Novel Metal Oxide Support with Water Activation Ability for Use in Direct Methanol Fuel Cell

A new principle for designing catalyst supports with water activation ability was proposed. According to this principle, stabilized nickel(+3) oxides with different dopants were tested as possible support and promoter for Pt catalyst in direct methanol fuel cells. It was found that the chemical and electrochemical stabilities of these novel supports in acidic solution were sufficient. The support doped with Al(+3) has catalytic activity towards methanol electrooxidation while that doped with Co(+3) can improve both activity and poisoning tolerance of the Pt catalyst.     

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.     

A novel Pt/Au/C cathode catalyst for direct methanol fuel cells with simultaneous methanol tolerance and oxygen promotion

A novel Pt/Au/C catalyst was prepared by depositing the Pt and Au nanoparticles on the carbon support. The synthesized catalysts were characterized by energy-dispersive X-ray (EDX) and transmission electron microscopy (TEM), and electrochemically analyzed for activity towards oxygen-reduction reaction and methanol oxidation reaction. EDX and TEM results reveal that Pt nanoparticles supported on carbon supports were separated by Au nanoparticles. The electrochemical analysis indicate that the novel catalyst showed the enhanced methanol tolerance while maintaining a high catalytic activity for the oxygen-reduction reaction, which could be attributed to the less methanol adsorption on Pt/Au/C catalyst.     

Surfacial carbonized palygorskite as support for high-performance Pt-based electrocatalysts

Pt nanoparticles deposited on a low-cost, surfacial, carbonized palygorskite (Pt/C-PLS) prepared by carbonizing sucrose were evaluated as a methanol oxidation catalyst for direct methanol fuel cells. Transmission electron microscopy and Fourier transfrom infrared spectrophotometry analyses revealed that carbon was formed on the surface of PLS and that free silica presented in the C-PLS support. The catalytic activity of methanol oxidation of Pt/C-PLS was higher than that of Pt/C, and the former catalyst had better CO tolerance.     

纳米颗粒结合ZIF-67衍生的PtCo-NC催化剂用于醇类燃料电氧化

Alcohols fuel electro-oxidation is significant to the development of direct alcohols fuel cells, that are considered as a promising power source for portable electronic devices. Currently, the catalyst was restricted by the serious poisoning effect and high cost of noble metals. Developing low-cost Pt alloy with high performance and anti-CO poisoning ability was highly desired. In this work, PtCo-NC catalyst was synthesized by combining Pt nanoparticles with ZIF-67 after annealing in the tube furnace and the in situ generated N-doped carbon from ZIF-67 was functionalized to support the PtCo alloy nanoparticle. The structure and morphology were probed by X-ray diffraction, scanning electron microscope and transmission electron microscope, and the electrochemical performance was evaluated for alcohols of methanol and ethanol oxidation in the acid electrolyte. Compared with the reference sample of Pt/C, several times performance enhancement for alcohols fuel oxidation was found on PtCo-NC catalyst as well as the good catalytic stability. Specifically, the peak current density of PtCo-NC was 79.61 mA∙cm⁻² for methanol oxidation, about 2.2 times higher than that of the Pt/C electrode (36.97 mA∙cm⁻²) and 2.5 times higher than that of the commercial Pt/C electrode (31.23 mA∙cm⁻²); it was 62.69 mA∙cm^–2 for ethanol oxidation, about 1.65 times higher than that of Pt/C catalyst (37.99 mA∙cm⁻²) and commercial Pt/C electrode (37.77 mA∙cm⁻²). These catalytic performances were also much higher than some analogous catalysts developed for alcohols fuel oxidation. A much higher anti-CO poisoning ability was demonstrated by the CO stripping voltammetry experiment, in which the CO_ad oxidation peak potential for PtCo-NC was 0.46 V, ca. 110 mV negative shift compared with Pt/C catalyst at 0.57 V. A strong electronic effect was indicated by the peak position shifting to the lower binding energy direction by 0.3 eV on PtCo-NC compared with Pt/C reference catalyst. According to the d-band center theory, the electron-enriched state of Pt will decrease the interaction strength of poisoning intermediates adsorbed on its surface; Moreover, according to the bifunctional catalytic mechanism, the presence of Co can form the adsorbed oxygen-containing species (―OH) more easily than Pt at low potentials, and this oxygen-species were helpful in the oxidation of CO_ad at neighboring Pt sites. The high catalytic performance for alcohols fuel oxidation could be due to the largely improved anti-CO poisoning ability and the synergistic effect between the in situ formed PtCo nanoparticles and the N-doped carbon support.     

具有高活性和突出的抗中毒性能的Pt修饰Ru/C催化剂的制备和表征(英文)

采用两步浸渍-还原法制备了一种具有高Pt利用效率,高性能的Pt修饰的Ru/C催化剂(Ru@Pt/C).对于甲醇的阳极氧化反应,该催化剂的单位质量铂的催化活性分别为Pt/C、自制PtRu/C和商业JMPtRu/C催化剂的1.9、1.5和1.4倍;其电化学活性比表面积分别为Pt/C和自制PtRu/C的1.6和1.3倍.尤为重要的是该催化剂对甲醇氧化中间体具有很好的去除能力,其正向扫描的氧化峰的峰电流密度(If)与反向扫描氧化峰的峰电流密度(Ib)之比可高达2.4,为Pt/C催化剂的If/Ib的2.7倍,表明催化剂具有很好的抗甲醇氧化中间体毒化的能力.另外,Ru@Pt/C催化剂的稳定性也高于Pt/C、自制PtRu/C和商业JMPtRu/C催化剂的稳定性.采用X射线衍射(XRD)、透射电镜(TEM)和X射线光电子能谱(XPS)对催化剂进行了表征,Pt在Ru表面的包覆结构得到了印证.Ru@Pt/C的高铂利用效率、高性能和高抗毒能力使其有望成为一种理想的直接甲醇燃料电池电催化剂.     

Pd-Co-Mo electrocatalyst for the oxygen reduction reaction in proton exchange membrane fuel cells

The catalytic activity of carbon supported Pd-Co-Mo for the oxygen reduction reaction (ORR) in a single cell proton exchange membrane fuel cell (PEMFC) has been investigated at 60 degrees C and compared with data from commercial Pt catalyst and our previously reported Pd-Co-Au and Pd-Ti catalysts. The Pd-Co-Mo catalyst with a Pd:Co:Mo atomic ratio of 70:20:10 exhibits slightly higher catalytic activity like the Pd-Co-Au catalyst than the commercial Pt catalyst, but with excellent chemical stability unlike the Pd-Co-Au catalyst. The Pd-Co-Mo catalyst also exhibits better tolerance to methanol poisoning than Pt. Investigation of the catalytic activity of the Pd-Co-Mo system with varying composition and heat treatment temperature reveals that a Pd:Co:Mo atomic ratio of 70:20:10 with a heat treatment temperature of 500 degrees C exhibits the highest catalytic activity. Although the degree of alloying increases with increasing temperature from 500 to 900 degrees C as indicated by the X-ray diffraction data, the catalytic activity decreases due to an increase in particle size and a decrease in surface area.     

Promoting performance and CO tolerance of Pt nanocatalyst for direct methanol fuel cells by supporting on high-surface-area silicon carbide

SiC-supported Pt nanocatalyst was prepared by electrodeposition of Pt nanoparticles on the surface of high-surface-area SiC, which was fabricated by a versatile carbothermal reduction method. Characterization studies show that such synthesis protocol leads to well distribution of Pt nanoparticles, with a mean particle size of 2.9 nm on the support. This catalyst has been electrochemically characterized toward methanol oxidation, which exhibits higher catalytic activity, durability, and electrochemical active surface area than the electrodeposited Pt on multiwalled carbon nanotubes (MWCNTs). Further investigation reveals that the SiC-supported Pt also shows superior CO tolerance to Pt/MWCNTs. These results suggest that high-surface-area SiC could be a promising supporting material for constructing high-performance methanol oxidation electrocatalysts.     

Au nanowires with high aspect ratio and atomic shell of Pt-Ru alloy for enhanced methanol oxidation reaction

The methanol oxidation reaction(MOR) is the limiting half-reaction in direct methanol fuel cell(DMFC).Although Pt is the most active single-metal electrocatalyst for MOR,it is hampered by high cost and CO poisoning.Constructing a Pt or Ru monolayer on a second metal substrate by means of galvanic replacement of underpotentially deposited(UPD) Cu monolayer has been shown as an efficient catalyst design strategy for the electrocatalysis of MOR because of the presumed 100% utilization of atoms and resistance to CO poisoning.Herein,we prepared one-dimensional surface-alloyed electrocatalyst from predominantly(111) faceted Au nanowires with high aspect ratio as the substrate of under-potential deposition.The electrocatalyst comprises a core of the Au nanowire and a shell of catalytically active Pt coated by Ru.Coverage-dependent electro-catalytic activity and stability is demonstrated on the Pt/Ru submonolayers on Au wires for MOR.Among all these catalysts,Au@Pt_(ML)@Ru_(ML) exhibits the best electrocatalytic activity and poisoning tolerance to CO.This presents a viable method for the rational catalyst design for achieving high noble-metal utilization efficiency and high catalytic performance.     

Influence of ultrathin poly-(3,4-ethylenedioxythiophene) (PEDOT) film supports on the electrodeposition and electrocatalytic activity of discrete platinum nanoparticles

Coating a carbon electrode surface, specifically highly oriented pyrolytic graphite (HOPG) with an ultrathin film of poly-(3,4-ethylenedioxythiophene), PEDOT, provides a support on which a high density of uniformly dispersed Pt nanoparticles (NPs) can readily be formed by electrodeposition. The NPs tend to be much smaller, have a higher surface coverage, better dispersion and show a much lower tendency to aggregate, than Pt NPs produced under identical electrochemical conditions on HOPG alone. The electrocatalytic activity of the NPs was investigated for methanol (MeOH) and formic acid (HCOOH) oxidation. Significantly, for similarly prepared particles, Pt NP-PEDOT arrays exhibited higher catalytic activity (in terms of current density, based on the Pt area), towards MeOH oxidation, by an order of magnitude, and towards HCOOH oxidation at high potentials, than Pt NPs supported on native HOPG. These findings can be rationalised in terms of the enhanced oxidation of adsorbed CO, a key reaction intermediate and a catalyst poison. This research provides strong evidence that employing conducting polymers, such as PEDOT, as a support substrate, can greatly improve particular catalytic reactions, allowing for better catalyst utilisation in fuel cell technology.     

Influence of ultrathin poly-(3,4-ethylenedioxythiophene) (PEDOT) film supports on the electrodeposition and electrocatalytic activity of discrete platinum nanoparticles

Coating a carbon electrode surface, specifically highly oriented pyrolytic graphite (HOPG) with an ultrathin film of poly-(3,4-ethylenedioxythiophene), PEDOT, provides a support on which a high density of uniformly dispersed Pt nanoparticles (NPs) can readily be formed by electrodeposition. The NPs tend to be much smaller, have a higher surface coverage, better dispersion and show a much lower tendency to aggregate, than Pt NPs produced under identical electrochemical conditions on HOPG alone. The electrocatalytic activity of the NPs was investigated for methanol (MeOH) and formic acid (HCOOH) oxidation. Significantly, for similarly prepared particles, Pt NP-PEDOT arrays exhibited higher catalytic activity (in terms of current density, based on the Pt area), towards MeOH oxidation, by an order of magnitude, and towards HCOOH oxidation at high potentials, than Pt NPs supported on native HOPG. These findings can be rationalised in terms of the enhanced oxidation of adsorbed CO, a key reaction intermediate and a catalyst poison. This research provides strong evidence that employing conducting polymers, such as PEDOT, as a support substrate, can greatly improve particular catalytic reactions, allowing for better catalyst utilisation in fuel cell technology.

     

炭载Pt-Ag双金属催化剂对甲醇氧化反应的电催化

以NaBH4为还原剂,将K2PtCl6和AgNO3前体进行共还原制备了一系列具有不同组成的碳载PtmAg/C合金催化剂（m为Pt/Ag原子比,m为0.05～1.0）,在酸性介质中考察了该系列催化剂对甲醇氧化反应的电催化性能。 与单组分Pt/C催化剂相比,系列PtmAg/C催化剂呈现出较高的催化氧化甲醇的活性与抗CO毒化能力,而且该催化剂的性能与其组成密切相关。 随m值增加,PtmAg/C催化剂对甲醇氧化反应的质量比催化活性(MSA)、本征催化活性(IA)与稳定性均逐步增加,当m=0.5时催化活性达到最高,其MSA和IA分别是Pt/C催化剂的5.1和4.8倍。     

Controllable pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells

We report a novel process to prepare well-dispersed Pt nanoparticles on CNTs. Pt nanoparticles, which were modified by the organic molecule triphenylphosphine, were deposited on multiwalled carbon nanotubes by the organic molecule, which acts as a cross linker. By manipulating the relative ratio of Pt nanoparticles and multiwalled carbon nanotubes in solution, Pt/CNT composites with different Pt content were achieved. The so-prepared Pt/CNT composite materials show higher electrocatalytic activity and better tolerance to poisoning species in methanol oxidation than the commercial E-TEK catalyst, which can be ascribed to the high dispersion of Pt nanoparticles on the multiwalled carbon nanotube surface.     

Pt的氧化状态对甲醇氧化活性的影响

采用NaBH4还原法制备了XC-72碳黑负载的Pt电催化剂,并在化学还原后用H2O2处理部分催化剂以改变Pt的氧化状态,以期改善Pt活性中心上水的离解而提高催化活性.X射线光电子能谱结果表明,经H2O2处理的催化剂含有较多的氧化态Pt.通过循环伏安法和记时电流法考察了经处理和未经处理的催化剂在酸性条件下的甲醇氧化的催化...     

POISONING OF ACTIVE SITES ON ZIEGLER-NATTA CATALYST FOR PROPYLENE POLYMERIZATION

The effects of poisoning materials on catalytic activity and isospecificity of the supported Ziegler-Natta catalyst were investigated.A minor amount of simple structure of Lewis base,i.e.,methanol,acetone,ethyl acetate,was introduced into the catalyst slurry for partial poisoning catalytic active centers.It was found that the variations in deactivation power were in the order of methanol>acetone>ethyl acetate.The kinetic investigation via stopped-flow polymerization showed that poisoning compounds caused...     

Synergistic enhancement of formic acid electro-oxidation on PtxCuy co-electrodeposited binary catalysts

A propitious binary catalyst composed of Pt and Cu which were electrodeposited simultaneously onto a glassy carbon (GC) substrate was recommended for the formic acid (FA) electro-oxidation reaction (FAOR); the principal anodic reaction in the direct FA fuel cells (DFAFCs). The simultaneous co-electrodeposition of Pt and Cu in the catalyst provided an opportunity to tune the geometric functionality of the catalyst to resist the adsorption of poisoning CO at the Pt surface that represented the major impediment for DFAFCs marketing. The catalytic activity of the catalyst toward FAOR was significantly influenced by the (Pt⁴⁺/Cu²⁺) molar ratio of the electrolyte during electrodeposition, which also affected the surface coverage of Pt and Cu in the catalyst. Interestingly, with a molar (Pt⁴⁺/Cu²⁺) ratio of (1:4), the catalyst sustained superior (3.58 compared to 0.65 obtained at the pristine Pt/GC catalyst) activity for FAOR, concurrently with up to four-times (0.73 compared to 0.18 obtained at the pristine Pt/GC catalyst) improvement in the catalytic tolerance against CO poisoning. This associated, surprisingly, a negative shift of ca. 336 mV in the onset potential of FAOR, in an indication for the competitiveness of the catalyst to minimize superfluous polarizations in DFAFCs. Furthermore, it offered a better (ended up with 20% loss in the activity) stability for continuous (1 h) electrolysis than pristine Pt/GC catalyst (the loss reached 35%). The impedance and CO stripping measurements together excluded the electronic element but confirmed the geometrical influence in the catalytic enhancement.     

Electrocatalytic properties of platinum nanoparticles supported on fluorine tin dioxide/multi-walled carbon nanotube composites for methanol electrooxidation in acidic medium

Fluorine tin oxide (FTO) and multi-walled carbon nanotube (MWCNT) composites synthesized by a sol-gel process followed by a hydrothermal treatment process have been explored as a support for Pt nanoparticles (Pt-FTO/MWCNTs). X-ray diffraction analysis and high resolution transmission electron microscopy show that the Pt and FTO nanoparticles with crystallite size of around 4-8 nm are highly dispersed on the surface of MWCNTs. Pt-FTO/MWCNT catalyst is evaluated in terms of the electrochemical catalytic activity for methanol electrooxidation using cyclic voltammetry, steady state polarization experiments, and electrochemical impedance spectroscopy technique in acidic medium. The Pt-FTO/MWCNT catalyst exhibits a higher intrinsic catalytic activity for methanol electrooxidation with high stability during potential cycling than Pt nanoparticles supported on tin dioxide/multi-walled carbon nanotube composites. The results suggest that FTO/MWCNT composites could be considered as an alternative support for Pt-based electrocatalysts in direct alcohol fuel cells.     

Hydrothermal Syntheses of NiO−GO Nanocomposite on 3D Nickel Foam as a Support for Pt Nanoparticles and its Superior Electrocatalytic Activity towards Methanol Oxidation

In this project, Pt/NiO?GO nanocatalyst is grown on nickel foam (NF) and, its catalytic activity towards electrochemical oxidation of methanol in acidic media is studied. The first step is devoted to the synthesis of NiO?GO support by a hydrothermal method. Then Pt nanoparticles (～34.3 nm) are electrodeposited on this supporting material. Hydrothermal and electrochemical deposition conditions are optimized. Surface of modified NF was inspected for physical characterization and Chemical composition by some techniques such as field emission scanning electron microscopy (FESEM), energy‐dispersive X‐ray spectra (EDS), and X‐ray diffraction (XRD). In the electrochemical section, the catalytic performance of Pt/NiO?GO/NF towards methanol oxidation is investigated by cyclic voltammetry and chronoamperometry measurements. The electrochemical impedance spectroscopy (EIS) is elected to deliberate charge transfer resistance on the catalyst surface. Mass activity, electrochemical surface area (ECSA) and durability of prepared catalysts are compared with commercial Pt/C. Deliberations prove the superiority of Pt/NiO?GO/NF towards methanol oxidation in acidic media. The Superior quality of synthesized nanocatalyst that is attributed to the synergetic effect of the NiO?GO support material and Pt nanoparticles, indicate that Pt/NiO?GO/NF can be successfully used as the anode in the direct methanol fuel cell (DMFC).     

Electrodeposited Pt and Pt-Sn nanoparticles on Ti as anodes for direct methanol fuel cells

Electro-oxidation of methanol was studied on titanium supported nanocrystallite Pt and Pt_x-Sn_y catalysts prepared by electrodeposition techniques. Their electro-catalytic activities were studied in 0.5mol/L H₂SO₄ and compared to those of a smooth Pt, Pt/Pt and Pt-Sn/Pt electrodes. Platinum was deposited on Ti by galvanostatic and potentiostatic techniques. X-ray diffractometer (XRD) and energy dispersive X-ray (EDX) techniques were applied in order to investigate the chemical composition and the phase structure of the modified electrodes. Scanning electron microscopy (SEM) was used to characterize the surface morphology and to correlate the results obtained from the two electrochemical deposition methods. Results show that modified Pt/Ti electrodes prepared by the two methods have comparable performance and enhanced catalytic activity towards methanol electro-oxidation compared to Pt/Pt and smooth Pt electrodes. Steady state Tafel plots experiments show a higher rate of methanol oxidation on a Pt/Ti catalyst than that on a smooth Pt.  Introduction of a small amount of Sn deposited with Pt improves the catalytic activity and the stability of prepared electrode with time as indicated from the cyclic votlammetry and the chronoamperometric experiments. The effect of variations in the composition for binary catalysts of the type Pt_x-Sn_y/Ti towards the methanol oxidation reaction is reported. Consequently, the Pt_x-Sn_y/Ti (x∶y (8∶1), molar ratio) catalyst is a very promising one for methanol oxidation.     

PtTe/C催化剂的制备及其对乙醇的电催化氧化性能

采用无机溶胶法制备了用于乙醇燃料电池的PtTe/C催化剂;利用X射线衍射仪分析了催化剂的结构,采用循环伏安法和电化学阻抗法测试了PtTe/C催化剂对乙醇的电催化氧化性能.结果表明,与商业Pt/C催化剂相比,PtTe/C催化剂对乙醇的催化氧化效率明显较高,可使乙醇氧化峰电流密度提高27%,且具有更高的抗CO中毒能力.