Palladium nanoclusters-coated polyfuran as a novel sensor for catecholamine neurotransmitters and paracetamol

A promising electrochemical biosensor was developed by electrodeposition of palladium nanoclusters on polyfuran film modified platinum electrode. This biosensor electrode was used to determine some catecholamines, namely dopamine, epinephrine and norepinephrine, ascorbic acid and paracetamol. The method of formation of the polymer film and deposition of Pd particles plays a key role in the electroactivity of the resulting hybrid material. This sensor effectively resolved the overlapping anodic peaks of ascorbic acid (AA), dopamine (DA) and paracetamol (ACOP) into three well-defined voltammetric peaks in differential pulse voltammetry analysis. The detection limit of DA in the absence and presence of AA and ACOP are eventually the same which indicates that the oxidation processes of DA, AA and ACOP are independent and that the simultaneous measurements of the three analytes are possible without interference. The electrodeposition of Pd on polyfuran improved exceptionally the detection limit about four decades. Moreover, diffusion coefficient measurements confirmed the fast electron transfer kinetics of the electrochemical oxidation of the analyte molecules at the sensor/solution interface. It is very interesting to note that the electrocatalytic effect of PF/Pd composite has been increased to be sometimes 21 times that of the pristine PF which has been considered for a long time to be of low conductivity and attracted low attention as a result of the difficulty of its formation and poor conductivity.     

Identification of Pd3+ ions in zeolite L by temperature programmed reduction and electron paramagnetic resonance spectroscopy

Pd supported on KL zeolite has been studied by temperature programmed reduction (TPR) and electron paramagnetic resonance (EPR) spectroscopy. It has been found that upon calcination in pure oxygen Pd³⁺ and Pd²⁺ ions are formed; the Pd³⁺ ions are identified by their EPR signal. As Pd³⁺ ions in the cancrinite cages are difficult to reduce, the H₂ consumption in conventional TPR is below the stoichiometric amount.     

α-丙二醇-水相中氯代二噁英的催化加氢脱氯降解

二噁英类物质由于具有亲脂性、高毒性、化学结构稳定、难生物降解而在环境中持久存在,成为持久性有机污染物的典型代表.二嗯英的去除方法研究,一直是国际研究的热点.以5％钯/炭为催化剂,氢气作为氢源,以环境友好的α-丙二醇-水为溶剂,在1 mol/L氢氧化钠的碱性条件下,研究了1,2,7,8-四氯代二噁英（1,2,7,8-TCDD）的催化加氢脱氯降解.探讨了反应温度、初始浓度、反应时间、催化剂用量等对1,2,7,8-TCDD去除率的影响.结果表明,在反应初期（前5 min）,反应速率较快;在反应温度为45℃,催化剂用量为0.5 g/mL,反应时间为150 min的条件下,1,2,7,8-TCDD的去除率达97.0％;初始浓度对1,2,7,8-TCDD的去除率没有影响.初步试验结果表明,催化加氢脱氯降解是去除环境中氯代二嗯英的有效手段,但实际应用还有待于进一步研究.     

Low-temperature catalytic combustion of methane over Pd/CeO2 prepared by deposition–precipitation method

Ceria supported 2 wt% Pd catalysts for low-temperature methane combustion were prepared by the impregnation (IM) and deposition–precipitation (DP) methods, which are denoted as Pd–IM and Pd–DP, respectively. DP was found to be an available method for achieving high activity and stability of the Pd/CeO₂ catalyst. The temperatures for methane ignition (T_10%) and total conversion (T_100%) over Pd–DP are 224 and 300 °C at GHSV of 50,000 h⁻¹, which are 83 and 110 °C lower than the corresponding temperatures of Pd/Al₂O₃. X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS) analyses show that palladium species in Pd–DP is highly dispersed, positively charged and difficultly reduced. Raman spectra disclosed that the largest concentration of defects and/or oxygen vacancies was formed in Pd–DP catalyst. A kind of cationic PdO^δ+ sites with higher binding energies than PdO are in close vicinity to the oxygen vacancies in the CeO₂ support and might act as the active centers for methane oxidation. Furthermore, the deactivation and steam aging tests for Pd–DP showed that the performance of this type of palladium was very stable and could be repeatedly recovered after several long time aging tests.     

Liquid phase hydrodechlorination of chlorophenols over Pd/C and Pd/Al2O3: a consideration of HCl/catalyst interactions and solution pH effects

The liquid phase hydrodechlorination (HDC) of 2-chlorophenol (2-CP) and 2,4-dichlorophenol (2,4-DCP) has been studied over 1% (w/w) Pd/C and Pd/Al₂O₃ under conditions of minimal mass transport constraints. The HDC of 2,4-DCP generated HCl and 2-CP as the only intermediate partially dechlorinated product which reacts further to yield phenol; cyclohexanone was formed over Pd/Al₂O₃, but not over Pd/C, prior to complete dechlorination. Pd/Al₂O₃ is characterized (on the basis of TEM analysis) by a narrow distribution of smaller Pd particles to give a surface area weighted mean particle DIAMETER = 2.4 nm that is appreciably lower than the value of 13.2 nm established for Pd/C, where the latter is characterized by a broader distribution of larger (spherical) particles. The addition of NaOH served to increase fractional dechlorination by suppressing HDC inhibition due to the HCl that is generated. Reuse of the catalysts revealed an appreciable deactivation of Pd/C and a limited loss of activity in the case of Pd/Al₂O₃. Deactivation of Pd/C can be linked to a decrease (up to ca. 60%) in the initial BET surface area allied to appreciable leaching (up to ca. 40%) of the starting Pd content through the corrosive action of HCl and, while the average Pd diameter is essentially unaffected, there is evidence of a preferred leaching of larger Pd particles. The stronger metal/support interactions prevalent in Pd/Al₂O₃ results in limited Pd leaching and comparable initial HDC activities during catalyst reuse with/without NaOH addition. Inclusion of HCl in the reaction mixture (pH 5–1.5) resulted in a marked decline in the initial HDC rate associated with Pd/Al₂O₃ and a lesser drop in HDC activity for Pd/C. The difference in response to bulk solution pH variations are discussed in terms of the nature of the reactive species in solution and the amphoteric behavior of the Pd supports.     

CH4检测元件中Pd/Al2O3催化剂的制备及反应性能

为提高矿井CH4浓度检测中催化元件的稳定性和可靠性，针对催化元件中催化剂性能这一核心问题进行研究是解决问题的关键．对催化剂结构的表征以及对催化元件工作性能和催化剂反应性能进行了测试，结果表明：经900℃焙烧处理的催化剂载体Al2O3具有适宜于反应的颗粒分散度与孔径分布，催化元件表现出较好工作性能．采用真空干燥处理制备的负载量为3％的Pd／Al2O3催化剂具有较高的反应活性；但助剂的加入使得反应活性有所降低；采用HCl作竞争吸附荆可使活性纽分均匀分布于Al2O3内孔；栽体的二次成型工艺在一定程度上降低了电桥的零点漂移，提高了催化元件的稳定性．     

印制电路板孔金属化相关研究

对印制电路板孔金属化所用胶体钯的性质、从废胶体钯溶液中回收金属Pd的工艺方法及染料对酸性镀铜液的均镀能力和深镀能力的影响等进行了研究。结果表明：在回收钯工艺中采用加热破胶法可使金属Pd的回收率达98．79％；添加剂对胶体钯￡电位有着直接影响，且Na2SnO4和香草醛对胶体钯的稳定性具有一定作用；并对镀层整平性和光亮性以及镀液均镀和深镀能力进行分析比较，确定了实验范围内的最佳染料添加剂是亚甲基蓝和罗丹明B，其均镀能力分别为75．05％和68．42％，深镀能力分别为85％和88％。     

共沉淀富集分离矿石中微量金、铂、钯

研究了硒、铜、银、砷作为共沉淀剂。富集分离地质样品中金、铂、钯的最佳条件。在3mol/L HCl介质中，以4mg硒和5mg铜、银、砷对金、铂、钯进行共沉淀富集，采用孔雀绿分光光度法测定金．DDO分光光度法测定铂、钯，回收率均在95％-102％之间。通过对含金矿样加入铂、钯标准样品的回收实验，结果令人满意。     

Thermal behaviors of deactivation catalysts for synthesizing 2, 3, 5-trimethylhydroquinone

The thermal behaviors of the deposits on supported noble metal catalysts for synthesizing 2, 3, 5-trimethylhydroquinone by DSC were studied. The results show that the supported Pd catalysts have two exothermic peaks at around 312 °C and 435 °C in the DSC thermograms, respectively, while the supported Pt catalysts have one exothermic peak at approximately 345 °C. Therefore, it is supposed that the adsorptive states of deposits on supported Pt catalysts and supported Pd catalysts are different, which may be one reason leading to the stability difference between supported Pt catalysts and supported Pd catalysts.     

花岗斑岩类岩石中Au、Pd溶解性状的实验研究

研究花岗斑岩类岩石中Au、Pd的溶解性状 ,对于研究其溶解、迁移、沉淀条件有着重要的理论价值。研究结果表明 ,花岗斑岩中Au、Pd地球化学性状明显不同 ,Au活性显著 ,Pd惰性特征明显。在T =2 5 0℃、P =2 0× 10 5～ 30× 10 5Pa、pH =7.5 6的条件下 ,Au浸出率最低 ,易于沉淀成矿 ;在T =10 0℃、P =10 0× 10 5Pa、pH =8.2时 ,Au浸出率高 ,最易被活化溶解 ;当T =5 0 0℃ ,P =5 0 0× 10 5Pa ,pH =8.5时 ,Au浸出率中等 ,易被搬运、迁移。Pd易于沉淀成矿的条件是T =10 0℃ ,P =5 0 0× 10 5Pa ,pH =8.2 ;Pd易于活化溶解的条件是T =2 5 0℃ ,P =10× 10 5Pa ,pH =8.5 ;在T =30 0℃、P =(2 0～ 30 )× 10 5Pa、pH =6条件下发生搬运迁移。