H interaction always decreases in magnitude and, accompanying this, the THS (terminal hydrogen solubility) always increases by alloying Pd.(1) The L1(2) ordered Pd(3)Mn alloy is an exception to this, and therefore, the generalization about THS must be restricted to disordered face centered cubic (fcc) Pd alloys.     

Thermodynamics of hydrogen solution and hydride formation in Pd-Mn alloys. 1. Disordered alloys and a correlation effect

The thermodynamics of H(2) solution and hydride formation/decomposition have been determined by reaction calorimetry (303 K) for disordered face centered cubic (fcc) Pd-Mn alloys. This alloy system belongs to the expanded lattice category which predicts that and DeltaH(plat) for H(2) absorption should be more exothermic than those for Pd; the experimental results are that the former is more exothermic, at least at the higher Mn contents, but the latter is not. There is a regular decrease in the H capacity (at p(H)2 = 0.2 MPa) with atom fraction Mn. A linear dependence of log p(H)2 upon H content is found in the single hydride phase for all of these alloys suggesting that DeltaH(H) and DeltaS(H) are also linear functions of r in this region. This is confirmed using the Pd(0.875)Mn(0.125) alloy which has no two-phase region (303 K). It is shown for the Pd(0.875)Mn(0.125) alloy and for Pd that the changes of partial enthalpies and entropies with H content are correlated so as to minimize changes of mu(H).     

镁基储氢合金的表面处理和表面催化

表面处理作为储氢合金性能改善的有效手段，近年来得到了很好的发展和应用，本文简要介绍了镁基储氢合金表面处理的主要方法及其对合金性能的影响。     

Metal alloys and carbon nanomaterials as potential hydrogen storage materials

Comparative analysis of metals (as well as their alloys and intermetallic compounds) and various carbon nanomaterials as working substances for hydrogen storage and transportation systems has been performed. It has been shown that, because of the fundamental difference in the nature of interaction with hydrogen of these two large classes of compounds, the fields of their application (as well as their performance) are certainly different. Some theoretical calculations and concepts concerning the hydrogen capacity of the materials under consideration have been critically surveyed.     

Structural and electrochemical properties of high-capacity Ml-Mg-Ni-based hydrogen storage alloys

The Ml-Mg-Ni-based (Ml = La-rich mixed lanthanide) hydrogen storage alloy Ml_0.88Mg_0.12Ni_3.0-Mn_0.10Co_0.55Al_0.10 was prepared by inductive melting. The micro-structure was analyzed by XRD and SEM. The alloy consists mainly of CaCu₅-type phase, Ce₂Ni₇-type phase and Pr₅Co₁₉-type phase. The electrochemical measurements show that the maximum discharge capacity is 386 mAh/g, 16.3% higher than that of the commercial AB₅-type alloy (332 mAh/g). At discharge current density of 1 100 mA/g, high rate dischargeability is 62%, while that of the AB5-type alloy is only 45%. The discharge capacity decreases to 315 mAh/g after 300 charge/ discharge cycles, 81.5% of the maximum discharge capacity. __________ Translated from Journal of Xi’an Jiao Tong University, 2008, 42(3) (in Chinese)     

高透量 PdAu/陶瓷复合膜的表征与性能评测

 采用化学镀方法在非对称氧化铝管状载体上制备出高性能 PdAu 合金膜. 采用阶段性热处理方法通过 X 射线衍射技术监测 PdAu 膜层合金化进程, 发现在 823 K 下 H2 气氛中厚度为 2 μm, Au 含量为 17.37% 的 PdAu 双金属膜层需要 200 h 达到完全合金化; N2/H2 气氛对 PdAu 合金化速率无显著影响, 但 N2 气氛中合金化后的 PdAu 合金膜表面粒子烧结更为严重. 在 623~823 K 下, 与未进行化学镀 Au 时的纯 Pd 膜相比, PdAu 合金膜的 H2 渗透速率平均增加 1.68 倍, 透氢活化能 (Ea) 降低 38.51%; 当温度低于 573 K 时, PdAu 合金膜的 Ea 由高温时的 8.83 kJ/mol 增加到 15.75 kJ/mol, 此时 PdAu 合金膜的 H2 渗透控速步骤由体相扩散为主的 H2 传质步骤过渡到由表面扩散为主的传质步骤. 通过扫描电镜和能谱联用仪对 PdAu 合金膜的膜厚度和截面组成进行了表征. 关键词     

Correlations between hydrogen electrosorption properties and composition of Pd-noble metal alloys

Hydrogen adsorption on and absorption into Pd alloys with other noble metals was studied in acidic solutions (0.5 M H₂SO₄) using cyclic voltammetry. Correlations were found between the potentials of adsorbed/absorbed hydrogen oxidation peaks and surface/bulk compositions of Pd–Rh alloys. The potential of the α–β-phase transition depends linearly on Pd bulk content in Pd–Au, Pd–Rh, Pd–Pt and Pd–Pt–Rh alloys. The obtained relationships can be utilized for the determination of the composition of homogeneous Pd-noble alloys from hydrogen electrosorption experiments.     

Bimetallic PdAu nanoparticles as hydrogenation catalysts in imidazolium ionic liquids

Metallic and bimetallic PdAu nanoparticles were solubilized in 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid (IL) by a phase-transfer method using poly(vinylpyrrolidone) (PVP) as a stabilizer. Nanoparticles were characterized by UV–vis spectroscopy and transmission electron microscopy. The bimetallic PdAu nanoparticles in the IL-phase were examined as catalysts for hydrogenation reactions; both the activity and selectivity of the hydrogenation reactions could be tuned by varying the composition of the bimetallic nanoparticles, with maximum activities seen at 1:3 Au:Pd ratios. These nanoparticles/IL catalysts were recycled and then reused for further catalytic reactions with minimal loss in activity.