以KMnO4改性炭黑为载体Pd-Ni催化剂的制备和性能

以不同浓度的KMnO_4溶液预处理的炭黑为载体,通过沉淀共还原法合成了3种Pd_1Ni_1/AC_x(x=3、5、7)催化剂。采用XPS、ICP、XRD和TEM对催化剂进行了表征。结果表明:Pd_1Ni_1/AC_5的Pd负载量(质量分数,下同)最大(3.66%),Pd晶粒的平均粒径最小(4.71 nm),且均匀地分布在KMn O_4氧化处理后的碳载体上,活性位点较多;XRD显示,3种Pd_1Ni_1/AC_x催化剂中大部分的Ni均以无定形形式存在。电化学性能测试结果表明:3种催化剂均表现出比商业Pd/C更好的电化学稳定性和存活率;其中,Pd_1Ni_1/AC_5电化学活性表面积达62.21 m~2/g_(Pd),且乙醇催化氧化活性为1797.85 A/g_(Pd)。     

还原法制备Pd-Ni/C阳极催化剂及其性能研究

以预处理的活性炭为载体、二氧化铈为修饰剂、NaBH_4为还原剂,制备了Pd_2Ni_3/C、Pd_(core)Ni_(shell)/C、Ni_(core)Pd_(shell)/C 3种不同结构的碱性燃料电池阳极催化剂。采用XPS、XRD、TEM表征了其结构及微观形貌,并通过电化学测试考察了其电化学性能。结果表明:NicorePdshell/C催化剂中n(Pd)∶n(Ni)=2∶3.3较接近理想比例(2∶3),催化剂颗粒分散均匀,粒径分布最窄,且平均粒径最小,为3.4 nm。电化学测试结果表明:在碱性环境下,Nicore Pdshell/C催化剂在100 m V/s扫描速度下,最高电流密度达到160 m A/cm2,在-0.5 V条件下,电流密度为2.80m A/cm2,其稳定性均优于Pd2Ni3/C和PdcoreNishell/C催化剂。     

活性炭改性对松香歧化用Pd/C催化剂性能的影响

采用沉积-沉淀法制备了4% Pd/C催化剂（Pd质量分数4%）,分别以硝酸、盐酸、双氧水和氨水4种溶剂对Pd/C的载体活性炭进行改性,并对载体活性炭的比表面积和孔结构、零电荷点（PZC）以及活性组分Pd的分散度进行了表征,研究了活性炭改性对Pd催化剂在松香歧化反应中催化性能的影响。结果表明：经氨水改性后活性炭比表面积孔径增大且活性炭PZC值升高,有利于活性组分Pd在载体表面的分散,以氨水改性活性炭为载体制备得到的Pd/C催化剂活性最高,在催化剂投料量为0.03%,280℃反应2 h条件下,脱氢枞酸质量分数高达81.7%。     

铜、钡对单钯型汽车尾气净化催化剂性能影响研究

制备了Pd/Ni/La-Ce-Al、Pd/cu/Ni La-Ce-Al、Pd/Ba/Ni-La-Ce-A1 3 种类型的汽车尾气净化催化剂,考察了3种催化剂对CO、C3H8和NO氧化还原活性.研究结果表明,铜不适合作为Pd/Ni/La-ce-Al催化剂的助剂;钡是提高Pd/Ni/La-Ce-Al催化剂性能特别是改善其NO还原性能的良好助剂.     

络合还原法制备的Pd/C催化剂对甲酸氧化的电催化性能

分别以硼氢化钠和乙二醇为还原剂,经络合还原法制备了炭载钯（Pd/C）催化剂。透射电镜（TEM）和X射线粉末衍射谱（XRD）结果表明,以乙二醇为还原剂制备的Pd/C催化剂中Pd粒子具有较小的粒径、均匀的粒径分布和较大的相对结晶度,Pd粒子的平均粒径和相对结晶度分别为4.2±2 nm和1.88。电化学测试结果显示,以乙二醇为还原剂制备的Pd/C催化剂具有较大的电化学活性面积,对甲酸氧化表现出较高的电催化活性和稳定性。     

载体的碱处理对Pd/C催化剂电催化性能的影响

将活性炭放入质量分数为10%的NaOH溶液中进行预处理,然后将其与未处理的活性炭分别作为载体制备Pd/C催化剂。对比两种催化剂的电化学性能发现,预处理的活性炭所制备的Pd/C催化剂,在甲酸电催化氧化活性和稳定性方面好于未处理的活性炭所制备的Pd/C催化剂。     

Pd/AC催化1,4-二氯苯加氢脱氯研究

以活性炭(AC)为载体,采用浸渍法制备Pd/AC催化剂,并利用XRD,BET,SEM,TEM等表征手段对AC和Pd/AC进行表征,结果表明,活性组分Pd在活性炭上分散均匀。研究了Pd/AC为催化剂,常压下对1,4-二氯苯(1,4-DCB)进行催化加氢脱氯。在以甲醇为溶剂,2 m L,12.5 g/L 1,4-二氯苯-甲醇溶液为反应原料,Pd/AC催化剂用量为100 mg,反应温度35℃,反应时间为4 h和常压氢气条件下,1,4-DCB的去除率达到100%,苯收率为100%。Pd/AC催化剂套用5次后活性下降,主要原因为有机物沉积和活性组分Pd团聚。     

Pd/rGO催化硝基苯无溶剂加氢合成苯胺

采用氧化石墨烯（GO）、还原石墨烯（rGO）和硝酸活化处理的活性碳（C-HNO3）负载Pd纳米粒子制得了3种Pd基催化剂Pd/GO、Pd/rGO和Pd/C-HNO3。通过XRD、XPS、N2吸附-脱附、SEM、TEM、HRTEM对其进行了表征。以商用Pd/C催化剂（Pd质量分数10%）作为对照，考察3种催化剂催化硝基苯无溶剂加氢的活性和选择性。结果表明，rGO纳米片高效网络结构和Pd纳米粒子之间的良好的耦合作用使得Pd/rGO在3种催化剂中表现出最高的Pd金属比表面积（178.37 m2/g）和分散度（43.75%）。在Pd/rGO催化剂质量浓度为10 g/L，1 MPa H2，90 ℃，5 mL 硝基苯的反应条件下，苯胺的产率随反应时间增加呈上升趋势。反应100 min后，硝基苯完全转化，苯胺产率达到100%。循环使用9次后，Pd/rGO仍可催化硝基苯高效转化获得97.1%的苯胺产率。     

高性能PtNi合金催化剂构筑及其对甲醇电催化

以多壁碳纳米管（CNTs）为载体，H2PtCl6·6H2O为铂源、Ni(NO3)2·6H2O为镍源，硼氢化钠和乙二醇为还原剂，采用一锅法制备了一种PtNi/CNTs合金电催化剂。采用XRD、SEM、TEM、HR-TEM、XPS、ICP-OES和Raman对催化剂结构进行表征。采用循环伏安法（CV）、计时安培法（i-t）和CO溶出曲线法评价了催化剂的电化学活性与稳定性。结果表明，PtNi/CNTs对甲醇电催化氧化（MOR）反应具有优异的电催化性能，峰值电流和稳态电流分别是商业Pt/C的5.89倍和38.97倍，同时，PtNi/CNTs还表现出良好的稳定性，主要归因于碳纳米管独特的结构与双金属合金的协同效应。     

添加ZrO2的Pd/Al2O3催化剂及其催化蒽醌加氢性能

以四氯合钯（II）酸（H2PdCl4）为前体,活性氧化铝（Al2O3）为载体,硝酸锆（Zr（NO3）4）为添加组分,采用不同方式的分步浸渍法制备了添加ZrO2的Pd/Al2O3催化剂。考察了制备方法和反应条件对催化剂蒽醌加氢催化性能的影响,发现催化剂活性与制备方法有关。当对添加锆的载体进行适当焙烧,控制Pd负载量为0.3%,还原温度低于300℃时,催化剂的蒽醌加氢活性较高,与未添加ZrO2的催化剂相比提高了约20%。X射线衍射（XRD）、氮气物理吸附（BET）、透射电镜（TEM）、X光电子能谱（XPS）和程序升温还原（TPR）等表征对催化剂物相结构、比表面积、表面形貌及组分间相互作用的分析表明,ZrO2的掺杂提高了载体Al2O3的高温稳定性,改善了催化剂中活性组分Pd与载体间的相互作用,促进了Pd在载体表面的分散,从而提高了催化活性。     

HI decomposition over active carbon supported binary Ni–Pd catalysts prepared by electroless plating

A series of binary Ni–Pd catalysts supported on active carbon was prepared by electroless plating method. For comparison, active carbon supported monometallic Pd and Ni catalysts were also prepared by liquid-phase reduction. Among the Pd, Ni and binary Ni–Pd catalysts, the catalyst of 1%Ni–1%Pd/C showed the best catalytic performance for the decomposition of HI. Furthermore, characterizations by BET and XRD revealed that the binary Ni–Pd catalyst had the higher stability in specific surface area and structure than monometallic Pd catalyst during HI decomposition.     

Pd-Cu/γ-Al_2O_3双金属催化剂脱除水中硝酸盐

采用分步浸渍法和共浸渍法制备系列Pd负载质量分数为1%的Pd-Cu/γ-Al2O3双金属催化剂,以氢气为还原剂研究其对水中硝酸盐催化脱除的性能。结果表明,催化剂中Cu与Pd物质的量比以及Cu、Pd的浸渍顺序对催化剂性能有重要影响,硝酸根转化率随着Cu与Pd物质的量比的增大而增大;硝酸根转化活性以Cu与Pd物质的量比为5∶1、先浸渍Pd再浸渍Cu所得催化剂较优;从氨氮选择性方面看,以先浸渍Cu后浸渍Pd制备的催化剂选择性较低,在Cu与Pd物质的量比为1∶1、先浸渍Cu再浸渍Pd所得催化剂较优。     

钯炭催化剂载体对莫西沙星侧链中间体合成的影响

改进了用于莫西沙星侧链中间体合成的钯炭催化剂制备工艺,主要讨论载体材质、粒度及处理方式对催化剂性能的影响。结果表明,选择椰壳炭为载体,粒度(300~400)目,用氢氧化钠处理的载体制备的催化剂与现售催化剂相比,选择性提高2个百分点,重复使用性能提高33%。     

Pd/HZSM-5催化剂催化加氢丙酮合成甲基异丁基酮

以HZSM-5为载体,采用浸渍法制备系列Pd/HZSM-5催化剂,在高压连续流动固定床反应器中考察Pd/HZSM-5催化剂催化加氢丙酮一步法合成甲基异丁基酮性能,并对工艺条件进行优化。结果表明,当HZSM-5载体上Pd负载质量分数为0.5%时,在反应温度140 ℃、氢压1 MPa、空速0.48 h^-1和氢酮物质的量比为1条件下,Pd/HZSM-5催化剂催化活性较高,丙酮转化率为45.91%,甲基异丁基酮选择性为94.33%。采用XRD、H₂-TPD、SEM、EDS和TGA等对催化剂进行表征,结果表明,负载质量分数0.5%的Pd在HZSM-5分子筛表面分散均匀,且0.5%Pd/HZSM-5催化剂具有较高氢吸附能力,失活的主要原因为催化剂表面积炭,采用流化床反应器取代传统的固定床反应器可以很好的解决催化剂积炭问题。     

ZrC–C and ZrO2–C as Novel Supports of Pd Catalysts for Formic Acid Electrooxidation

The Pd/ZrC–C and Pd/ZrO₂–C catalysts with zirconium compounds ZrC or ZrO₂ and carbon hybrids as novel supports for direct formic acid fuel cell (DFAFC) have been synthesized by microwave‐assisted polyol process. The Pd/ZrC–C and Pd/ZrO₂–C catalysts have been characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), energy dispersive analysis of X‐ray (EDAX), transmission electron microscopy (TEM), and electrochemical measurements. The physical characteristics present that the zirconium compounds ZrC and ZrO₂ may promote the dispersion of Pd nanoparticles. The results of electrochemical tests show that the activity and stability of Pd/ZrC–C and Pd/ZrO₂–C catalysts show higher than that of Pd/C catalyst for formic acid electrooxidation due to anti‐corrosion property of zirconium compounds ZrC, ZrO₂, and metal–support interaction between Pd nanoparticles and ZrC, ZrO₂. The Pd/ZrC–C catalyst displays the best performance among the three catalysts. The peak current density of formic acid electrooxidation on Pd/ZrC–C electrode is nearly 1.63 times of that on Pd/C. The optimal mass ratio of ZrC to XC‐72 carbon is 1:1 in Pd/ZrC–C catalyst with narrower particle size distribution and better dispersion on surface of the mixture support, which exhibits the best activity and stability for formic acid electrooxidation among all the samples.     

Comparison of CNF and XC-72 carbon supported palladium electrocatalysts for magnesium air fuel cell

Palladium catalysts supported on carbon nanofibers (CNFs) and XC-72 carbon were developed by chemically reducing palladium chloride with ethylene glycol. The morphologies and crystal structure of the Pd/CNF catalyst and Pd/XC-72 catalyst were investigated by TEM and XRD, respectively. The electrocatalytical activity of the catalysts was examined via cyclic voltammetry testing techniques. The performance of the air electrodes was examined by linear polarization methods. Magnesium air fuel cells with Pd/CNF catalyst and Pd/XC-72 catalyst were fabricated and characterized. The results showed that the Pd/CNF catalyst had higher catalytic activity for the oxygen reduction reaction and achieved better performance of the magnesium air fuel cell compared with the Pd/XC-72 catalyst.     

Performance characterization of direct formic acid fuel cell using porous carbon-supported palladium anode catalysts

Palladium particles supported on porous carbon of 20 and 50 nm pore diameters were prepared and applied to the direct formic acid fuel cell (DFAFC). Four different anode catalysts with Pd loading of 30 and 50 wt% were synthesized by using impregnation method and the cell performance was investigated with changing experimental variables such as anode catalyst loading, formic acid concentration, operating temperature and oxidation gas. The BET surface areas of 20 nm, 30 wt% and 20 nm, 50 wt% Pd/porous carbon anode catalysts were 135 and 90 m²/g, respectively. The electro-oxidation of formic acid was examined in terms of cell power density. Based on the same amount of palladium loading with 1.2 or 2 mg/cm², the porous carbon-supported palladium catalysts showed higher cell performance than unsupported palladium catalysts. The 20 nm, 50 wt% Pd/porous carbon anode catalyst generated the highest maximum power density of 75.8 mW/cm² at 25 °C. Also, the Pd/porous carbon anode catalyst showed less deactivation at the high formic acid concentrations. When the formic acid concentration was increased from 3 to 9 M, the maximum power density was decreased from 75.8 to 40.7 mW/cm² at 25 °C. Due to the high activity of Pd/porous carbon catalyst, the cell operating temperature has less effect on DFAFC performance.     

Heterogeneous catalytic hydrogenation of canola oil using palladium

The hydrogenation of canola oil was studied using palladium black as a potential catalyst for producing partially hydrogenated fats with lowtrans-isomer content. Pressure (150\s-750 psig) appeared to have the largest effect ontrans-isomer formation. At 750 psig, 90 C and 560 ppm metal concentration, a maximum of 18.7%trans isomers was obtained at IV 53. A nickel catalyst produces about 50%rans isomers at the same IV. For palladium black, the linolenate and linoleate selectivities were 1.2 and 2.7, respectively. The maximum level oftrans isomers observed ranged from 18.7% to 42.8% (150 psig). Temperature (30\s-90 C) and catalyst concentration (80\s-560 ppm) affected the reaction rate with little effect ontrans-isomer formation and selectivities. At 250 psig and 50 C, supported palladium (5% Pd/C) appeared to be twice as active as palladium black. At 560 ppm Pd, 5% Pd/C produced 30.2%trans (IV 67.5), versus 19.0%trans for palladium black (IV 68.9). Respective linoleate selectivities were 15 and 6.6, while linolenate selectivities were approximately unity. Analysis of the oil samples by neutron activation showedapproximately a 1 ppm, Pdresidue after filtration.     

Hydroformylation of 1-hexene for oxygenate fuels via promoted cobalt/active carbon catalysts at low-pressure

The hydroformylation of 1-hexene was catalyzed with active carbon-supported cobalt catalysts under the low syngas pressure. Small amount of Pt, Pd and Ru, added as promoters in Co/AC, led to a great improvement of catalytic activity for hydroformylation of 1-hexene. The promotional effect of Ru for Co/AC catalyst was the best in this study as the highest activity and selectivity for oxygenate formation. Meanwhile, the activity of 1-hexene hydroformylation increased with increasing Ru loading. Ru added was bulk-rich in the active carbon supported cobalt particles, showing very low surface Ru density. This kind of unbalanced alloy formation determined the highest performance of Ru added Co/AC catalyst, via small particles but high reduction degree, keeping more CO in non-dissociative state and lowering surface hydrogen pressure.     

碳载PdCo合金催化剂对甲酸的电催化氧化

用间歇式微波法制备了不同Pt：Co原子比的碳载PdCo合金催化剂（PdCo／C）,发现在酸性溶液中Pd：Co原子比2：1催化剂对甲酸的电氧化有良好的催化活性和稳定性。从H在电极表面的吸脱附峰计算出来的结果表明,催化剂中加入一定比例的金属Co能够增加催化剂的电化学比表面。