A silica-immobilized Pt2+catalyst for the selective, aerobic oxidation of methane via an electron-transfer chain

The combination of Pt^2＋, benzoquinone and NaNO2 forms an electron-transfer chain, which leads to the oxidation of methane by O2 in CF3COOH aqueous solution. The overall turnover number per hour （TOF） of methane at 120 ℃ is 0.5 h^-1, however, only about one fourth （23%） of methane is converted to the desired product of methanol in the formation of CF3COOCH3. The over-oxidation of methane to CO2, over the catalyst with the Pt^2＋ species immobilized via 2,2＇-bipyridyl as a ligand on the silica substrate, is depressed distinctly. Under the same conditions, the conversion to methanol dominates, and no CO2 is observed, on account of the over-oxidation of methane, as confirmed by the isotope experiment.     

Methanol oxidation on a Pt(111)-OH/O surface

The methanol oxidation on a hydroxylated Pt (Pt(111)-OH) surface has been investigated by means of infrared reflection absorption spectroscopy (IRAS) in ultra-high vacuum (UHV) and in acidic solution. The Pt(111)-OH surface in UHV was prepared by introducing water molecules on a Pt(111)-(2 x 2)-O surface and annealed at temperature higher than 160 K. Methanol was then, introduced to the Pt(111)-OH surface to show the dependence of the reaction intermediate on the annealing temperature. At an annealing temperature below 160 K, IR bands assignable to methanol overlayer were observed and no detectable intermediates, such as CO, formaldehyde and formate, were formed, suggesting that methanol molecules remain stable on Pt(111) surface without dissociation at this temperature region. At an annealing temperature above 160 K, on the other hand, CO and formate were observed. In addition, the oxidation of CO on Pt(111)-OH showed no sign of formate formation, indicating that formate is not derived from CO, but from a direct oxidation of methanol. Methanol oxidation was carried out in 0.1 mol dm(-3) HClO(4) solution on Pt(111) with a flow cell configuration and showed the formation of formate. These results indicate that the formate is the dominant non-CO intermediate both in UHV and in acidic solution, and the preadsorbed oxygen-containing species, in particular OH adsorbates, on Pt(111) surface plays a very important role in the formate formation process in methanol oxidation reaction.     

Methanol dehydrogenation and oxidation on Pt(111) in alkaline solutions

Adsorption, dehydrogenation, and oxidation of methanol on Pt(111) in alkaline solutions has been examined from a fundamental mechanistic perspective, focusing on the role of adsorbate-adsorbate interactions and the effect of defects on reactivity. CO has been confirmed as the main poisoning species, affecting the rate of methanol dehydrogenation primarily through repulsive interactions with methanol dehydrogenation intermediates. At direct methanol fuel cell (DMFC)-relevant potentials, methanol oxidation occurs almost entirely through a CO intermediate, and the rate of CO oxidation is the main limiting factor in methanol oxidation. Small Pt island defects greatly enhance CO oxidation, though they are effective only when the CO coverage is 0.20 ML or higher. Large Pt islands enhance CO oxidation as well, but unlike small Pt islands, they also promote methanol dehydrogenation. Perturbations in electronic structure are responsible for the CO oxidation effect of defects, but the role of large Pt islands in promoting methanol dehydrogenation is primarily explained by surface geometric structure.     

Electrocatalytic oxidation of methanol onto platinum particles decorated nanostructured poly (1,5-diaminonaphthalene) film

In this work, platinum particles decorated nanostructured poly (1,5-diaminonaphthalene) modified glassy carbon electrode (Pt/Nano-PDAN/MGCE) is prepared. The composite catalysts are characterized by scanning electron microscopy, energy dispersive spectroscopy, and electrochemical methods. The electrochemical methanol oxidation reaction is studied at the surface of this modified electrode. At same Pt loading, the Pt/Nano-PDAN/MGCE can act as higher efficient catalyst for methanol oxidation than that Pt/MGCE. Then, the influence of some parameters such as potential scan rates, switching potential, and methanol concentration on its oxidation as well as long-term stability of the modified electrode have studied by electrochemical methods. Also, ability of the modified electrode toward electrocatalytic oxidation of formaldehyde as an intermediate in methanol oxidation has been investigated.     

On-line mass spectrometry investigation of the reduction of carbon dioxide in acidic media on polycrystalline Pt

Differential electrochemical mass spectrometry (DEMS) is used to investigate the reaction of electroreduction of CO₂ on platinum porous electrode in acidic media. This technique, which gives molecular specificity, permits the reaction products to be followed concurrently with potential and time. These results showed for the first time the on-line production of methanol in acidic media using a Pt electrodeposited electrode. Reduction of CO₂ in perchloric acid on Pt occurs in the H₂ evolution region leading to the formation of formic acid methanol and traces of methane. Experiments using CO show that this substance is the intermediate of the pathway leading to methanol.     

Direct oxidation of methane at low temperature using Pt/C,Pd/C,Pt/C-ATO and Pd/C-ATO electrocatalysts prepared by sodium borohydride reduction process

The main objective of this paper was to characterize the voltammetric profiles of the Pt/C,Pt/C-ATO,Pd/C and Pd/CATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte at 25 ℃ and in a direct methane proton exchange membrane fuel cell at 80 ℃. The electrocatalysts prepared also were characterized by X-ray diffraction( XRD) and transmission electron microscopy( TEM). The diffractograms of the Pt/C and Pt/C-ATO electrocatalysts show four peaks associated with Pt face-centered cubic( fcc) structure,and the diffractograms of Pd/C and Pd/C-ATO show four peaks associated with Pd face-centered cubic( fcc) structure. For Pt/C-ATO and Pd/C-ATO,characteristic peaks of cassiterite( SnO_2) phase are observed,which are associated with Sb-doped SnO_2( ATO) used as supports for electrocatalysts. Cyclic voltammograms( CV) of all electrocatalysts after adsorption of methane show that there is a current increase during the anodic scan. However,this effect is more pronounced for Pt/C-ATO and Pd/C-ATO. This process is related to the oxidation of the adsorbed species through the bifunctional mechanism,where ATO provides oxygenated species for the oxidation of CO or HCO intermediates adsorbed in Pt or Pd sites. From in situ ATR-FTIR( Attenuated Total Reflectance-Fourier Transform Infrared) experiments for all electrocatalysts prepared the formation of HCO or CO intermediates are observed,which indicates the production of carbon dioxide. Polarization curves at 80 ℃in a direct methane fuel cell( DMEFC) show that Pd/C and Pt/C electroacatalysts have superior performance to Pd/C-ATO and Pt/C-ATO in methane oxidation.     

Modification of a Pt surface by spontaneous Sn deposition for electrocatalytic applications. 2. Oxidation of CO,formaldehyde, formic acid,and methanol

The electrocatalytic activity of a spontaneously tin-modified Pt catalyst, fabricated through a simple dip-coating method under open-circuit conditions and characterized using surface analysis methods, was studied in electrooxidation reactions of a preadsorbed CO monolayer and continuous oxidation of methanol, formic acid, and formaldehyde in the potentiodynamic and potentiostatic modes. The catalytic activity of the tin-modified Pt surface is compared with that of a polycrystalline Pt electrode. Spontaneously Sn-modified Pt catalyst shows a superior activity toward adsorbed CO oxidation and thus can be promising for PEFC applications. The methanol oxidation rate is not enhanced on the Sn-modified Pt surface, compared to the Pt electrode. Formic acid oxidation is enhanced in the low potential region on the Sn-modified surface, compared to the Pt electrode. The formaldehyde oxidation rate is dramatically increased by modifying tin species at the most negative potentials, where anodic formaldehyde oxidation is completely suppressed on the pure Pt electrode. The results are discussed in terms of poisoning CO intermediate formation resulting from dehydrogenation of organic molecules on Pt sites, and oxidation of poisoning adsorbed CO species via the surface reaction with OH adsorbed on neighboring Sn sites.     

甲醇在铂微粒修饰的聚硫堇电极上的电催化氧化

利用电化学循环伏安和现场ＦＴＩＲ反射光谱等技术研究了甲醇在铂微粒修饰的聚硫堇电极上的电催化氧化。结果表明，循环伏安法制备的铂微粒均匀分散于聚合物膜上，其粒径大小约为３０－１３０ｎｍ；复合修饰电极对甲醇电化学氧化呈现了较高的催化活性，其催化活性的大小依赖于Ｐｔ载量。现场ＦＴＩＲ光谱实验揭示了线性吸附的ＣＯ物种是甲醇在复合电极上氧化的唯一中间体，这种吸附的ＣＯ物种在复合修饰电极上更容易被氧化为最终产物     

一步法制备还原态氧化石墨烯载铂纳米粒子及其对甲醇氧化的电催化性能

以天然石墨为原料,采用改进的Hummers法制备氧化石墨.然后采用简单的一步化学还原法在乙二醇(EG)中同时还原氧化石墨烯(GO)和H₂PtCl₆制备高分散的铂/还原态氧化石墨烯(Pt/RGO)催化剂.采用傅里叶变换红外(FTIR)光谱、X射线衍射(XRD)和透射电子显微镜(TEM)对催化剂的微结构、组成和形貌进行表征.结果表明, GO已被还原成RGO, Pt纳米粒子均匀分散在RGO表面,粒径约为2.3 nm.采用循环伏安法和计时电流法评价催化剂对甲醇氧化的电催化性能,测试结果表明, Pt/RGO催化剂对甲醇氧化的电催化活性和稳定性与Pt/C和Pt/CNT相比有了很大提高.另外其对甲醇电催化氧化的循环伏安图中正扫峰电流密度(I_f)和反扫峰电流密度(I_b)的比值高达1.3,分别是Pt/C和Pt/CNT催化剂的2.2和1.9倍,表明Pt/RGO催化剂具有高的抗甲醇氧化中间体CO_ad的中毒能力.     

甲醇在铂修饰的氧化钛电极上电催化氧化行为的研究

运用电化学方法评价了电化学阴极还原-阳极氧化两步法制得的以钛为基体的铂修饰的钛氧化物(Pt-TiO_x/Ti)电极对甲醇电催化氧化的性能,结果表明,制得的修饰电极对甲醇氧化呈现了很高的电催化活性和好的稳定性.通过X光电子能谱(XPS)、扫描隧道显微镜(STM)和现场傅立叶变换红外(FTIR)反射光谱等技术,发现修饰电极对甲醇氧化具有高的电催化性能,可归属于纳米级Pt粒子在TiO_x中的高度分散及由于Pt和TiO_x的相互作用,使电极表面对甲醇氧化中间产物CO的吸附量大大降低.     

Formate,an active intermediate for direct oxidation of methanol on pt electrode

The electro-oxidation of methanol on a Pt thin film electrode in acidic solution has been investigated by in situ surface-enhanced IR absorption spectroscopy. A new IR peak is observed at around 1320 cm-1 when the electrode potential is more positive than 0.5 V, where the bulk oxidation of MeOH occurs. This peak has been assigned to the symmetric stretching of formate species adsorbed on the Pt electrode surface. It is the first observation of formate adsorption during the electro-oxidation of methanol on a Pt surface. A near proportional relationship between the intensity of the IR band of the formate species and MeOH electro-oxidation current is observed. A new reaction scheme via non-CO pathway with formate as the active intermediate is proposed for the methanol electro-oxidation process.     

Structural and mechanistic investigations of the oxidation of dimethylplatinum(II) complexes by dioxygen

The oxidation of (tmeda)Pt(II)(CH(3))(2) (1, tmeda = N,N,N',N'-tetramethylethylenediamine) to (tmeda)Pt(IV)(OH)(OCH(3))(CH(3))(2) (3) by dioxygen in methanol proceeds via a two-step mechanism. The initial reaction between (tmeda)Pt(CH(3))(2) and dioxygen yields a hydroperoxoplatinum(IV) intermediate, (tmeda)Pt(OOH)(OCH(3))(CH(3))(2) (2), which reacts with a second equivalent of (tmeda)Pt(CH(3))(2) to afford the final product 3. Both 2 and 3 have been fully characterized, including X-ray crystallographic structure determinations. The effect of ligand variation on the oxidation of several dimethylplatinum(II) complexes by 2 as well as by dioxygen has been examined.     

Pt及其修饰电极上甲醇吸附和氧化的CV和EQCM研究

运用电化学循环伏安和石英晶体微天平 (EQCM )研究了 0 .1mol·L- 1H2 SO4 溶液中甲醇在Pt电极和以Sb ,S不可逆吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的吸附和氧化过程 .结果表明甲醇的氧化与电极表面氧物种有着极其密切的关系 .Pt电极表面Sb吸附原子能在较低的电位下吸附氧 ,可显著提高甲醇电催化氧化活性 .与Pt电极相比较 ,Sb吸附原子修饰的Pt电极使甲醇氧化的峰电位负移了 0 .13V .相反 ,Pt电极表面S吸附原子的氧化会消耗表面氧物种 ,抑制了甲醇的电氧化 .本文从表面质量变化提供了吸附原子电催化作用的新数据     

Pt-CNTs 修饰玻碳电极(Pt-CNTs/GC)电氧化活性的研究

采用透射电镜(TEM)和选区电子衍射(SAED)技术, 分别表征了Pt-CNTs/GC电极的表面形貌和所负载铂纳米原子簇的结构. 以CO和CH3OH为探针分子, 用循环伏安和计时电流等常规电化学方法检测了CO和CH3OH在Pt-CNTs/GC电极上的氧化行为. 研究结果表明, CO在Pt-CNTs/GC电极上有3个氧化电流峰(Ⅰ, Ⅱ, Ⅲ), 其中峰Ⅰ为CO桥式吸附的氧化峰, 而峰Ⅱ和Ⅲ则分别为CO线形吸附在碳纳米管负载的不同粒径的Pt纳米原子簇以及Pt原子薄膜上所分裂的氧化峰; CH3OH在Pt-CNTs/GC电极上也能自发解离吸附强吸附中间体CO; Pt-CNTs/GC电极对CH3OH的氧化峰电流不总是随CNTs上载铂量的增加而增大, 表明在制备直接甲醇燃料电池阳极时, 应选择合适的载铂量.     

Kinetics and mechanism of methane, methanol, and dimethyl ether C-H activation with electrophilic platinum complexes

The relative rates of C-H activation of methane, methanol, and dimethyl ether by [(N-N)PtMe(TFE-d(3))](+) ((N-N) = ArN=C(Me)-C(Me)=NAr; Ar = 3,5-di-tert-butylphenyl, TFE-d(3) = CF(3)CD(2)OD) (2(TFE)) were determined. Methane activation kinetics were conducted by reacting 2(TFE)-(13)C with 300-1000 psi of methane in single-crystal sapphire NMR tubes; clean second-order behavior was obtained (k = 1.6 +/- 0.4 x 10(-3) M(-1) s(-1) at 330 K; k = 2.7 +/- 0.2 x 10(-4) M(-1) s(-1) at 313 K). Addition of methanol to solutions of 2(TFE) rapidly establishes equilibrium between methanol (2(MeOD)) and trifluoroethanol (2(TFE)) adducts, with methanol binding preferentially (K(eq) = 0.0042 +/- 0.0006). C-H activation gives [(N-N)Pt(CH(2)OD)(MeOD)](+) (4), which is unstable and reacts with [(RO)B(C(6)F(5))(3)](-) to generate a pentafluorophenyl platinum complex. Analysis of kinetics data for reaction of 2 with methanol yields k = 2.0 +/- 0.2 x 10(-3) M(-1) s(-1) at 330 K, with a small kinetic isotope effect (k(H)/k(D) = 1.4 +/- 0.1). Reaction of dimethyl ether with 2(TFE) proceeds similarly (K(eq) = 0.023 +/- 0.002, 313 K; k = 5.5 +/- 0.5 x 10(-4) M(-1) s(-1), k(H)/k(D) = 1.5 +/- 0.1); the product obtained is a novel bis(alkylidene)-bridged platinum dimer, [(diimine)Pt(mu-CH(2))(mu-(CH(OCH(3)))Pt(diimine)](2+) (5). Displacement of TFE by a C-H bond appears to be the rate-determining step for all three substrates; comparison of the second-order rate constants (k((methane))/k((methanol)) = 1/1.3, 330 K; k((methane))/k((dimethy)(l e)(ther)) = 1/2.0, 313 K) shows that this step is relatively unselective for the C-H bonds of methane, methanol, or dimethyl ether. This low selectivity agrees with previous estimates for oxidations with aqueous tetrachloroplatinate(II)/hexachloroplatinate(IV), suggesting a similar rate-determining step for those reactions.     

In-situ flow-cell IRAS observation of intermediates during methanol oxidation on low-index platinum surfaces.

Structural effects on intermediate species of methanol oxidation are studied on low-index planes of platinum using in-situ infrared (IR) spectroscopy. A flow cell is designed for rapid migration of reactant and product species on the electrode surface. IR spectra show adsorption of formate and the formation of carbonate species on the Pt(111) surface at potentials higher than that of CO oxidation. The band assignments for carbonate and formate are confirmed by vibrational isotope shifts. On Pt(100), the absorption band of adsorbed formate is much smaller than that on Pt(111). On the other hand, there is no adsorbed formate on Pt(110) in the potential region examined. The band intensity of formate follows the order: Pt(111)>Pt(100)>Pt(110). This order is opposite to that of the current density in the regions of higher potential. Adsorbed formate on Pt(111) behaves like a catalyst-poisoning intermediate, like adsorbed CO.     

At least three contiguous atoms are necessary for CO formation during methanol electrooxidation on platinum

We have used cyanide-modified Pt(111) electrodes to investigate the size and geometry of the minimum atomic ensemble necessary for the oxidation of methanol on Pt electrodes. Poison formation on cyanide-modified Pt(111) is completely inhibited, the corresponding electrooxidation reaction proceeding, hence, exclusively through the reactive intermediate pathway. These results suggest that formation of adsorbed CO would require the presence of at least three contiguous Pt atoms.     

Electrochemical oxidation of alkyl-substituted allenes in methanol

Mono-, di- and tri-alkyl-substituted allenes were potentiostatically oxidized in methanol at graphite and Pt anodes. At the former electrode, α-methoxylated ketones (due to 4F/mole electricity consumption) and esters (6F/mole) were the major products. At a Pt anode, intermediate products such as vinyl-ether derivatives (2F/mole) were characterised too. Unlike the anodic oxidation of alkenes and alkynes previously reproted in the literature, dimerisation is not a typical process in the allenes' oxidation, since of all the products obtained only a sole dimer has been observed. The mechanism for the formation of most products is discussed.     

Sm3+对甲醇电化学氧化反应的助催化作用

分别以相同面积的光滑Pt电极和吸附了Sm3+的铂电极作为工作电极,在酸性介质中采用循环伏安法对甲醇氧化进行测定.结果表明,吸附了Sm3+的Pt电极上产生了更大的氧化电流,表明Sm3+的加入对甲醇的电催化氧化起到了促进作用.这一研究结果在直接甲醇燃料电池(DMFC)阳极催化剂研制方面具有较大的应用潜力.     

Pt微粒修饰纳米纤维聚苯胺电极对甲醇氧化电催化

以脉冲电流法制备的纳米纤维状聚苯胺(PANI)为Pt催化剂载体，用它制备了甲醇阳极氧化的催化电极Pt/（nano-fibular PANI）.研究结果表明, Pt/（nano-fibular PANI）电极对甲醇氧化具有很好的电催化活性,并有协同催化作用.在相同的Pt载量条件下， Pt/（nano-fibular PANI）电极比Pt微粒修饰的颗粒状聚苯胺电极Pt/(granular PANI)具有更好的电催化活性.此外， Pt的电沉积修饰方法同样影响Pt/（nano-fibular PANI）电极对甲醇氧化的催化活性.脉冲电流法沉积Pt形成的复合电极较循环伏安法电沉积得到的Pt复合电极具有更优异的催化活性.