Catalytic effects of ruthenium and osmium spontaneous deposition on platinum surfaces toward methanol oxidation

The influence of ruthenium and osmium spontaneous deposition on polycrystalline platinum in sulfuric acid was studied by conventional electrochemical techniques. The inhibition of the hydrogen adatom voltammetric profile by the foreign adatoms was used to calculate the degree of surface coverage of ruthenium, osmium, and a mixture of both metal ions from solutions of different composition. Methanol adsorption and oxidation were compared on bare platinum, platinum/ruthenium, platinum/osmium, and ternary compounds, considering the efficiency of methanol oxidation per hydrogen adatom displaced by the foreign metal on platinum.     

甲醇在欠电位沉积Ru修饰Pt电极上的催化氧化

采用欠电位沉积(upd)方法在Pt 表面沉积亚单层的Ru制备出upd-Ru/Pt 电极. 通过欠电位沉积前后电极在0.5 mol·L-1 H2SO4溶液中循环伏安图-152 - 128 mV(vs Ag/AgCl)电位范围内对氢区的数值积分确定Pt表面Ru 的覆盖度. 用电化学方法测试了甲醇在upd-Ru/Pt电极上的催化氧化, 并讨论分析了欠电位沉积电位和Ru的表面覆盖度对甲醇氧化的影响. 结果表明, Ru能够欠电位沉积到Pt表面. Pt表面欠电位沉积少量的Ru 即能大大促进甲醇的氧化.只要控制upd-Ru的沉积量, upd-Ru原子就能大大促进甲醇氧化而与沉积电位无关. Ru原子对甲醇氧化的促进作用与Ru和Pt是否形成合金无关, 而取决于Ru 在Pt表面的百分含量.     

Electrooxidation of methanol on upd-Ru and upd-Sn modified Pt electrodes

The electrochemical oxidation of methanol has been investigated on underpotentially deposited-ruthenium-modified platinum electrode (upd-Ru/Pt) and on underpotentially deposited-tin-modified platinum electrode (upd-Sn/Pt). The submonolayers of upd-Ru and upd-Sn on a Pt electrode increased the rate of methanol electrooxidation several times as large as that on a pure Pt electrode. The best performance for methanol electrooxidation was obtained on a ternary platinum based catalyst modified by upd-Ru and upd-Sn simultaneously. The influence of the submonolayers of upd-Ru adatoms and upd-Sn adatoms on the oxidation of methanol in acid has been investigated. The effect of Ru on methanol electrooxidation lies on the distribution of Ru adatoms on a Pt surface. It has been shown that as long as the amount of upd-Ru deposits were controlled in a proper range, upd-Ru deposits would enhance the methanol oxidation obtained on a Pt electrode at whichever deposition potential the upd-Ru deposits were obtained. The effects of tin are sensible to the potential range. The enhancement effect of upd-Sn adatoms for the oxidation of methanol will disappear as the electrode potential is beyond a certain value. It is speculated that there exists a synergetic effect on the Pt electrode as adatoms Ru and Sn participate simultaneously in the methanol oxidation.     

Catalytic effects on methanol oxidation produced by cathodization of platinum electrodes

A catalytic effect is found for methanol oxidation after new active surface states are produced on polycrystalline platinum by potentiostatic cathodization in acid media at room temperature. This procedure originates surface states not available on the original polycrystalline electrodes with unexpected cyclic voltammetric responses; i.e., at least four new peaks below 0.9 V are observed. The cathodization process also induces a rearrangement of the bulk platinum oxide, showing a defined peak at 1.2 V. The appearance of these new states is also proven by open-circuit potential decays. The electrocatalytic activity of these new surfaces in methanol oxidation is compared with that of the untreated electrodes by electrochemical impedance spectroscopy, chronoamperometry, and cyclic voltammetry. The cathodic procedure enhances the methanol oxidation voltammetric current peaks with charge density values higher than those on untreated platinum. The integration of chronoamperometric plots over 10 min in methanol acid media presents the largest difference between 0.6 and 0.7 V with respect to the original surface. Analysis of the impedance data shows that the values of polarization resistance for methanol oxidation on the cathodically treated platinum are lower than those of the original surface. According to the time constant values for methanol oxidation, the original surface can be considered less tolerant of the formation of catalytic poisons. A discussion of the most likely mechanism for the formation of the new active sites on platinum is presented here, assuming the presence of hydrogen subsurface states, ordered water clusters, and low-coordinated platinum atoms.     

Electrocatalysis by foreign metal monolayers: Oxidation of formic acid on platinum

It was demonstrated that some foreign metal monolayers formed by underpotential deposition have pronounced catalytic effects on the oxidation of formic acid on platinum. The explanation of these effects was sought within the framewor of existing data on the formic acid oxidation and the underpotential deposition. It was found that the catalytic effect of foreign metal monolayers originates in the decrease of hydrogen adsorption thus preventing the formation of the main poisoning species COH. At the same time these experiments confirm the previously postulated mechanism of formation of the poisoning species involving adsorbed hydrogen.     

吸附原子电催化机理的研究——铂单晶(100)晶面上Pb、Cd吸附原子在甲酸电氧化中的助催化特性

In this work a modified adsorption method was used to form firstly a saturated Cd or Pb adlayer on platinum single crystal (100) surface, then its surface structure, the electrochemical stability and the desorption-readsorption CV properties were studied. The HCOOH oxidation has been used as a probe to determine the electrocatalytic propertics of Pt (100) with different surface concentration of Cd or Pb adatoms. The results show that Cd adatoms on Pt(100) inhibit both HCOOH dissociation adsorption (to form poisoning intermediates) and HCOOH oxidation via the reactive intermediate, and that Pb adatoms on Pt(100) inhibit only HCOOH disociation adsorption but catalyse HCOOH oxidation via the reactive intermediate, in this case the more Pb adatoms on Pt(100), the higher te catalytic effect. The highest enhanced catalytic effet has been found with the saturated Pb adlayer on Pt(100) (the coverage of Pb, calibrated by hydrogen adsorption, is then equal to 1.0), i.e. with a surface structure of C(2×2)-bridged Pb. The difference of influence to the hydrogen adsorption-desorption process and the different catalytic effect on HCOOH oxidation of Cd and Pb adatoms on Pt(100) were attributed to the intrinsic properties of Cd and Pd elements and also to their interaction with Pt(100). This results indicate that the electrocatalytic mechanism of Cd and Pb adatom on Pt(100) depends on the geometrical surface structure effect and, more importantly, on the electro structure effect during the interaction of adatoms with Pt(100) surface atoms.     

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     

Interfacial Study of Nickel-Modified Pt(111) Surfaces in Phosphate-Containing Solutions: Effect on the Hydrogen Evolution Reaction

The surface modification of electrodes attracts great interest in electrocatalysis. It has often been observed that deposition of foreign adatoms on the surface of an electrode can originate a significant enhancement in the catalytic activity. For example, it has been reported that nickel deposits on Pt surfaces improve the rate of the hydrogen evolution reaction (HER, Nature Energy 2017, 2, 17031). During the deposition process of such metal adlayers, the pH and the nature of the ions in the electrolyte play an important role. Phosphate species are typically used to prepare buffer solutions in a wide range of pH. Therefore, electrolytes containing phosphate species are used in a large number of applications. However, the effect of phosphate on platinum surface modification with nickel deposits has not been studied yet. In this work, new data about the interaction of phosphate with nickel adatoms deposited on Pt(111) at pH 5 is investigated using cyclic voltammetry and infrared spectroscopy. The results show that, when nickel is in solution, the phosphate ions are adsorbed at lower potentials than in the absence of nickel. In addition, Laser-Induced Temperature Jump Technique demonstrates that nickel facilitates the adsorption of phosphate because of a shift of the potential of zero charge (pzc) toward negative potentials. This increases the magnitude of the positive electric field on the electrode surface, at a given potential E>pzc, facilitating the adsorption of anions. CO displacement technique has been also employed to obtain additional information about co-adsorbed phosphate on nickel adlayers. Finally, the HER has been studied at pH 5 in the presence of nickel, with and without phosphate in the bulk solution.     

Decomposition and oxidation of methanol on platinum: A study by in situ X-ray photoelectron spectroscopy and mass spectrometry

The reactions of the catalytic oxidation and decomposition of methanol on the atomically smooth and high-defect Pt(111) single-crystal surfaces were studied using in situ temperature-programmed reaction and X-ray photoelectron spectroscopy. It was found that the decomposition of methanol on both of the surfaces occurred via two reaction pathways: complete dehydrogenation to CO and decomposition with the C-O bond cleavage. Although the rate of reaction via the latter pathway was lower than the rate of dehydrogenation by three orders of magnitude, the carbon formed as a result of the C-O bond cleavage can be accumulated on the surface of platinum to prevent the further course of the reaction. It was shown that oxygen exhibits high activity toward the formed carbon deposits. As a result, the rate of methanol conversion in the presence of oxygen in a gas phase increased by one or two orders of magnitude; in this case, CO₂ and water appeared in the composition of the reaction products as a result of the oxidation of CO and hydrogen, respectively. The high-defect surface of platinum was more active in the reactions of methanol decomposition and oxidation than the atomically smooth Pt(111) single-crystal surface. On the former, selectivity for the formation of methanol dehydrogenation products in oxygen deficiency was higher than on the latter. The main reaction pathways of the decomposition and oxidation of methanol on platinum were considered.     

Open-mouthed metallic microcapsules: exploring performance improvements at agglomeration-free interiors

Although artificial capsule structures have been thoroughly investigated, functionality at the surfaces of their interiors has been surprisingly overlooked. In order to exploit this aspect of capsular structure, we here report the breakthrough fabrication of metallic (platinum) microcapsules with sufficient accessibility and electroactivity at both interior and exterior surfaces (open-mouthed platinum microcapsules), and also we demonstrate improvements in electrochemical and catalytic functions to emphasize the practical importance of our concept. The open-mouthed platinum microcapsules were prepared by template synthesis using polystyrene spheres, where surface-fused crystalline nanoparticles formed a capsule shell. Subsequent removal of the polystyrene spheres induced formation of mouth-like openings. The open-mouthed platinum microcapsules exhibit a substantial increase of their electrode capability for methanol oxidation and catalytic activities for carbon monoxide (CO) oxidation. Notably, activity loss during CO oxidation due to undesirable particle agglomeration can be drastically suppressed using the open-mouthed microcapsules.     

The effect of electrochemically treated glassy carbon on the activity of supported Pt catalyst in methanol oxidation

Effect of electrochemical oxidation of glassy carbon on deposition of platinum particles and electrocatalytic activity of platinum supported on oxidized glassy carbon (Pt/GC_OX) were studied for methanol oxidation in H₂SO₄ solution. Platinum was potentiostatically deposited from H₂SO₄ + H₂PtCl₆ solution. Glassy carbon was anodically polarised in 0.5 M H₂SO₄ at 2.25 V vs. saturated calomel electrode (SCE) during 35 s. Electrochemical treatment of GC support, affecting not significantly the real Pt surface area, leads to a better distribution of platinum on the substrate and has remarkable effect on the activity. The activity of the Pt/GC_OX electrode for methanol oxidation is larger than polycrystalline Pt and for more than one order of magnitude larger than Pt/GC electrode. This increase in activity indicates the pronounced role of organic residues of GC support on the properties of Pt particles deposited on glassy carbon.     

甲醇在欠电位沉积Sn/Pt电极上催化氧化

在欠电位沉积（upd）锡修饰的铂电极（upd-Sn/Pt）上,对甲醇电化学催化氧化过程进行了研究.发现当Pt表面upd-Sn的覆盖率在20％附近时,对甲醇的催化氧化的增强作用最为明显；在电位低于0.35 V （vs RHE）时,甲醇在Pt与upd-Sn/Pt电极上氧化只进行到脱氢生成CO的步骤;在0.35 V以后,表面Sn－OH形成,反应Sn－OH＋COads=Sn＋CO2＋H＋＋e有利于表面CO的去除;而Pt电极上,只有0.6 V以后,才有反应Pt－OH＋COads=Pt＋CO2＋H＋＋e发生.因此,Sn的存在有利于甲醇在较低的电位下氧化; Pt电极上CH3OH脱氢并释放出电子的过程是一个快速的过程,表面CO的去除是甲醇氧化过程的控制步骤;甲醇氧化产生的表面吸附态CO 以线式吸附为主,少量的桥式吸附态CO在反应初期即达到吸附饱和; Pt表面上upd-Sn表现的催化增强作用,在光亮铂电极和在高分散铂黑电极上是一致的.     

Electrochemical and spectroscopic studies of ethanol oxidation on Pt stepped surfaces modified by tin adatoms

Ethanol oxidation on platinum stepped surfaces vicinal to the (111) pole modified by tin has been studied to determine the role of this adatom in the oxidation mechanism. Tin has been slowly deposited so that the initial stages of the deposition take place on the step, and deposition on the terrace only occurs when the step has been completely decorated. Voltammetric and chronoamperometric experiments demonstrate that tin on the step catalyzes the oxidation. The maximum enhancement is found when the step is completely decorated by tin. FTIR experiments using normal and isotopically labeled ethanol have been used to elucidate the effect of the tin adatoms in the mechanism. The obtained results indicate that the role of tin is double: (i) when the surface has sites capable of breaking the C-C bond of the molecule, that is, when the step sites are not completely covered by tin, it promotes the oxidation of CO formed from the molecular fragments to CO(2) through a bifunctional mechanism and (ii) it catalyzes the oxidation of ethanol to acetic acid.     

Platinum/Carbon nanotube nanocomposite synthesized in supercritical fluid as electrocatalysts for low-temperature fuel cells

Carbon nanotube (CNT)-supported Pt nanoparticle catalysts have been synthesized in supercritical carbon dioxide (scCO(2)) using platinum(II) acetylacetonate as metal precursor. The structure of the catalysts has been characterized with transmission electron micrograph (TEM) and X-ray photoelectron spectroscopy (XPS). TEM images show that the platinum particles' size is in the range of 5-10 nm. XPS analysis indicates the presence of zero-valence platinum. The Pt-CNT exhibited high catalytic activity both for methanol oxidation and oxygen reduction reaction. The higher catalytic activity has been attributed to the large surface area of carbon nanotubes and the decrease in the overpotential for methanol oxidation and oxygen reduction reaction. Cyclic voltammetric measurements at different scan rates showed that the oxygen reduction reaction at the Pt-CNT electrode is a diffusion-controlled process. Analysis of the electrode kinetics using Tafel plot suggests that Pt-CNT from scCO(2) provides a strong electrocatalytic activity for oxygen reduction reaction. For the methanol oxidation reaction, a high ratio of forward anodic peak current to reverse anodic peak current was observed at room temperature, which implies good oxidation of methanol to carbon dioxide on the Pt-CNT electrode. This work demonstrates that Pt-CNT nanocomposites synthesized in supercritical carbon dioxide are effective electrocatalysts for low-temperature fuel cells.     

球型Pt微粒电极的构建及其对甲醇电氧化的研究

以镍铬合金为基体,在其表面电化学沉积制备了Pt微粒电极,用扫描电子显微镜（SEM）对电极的表面形貌进行了表征,电化学方法考察了电极的电化学性能和甲醇在该电极上的电催化行为．结果表明镍铬合金表面沉积的球型Pt微粒电极对甲醇的电氧化具有良好的催化活性,相同实验条件下,该电极的催化活性比纯Pt电极高30倍．该电极对甲醇的电氧化显示出较高的催化性能．     

Characterization of stainless steel electrode modified by a thin film of polyaniline containing pt particles and its electrocatalytic activity for methanol oxidation

The catalytic behavior of stainless steel (SS) electrode modified by a thin film of polyaniline (PANI) containing platinum particles was studied for electrooxidation of methanol and compared with a platinated Pt/PANI electrode in acidic aqueous solution. Cyclic voltammetry (CV), chronoamperometry, CO stripping techniques were used to investigate electrochemical properties and electrocatalytic activity of SS/PANI/Pt and Pt/PANI/Pt electrodes. The morphology and particle size of Pt catalysts were characterized by Transmission Electron Microscopy (TEM) measurement. The effects of various parameters such as thickness of polymer film, medium temperature and stability of the modified electrodes on methanol oxidation were also investigated. The results indicated that the modified SS electrode exhibited a considerably high electrocatalytic activity on the methanol oxidation as well as the modified Pt electrode.     

Electro‐oxidation of Methanol and Ethanol Catalyzed by Pt/ZSM‐5/C

Direct alcohol fuel cells are a promising source of future energy generation for small and portable devices. Platinum is considered the best catalyst for electro‐oxidation of alcohols in fuel cells but the major hurdles with platinum catalysts are high cost of platinum as well as low selectivity, slow reaction kinetics and carbonaceous poisoning associated with platinum. This particular research reports electro‐oxidation of methanol and ethanol over platinum electrodeposited on ZSM‐5 without any carbon additive. From the cyclic voltammetry and chronoamperometry, linear sweep voltammetry, tafel plot and multiple scan analyses, it is found that Pt/ZSM‐5/C electrodes can catalyze electro‐oxidation of methanol and ethanol with higher efficiency. ZSM‐5 supports the formation of smaller sized platinum nanoparticles in a dispersed manner on the zeolite support and thus increases the active surface area of the metal for catalytic activity. It favors adsorption of alcohol molecules on the modified electrode surface and thus increases the diffusion process. It also stabilizes the modified electrodes.     

A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction

Theoretical studies of the possibility of forming ammonia electrochemically at ambient temperature and pressure are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free energy profile for the reduction of N(2) admolecules and N adatoms on several close-packed and stepped transition metal surfaces in contact with an acidic electrolyte. Trends in the catalytic activity were calculated for a range of transition metal surfaces and applied potentials under the assumption that the activation energy barrier scales with the free energy difference in each elementary step. The most active surfaces, on top of the volcano diagrams, are Mo, Fe, Rh, and Ru, but hydrogen gas formation will be a competing reaction reducing the faradaic efficiency for ammonia production. Since the early transition metal surfaces such as Sc, Y, Ti, and Zr bind N-adatoms more strongly than H-adatoms, a significant production of ammonia compared with hydrogen gas can be expected on those metal electrodes when a bias of -1 V to -1.5 V vs. SHE is applied. Defect-free surfaces of the early transition metals are catalytically more active than their stepped counterparts.     

Oxidation of Hydrogen by Metal Complexes of Platinum and Palladium Immobilized on Silica

The thermal stability of metal complexes immobilized on the surface of silica and its connection with the catalytic activity in the oxidation of hydrogen were investigated. High catalytic activity was exhibited by heterogenized platinum and palladium acetylacetonate near room temperatures in the initial state and by γ-aminopropylsilicas treated with platinum and palladium complexes. The catalytic activity of the metal complexes correlates with their thermal stability and with the ability to undergo oxidation to a metal state with high valence. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electrocatalytic Oxidation of Methanol on a Nickel‐Porphyrin IX Complex Modified Glassy Carbon Electrode in Alkaline Medium

Electrocatalytic oxidation of methanol on a glassy carbon disc electrode modified with Ni(II)‐hematoporphyrin IX, complex and conditioned by potential recycling in a limited range (between 100 and 600 mV vs. SCE) in 0.10 M NaOH solution, abbreviated as NiOHPME(A), was studied by cyclic voltammetry in alkaline medium. The results were compared with those obtained for a NiO modified glassy carbon electrode, NiOME, prepared in similar conditions. The findings show that the NiOHP film at NiOHPME(A) behaves as an efficient electrocatalyst for the oxidation of methanol in alkaline medium via Ni(III) species with the cross‐exchange reaction occurring throughout the layer at a low concentration of methanol and for a thin film of modifier. A plausible mechanism was proposed for catalytic oxidation of methanol at NiOHP modified electrode. Moreover, the effects of various parameters such as the scan rate, methanol concentration, thickness of NiOHP film and the real surface area of modified electrode on the oxidation of methanol were investigated. Finally, it has been shown that the NiOHPME(A) has a long‐term stability toward the oxidation of methanol.