Synthesis and electrocatalytic activity of Au@Pd core-shell nanothorns for the oxygen reduction reaction

Bimetallic core-shell nanostructures with porous surfaces have drawn considerable attention due to their promising applications in various fields, including catalysis and electronics. In this work, Au@Pd core-shell nanothorns （CSNTs） with rough and porous surfaces were synthesized for the first time through a facile co-chemical reduction method in the presence of polyallylamine hydrochloride （PAH） and ethylene glycol （EG） at room temperature. The size, morphology, and composition of Au@Pd CSNTs were investigated by transmission electron microscopy （TEM）, X-ray diffraction （XRD）, energy dispersive spec- troscopy （EDX）, EDX mapping, and X-ray photoelectron spectroscopy （XPS）. The electrochemical properties of as-synthesized Au@Pd CSNTs were also studied by various electrochemical techniques. Au@Pd CSNTs exhibited remarkably high electrocatalytic activity and durability for the oxygen reduction reaction （ORR） in the alkaline media, owing to the unique porous structure and the synergistic effect between the Au core and Pd shell.     

Shape-controlled synthesis of porous AuPt nanoparticles and their superior electrocatalytic activity for oxygen reduction reaction

Control of structure and morphology of Pt-based nanomaterials is of great importance for electrochemical energy conversions. In this work, we report an efficient one-step synthesis of bimetallic porous AuPt nanoparticles (PAuPt NPs) in an aqueous solution. The proposed synthesis is performed by a simple stirring treatment of an aqueous reactive mixture including K₂PtCl₄, HAuCl₄, Pluronic F127 and ascorbic acid at a pH value of 1 without organic solvent or high temperature. Due to their porous structure and bimetallic composition, as-made PAuPt NPs exhibit excellent electrocatalytic activity for oxygen reduction reaction.     

Construction of multilayers of bare and Pd modified gold nanoclusters and their electrocatalytic properties for oxygen reduction

Abstract

Multilayers of gold nanoclusters (GNCs) coated with a thin Pd layer were constructed using GNCs modified with self-assembled monolayers (SAMs) of mercaptoundecanoic acid and a polyallylamine hydrochloride (PAH) multilayer assembly, which has been reported to act as a three-dimensional electrode. SAMs were removed from GNCs by electrochemical anodic decomposition and then a small amount of Pd was electrochemically deposited on the GNCs. The kinetics of the oxygen reduction reaction (ORR) on the Pd modified GNC/PAH multilayer assembly was studied using a rotating disk electrode, and a significant increase in the ORR rate was observed after Pd deposition. Electrocatalytic activities in alkaline and acidic solutions were compared both for the GNC multilayer electrode and Pd modified GNC electrode.     

Rapid preparation and photocatalytic properties of octahedral Cu2O@Cu powders

To improve the photocatalytic properties of Cu₂O, octahedral Cu₂O@Cu powders were prepared by a convenient and rapid two-step liquid phase reduction method. Glucose (C₆H₁₂O₆) and thiourea dioxide (CH₄N₂O₂S, TD for short) were used as pre-reductant and secondary-reductant separately. The microstructure and composition of the products obtained after the reduction processes were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). With the increasing of TD content, the secondary reduced products changed from solid octahedral Cu₂O to octahedral Cu₂O@Cu composites and finally hollow octahedral Cu₂O/Cu composites. The corresponding calculated mass of Cu increased from 6.2 wt% to 80.2 wt%. The photocatalytic behavior of the reduced particles were analyzed by monitoring the degradation of methyl orange solution (MO for short) and electrochemical tests. Photocatalytic performance tests showed that octahedral Cu₂O@Cu powders had an excellent photocatalytic activity. The MO degradation rate was improved from 1.4% for photocatalysts without CuNPs to 92.9% after introducing 13.4 wt% CuNPs under visible light irradiation for 60 min. This simple and rapid synthesis process allowed for the fabrication of octahedral Cu₂O@Cu material with photocatalytic performance superior to pure octahedral Cu₂O and hollow octahedral Cu₂O/Cu materials.     

Template-directed synthesis of nitrogen- and sulfur-codoped carbon nanowire aerogels with enhanced electrocatalytic performance for oxygen reduction

Heteroatom doping,precise composition control,and rational morphology design are efficient strategies for producing novel nanocatalysts for the oxygen reduction reaction (ORR) in fuel cells.Herein,a cost-effective approach to synthesize nitrogen-and sulfur-codoped carbon nanowire aerogels using a hard templating method is proposed.The aerogels prepared using a combination of hydrothermal treatment and carbonization exhibit good catalytic activity for the ORR in alkaline solution.At the optimal annealing temperature and mass ratio between the nitrogen and sulfur precursors,the resultant aerogels show comparable electrocatalytic activity to that of a commercial Pt/C catalyst for the ORR.Importantly,the optimized catalyst shows much better long-term stability and satisfactory tolerance for the methanol crossover effect.These codoped aerogels are expected to have potential applications in fuel cells.     

石墨烯负载Pt-Co纳米粒子及其在氧化还原反应中的应用

采用微波-乙二醇方法还原氧化石墨烯和Pt(v)、Co(Ⅱ)粒子混合物,再经300℃H2还原,制备了石墨烯负载Pt-Co合金催化剂(Pt-Co/G).利用透射电镜、X-射线能谱、X-射线衍射和光电子能谱对所制催化剂进行表征.Pt-Co合金的粒径为3nm～8 nm,均匀地分散在石墨烯片上.与单金属的Pt/G和商品化的Pt/C催化剂相比,所制合金化的Pt-Co/G催化剂对氧还原反应展现出高的催化活性和可比拟的稳定性,显示了其在燃料电池中的应用潜力.     

<Emphasis Type="Italic">In situ</Emphasis> development of highly concave and composition-confined PtNi octahedra with high oxygen reduction reaction activity and durability

Controlled syntheses of PtNi metal nanocrystals with unique structures for catalyzing oxygen reduction reactions (ORRs) have attracted great interest. Here, we report the one-step synthesis of single-crystal PtNi octahedra with in situ-developed highly concave features and self-confined composition that are optimal for ORR. Detailed studies revealed that the Pt-rich seeding, subsequent Pt/Ni co-reduction, and Pt–Ni interfusion resulted in uniform single-crystal PtNi octahedra, and that the combination of Ni facet segregation and oxygen etching of a Ni-rich surface led to the concavity and confined Ni content. The concave PtNi nanocrystals exhibited much higher ORR performance than the commercially available Pt/C catalyst in terms of both specific activity (29.1 times higher) and mass activity (12.9 times higher) at 0.9 V (vs. reversible hydrogen electrode (RHE)). The performance was also higher than that of PtNi octahedra without concavity, confirming that the higher activity was closely related to its morphology. Moreover, the concave octahedra also exhibited remarkable stability in ORR (93% mass activity remained after 10,000 cycles between 0.6 and 1.1 V vs. RHE) owing to the passivation of the unstable sites.

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磷氮掺杂石墨烯层封装FeP纳米颗粒的增强ORR催化性能

开发高效的非贵金属氧还原反应(ORR)催化剂来替代铂基催化剂受到了广泛关注.设计合成在碱性电解质和酸性电解质中均表现出高催化活性的非贵金属催化剂仍然是一个挑战.在本文中,我们通过前驱体热解法制备了一种纳米复合催化剂(FeP@PGL),该催化剂由氮掺杂的碳纳米片以及镶嵌在片层上的磷掺杂石墨烯层封装磷化铁(FeP)纳米颗粒组成.FeP@PGL催化剂表现出优异的ORR催化性能,在碱性介质中的起始电位和半波电势分别高达1.01 V和0.90 V vs.RHE;在酸性介质中的起始电位和半波电势分别高达0.95 V和0.81 V vs.RHE.通过详细的电子显微和谱学表征,我们发现碳纳米片基质与包裹纳米颗粒的碳包裹层存在组成的差别,磷掺杂主要发生在包裹FeP纳米颗粒的石墨烯层上.封装的FeP纳米颗粒与外层磷掺杂石墨烯层之间存在界面电荷转移,并且通过界面相互作用降低了催化剂表面的功函数.FeP和磷掺杂石墨烯层之间的界面协同作用对于增强催化剂ORR活性至关重要.本文不仅证明了封装型FeP基纳米复合催化剂在氧还原反应上的应用价值,而且为界面电荷转移效应及其在ORR过程中的作用提供了实验证据.     

Porous Pt/Ag nanoparticles with excellent multifunctional enzyme mimic activities and antibacterial effects

Enhancing the activity of Pt-based nanocatalysts is of great significance yet a challenge for the oxygen reduction reaction (ORR).In this work,a series of porous Pt/Ag nanoparticles (NPs) were fabricated from regular PtxAg100-x (x =25,50,75) octahedra by a facile and economical dealloying process.Remarkable enhancement in multiple enzyme-mimic activities related to ORR was observed for the dealloyed Pt50Ag50 (D-Pt50Ag50) NPs.This effect can be attributed to the resulting Pt-rich surface structure,increased surface area,and a synergistic effect of Pt and Ag atoms in the D-Pt50Ag50 NPs.Furthermore,the D-Pt50Ag50 NPs exerted excellent antibacterial effects on two model bacteria (gram-negative Escherichia coli and gram-positive Staphylococcus aureus).The present work represents a significant advance in the exploration of the relation between controllable synthesis of high-quality nanoalloys and their novel catalytic properties for various promising applications,including catalysts,biosensors,and biomedicine.     

Nitrogen-doped graphite encapsulated Fe/Fe_3C nanoparticles and carbon black for enhanced performance towards oxygen reduction

Non-noble metal(NNM) catalysts have recently attracted intensive interest for their high catalytic performance towards oxygen reduction reaction(ORR) at low cost.Herein,a novel NNM catalyst was synthesized by the simple pyrolysis of carbon black,urea and a Fe-containing precursor,which exhibits excellent ORR catalytic activity,superior durability and methanol tolerance versus the Pt/C catalyst in both alkaline and acidic solutions.Scanning electron microscopy(SEM),transmission electron microscopy(TEM) and X-ray diffraction(XRD) characterizations demonstrate that the product is a nitrogen-doped hybrid of graphite encapsulated Fe/Fe_3C nanoparticles and carbon black.X-ray photoelectron spectrum(XPS) and electrochemical analyses indicate that the catalytic performance and chemical stability correlate closely with a nitrogen-rich layer on the Fe/Fe_3C nanoparticle after pyrolysis with presence of urea,leading to the same four-electron pathway towards ORR as the Pt/C catalyst.The hybrid is prospective to be an efficient ORR electrocatalyst for direct methanol fuel cells with high catalytic performance at low cost.     

氧还原电催化剂Pt/WO3-C的制备及稳定性研究

采用化学沉淀法由HCl-Na₂WO₄制备WO₃-C复合载体, 通过微波辅助乙二醇还原法制备Pt/WO₃-C复合载体催化剂。研究了WO₃含量以及热处理温度对Pt/WO₃-C催化剂性能的影响, 采用X射线衍射、透射电子显微镜和能量散射光谱对Pt/WO₃-C的物化结构和组成进行了表征。结果表明, WO₃的最佳含量为10wt%, N₂气氛中热处理适宜温度为250℃。所制备的Pt/WO₃-C催化剂中WO₃以单斜晶型存在, Pt颗粒的平均粒径为2.77 nm。通过循环伏安法和单体质子交换膜燃料电池极化曲线测试了Pt/WO₃-C催化剂的电化学性能, 证实了Pt与WO₃之间存在协同催化作用, 与Pt/C催化剂相比, Pt/WO₃-C的催化活性和稳定性都有明显改善。     

The composite of carbon nanotubes and cobalt(II)-intercalated montmorillonite for enhanced electrocatalytic oxygen reduction

Abstract

Due to the rapid development of fuel cells, the fabrication of electrocatalysts for oxygen reduction (ORR) with high performance and low-cost is of great significance. Herein, cobalt cations-intercalated montmorillonite (Co-MMT) was prepared by a simple cation-exchange reaction between Na-MMT and cobalt cations. A detailed ORR investigation indicates that the as-prepared nanocomposite of Co-MMT and multiwalled carbon nanotubes (Co-MMT/MWCNT) exhibits better ORR catalytic activity in aqueous alkaline medium with a 4e-route mechanism than Na-MMT, Co-MMT and MWCNT, suggesting the synergistic effect between Co-MMT and MWCNT. Moreover, further research shows that Co-MMT/MWCNT hybrid demonstrated more positive onset potential for ORR, higher oxygen reduction peak current than commercial 5% Pt/C ORR electrocatalyst.     

N- and S-doped high surface area carbon derived from soya chunks as scalable and efficient electrocatalysts for oxygen reduction

Highly stable, cost-effective electrocatalysts facilitating oxygen reduction are crucial for the commercialization of membrane-based fuel cell and battery technologies. Herein, we demonstrate that protein-rich soya chunks with a high content of N, S and P atoms are an excellent precursor for heteroatom-doped highly graphitized carbon materials. The materials are nanoporous, with a surface area exceeding 1000 m² g⁻¹, and they are tunable in doping quantities. These materials exhibit highly efficient catalytic performance toward oxygen reduction reaction (ORR) with an onset potential of −0.045 V and a half-wave potential of −0.211 V (versus a saturated calomel electrode) in a basic medium, which is comparable to commercial Pt catalysts and is better than other recently developed metal-free carbon-based catalysts. These exhibit complete methanol tolerance and a performance degradation of merely ∼5% as compared to ∼14% for a commercial Pt/C catalyst after continuous use for 3000 s at the highest reduction current. We found that the fraction of graphitic N increases at a higher graphitization temperature, leading to the near complete reduction of oxygen. It is believed that due to the easy availability of the precursor and the possibility of genetic engineering to homogeneously control the heteroatom distribution, the synthetic strategy is easily scalable, with further improvement in performance.     

N- and S-doped high surface area carbon derived from soya chunks as scalable and efficient electrocatalysts for oxygen reduction

Abstract

Highly stable, cost-effective electrocatalysts facilitating oxygen reduction are crucial for the commercialization of membrane-based fuel cell and battery technologies. Herein, we demonstrate that protein-rich soya chunks with a high content of N, S and P atoms are an excellent precursor for heteroatom-doped highly graphitized carbon materials. The materials are nanoporous, with a surface area exceeding 1000 m² g^?1, and they are tunable in doping quantities. These materials exhibit highly efficient catalytic performance toward oxygen reduction reaction (ORR) with an onset potential of ?0.045 V and a half-wave potential of ?0.211 V (versus a saturated calomel electrode) in a basic medium, which is comparable to commercial Pt catalysts and is better than other recently developed metal-free carbon-based catalysts. These exhibit complete methanol tolerance and a performance degradation of merely ～5% as compared to ～14% for a commercial Pt/C catalyst after continuous use for 3000 s at the highest reduction current. We found that the fraction of graphitic N increases at a higher graphitization temperature, leading to the near complete reduction of oxygen. It is believed that due to the easy availability of the precursor and the possibility of genetic engineering to homogeneously control the heteroatom distribution, the synthetic strategy is easily scalable, with further improvement in performance.     

石墨烯负载四硫化三钴复合物氧还原催化剂的制备与性能

选取二氯化钴和硫脲为钴源和硫源,以自制的还原氧化石墨烯(rGO)为载体,采用回流法在乙二醇溶剂中一步合成出Co₃S₄/rGO复合物。利用X射线衍射、扫描电镜和拉曼光谱(Raman)等手段对催化剂进行结构与形貌表征。结果表明:Co₃S₄/rGO样品中生成了具有立方结构的Co₃S₄细小晶粒,生长在rGO上的Co₃S₄晶粒发生聚集,具有较好的分散性。Co₃S₄/rGO的拉曼谱图的峰强比(I_D/I_G)为0.92,Co₃S₄对石墨烯结构无明显影响,石墨烯起到载体作用。在0.5mol/L H₂SO_4电解液中,线扫伏安测试表明,Co₃S₄/rGO催化剂具有良好的氧还原催化性能,氧还原起始电位为0.75V(vs.RHE),在动力学电位区,Tafel斜率和传递系数分别为119.5mV和0.49,氧分子在Co₃S₄/rGO催化剂上按四电子机理直接还原成水。