Microfluidic Synthesis Enables Dense and Uniform Loading of Surfactant‐Free PtSn Nanocrystals on Carbon Supports for Enhanced Ethanol Oxidation

Developing new synthetic methods for carbon supported catalysts with improved performance is of fundamental importance in advancing proton exchange membrane fuel cell (PEMFC) technology. Continuous‐flow, microfluidic reactions in capillary tube reactors are described, which are capable of synthesizing surfactant‐free, ultrafine PtSn alloyed nanoparticles (NPs) on various carbon supports (for example, commercial carbon black particles, carbon nanotubes, and graphene sheets). The PtSn NPs are highly crystalline with sizes smaller than 2 nm, and they are highly dispersed on the carbon supports with high loadings up to 33 wt %. These characteristics make the as‐synthesized carbon‐supported PtSn NPs more efficient than state of the art commercial Pt/C catalysts applied to the ethanol oxidation reaction (EOR). Significantly enhanced mass catalytic activity (two‐times that of Pt/C) and improved stability are obtained.     

Recent developments in Pt–Co catalysts for proton-exchange membrane fuel cells

Development of Pt-based oxygen reduction reaction catalysts with high efficiency and high durability is central to the application of proton-exchange membrane fuel cell systems. Pt–Co bimetallic catalysts have drawn extensive attention owing to their capability of delivering high performance and long lifetime for fuel cell applications including light-duty and heavy-duty vehicles. However, further improvements in durability and performance are needed to meet market requirements. To fully exploit the potential of Pt–Co catalysts, new insights into the relationship between catalyst properties and fuel cell performance and durability are needed, and more effective methods to tailor the features of Pt–Co catalysts need to be developed. This review provides a summary and perspective on recent efforts, including work on customizing the Pt shell and Pt:Co ratio, tailoring the crystal structure, and improving carbon support properties, with a particular emphasis on mechanisms leading to enhancement of mass activity, power density, and durability in membrane electrode assembly testing.     

Perfluorosulfonic acid-functionalized Pt/graphene as a high-performance oxygen reduction reaction catalyst for proton exchange membrane fuel cells

Platinum nanoparticles (Pt NPs) on carbon black (CB) have been used as catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells for a while. However, this catalyst has suffered from aggregation and dissolution of Pt NPs as well as CB dissolution. In this study, we resolve those issues by developing perfluorosulfonic acid (PFSA)-functionalized Pt/graphene as a high-performance ORR catalyst. The noncovalently bonded PFSA remarkably decreases the dissolution and aggregation of Pt NPs. Moreover, unlike typical NP functionalization with other capping agents, PFSA is a proton conductor and thus efficiently develops a triple-phase boundary. These advantageous features are reflected in the improved cell performance in electrochemical active surface area, catalytic activity, and long-term durability, compared to those of the commercial Pt/C catalysts and graphene-based catalysts with no such treatment.     

Electrocatalytic Oxidation of Ethanol on the Surface of Graphene Based Nanocomposites: An Introduction and Review to it in Recent Studies

This review gives an overview of the electrochemical investigations about the properties of various types of graphene composites in the ethanol oxidation. Various routes to provide appropriate graphene‐based materials required electrochemical techniques for investigation of different types of the materials as well as their performance and efficacy in ethanol oxidation are discussed in detail. Furthermore, it is demonstrated that the incorporation of suitable materials, e. g. noble metals (graphene‐supported binary and ternary metal nanoparticles), metal oxides, conductive polymer, etc, with graphene results in excellent electrocatalytic activity, superb durability and selectivity in ethanol oxidation. Immobilization of electrocatalytically active NPs on graphene supports using physical approaches is considered as an effective route to prepare direct ethanol fuel cell (DEFC) anode catalysts.     

有序化膜电极研究进展

燃料电池的性能方面在近年来有很大提高,但要实现商业化其成本和Pt用量需要进一步的降低. 大量的文献工作证明了有序化膜电极有助于提高电极中催化剂的利用率、降低Pt的用量以及增加反应的三相界面,特别是3M公司制备的纳米薄膜电极（NSTFs）是一种高活性,高稳定性的薄膜状催化层,从而电极稳定性也大幅提高. 此外也有不少工作使用导电性好的碳纳米管阵列,以及稳定性高的金属氧化物阵列等作为这种3D结构催化层中催化剂的有序载体,研究进一步提高Pt基催化剂的活性,降低Pt担载量,构效关系等一些基础性的工作. 但是总体上看,现有的有序化膜电极,均需要进一步改进. 本文评述了目前国内外有序化膜电极的研究现状.     

Platinum Nanoparticles Modified with Perfluorinated Alkylamines as a Model Cathode Catalyst for Fuel Cells

Platinum nanoparticles (NPs) modified with undecafluorohexylamine (UFHA) and octylamine were synthesized as a novel model cathode catalyst for fuel cells. The modified Pt NPs were well characterized by FTIR, X‐ray photoelectron spectroscopy, thermogravimetric analysis, and transmission electron microscopy. These NPs supported on carbon black were applied as electrocatalysts for the oxygen reduction reaction. The UFHA‐modified Pt NP catalyst showed high electrocatalytic activity and durability compared to a commercial catalyst. Besides suppression of undesired oxide formation on the Pt surface, the affinity between the perfluorinated alkyl chains of UFHA and Nafion^® improved the catalyst activity by creating a desirable proton conduction path. Additionally, UFHA modification improved durability by suppressing Pt dissolution and carbon corrosion because of restricted water accessibility. The β ‐oxide formation, which is responsible for Pt dissolution, was significantly attenuated by surface modification.     

氮掺杂有序介孔碳负载超小尺寸铂纳米颗粒催化硝基苯类化合物选择加氢

氮掺杂有序介孔碳材料不仅具有高的比表面积、大的孔容和均一可调的孔径等优点,其骨架中丰富的氮原子还可以对材料的物理化学性质、配位金属电荷密度等进行调控,是一类优异的催化剂载体.本文利用软模板(嵌段共聚物F127为模板),以间氨基苯酚为碳源和氮前体,制备出较高含氮量(9.58 wt%)和比表面积(417 m2/g),以及规则孔径分布的介孔碳材料.结果表明,制备的材料具有三维立方相结构.以该碳材料作为载体,使用传统浸渍氢气还原的策略负载纳米铂颗粒.发现氮掺杂的载体能够有效控制金属纳米颗粒的尺寸,可实现超小尺寸Pt纳米颗粒的有效负载(1.0±0.5 nm),且纳米颗粒均匀分布于介孔碳材料的孔道中.相比而言,使用相同负载方法的情况下,以不掺氮的介孔碳材料为载体,纳米粒子的尺寸较难控制(4.4±1.7 nm)且会发生孔道外颗粒聚集的情况.研究表明,骨架中的氮原子与金属间弱的相互作用对纳米粒子有稳定作用.这对制备超小尺寸的金属纳米粒子催化剂具有一定的指导意义.此外,由于纳米粒子的尺寸将大大影响催化剂活性中心的暴露程度,进而影响催化剂活性.因此,我们以硝基苯类化合物的氢化反应来评价该催化剂的催化性能.在室温和1 MPa H2的温和条件下,氮掺杂的介孔碳负载催化剂表现出了优异的催化性能.反应0.5 h,对氯硝基苯可完全转化,且选择性高达99%.相比而言,商业化的Pt/C催化剂上反应的转化率和选择性分别为89%和90%.其它传统催化剂的比较,如Pt/SiO2,Pt/TiO2,同样表明,氮掺杂介孔碳负载的催化剂具有更优异的催化性能.在相同反应条件下,Pt/SiO2催化剂只能得到46%的转化率和93%的选择性,而Pt/TiO2催化剂虽然能够实现完全转化,但选择性也仅为91%.由此可见,氮掺杂的负载催化剂可大大提高反应活性和选择性,能有效抑制脱氯现象的发生.这种高的催化性能可能与催化剂的介孔结构、氮功能化载体以及超小尺寸的Pt纳米粒子的稳定有关.由于氮原子和介孔孔道的限域作用,氮掺杂介孔碳负载的催化剂也具有良好的催化稳定性,循环使用10次后,催化活性和选择性几乎没有下降.结果表明,循环使用后的催化剂金属粒子尺寸变化不大,进一步表明氮掺杂介孔碳载体对金属纳米颗粒的稳定作用.     

Pt 纳米颗粒在聚二甲基二烯丙基氯化铵功能化碳纳米管上的自发沉积及其对甲醇的电氧化性能

利用聚二甲基二烯丙基氯化铵(PDDA)非共价修饰的碳纳米管(CNTs)与PtCl₆^2-之间的自发氧化还原作用, 制备了Pt 纳米颗粒(Pt NPs)/CNTs-PDDA复合催化剂. PDDA在该催化剂中具有三种作用: (1) 作为金属前驱体PtCl₆^2-还原为Pt NPs 的还原剂; (2) 作为原位产生的Pt NPs 的稳定剂; (3) 在CNTs 表面形成保护膜抑制CNTs 在甲醇电催化氧化过程中的腐蚀. 采用傅里叶变换红外(FTIR)光谱、热重分析和拉曼光谱对CNTs-PDDA进行了表征, 表明PDDA通过π-π作用已成功覆盖在CNTs 表面, 并且修饰过程没有导致CNTs 结构的破坏. 采用透射电子显微镜(TEM)对Pt NPs/CNTs-PDDA 催化剂进行了表征, 结果表明, Pt NPs 均匀地分散在CNTs上, 平均粒径约2 nm, 且粒径分布范围窄. 用循环伏安法、计时电流法进一步考察了Pt NPs/CNTs-PDDA催化剂在酸性介质中对甲醇的电催化氧化的性能. 电化学测试结果表明, 与原始CNTs 负载的Pt NPs催化剂相比,Pt NPs/CNTs-PDDA催化剂具有更高的电化学活性表面积、电催化质量比活性和稳定性.     

Designed Synthesis of Well‐Defined Pd@Pt Core–Shell Nanoparticles with Controlled Shell Thickness as Efficient Oxygen Reduction Electrocatalysts

Improving the electrocatalytic activity and durability of Pt‐based catalysts with low Pt content toward the oxygen reduction reaction (ORR) is one of the main challenges in advancing the performance of polymer electrolyte membrane fuel cells (PEMFCs). Herein, a designed synthesis of well‐defined Pd@Pt core–shell nanoparticles (NPs) with a controlled Pt shell thickness of 0.4–1.2 nm by a facile wet chemical method and their electrocatalytic performances for ORR as a function of shell thickness are reported. Pd@Pt NPs with predetermined structural parameters were prepared by in situ heteroepitaxial growth of Pt on as‐synthesized 6 nm Pd NPs without any sacrificial layers and intermediate workup processes, and thus the synthetic procedure for the production of Pd@Pt NPs with well‐defined sizes and shell thicknesses is greatly simplified. The Pt shell thickness could be precisely controlled by adjusting the molar ratio of Pt to Pd. The ORR performance of the Pd@Pt NPs strongly depended on the thickness of their Pt shells. The Pd@Pt NPs with 0.94 nm Pt shells exhibited enhanced specific activity and higher durability compared to other Pd@Pt NPs and commercial Pt/C catalysts. Testing Pd@Pt NPs with 0.94 nm Pt shells in a membrane electrode assembly revealed a single‐cell performance comparable with that of the Pt/C catalyst despite their lower Pt content, that is the present NP catalysts can facilitate low‐cost and high‐efficient applications of PEMFCs.     

Tailoring the surface structure of iron compounds to optimize the selectivity of 3-nitrostyrene hydrogenation reaction over Pt catalyst

Selective hydrogenation of substituted nitroarenes is an important reaction to obtain amines.Supported metal catalysts are wildly used in this reaction because the surface structure of supports can tune the properties of the supported metal nanoparticles （NPs） and promote the selectivity to amines.Herein,Pt NPs were immobilized on Fe OOH,Fe₃O₄andα-Fe₂O₃nanorods to synthesize a series of iron compounds supported Pt catalysts by liquid phase reduction me...     

Key Factors for Simultaneous Improvements of Performance and Durability of Core‐Shell Pt3Ni/Carbon Electrocatalysts Toward Superior Polymer Electrolyte Fuel Cell

It remains a big challenge to remarkably improve both oxygen reduction reaction (ORR) activity and long‐term durability of Pt?M bimetal electrocatalysts simultaneously in the harsh cathode environment toward widespread commercialization of polymer electrolyte fuel cells (PEFC). In this account we found double‐promotional effects of carbon micro coil (CMC) support on ORR performance and durability of octahedral Pt₃Ni nanoparticles (Oh Pt₃Ni/CMC). The Oh Pt₃Ni/CMC displayed remarkable improvements of mass activity (MA; 13.6 and 34.1 times) and surface specific activity (SA; 31.3 and 37.0 times) compared to those of benchmark Pt/C (TEC10E20E) and Pt/C (TEC10E50E‐HT), respectively. Notably, the Oh Pt₃Ni/CMC revealed a negligible MA loss after 50,000 triangular‐wave 1.0–1.5 V_RHE (startup/shutdown) load cycles, contrasted to MA losses of 40 % (TEC10E20E) and 21.5 % (TEC10E50E‐HT) by only 10,000 load cycles. It was also found that the SA increased exponentially with the decrease in the CO stripping peak potential in a series of Pt?M/carbon (M: Ni and Co), which predicts a maximum SA at the curve asymptote. Key factors for simultaneous improvements of performance and durability of core‐shell Pt₃Ni/carbon electrocatalysts toward superior PEFC is also discussed.     

Enhanced stability of Pt electrocatalysts by nitrogen doping in CNTs for PEM fuel cells

Electrochemical stabilities of Pt deposited on carbon nanotubes (CNTs) and nitrogen-doped carbon nanotubes (CN_x) of different nitrogen contents are compared with accelerated durability tests (ADT) for the first time. Transmission electron microscopy (TEM) images reveal the different structures of CNTs and CN_x, and the decrease of Pt particle size with the nitrogen incorporation into CNTs. Based on the loss of electrochemical surface area (ESA) and TEM images, Pt/CN_x exhibited much higher stability than Pt/CNTs, and the Pt stability increases with the increase of nitrogen contents in the CN_x supports.     

Ru Nanoparticles Supported on Co-Embedded N-Doped Carbon Nanotubes as Efficient Electrocatalysts for Hydrogen Evolution in Basic Media

A challenging but urgent task is to construct efficient and robust hydrogen evolution reaction(HER) electrocatalysts for practically feasible and sustainable hydrogen production through alkaline water electrolysis. Herein we report a simple and mild pyrolysis method to synthesize the efficient Ru nanoparticles(NPs) supported on Co-embedded N-doped carbon nanotubes(Ru/Co-NCNTs) catalyst for HER in basic media. The Ru/Co-NCNTs display remarkable performance with a low overpotential of only 35 mV at 10 mA/cm², a small Tafel slope(36 mV/dec), and a high mass activity in 1 mol/L KOH, which is superior to commercial 20% Pt/C catalyst. This excellent performance is benefited from the enhanced conductivity of N-doped carbon nanotubes(NCNTs) and high intrinsic activity triggered by synergistic coupling between Ru NPs and Co-embedded N-doped carbon nanotubes(Co-NCNTs).     

通过载体提高燃料电池催化剂的稳定性

Pt/C是目前质子交换膜燃料电池使用最广泛的一种催化剂,制约其实际应用的关键技术之一是稳定性,增强燃料电池催化剂稳定性研究一直是该领域的热点. 本文结合作者课题组的研究工作,综述了通过改进载体材料来提高Pt基催化剂稳定性的一些方法,指出采用更稳定的载体材料以及发展与金属催化剂纳米颗粒有强相互作用的载体材料,是增强催化剂稳定性的努力方向.     

Support Morphology Effect on Selective Hydrogenation of 3-Nitrostyrene to 3-Vinylaniline over Pt/α-Fe2O3 Catalysts

Selective hydrogenation of substituted nitroaromatic compounds is an extremely important and challenging reaction. Supported metal catalysts attract much attention in this reaction because the properties of metal nanoparticles (NPs) can be modified by the nature of the support. Herein, the support morphology on the catalytic performance of selective hydrogenation of 3-nitrostyrene to 3-vinylaniline was investigated. Pt NPs supported on octadecahedral α-Fe₂O₃ supports with a truncated hexagonal bipyramid shape (Pt/α-Fe₂O₃-O) and rod-shaped α-Fe₂O₃ supports (Pt/α-Fe₂O₃-R) were prepared by glycol reduction method. Detailed characterizations reveal that the electronic structure and dispersion of Pt NPs can be modified by the supports. The Pt/α-Fe₂O₃-O catalyst exhibited superior catalytic performance for hydrogenation of 3-nitrostyrene because of its low coordinated Pt sites and the small Pt NPs size, which is benefit from the high-index exposed surfaces of truncated hexagonal bipyramid-shaped α-Fe₂O₃ support. The structural evolution during the catalytic reaction was investigated in detail by identical location transmission electron microscopy (IL-TEM) method, which found that the high cycling activity of Pt/α-Fe₂O₃-O catalyst during the cycle experiment results from the stability of Pt NPs.     

FePt nanoparticles assembled on graphene as enhanced catalyst for oxygen reduction reaction

Seven-nanometer FePt nanoparticles (NPs) were synthesized and assembled on graphene (G) by a solution-phase self-assembly method. These G/FePt NPs were a more active and durable catalyst for oxygen reduction reaction (ORR) in 0.1 M HClO(4) than the same NPs or commercial Pt NPs deposited on conventional carbon support. The G/FePt NPs annealed at 100 °C for 1 h under Ar + 5% H(2) exhibited specific ORR activities of 1.6 mA/cm(2) at 0.512 V and 0.616 mA/cm(2) at 0.557 V (vs Ag/AgCl). As a comparison, the commercial Pt NPs (2-3 nm) had specific activities of 0.271 and 0.07 mA/cm(2) at the same potentials. The G/FePt NPs were also much more stable in the ORR condition and showed nearly no activity change after 10?000 potential sweeps. The work demonstrates that G is indeed a promising support to improve NP activity and durability for practical catalytic applications.     

预制铂纳米颗粒对质子交换膜燃料电池用铂纳米线阴极的结构影响

铂纳米线（Pt NWs）由于其独特的结构特点,比商业Pt/C具有更高的氧还原反应（ORR）比活性。在本工作中,我们将预先制备好的铂纳米颗粒（Pt NPs）引入到碳基体中,用于诱导生长Pt NWs,获得了均匀分布Pt NWs的阴极。通过改变Pt NP载量（0~0.015 mg·cm^-2）和Pt NP来源（不同Pt含量的Pt/C）研究了所制备阴极的结构和性能。用扫描电镜对阴极表面进行了表征,并用透射电镜和X射线衍射分析了Pt NW的形貌和晶体结构。在单电池中分别进行了极化曲线和循环伏安曲线测试。当Pt NP来源为40% Pt/C且其载量为0.005 mg·cm^-2时,制备的Pt NW阴极具有最佳的单电池性能和最大的电化学表面积（ECSA）。最后,提出了预制Pt NP影响Pt NWs分布的可能机制。     

Nanocomposite based on depositing platinum nanostructure onto carbon nanotubes through a one-pot, facile synthesis method for amperometric sensing

Platinum nanoparticles (Pt NPs) were deposited onto multi-walled carbon nanotubes (MWNTs) through direct chemical reduction without any other stabilizing agents. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry were employed to characterize the morphology of the as-prepared nanocomposite (noted as Pt NPs-MWNTs) and further identify the Pt NPs on the surface of MWNTs. The nanocomposite demonstrated the ability to electrocatalyze the oxidation of hydrogen peroxide and substantially raises the response current. A sensitivity of 591.33 μA mM⁻¹ cm⁻² was obtained at Pt NPs-MWNTs modified electrode. Thus, we immobilized glucose oxidase (GOD) as a model enzyme on the nanocomposite-based electrode with a thin layer of Nafion to fabricate a glucose biosensor, which showed sensitive and fast response to glucose. The influence of the GOD loading was investigated and the biosensor with an enzyme loading concentration of 10 mg/mL shows optimal performance for glucose detection, that is, a detection limit of 3 μM and a response time of 3 s, respectively.     

Trimetallic Au@PdPt core-shell nanoparticles with ultrathin PdPt skin as highly stable electrocatalysts for the oxygen reduction reaction in acid solution

To design efficient and low-cost core-shell electrocatalysts with an ultrathin platinum shell, the balance between platinum dosage and durability in acid solution is of great importance. In the present work, trimetallic Au@PdPt core-shell nanoparticles(NPs)with Pd/Pt molar ratios ranging from 0.31:1 to 4.20:1 were synthesized based on the Au catalytic reduction strategy and the subsequent metallic replacement reaction. When the Pd/Pt molar ratio is 1.19:1(designated as Au@Pd_(1.19) Pt_1 NPs), the superior electrochemical activity and stability were achieved for oxygen reduction reaction(ORR) in acid solution. Especially, the specific and mass activities of Au@Pd_(1.19) Pt_1 NPs are 1.31 and 6.09 times higher than those of commercial Pt/C catalyst. In addition, the Au@Pd_(1.19) Pt_1 NPs presented a good durability in acid solution. After 3000 potential cycles between 0.1 and 0.7 V(vs. Ag/AgCl), the oxygen reduction activity is almost unchanged. This study provides a simple strategy to synthesize highperformance trimetallic ORR electrocatalyst for fuel cells.     

In Situ Fabrication of Noble Metal Nanoparticles Modified Multiwalled Carbon Nanotubes and Related Electrocatalysis

Using multiwalled carbon nanotubes (MWNTs) as templates, noble metal (Au, Ag, Pt or Pd) nanoparticles (NPs) were fabricated in situ by electrochemistry with a diameter of 40–60 nm. Further, catalytic behaviors of these composite materials were investigated. Experiments showed that such carbon nanotubes decorated with Pd NPs modified glassy carbon electrodes exhibited higher electrocatalytic ability to some molecules such as evolution of hydrogen, reduction of oxygen and oxidation of ascorbic acid. Atomic force microscopy, X‐ray photoelectron spectroscopy and cyclic voltammetry were used to characterize the film formation and their properties.