A three-dimensional hierarchical nanoporous PdCu alloy for enhanced electrocatalysis and biosensing

Nanoporous copper (NPC) obtained by dealloying CuAl alloy is used as both three-dimensional template and reducing agent for the fabrication of nanoporous PdCu alloy with hollow ligaments by a simple galvanic replacement reaction with H₂PdCl₄ aqueous solution. Electron microscopy and X-ray diffraction characterizations demonstrate that after the replacement reaction, the ligaments become hollow tubular structure and the ligament shell is also comprised of small pores and nanoparticles with a typical size of ∼4 nm (third order porosity). The as-prepared nanotubular mesoporous PdCu alloy (NM-PdCu) structure exhibits remarkably improved electrocatalytic activity towards the oxidation of formic acid and H₂O₂ compared with nanoporous Pd (NP-Pd), and can be used for sensitive electrochemical sensing applications. After coupled with glucose oxidase (GOx), the enzyme modified NM-PdCu electrode can sensitively detect glucose over a wide linear range (0.5–20 mM).     

CoPt纳米空心球甲醇电催化氧化和原位电化学傅里叶变换红外光谱研究

采用化学还原和电位置换法制备了CoPt 纳米空心球, 该催化剂对甲醇氧化表现出较好的电催化活性.透射电镜(TEM)、能量散射光谱(EDS)和电化学循环伏安实验结果表明, 在0.1 mol·L^-1 H₂SO₄+0.1 mol·L^-1CH₃OH中进行测试时, CoPt 纳米空心球发生了去合金化过程, 催化剂表面Co元素溶解, 形成了富Pt 表面, 表现出更好的电催化活性, 同时表现出较好的结构稳定性. 采用原位电化学红外光谱在分子水平研究了CoPt 纳米空心球上甲醇氧化过程, 发现甲醇在CoPt 纳米空心球氧化中间产物主要为CO, 且CO表现出异常红外效应, 与CO为探针分子在CoPt纳米空心球上得到的红外光谱结果一致. 研究结果表明, 去合金化方法是一种有效调节催化剂表面组成和性能的手段, 原位电化学红外光谱是潜在的原位研究有机小分子氧化机理的方法, 在燃料电池中将得到广泛的应用.     

纳米多孔Ni和NiO的制备及电催化析氧性能

采用快速凝固与脱合金相结合的方法制备了纳米多孔Ni, 经热处理氧化获得纳米多孔NiO, 利用X射线衍射仪(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)和氮气吸附-脱附仪(BET)对纳米多孔Ni和NiO的物相、 形貌结构和孔径分布进行了表征, 并通过循环伏安、 稳态极化和电化学阻抗分析研究了电极的电催化析氧性能. 结果表明, 由Ni₃₀Al₇₀所得纳米多孔Ni具有多层次纳米多孔结构, 在10 mA/cm ²电流密度下析氧过电位仅为224 mV, 交换电流密度为0.63297 mA/cm ², 表观活化自由能为40.297 kJ/mol, 经1000次循环后, 过电位降低了5 mV(j=10 mA/cm ²), 表现出良好的催化稳定性和耐久性; 热处理氧化降低了NiO的比表面积与电化学活性面积, 平衡电位下扩散传质速率明显减小, 析氧活性较Ni电极有所下降.     

Structural transformations of metal alloys under electrocatalytic conditions

Nanostructured alloys are efficient catalysts for mediating renewable energy storage and recovery reactions. The morphology and composition of an alloy can change during catalysis; particularly for potentials more oxidizing than the reversible hydrogen electrode. The formation of noble-metal shells covering an alloy core, or bi-continuous nanoporosity, is a common way an alloy can evolve by a corrosion mediated process. Recently, it was found that alloys can reconstruct within the bulk and form an ordered intermetallic material with different crystal structures and compositions than the starting material during corrosion. This review will discuss the different pathways alloys can be altered by electrochemistry. We will discuss the mechanisms which cover known structural changes and the more recently discovered process involving electrochemically driven incongruent phase transformations. Insights into the transformation of alloy materials are important for understanding how to prepare catalysts with improved electrochemical stability, and for synthesizing materials.     

Preparation and Pseudo-capacitance Performance of NiCo2O4 Nanosheets

Ternary nickel cobaltite(NiCo₂O₄), as a promising electrode material for supercapacitors, has attracted increasing attention for its excellent electrochemical properties. In this study, novel NiCo₂O₄ nanosheets were rationally designed and prepared using dealloying process, followed by an oxidation treatment. The as-prepared sample was characterized by microstructural and electrochemical techniques in view of its possible application in supercapacitors. The as-prepared sample exhibited high specific capacitance and excellent durability. The specific capacitance reached 663 F/g at 1 A/g and the rate capacitance high up to 73.6% when the current density increased from 1 A/g to 20 A/g. After 5000 cycles of galvanostatic charge-discharge durability test at 4 A/g, the capacity retention rate was 82.1%. The results indicate that versatile dealloying can be used to prepare robust electrode for supercapacitor application.     

纳米多孔金属电催化剂在氧还原反应中的应用

燃料电池是将化学能直接转化为电能的能量转换装置,具有绿色、高效、便携等特点。对于大多数使用氧气或者空气为氧化剂的燃料电池而言,其阴极氧还原反应动力学缓慢、稳定性差是阻碍该技术走向商业化的主要因素,因此开发高催化活性和良好稳定性的低成本氧还原催化剂非常重要。基于脱合金法制得的纳米多孔金属是一类新型的宏观尺度纳米结构材料,其独特的开放型孔道结构、优良的导电性和结构的可调控性使其在电催化相关领域具有广泛的应用。本文侧重于讨论纳米多孔金属作为氧还原催化剂时所展示的一系列结构特性,及其在发展新一代高性能一体化燃料电池催化剂中所展示的机会。     

Ir-skinned Ir-Cu Nanoparticles with Enhanced Activity for Oxygen Reduction Reaction

The development of methanol-tolerate oxygen reduction reaction(ORR) electrocatalysts is of special significance to direct methanol fuel cells system. Iridium is known for its better methanol tolerance than platinum and able to survive in harsh acidic environment. However, its activity is relatively low and thus the approach to improve Ir's ORR is desired. Herein, bimetallic Ir-Cu nanoparticles(NPs) with controllable Ir/Cu compositions(ca. 1:2 to 4:1, atomic ratio) are synthesized via a galvanic replacement-based chemical method. The as-synthesized Ir-Cu NPs are investigated as ORR catalysts after electrochemically leaching out the surface Cu and forming Ir-skinned structures. Around 2- to 3-fold enhancement in the intrinsic activity has been observed in these Ir-skinned Ir-Cu catalysts compared to Ir counterpart. The approach is demonstrated to be a promising way to prepare efficient Ir ORR catalysts and lower catalyst cost.     

Facile fabrication of nanoporous PdFe alloy for nonenzymatic electrochemical sensing of hydrogen peroxide and glucose

Nanoporous (NP) PdFe alloy is easily fabricated through one step mild dealloying of PdFeAl ternary source alloy in NaOH solution. Electron microscopy characterization demonstrates that selectively dissolving Al from PdFeAl alloy generates three-dimensional bicontinuous nanospongy architecture with the typical ligament size around 5 nm. Electrochemical measurements show that the NP-PdFe alloy exhibits the superior electrocatalytic activity and durability towards hydrogen peroxide (H₂O₂) detection compared with NP-Pd and commercial Pd/C catalysts. In addition, NP-PdFe performs high sensing performance towards H₂O₂ in a wide linear range from 0.5 to 6 mM with a low detection limit of 2.1 μM. This nanoporous structure also can sensitively detect glucose over a wide concentration range (1–32 mM) with a low detection limit of 1.6 μM and high resistance against chloride ions. Along with these attractive features, the as-made NP-PdFe alloy also has a good anti-interference towards ascorbic acid, uric acid, and dopamine.     

Pd-based nanoporous metals for enzyme-free electrochemical glucose sensors

Nanoporous metals （NPMs） show potential applications as enzyme-free glucose sensors. There are few reports on nanoporous Pd in this area even though their cost is much lower than other NPMs. In this work, we report the formation of Pd-based NPM with improved catalytic activity towards the oxidation of glucose. By dealloying metallic glasses, Pd-based NPMs with hi-continuous networks were obtained. All the Pd-based NPMs show high electrochemical catalytic activity towards glucose oxidation. In this study, NPM with an open, three-dimensional, ligament-channel nanoporous structure resulted by dealloying metallic Pd3oCu4oNiloP2o, producing a pore size of 11 nm and a ligament size of 7 nm as the best configuration towards the direct oxidation reaction of glucose.     

High catalytic activity of ultrafine nanoporous palladium for electro-oxidation of methanol, ethanol, and formic acid

Nanoporous palladium (NPPd) with ultrafine ligament size of 3–6 nm was fabricated by dealloying of an Al–Pd alloy in an alkaline solution. Electrochemical measurements indicate that NPPd exhibits significantly high electrochemical active specific surface area (23 m² g⁻¹), and high catalytic activity for electro-oxidation of methanol, ethanol, and formic acid. Mass activities can reach 149, 148, 262 mA mg⁻¹ for the oxidation of methanol, ethanol and formic acid, respectively. Moreover, superior steady-state activities can be observed for all the electro-oxidation processes. NPPd will be a promising candidate for the anode catalyst for direct alcohol or formic acid fuel cells.