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.     

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.     

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.     

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.     

Ni catalyst promotion of a Cis-selective Pd catalyst for canola oil hydrogenation

A Ni catalyst was added to a cis-selective Pd catalyst in an attempt to further improve the Pd catalyst's cis-selectivity and activity for canola oil hydrogenation. The system was tested under reaction conditions known to be suitable for cis-selective hydrogenation with the Pd catalyst (50 ppm Pd, 70 °C, and 5.2 MPa). Although inactive on its own under these conditions, the addition of 100 ppm Ni increased the hydrogenation activity (from 2.12 to 2.49 10⁻² min⁻¹). Further addition of Ni up to 1000 ppm resulted in no further improvements in activity. The trans isomer contents of the oils hydrogenated with Pd and the Pd/Ni systems were similar. The level of conjugated dienes decreased rapidly during hydrogenation with both Pd alone and with the Pd/Ni combination and no changes in conjugation were detected in the presence of the Ni catalyst alone. The increased activity of the Pd/Ni system over Pd alone was attributed to adsorption of catalyst poisons from the oil by Ni.     

无机膜的应用与展望

本文综述了无机膜的发展、制备方法和应用。     

助剂对Pd/树脂醚化催化剂催化性能的影响 Ⅰ.铝助剂的影响

研究了不同助剂对Ｐｄ／树脂醚化催化剂在临氢条件下对催化裂化汽油Ｃ５馏份与甲醇和Ｈ２反应的催化性能的影响。结果表明，在Ｐｄ／树脂醚化催化剂中引入Ｚｒ、Ｔｉ、Ｂ、Ｓｎ和Ａｌ等助剂后，都能改善催化剂的醚化、双键异构和二烯烃选择性加氢活性，其中以Ａｌ、Ｓｎ为最好。Ａｌ助剂的体积质量和负载方式对Ｐｄ－Ａｌ／树脂醚化催化剂的活性有影响。ＢＥＴ方法和Ｘ－射线荧光光谱分析（ＸＦＳＡ）表明，Ａｌ助剂对Ｐｄ－Ａｌ／树脂醚化催化剂的表面积、孔结构和Ｐｄ离子交换量影响较小。     

Formation of C4 species in the deactivation of a Pd/SiO2 catalyst during the selective hydrogenation of acetylene

The deactivation characteristics of Pd/SiO₂ in the selective hydrogenation of acetylene were correlated with changes in the amount of the C4 species produced. The amounts of butenes produced changed in parallel with the catalyst activity, indicating that the rate limiting step for butene production was the same as that for acetylene hydrogenation. On the other hand, the amount of 1,3-butadiene produced changed, showing a maximum with catalyst deactivation because 1,3-butadiene is an intermediate in the sequential reaction process which involves both the production and consumption of 1,3-butadiene. This was verified by a simultaneous TG/reaction experiment showing that 1,3-butadiene was a precursor of green oil. The catalyst showed a self-regenerative behavior in its activity and the amounts of C4 species produced during the early stage of deactivation because two opposite factors, which contributed to either the lowering or the promotion of activity, were involved in the process. A specific type of polymer species, produced during the initial period of deactivation, is proposed to be responsible for the promotion of catalyst activity.     

乙炔在磁稳定床中的选择性加氢研究

 制备了一种磁性Pd/Al₂O₃催化剂，采用磁稳定床考察了活性组分负载量、反应条件及CO浓度对乙炔加氢反应性能的影响。结果表明，当反应温度80℃、反应压力1.5MPa、空速9000h－1、磁场强度（H）25kA/m时，乙炔转化率为100％，乙烯选择性可达81％，具有优良的乙炔加氢活性和乙烯选择性，优于相同反应条件下的进口催化剂；250h稳定性实验结果表明，磁性Pd/Al2O3催化剂具有良好的初活性和乙烯选择性，催化剂性能稳定。     

延长Pd/C催化剂使用寿命的途径

影响钯 炭催化剂使用寿命的因素主要有催化剂失活 ,运输、装填过程中的磨损 ,工艺操作条件等。延长催化剂的使用寿命的途径有正确的运输、装填方法 ,定期冲洗 ,定期碱洗和分阶段调整氢气加入量