不同体系Pd/C催化剂的制备及对甲酸的电催化氧化

采用不同体系制备了碳载Pd催化剂(Pd/C),发现在乙二醇体系中制备的Pd/C催化剂对甲酸氧化具有最负的峰电位和最低的起始氧化电位,Tafel斜率最小为155mV,并且在1h的计时电流曲线测试表明,用乙二醇体系制备的Pd/C-3催化剂具有较高的稳定电流。TEM结果可以看出,用乙二醇体系制备的Pd/C催化剂Pd粒子在活性碳表面分散得最好,Pd粒径的大小约为4～5nm。     

聚吡咯碳载PdAu催化剂对甲酸的电催化氧化

通过低温氧化法制备了聚吡咯碳(PPyC),并以PPyC为载体制备了纳米Pd催化剂(Pd/PPyC)及PdAu催化剂(PdAu/PPyC),研究发现不同比例的Pd∶Au催化剂PdAu/PPyC对甲酸的甲催化活性不同。通过计算发现,催化剂的电化学比表面积催化剂中加入少量Au能够提高催化剂中活性粒子Pd的分散度,其中Pd∶Au为4∶1时电化学比表面最大,且对甲酸有最高的电催化氧化活性。     

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。     

PdNi/C催化剂的制备及对甲酸的电催化氧化

采用化学还原法,在乙二醇体系中制备了碳载PdNi催化剂(PdNi/C),与相同方法制备的Pd/C催化剂比较,发现PdNi/C催化剂对甲酸氧化具有较负的峰电位和较高的峰电流,且起始氧化电位也较低。计时电流曲线测试表明,与Pd/C催化剂相比,甲酸在PdNi/C催化剂上的氧化电流密度随时间衰减得比较慢,且具有较高的稳定电流。     

纳米碳载Pt-TiO_2催化剂制备及对甲醇电催化氧化性能研究

炭载TiO_2与PEG混合,超声振荡1 h,80℃搅拌2 h。滴加氯铂酸,调节p H值,分别用Na BH4,甲醛及甲酸还原,制得Pt-TiO_2/C催化剂a,b及c。用循环伏安法研究甲醇及CO分别在25℃和60℃的0.5 mol/L H2SO4溶液中在Pt-TiO_2/C上的氧化情况。结果表明,甲醇在60℃的酸性溶液中氧化时3种催化剂的氧化峰电位增大,峰电流密度升高,起始峰电位负移,说明升高温度有利于甲醇氧化,并且无论在25℃还是在60℃,催化剂c的电氧化能力最好,起始氧化电位最低,峰电流和峰电位最大。60℃时CO的峰电流密度和25℃时相比无太大变化,但起始氧化电位和峰电位明显负移,说明升高温度对CO的电氧化很有利,催化剂c的抗CO能力比a,b强,活性最高。     

碳载Pt-TiO2催化剂对甲醇的电催化氧化

采用TiO2溶胶法,选用3种不同还原剂(甲酸、甲醛、硼氢化钠)制备了碳载Pt-TiO2催化剂。通过XRD衍射,循环伏安法(CV)和计时电流法(CA)对碳载Pt-TiO2催化剂的结构及其对甲醇的电氧化特性进行了研究。结果表明不同还原剂制备的催化剂中,TiO2的结晶度不同,Pt的粒径不同,电化学比表面不同,对甲醇的电催化氧化的催化活性也不同。其中用甲酸还原所制得的碳载Pt-TiO2催化剂对甲醇的电催化氧化活性分别是采用甲醛或硼氢化钠方法的1.41倍和1.76倍。     

碳载体处理对Pd催化氧化甲酸的影响

采用饱和Co盐浸渍碳黑,然后高温热处理.发现处理后的碳黑微孔体积减少,介孔体积增加,更适于作为催化剂的载体.用处理后的碳黑制备的碳载Pd催化剂比未处理的碳黑做载体制备的催化剂对甲酸氧化具有更高的电催化活性.XRD结果可以看出,经Co盐浸渍处理过的碳黑中含有一定量的Co,有助于金属Pd在碳黑表面的分散,增加活性金属的电化...     

碳载PtCu催化剂的制备及对甲醇的电催化氧化性能研究

以L-抗坏血酸(VC)为还原剂通过微波辅助法在乙二醇(EG)体系中制备了不同原子比的碳载PtCu纳米催化剂,运用循环伏安法、计时电流法、X射线粉末衍射仪(XRD)、场发射扫描电子显微镜(FESEM)等方法和手段,对催化剂在酸性甲醇溶液中的电催化活性、稳定性、结构和形貌进行了研究。电化学测试结果表明,在pH=5时进行还原的Pt、Cu原子比为1∶1的PtCu/C催化剂活性最高,稳定性最好。表征后发现该催化剂粒径最小,比表面积最大,并且分布均匀,与测试结果一致,即对甲醇的氧化具有优异的电催化性能。在降低铂基催化剂成本和提高催化剂活性方面具有一定的价值。     

Pt/PAn/GC电极的制备及对甲酸电催化氧化性能的研究

利用循环伏安法电聚合导电高分子聚苯胺，并制备了Pt／PAn／GC电极和Pt／GC电极，优化了苯胺在玻碳电极上的聚合条件，用在H2SO4中的循环伏安曲线对其进行了表征，Pt／PAn／GC电极的制备提高了Pt的分散度，增加了催化剂Pt的利用率。实验结果表明Pt／PAn／GC电极对甲酸电氧化的催化活性明显高于Pt／GC电极和Pt电极，正向扫描和反向扫描时对应的氧化峰电位分别是0．68V、0．45V。峰电流为54．23mA／cm^2和84．23mA／cm^2，为Pt／GC电极的修饰电极1．7倍和1．9倍，为Pt片电极的3．8倍和4．9倍，有效地提高了铂微粒的催化活性，并得到聚合苯胺的最佳条件为扫描速度50mV／s、扫描上限1．2V。     

WO3/CNTs担载Pd催化剂对甲酸电催化氧化性能的研究

采用WO3和CNTs混合作为Pd催化剂的载体,通过微波辅助乙二醇法合成Pd-WO3/CNTs催化剂,用于直接甲酸燃料电池,研究其对甲酸电催化氧化的性能.通过循环伏安法、电化学阻抗和计时安培技术证实,在Pd/CNTs催化剂中添加适量的WO3,催化剂的活性和稳定性都有所提高.当WO3含量为载体质量的10％时,甲酸电催化氧化...     

Formic acid oxidation by carbon-supported palladium catalysts in direct formic acid fuel cell

The oxidation of formic acid by the palladium catalysts supported on carbon with high surface area was investigated. Pd/C catalysts were prepared by using the impregnation method. 30 wt% and 50 wt% Pd/C catalysts had a high BET surface area of 123.7 m²/g and 89.9 m²/g, respectively. The fuel cell performance was investigated by changing various parameters such as anode catalyst types, oxidation gases and operating temperature. Pd/C anode catalysts had a significant effect on the direct formic acid fuel cell (DFAFC) performance. DFAFC with Pd/C anode catalyst showed high open circuit potential (OCP) of about 0.84 V and high power density at room temperature. The fuel cell with 50 wt% Pd/C anode catalyst using air as an oxidant showed the maximum power density of 99 mW/cm². On the other hand, a fuel cell with 50 wt% Pd/C anode catalyst using oxygen as an oxidant showed a maximum power density of 163 mW/cm² and the maximum current density of 590 mA/cm² at 60 °C.     

Preparation of high performance Pd catalysts supported on untreated multi-walled carbon nanotubes for formic acid oxidation

Due to the inherent inertness of carbon nanotubes (CNTs), one of the most significant challenges in the preparation of CNT-supported catalysts is achieving a uniform deposition of nanoparticles on the surface of the nanotubes. In this paper, we report on the preparation and characterization of Pd nanoparticles supported on untreated multi-walled carbon nanotubes (MWCNTs), synthesized in the presence of glutamate. The results of Raman spectroscopy revealed that this synthetic procedure does not have a detrimental effect on the surface structure of MWCNTs. Transmission electron microscopy (TEM) measurements indicated that the dispersion of Pd nanoparticles on untreated-MWCNTs in the presence of glutamate were uniform, and a narrow particle size was observed. X-ray diffraction (XRD) patterns indicated that the Pd/MWCNT catalyst possessed a face-centered cubic crystal structure. Cyclic voltammetry and chronoamperometry tests demonstrated that the obtained Pd/MWCNT catalyst displayed superior electrocatalytic activity and stability in formic acid oxidation, as compared to both a Pd/MWCNT catalyst synthesized without glutamate and a Pd catalyst on acid-oxidized MWCNTs, under otherwise identical experimental conditions. These results indicate that the catalyst developed in this study is a superior candidate for direct formic acid fuel cells (DFAFCs).     

Methanol partial oxidation on carbon-supported Pt and Pd catalysts

Different Pt and Pd catalysts supported on an activated carbon were prepared by using different metal precursors. Prepared catalysts were pretreated at 400 °C under different atmospheres to decompose the precursor compound and reduce the metal. After pretreatments, the supported catalysts were characterized by H₂ chemisorption, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy to know their metal dispersion, particle size, distribution and oxidation state. Afterwards, the catalysts were tested in methanol partial oxidation with two different O₂/CH₃OH molar ratios. Results obtained in this reaction were compared with those obtained for methanol decomposition in inert atmosphere. For Pt catalysts, there was an increase in methanol conversion and hydrogen production and a decrease in carbon monoxide production under oxidizing conditions. Both methanol conversion and partial oxidation reactions appear to be sensitive to Pt particle structure in the particle size range studied. Results obtained under oxidizing conditions differed between Pd and Pt catalysts. Finally, catalytic activity in methanol partial oxidation was more affected by Pt than Pd particle size in the size range studied.     

EXAFS study on the sulfidation behavior of Pd, Pt and Pd–Pt catalysts supported on amorphous silica and high-silica USY zeolite

The sulfur tolerance of monometallic Pd, Pt and bimetallic Pd–Pt catalysts supported on slightly acidic ultra-stable Y (USY) zeolite (SiO₂/Al₂O₃ = 390) and on non-acidic silica, having mesopores with a pore diameter of 3 or 10 nm, were investigated using the CO adsorption method and the extended X-ray adsorption fine structure (EXAFS) method. Well-dispersed noble metal particles supported on USY zeolite and silica with an average pore diameter of 3 nm showed high surface sulfur tolerance and high catalytic hydrogenation activity, although bulk phase sulfidation simultaneously occurred. The synergistic effects of sulfur tolerance were significant in the bimetallic Pd–Pt particles supported on USY zeolite and silica with an average pore diameter of 3 nm. On the other hand, on silica with an average pore diameter of 10 nm, the surface sulfur tolerance of low dispersed noble metals was the lowest, although its bulk phase sulfur tolerance was the highest. The Pd K-edge and Pt L_III-edge EXAFS spectra indicated a strong interaction between the well-dispersed noble metal particles and the supports of the USY zeolite and silica with an average pore diameter of 3 nm. This distorted structure may increase the sulfur tolerance of noble metals, though some surface and bulk phase sulfidation simultaneously occurred.     

Low-temperature catalytic combustion of methanol and its decomposed derivatives over supported gold catalysts

Gold can be compared favorably with Pd and Pt in the catalytic combustion of CH₃OH, HCHO and HCOOH when it is deposited on some reducible metal oxides (-Fe₂O₃, TiO₂, etc.). While the supported gold catalysts are less active in H₂ oxidation, they exhibit much higher activities in CO oxidation. For Au/TiO₂, the effect of catalyst preparation was further investigated. Since the activity for CO oxidation of the gold catalysts is not depressed but enhanced by moisture, they are practically applicable to CO removal from air at room temperature. Gold supported on manganese oxide is especially effective in the selective CO removal from hydrogen, indicating its potential applicability to polymer electrolyte fuel cells using the reformed gas of methanol.     

Carbon nanotube supported platinum-palladium nanoparticles for formic acid oxidation

Pt, Pd and Pt_xPd_y alloy nanoparticles (Pt₁Pd₁, Pt₁Pd₃, atomic ratio of Pt to Pd is 1:1, 1:3, respectively) supported on carbon nanotube (CNT) with high and uniform dispersion were prepared by a modified ethylene glycol method. Transmission electron microscopy images show that small Pt and Pt_xPd_y nanoparticles are homogeneously dispersed on the outer walls of CNT, while Pd nanoparticles have some aggregations and comparatively larger particle size. The average particle sizes of Pt/CNT, Pt₁Pd₁/CNT, Pt₁Pd₃/CNT and Pd/CNT obtained from the Pt/Pd (2 2 0) diffraction peaks in the X-ray diffraction patterns are 2.0, 2.4, 3.1 and 5.4 nm, respectively. With increasing Pd amount of the catalysts, the mass activity of formic acid oxidation reaction (FAOR) on the CNT supported catalysts increases in both cyclic voltammetry (CV) and chronoamperometry (CA) tests, although the particle size gets larger (thus, the relative surface area gets smaller). The CV study indicates a ‘direct oxidation pathway’ of FAOR occurred on the Pd surface, while on the Pt surface, the FAOR goes through ‘CO_ads intermediate pathway’. Pd/CNT demonstrates 7 times better FAOR mass activity than Pt/CNT (2.3 mA/mgPd vs. 0.33 mA/mgPt) at an applied potential of 0.27 V (vs. RHE) in the CA test.