Selective and efficient hydrogen separation of Pd–Au–Ag ternary alloy membrane

The widespread demand for clean energy stimulates great interest to hydrogen energy with high energy density and conversion efficiency. Separation technologies by membranes are increasingly applied for hydrogen separation because of its excellent performance and low consumption. In this work, density functional theory simulations is used to study hydrogen separation of Pd–Au–Ag membrane, and the performance of Pd–Au alloy is also compared and discussed. The results indicate that Pd–Au alloy shows superior selectivity to H₂ gas over CO, N₂, CH₄, CO₂ and H₂S gases, which is in line with experimental results. In particular, the separation selectivity of Pd–Au–Ag to H₂ is significantly greater than those for Pd–Au alloy and several currently reported materials. Moreover, the permeability of H₂ in Pd–Au–Ag exceeds the limits for industrial production at deferent temperatures. Our calculations demonstrate that Pd–Au–Ag alloy present excellent performance as a promising membrane for hydrogen separation.     

High performance H2 sensor based on rGO-wrapped SnO2–Pd porous hollow spheres

Hydrogen (H₂) sensors based on metal oxide semiconductors (MOS) are promising for many applications such as a rocket propellant, industrial gas and the safety of storage. However, poor selectivity at low analyte concentrations, and independent response on high humidity limit the practical applications. Herein, we designed rGO-wrapped SnO₂–Pd porous hollow spheres composite (SnO₂–Pd@rGO) for high performance H₂ sensor. The porous hollow structure was from the carbon sphere template. The rGO wrapping was via self-assembly of GO on SnO₂-based spheres with subsequent thermal reduction in H₂ ambient. This sensor exhibited excellently selective H₂ sensing performances at 390 °C, linear response over a broad concentration range (0.1–1000 ppm) with recovery time of only 3 s, a high response of ～8 to 0.1 ppm H₂ in a minute, and acceptable stability under high humidity conditions (e. g. 80%). The calculated detection limit of 16.5 ppb opened up the possibility of trace H₂ monitoring. Furthermore, this sensor demonstrated certain response to H₂ at the minimum concentration of 50 ppm at 130 °C. These performances mainly benefited from the special hollow porous structure with abundant heterojunctions, the catalysis of the doped-PdO_x, the relative hydrophobic surface from rGO, and the deoxygenation after H₂ reduction.     

Effect of support and reduction temperature in the hydrogenation of CO2 over the Cu–Pd bimetallic catalyst with high Cu/Pd ratio

Metal-support interaction and catalyst pretreatment are important for industrial catalysis. This work investigated the effect of supports (SiO₂, CeO₂, TiO₂ and ZrO₂) for Cu–Pd catalyst with high Cu/Pd ratio (Cu/Pd = 33.5) regarding catalyst cost, and the reduction temperatures of 350 °C and 550 °C were compared. The activity based on catalyst weight follows the order of Si > Ce > Zr > Ti when reduced at 350 °C. The reduction temperature leads to the surface reconstruction over the SiO₂, CeO₂ and TiO₂ catalysts, while results in phase transition over Cu–Pd/ZrO₂. The effect of reduction temperature on catalytic performance is prominent for the SiO₂ and ZrO₂ supported catalysts but not for the CeO₂ and TiO₂ ones. Among the investigated catalysts, Zr-350 exhibits the highest methanol yield. This work reveals the importance of the supports and pretreatment conditions on the physical-chemical properties and the catalytic performance of the Cu–Pd bimetallic catalysts.     

Improved formic acid oxidation using electrodeposited Pd–Cd electrocatalysts in sulfuric acid solution

In the present research, nanostructured Pd–Cd alloy electrocatalysts with different compositions were produced using the electrodeposition process. The morphology of the samples was studied by scanning electron microscopy analysis. Also, the elemental composition of the samples was determined by energy-dispersive X-ray spectroscopy and elemental mapping tests. Tafel polarization and electrochemical impedance spectroscopy methods were employed to determine the electrochemical corrosion properties of the synthesized samples in a solution containing 0.5 M sulfuric acid and 0.1 M formic acid. The linear sweep voltammetry, cyclic voltammetry, and chronoamperometry techniques were also employed to evaluate the electrocatalytic activity of prepared samples toward the oxidation of formic acid. In this respect, the influence of some factors such as formic acid and sulfuric acid concentrations and also potential scan rate was investigated. Compared to the pure Pd sample, the Pd–Cd samples were more reactive for the oxidation of formic acid. Besides, the sample with a lower amount of Pd (Pd_1·3Cd) demonstrated much higher electrocatalytic activity than the Pd_7·1Cd and Pd_2·1Cd samples. The observed high mass activity of 15.06 A mg^?1_Pd for the Pd_1·3Cd sample which is 21.1 times higher than Pd/C is an interesting result of this study.     

Synthesis of highly active and stable Pd/C catalysts toward HCOOH dehydrogenation by a simple NH3 adsorption method

Pd catalysts supported on activated carbon (Pd/C–NH₃) toward HCOOH dehydrogenation were prepared by a simple adsorption method using ammonia (NH₃) and Ar as the working gas. The results show that the TOF_initial of Pd/C–NH₃ was 459.8 h⁻¹ at 50 °C. When the reaction was carried out for 4 h, the HCOOH dehydrogenation ratio over Pd/C–NH₃ was about 81.2%, which was 1.15 and 1.13 times, respectively, as that of the as-prepared Pd/C catalyst without any treatment (Pd/C–As) and the Pd/C catalyst purchased from Sigma-Aldrich (Pd/C-CM). The total amount of H₂ and CO₂ produced by using Pd/C–NH₃ to decompose HCOOH in the third cycle was 99.4% of the gas produced by the first reaction cycle, and 1.80 and 12.60 times, respectively, as that of Pd/C–As and Pd/C-CM. The characterization results indicated that the Pd active species in Pd/C–NH₃ migrated to the outer surface of the carbon support during the reaction, and the pore volume of the carbon support became larger, which were beneficial to the reaction. These factors made Pd/C–NH₃ exhibit excellent HCOOH dehydrogenation activity and stability. NH₃ adsorption is a simple and effective method for preparing high-performance Pd/C HCOOH dehydrogenation catalysts, and has important guiding significance for the preparation of other carbon supported noble metal catalysts.     

Et-Ph-BCTABipy的合成及其对Pd2+的萃取性能

合成了N，N′-二乙基-N，N′-二苯基-［2，2′-联吡啶］-6，6′-二硫代酰胺(Et-Ph-BCTABipy)萃取剂，并利用¹³C NMR和¹H NMR对其进行了表征；研究了相接触时间、萃取剂浓度、水相初始酸度和Pd²⁺浓度等因素对Et-Ph-BCTABipy萃取Pd²⁺性能的影响，利用摩尔比法确定了Et-Ph-BCTABipy与Pd²⁺所形成的配合物组成；同时，在Ln(Ⅲ)与Pd²⁺共存体系中研究了Et-Ph-BCTABipy对Pd²⁺的萃取选择性。结果表明：Et-Ph-BCTABipy在HNO₃体系中对Pd²⁺具有较强的萃取性能和较高的萃取选择性；萃取过程中Et-Ph-BCTABipy与Pd²⁺以1∶2的比例结合，其萃取平衡常数K_ex=3.42×10⁶。     

Selective hydrogenation of acetylene over Pd/CeO2

Five hundred ppm Pd/CeO₂ catalyst was prepared and evaluated in selective hydrogenation of acetylene in large excess of ethylene since ceria has been recently found to be a reasonable stand-alone catalyst for this reaction. Pd/CeO₂ catalyst could be activated in situ by the feed gas during reactions and the catalyst without reduction showed much better ethylene selectivity than the reduced one in the high temperature range due to the formation of oxygen vacancies by reduction. Excellent ethylene selectivity of ~100% was obtained in the whole reaction temperature range of 50°C–200°C for samples calcined at temperatures of 600°C and 800°C. This could be ascribed to the formation of Pd_xCe_1−xO_2−y or Pd-O-Ce surface species based on the X-ray diffraction and X-ray photoelectron spectroscopy results, indicating the strong interaction between palladium and ceria.     

Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

In this study, the decomposition of methanol into the CO and H species on the Pd/tungsten carbide (WC)(0001) surface is systematically investigated using periodic density functional theory (DFT) calculations. The possible reaction pathways and intermediates are determined. The results reveal that saturated molecules, i.e., methanol and formaldehyde, adsorb weakly on the Pd/ WC(0001) surface. Both CO and H prefer three-fold sites, with adsorption energies of −1.51 and −2.67 eV, respectively. On the other hand, CH₃O stably binds at three-fold and bridge sites, with an adsorption energy of −2.58 eV. However, most of the other intermediates tend to adsorb to the surface with the carbon and oxygen atoms in their sp³ and hydroxyl-like configurations, respectively. Hence, the C atom of CH₂OH preferentially attaches to the top sites, CHOH and CH₂O adsorb at the bridge sites, while COH and CHO occupy the three-fold sites. The DFT calculations indicate that the rupture of the initial C–H bond promotes the decomposition of CH₃OH and CH₂OH, whereas in the case of CHOH, O–H bond scission is favored over the C–H bond rupture. Thus, the most probable methanol decomposition pathway on the Pd/WC(0001) surface is CH₃OH → CH₂OH → trans-CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH₃OH decomposition pathway and reduces the noble metal utilization.     

Selective hydrogenation of levoglucosenone over Pd/C using formic acid as a hydrogen source

Selective hydrogenation of lignocellulosic biomass-derived chemicals is of great importance for future energy and chemical supply. So far formic acid is considered as one of the most promising materials for hydrogen storage. Herein, we report a novel pathway for the hydrogenation of Levogluosenone (LGO), a biorenewable platform chemical, to dihydrolevoglucosenone (Cyrene) and levoglucosanol (Lgol) using formic acid as a hydrogen source. Testing with typical hydrogenation catalysts indicated the crucial influence of the type on reaction selectivity and identified Pd/C as the most suitable catalyst. Among solvents screened, THF in combination with Pd/C showed the best performance for LGO hydrogenation, producing Cyrene in >99% yield at a low temperature (60 °C). Nevertheless, hydrogenation of Cyrene to Lgol required a harsher condition as a result of the difficult reduction property of its C=O bond. Elevating the reaction temperature to 180 °C and increasing double Pd dosage enabled a high yield of Lgol, attaining to 94.8%.     

Facile synthesis of PdAu/C by cold plasma for efficient dehydrogenation of formic acid

Decomposition of formic acid biomass to generate hydrogen is vital for coping with fossil energy depletion, environmental pollution, and developing clean, efficient, safe, and sustainable modern energy system. In this study, a PdAu/C−C bimetallic catalyst was prepared by the co-impregnation method followed by an atmospheric pressure (AP) cold plasma treatment to synthesize PdAu/C−P catalysts. The resulting PdAu/C−P showed excellent catalytic activity for the formic acid dehydrogenation (FAD) reaction. The total volume of H₂ and CO₂ released from the FAD reaction was about 375 mL after 4 h at 50 °C, and the initial turnover frequency (TOF_initial) was 808.6 h⁻¹. We used X−ray diffractometry (XRD), temperature programmed reduction (TPR) and high-resolution transmission electron microscopy (HRTEM) to show that plasma can effectively promote the redispersion of Pd−Au particles on the surface of the support. The average particle size of PdAu/C−P (3.5 ± 1.5 nm) was less than PdAu/C−C (4.4 ± 1.9 nm) and uniformly distributed. X-ray photoelectron spectroscopy (XPS), TPR, and HRTEM showed that PdAu/C−P has a higher degree of alloying. In addition, the strong electric field in the plasma facilitated more metal sites located on the outer surface of the support in PdAu/C−P, and the atomic ratio of M/C (M = Pd and Au) (0.0134) was much larger than that of PdAu/C−C (0.0060). The apparent activation energy (E_a) of PdAu/C−P for the FAD reaction was only 27.25 kJ mol⁻¹, and it had much higher activity and stability than the commercial Pd/C (Sigma−Aldrich). The total volume of H₂ and CO₂ produced over the PdAu/C−P for three cycles was 1.33, 5.87, and 8.56 times that of commercial Pd/C. Overall, the cold plasma enhanced the degree of alloying, promoted the redispersion of agglomerated particles, and regulated the surface enrichment of the active metal components. This is of great significance for guiding the preparation of high−performance multi-metal catalysts by cold plasma.