Single-wall carbon nanotubes supported platinum nanoparticles with improved electrocatalytic activity for oxygen reduction reaction

Significant enhancement in the electrocatalytic activity of Pt particles toward oxygen reduction reaction (ORR) has been achieved by depositing them on a single wall carbon nanotubes (SWCNT) support. Compared to a commercial Pt/carbon black catalyst, Pt/SWCNT films cast on a rotating disk electrode exhibit a lower onset potential and a higher electron-transfer rate constant for oxygen reduction. Improved stability of the SWCNT support is also confirmed from the minimal change in the oxygen reduction current during repeated cycling over a period of 36 h. These studies open up ways to utilize SWCNT/Pt electrocatalyst as a cathode in the proton-exchange-membrane-based hydrogen and methanol fuel cells.     

弱磁性Co0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

氢气是一种环境友好可再生的清洁能源,电解水无疑是一种很好的制氢方法.然而,电催化分解水析氢受到其缓慢的动力学过程、较低的催化性能和较差的稳定性的限制.为了使整个过程更节能,具有高电流密度和低的过电势的高效电催化剂被广泛研究.非化学计量相硒化钴(Co0.85Se)作为一种重要的金属硫属化合物具有优异的催化性能而广受关注.但是低维的Co0.85Se活性位点少,分散性差,电子传递能力低,导致其电催化剂活性差.多壁碳纳米管(MWCNTs)具有多种电性能,包括金属导电性和电子存储能力等.因此,MWCNTs的特殊结构和高导电性可以有效地促进电子从电催化剂向碳纳米管的转移,实现高效电分解水制氢性能.本文在不使用表面活性剂和模板的情况下,通过一步水热溶剂热法合成弱磁性Co0.85Se纳米片负载碳纳米管电催化剂.采用磁滞回线研究Co0.85Se和MWCNTs/Co0.85Se的磁性能,结果表明其有弱顺磁性,Co0.85Se纳米片之间的空间距离增强导致粒子间偶极相互作用减弱,从而使MWCNTs/Co0.85Se纳米复合材料的矫顽力值增加到158 Oe.随着微晶尺寸的减小和纳米颗粒间距的增大,MWCNTs/Co0.85Se催化剂的比表面积增大,有利于提高其电催化活性.扫描电镜和透射电镜展示出Co0.85Se纳米片分散性较差,且团聚现象严重,而MWCNTs/Co0.85Se纳米复合催化剂显示Co0.85Se纳米片均匀分散在MWCNTs表面,且纳米片尺寸明显减小,有利于Co0.85Se纳米片暴露更多的活性位点.线性扫描伏安曲线测量表明,在酸性溶液中Co0.85Se纳米片在电流密度为10 mA cm?2时,其过电势为319 mV(vs.RHE),30 wt%MWCNTs/Co0.85Se的过电势为266 mV(vs.RHE).Co0.85Se和MWCNTs/Co0.85Se的Tafel斜率分别为92.6和60.5 mV dec?1.此外,MWCNTs/Co0.85Se的电流交换密度(j0)为0.07 mA cm?2.较小的Tafel斜率和高的电流交换密度表明,MWCNTs/Co0.85Se具有良好的反应动力学和快速的质子分离速率.交流阻抗谱表明MWCNTs/Co0.85Se比Co0.85Se电阻更小,电子传输速率更快.电化学活性表面积与双电层在固液界面处的电容测量值成正比.结果显示,30 wt%MWCNTs/Co0.85Se的双电层电容为0.22 mF cm^-2,高于Co0.85Se和15 wt%的rGO/Co0.85Se(0.04 mF cm^-2,0.17 mF cm^-2),这表明较大的电化学活性表面积有利于析氢反应进行.30 wt%MWCNTs/Co0.85Se的循环稳定测试表明其具有较好的稳定性.综上,本文介绍了通过一步水热法合成具有弱磁性的Co0.85Se和MWCNTs/Co0.85Se电催化剂,碳纳米管作为一种高导电性材料被引入Co0.85Se纳米片中以减少Co0.85Se的团聚,使Co0.85Se的活性位点增加,进而提高电催化制氢性能.     

Highly exposed NiFeOx nanoclusters supported on boron doped carbon nanotubes for electrocatalytic oxygen evolution reaction

The development of efficient and cost-effective electrocatalysts for oxygen evolution reaction (OER) is crucial for the overall water splitting. Herein, we prepared a highly exposed NiFeO_x ultra-small nanoclusters supported on boron-doped carbon nonotubes catalyst, which achieves a 10 mA/cm² anodic current density at a low overpotential of 213 mV and the Tafel slope of 52 mV/dec in 1.0 mol/L KOH, superior to the pristine NiFeO_x-CNTs and other state-of-the-art OER catalysts in alkaline media. A combination study (XPS, sXAS and XAFS) verifies that the local atomic structure of Ni and Fe atoms in the nanoclusters are similar to NiO and Fe₂O₃, respectively, and the B atoms which are doped into the crystal lattice of CNTs leads to the optimization of Ni 3d e_g orbitals. Furthermore, in-situ X-ray absorption spectroscopies reveal that the high valence state of Ni atoms are served as the real active sites. This work highlights that the precise control of highly exposed multicomponent nanocluster catalysts paves a new way for designing highly efficient catalysts at the atomic scale.     

石墨化氮化碳负载Cu纳米颗粒用作高效氧还原电催化剂

高活性低成本氧还原反应(ORR)电催化剂是燃料电池和金属/空气电池等可再生能源技术的关键组成部分.在离子液体[(C16mim)2CuCl4]和质子化的石墨化氮化碳(g-CN)的存在下,采用简易的水热反应制备了Cu/g-CN电催化剂用于ORR.与纯的g-CN相比,所制Cu/g-CN表现出高的ORR催化活性:起始电势正移99 mV,为2倍动力学电流密度.另外,Cu/g-CN还表现出比商用Pt/C(HiSPECTM 3000,20%)催化剂更好的稳定性和甲醇容忍性.因此,该催化剂作为廉价的高效ORR电催化剂有望应用于燃料电池中.     

Iron (II) tetrakis(diaquaplatinum) octacarboxyphthalocyanine supported on multi-walled carbon nanotubes as effective electrocatalyst for oxygen reduction reaction in alkaline medium

Oxygen reduction reaction (ORR) in alkaline medium at iron (II) tetrakis (diaquaplatinum) octacarboxyphthalocyanine (PtFeOCPc) catalyst supported on multi-walled carbon nanotubes (MWCNTs) has been described. The ORR followed the direct 4-electron transfer process, with a very low onset potential (approximately zero volts vs. Ag|AgCl, saturated KCl) and at a kinetic rate constant, 2.78 × 10^? 2 cm s^? 1. The results clearly showed that the ORR activity at the MWCNT-PtFeOCPc platform is comparable or even better than recent reports with other electrocatalysts, thus a promising catalytic platform for cathodic process in fuel cell device.     

The whole is more than the sum of its parts: Modeling community-level effects of UVR in marine ecosystems

The effect of UVB radiation (UVBR, 290-320 nm) on the dynamics of the lower levels of the marine plankton community was modeled. The model was built using differential equations and shows a good fit to experimental data collected in mesocosms (defined as large enclosures of 1500 L filled with natural marine waters). Some unexpected results appear to be possible by indirect effects in prey (bacteria, phytoplankton and heterotrophic flagellates). In particular, apparent competition appears between small phytoplankton and bacteria. This effect is caused by a shared predator (ciliates). Another remarkable effect is an increase in bacteria and flagellates populations due to enhanced UVBR. This effect is similar to that observed under mesocosm experimental conditions and is related to the decrease of predation due to the direct damage to predators (ciliates) by UVBR. The effect of UVBR changing interaction coefficients may be dramatic on the community structure, producing big changes in equilibrium populations, as demonstrated by sensitivity analysis of the model. In order to generalize these results to field conditions it will be necessary to increase model complexity and include extra organic mater sources, mixing and sinking effects and predation by large zooplankton. This work shows that UVBR may produce community global responses that are consequence of both direct and indirect effects among populations.     

Electrodeposition and electrocatalytic properties of platinum nanoparticles on multi-walled carbon nanotubes: effect of the deposition conditions

Platinum (Pt) nanoparticles were electrochemically deposited on multi-walled carbon nanotubes (MWCNTs) through a three-step process, including an electrochemical treatment of MWCNT, electro-oxidation of PtCl₄ ²⁻ to Pt(IV) complex, and an electro-conversion of Pt(0) on MWCNT. The effect of formation conditions for Pt(IV) complexes on the Pt nanoparticals transformed was investigated. The structure and elemental composition of the resulting Pt/MWCNT electrode were characterized by transmission electron micrograph (TEM) and energy dispersive X-ray spectroscopy (EDX). The electrocatalytic properties of the resulting Pt/MWCNT electrode for methanol oxidation have been investigated. The high electrocatalytic activity and good stability of Pt/MWCNT electrode may be attributed to the high dispersion of platinum nanoparticles and the particular properties of the MWCNT supports.     

Stabilization of high-performance oxygen reduction reaction pt electrocatalyst supported on reduced graphene oxide/carbon black composite

Oxygen reduction reaction (ORR) catalyst supported by hybrid composite materials is prepared by well-mixing carbon black (CB) with Pt-loaded reduced graphene oxide (RGO). With the insertion of CB particles between RGO sheets, stacking of RGO can be effectively prevented, promoting diffusion of oxygen molecules through the RGO sheets and enhancing the ORR electrocatalytic activity. The accelerated durability test (ADT) demonstrates that the hybrid supporting material can dramatically enhance the durability of the catalyst and retain the electrochemical surface area (ECSA) of Pt: the final ECSA of the Pt nanocrystal on the hybrid support after 20?000 ADT cycles is retained at >95%, much higher than the commercially available catalyst. We suggest that the unique 2D profile of the RGO functions as a barrier, preventing leaching of Pt into the electrolyte, and the CB in the vicinity acts as active sites to recapture/renucleate the dissolved Pt species. We furthermore demonstrate that the working mechanism can be applied to the commercial Pt/C product to greatly enhance its durability.     

High-density assembly of gold nanoparticles with zwitterionic carbon nanotubes and their electrocatalytic activity in oxygen reduction reaction

Gold nanoparticles (AuNPs) were assembled with high density onto multi-walled carbon nanotubes, which were functionalized with zwitterionic poly(imidazoliumsulfonate). The AuNP/zwitterionic CNT hybrids exhibited decent electrocatalytic activity in oxygen reduction reaction as the AuNP-based catalysts.     

Electrocatalysis of oxygen reduction on multi-walled carbon nanotube supported copper and manganese phthalocyanines in alkaline media

Manganese phthalocyanine (MnPc) and copper phthalocyanine (CuPc)-modified electrodes were prepared using multi-walled carbon nanotubes (MWCNTs) as a support material. The catalyst materials were heat treated at four different temperatures to investigate the effect of pyrolysis on the oxygen reduction reaction (ORR) activity of these electrocatalysts. The MWCNT to metal phthalocyanine ratio was varied. Scanning electron microscopy (SEM) was employed to visualise the surface morphology of the electrodes and the x-ray photoelectron spectroscopic (XPS) study was carried out to analyse the surface composition of the most active catalyst materials. The ORR was studied in 0.1 M KOH solution employing the rotating disk electrode (RDE) method. Glassy carbon (GC) electrodes were modified with carbon nanotube-supported metal phthalocyanine catalysts using Tokuyama AS-4 ionomer. The RDE results revealed that the highest electrocatalytic activity for ORR was achieved upon heat treatment at 800 °C. CuPc-derived catalyst demonstrated lower catalytic activity as compared to the MnPc-derived counterpart, which is in good agreement with previous literature, whereas the activity of MnPc-based catalyst was higher than that reported earlier.     

Ce掺杂对碳纳米管负载Mn催化剂结构及SCR反应性能的影响

采用等体积浸渍法制备多壁碳纳米管(MWCNTs)负载Ce-Mn的催化剂,考察了Ce掺杂对Mn/MWCNTs催化剂上NH₃选择性催化还原(SCR)NO_x反应活性的影响.并运用透射电镜扫描、N₂吸附-脱附、程序升温还原、X射线光电子能谱、X射线衍射等手段,重点考察了Ce掺杂对Mn/MWCNTs催化剂结构性质的影响.结果表明,Ce掺杂能显著提高催化剂的SCR活性,其活性增量随着Ce含量的增加先增大后减小;当Ce/Mn为0.6时,催化剂活性最佳.表征结果显示,Mn/MWCNTs中添加Ce后,金属氧化物在MWCNTs上的分散程度提高;催化剂的比表面积和孔体积增大,平均孔径减小;氧化能力提高;表面氧含量增加,Mn化合价升高;结晶度降低,Mn主要以无定形或微晶形式存在,Ce主要以CeO₂物相存在.     

Enhanced electrocatalytic activity for H2O2 production by the oxygen reduction reaction: Rational control of the structure and composition of multi-walled carbon nanotubes

Hydrogen peroxide (H₂O₂) is a very useful chemical reagent, but the current industrial methods for its production suffer from serious energy consumption problems. Using high-activity and high-selectivity catalysts to electrocatalyze the oxygen reduction reaction (ORR) through a two-electron (2e^?) pathway is a very promising route to produce H₂O₂. In this work, we obtained partially oxidized multi-walled carbon nanotubes (MWCNTs) with controlled structure and composition by oxidation with concentrated sulfate and potassium permanganate at 40°C for 1 h (O-CNTs-40-1). The outer layers of O-CNTs-40-1 are damaged with defects and oxygen-containing functional groups, while the inner layers are maintained intact. The optimized structure and composition of the partially oxidized MWCNTs ensure that O-CNTs-40-1 possesses both a sufficient number of catalytic sites and good conductivity. The results of rotating ring disk electrode measurements reveal that, among all oxidized MWCNTs, O-CNTs-40-1 shows the greatest improvement in hydrogen peroxide selectivity (from ～ 30% to ～ 50%) and electron transfer number (from ～ 3.4 to ～ 3.0) compared to those of the raw MWCNTs. The results of electrochemical impedance spectroscopy measurements indicate that both the charge-transfer and intrinsic resistances of O-CNTs-40-1 are lower than those of the raw MWCNTs and of the other oxidized MWCNTs. Finally, direct tests of the H₂O₂ production confirm the greatly improved catalytic activity of O-CNTs-40-1 relative to that of the raw MWCNTs.     

Preparation of hybrid thin film modified carbon nanotubes on glassy carbon electrode and its electrocatalysis for oxygen reduction

A hybrid thin film containing Pt nanoparticles and [tetrakis(N-methylpyridyl)porphyrinato]cobalt (CoTMPyP) modified multi-walled carbon nanotubes (MWNTs) on a glassy carbon (GC) electrode surface was fabricated. This hybrid film electrode exhibited remarkable electrocatalytic activity for oxygen reduction and high stability with promising applications in fuel cells.     

Enhanced electrochemiluminescence from luminol at multi-walled carbon nanotubes decorated with palladium nanoparticles: a novel route for the fabrication of an oxygen sensor and a glucose biosensor

Incorporation of palladium nanoparticles on the surface of multi-walled carbon nanotubes and modification of glassy carbon electrode with the prepared nano-hybrid material led to the fabrication of a novel electrode. The modified electrode showed attractive electrocatalytic activity and sensitizing effect on luminol-O(2) and luminol-H(2)O(2) electrochemiluminescence (ECL) reactions at neutral media. The sensitized luminol-O(2) and luminol-H(2)O(2) reactions were successfully applied for the ECL determination of dissolved O(2) and glucose, respectively. Under the optimal conditions for luminol-O(2) system, the ECL signal intensity of luminol was linear with the concentration of dissolved oxygen in the range between 0.08 and 0.94 mM (r=0.9996) and for luminol-H(2)O(2) system, the ECL signal intensity of luminol was linear with the concentration of glucose in the range between 0.1 and 1000 μM (r=0.9998). The limits of detection (S/N=3) for dissolved oxygen and glucose were 0.02 mM and 54 nM, respectively. The relative standard deviations (RSD) for repetitive measurements of 0.50 mM oxygen (n=10) and 10 μM glucose (n=30) were 3.5% and 0.3%, respectively. Also, under the optimal conditions for luminol-H(2)O(2) system, the ECL signal intensity of luminol was linear with the concentration of H(2)O(2) in the range between 1 nM and 0.45 mM (r=0.9997). The limit of detection (S/N=3) for H(2)O(2) detection was 0.5 nM and the relative standard deviation for repetitive measurements of 10 μM H(2)O(2) (n=10) was 0.8%.     

Potential dependent and structural selectivity of the oxygen reduction reaction on nitrogen-doped carbon nanotubes: a density functional theory study

Nitrogen-doped carbon nanotubes (NCNTs) are attractive for electrocatalytic applications in fuel cells due to their low cost and high electrocatalytic activity. By using density functional theory calculations, the electrocatalytic mechanisms of the oxygen reduction reaction (ORR) under electrochemical conditions are studied at graphite-like N groups (N(G)) and pyridine-like N groups (N(P)) of NCNTs, in which the effect of electrode potentials on the activation energy (E(a)) and reaction energy (E(r)) is taken into account. The ORR occurs at both N(G) and N(P) defect sites via two different four-electron OOH and two-electron H(2)O(2) mechanisms. At the lower potential region, both mechanisms are simultaneously responsible for the reaction at N(G) and N(P) defect sites; while at higher potentials, the four-electron mechanism becomes dominant and the ORR at N(P) defect sites is more energetically favorable than that at N(G) defect sites.     

Decoration of silver nanoparticles on multi-walled carbon nanotubes: Investigation of its anti-acute leukemia property against acute myeloid leukemia and acute T cell leukemia

Recently, the development of carbon nanocomposites composed of carbon nanotubes and metal nanoparticles has attracted many interests because of their large potential for technological applications such as catalysts, sensors, biomedicine, and disinfection. In the present study, we described a simple chemistry method to synthesize multi-walled carbon nanotubes (MWCNTs) decorated with silver nanoparticles (Ag-NPs). Also, we investigated the antioxidant and anti-acute leukemia activities against acute myeloid leukemia and acute T cell leukemia cell lines. Ag NPs-MWCNTs were characterized and analyzed using common nanotechnology techniques including transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), field emission-scanning electron microscopy (FE-SEM) and elemental mapping analysis. Also, 2,2-diphenyl-1-picrylhydrazyl (DPPH) test was performed to assess the antioxidant capacities of AgNO₃, MWCNTs, and Ag NPs-MWCNTs. It revealed similar antioxidant potentials for Ag NPs-MWCNTs and butylated hydroxytoluene. In MTT assay, Ag NPs-MWCNTs had very low cell viability (very high anti-acute leukemia properties) dose-dependently against 32D-FLT3-ITD (Acute myeloid leukemia cell line), Human HL-60/vcr (Acute myeloid leukemia cell line), Jurkat, Clone E6–1 (Acute T cell leukemia cell line), and J.RT3-T3.5 (Acute T cell leukemia cell line) without any cytotoxicity on human umbilical vein endothelial cell line (HUVEC; Normal cell line). In conclusion, the synthesized Ag NPs-MWCNTs revealed excellent antioxidant and cytotoxicity activities against acute myeloid leukemia and acute T cell leukemia cell lines in a dose depended manner. After confirming in the in vivo and clinical trials, these nanoparticles can be administrated in humans for the treatment of acute leukemia especially acute myeloid leukemia and acute T cell leukemia.     

电沉积制备的PtNi纳米粒子用于氧还原反应:成核和生长机理

质子交换膜燃料电池(PEMFCs)电堆中阴极Pt基催化剂的高用量造成其成本居高不下,成为阻碍燃料电池汽车商业化推进的重要原因,因此开发低Pt、高活性的Pt基催化剂势在必行.Pt合金催化剂能够有效地降低Pt用量,并通过对合金颗粒的元素比例、晶面、粒径等实行精确调控,显著提升氧还原(ORR)催化活性.然而,目前常用的制备方法由于原料与制备成本高昂、过程复杂大都难以适应规模化生产需求.电化学方法通过控制施加的电流或电位控制晶体生长.在水体系中该方法已得到验证,但由于Pt化合物的热力学标准电极电位与过渡金属元素之间相差较大,且对于过渡金属来说,电负性大多小于铂,因此还原电位通常负于析氢电位,使得二者难以实现共沉积.有机体系中电位窗口比水体系大得多,Pt与电位较负的过渡金属可实现共沉积,采用小分子有机溶剂也可避免溶剂清洗问题,具有应用潜力.本文提出了一种简单的一步电沉积方法,选择易溶于水的N,N-二甲基甲酰胺(DMF)作为溶剂,将碳载体滴涂到玻碳电极上作为工作电极,通过电化学方法直接将Pt-Ni合金沉积到碳载体上,并利用物化表征与密度泛函理论(DFT)理论计算来探究共沉积机理.透射电镜表征结果表明,在不同的沉积电位下均可得到分散均匀、粒径适当的催化剂;且随着电位值降低,催化剂颗粒分散得更均匀,颗粒粒径不断减小.元素分布和晶面结果表明,铂镍元素均匀分布于颗粒中.所有样品均表现出优异的ORR性能,最高的面积比活性达到商业催化剂的6.85倍.将材料表征、电化学表征与DFT计算结合,建立起了铂镍合金生长过程的模型,并发现了有机体系中独特的成核-生长机理.将体系中的DMF换成超纯水,用同样的方法进行沉积,得到的催化剂颗粒团聚严重,说明DMF的使用能够避免颗粒团聚.在单独铂的体系中沉积发现,负载量极小,表明体系中镍前驱体的添加对于催化剂的沉积过程起到重要作用.电化学表征结果表明,在所选用的DMF有机体系中,镍的还原电位与铂的十分接近,但还原动力学更慢,趋向于先形成吸附原子后快速还原.由此可以推测,在二者合金的形成过程中,镍在碳载体表面的缓慢还原而形成的吸附原子能够成为铂还原的活性位点,从而降低了铂还原成核所需的能量,使得载体上的成核位点大大增加,这与DFT模拟结果一致.DFT建立了碳上镍的位点和铂的位点,分别在上面进行铂的还原,发现镍位点上比铂位点上更容易实现铂沉积.本文提出了铂镍共沉积的机理:在过电位(即还原能量)下,铂的还原动力学较镍稍快,于是铂先还原形成晶核,但难以达到生长的临界半径,于是单独铂体系中的沉积负载量很少.载体上还原的镍为铂还原提供了大量的活性位点,促进了铂还原,并与镍共沉积.Pt-Ni表面则进一步促进了铂的沉积和颗粒的生长.综上,本文提出了一种用于制备铂合金催化剂的有机电沉积体系,实现了单分散的碳载铂镍合金催化剂的一步制备.随后,本文将材料表征、电化学表征与DFT计算相结合,建立起了有机体系中铂镍合金成核-生长过程的机理模型.     

电沉积制备的PtNi纳米粒子用于氧还原反应:成核和生长机理

质子交换膜燃料电池(PEMFCs)电堆中阴极Pt基催化剂的高用量造成其成本居高不下,成为阻碍燃料电池汽车商业化推进的重要原因,因此开发低Pt、高活性的Pt基催化剂势在必行.Pt合金催化剂能够有效地降低Pt用量,并通过对合金颗粒的元素比例、晶面、粒径等实行精确调控,显著提升氧还原(ORR)催化活性.然而,目前常用的制备方法由于原料与制备成本高昂、过程复杂大都难以适应规模化生产需求.电化学方法通过控制施加的电流或电位控制晶体生长.在水体系中该方法已得到验证,但由于Pt化合物的热力学标准电极电位与过渡金属元素之间相差较大,且对于过渡金属来说,电负性大多小于铂,因此还原电位通常负于析氢电位,使得二者难以实现共沉积.有机体系中电位窗口比水体系大得多,Pt与电位较负的过渡金属可实现共沉积,采用小分子有机溶剂也可避免溶剂清洗问题,具有应用潜力.本文提出了一种简单的一步电沉积方法,选择易溶于水的N,N-二甲基甲酰胺(DMF)作为溶剂,将碳载体滴涂到玻碳电极上作为工作电极,通过电化学方法直接将Pt-Ni合金沉积到碳载体上,并利用物化表征与密度泛函理论(DFT)理论计算来探究共沉积机理.透射电镜表征结果表明,在不同的沉积电位下均可得到分散均匀、粒径适当的催化剂;且随着电位值降低,催化剂颗粒分散得更均匀,颗粒粒径不断减小.元素分布和晶面结果表明,铂镍元素均匀分布于颗粒中.所有样品均表现出优异的ORR性能,最高的面积比活性达到商业催化剂的6.85倍.将材料表征、电化学表征与DFT计算结合,建立起了铂镍合金生长过程的模型,并发现了有机体系中独特的成核-生长机理.将体系中的DMF换成超纯水,用同样的方法进行沉积,得到的催化剂颗粒团聚严重,说明DMF的使用能够避免颗粒团聚.在单独铂的体系中沉积发现,负载量极小,表明体系中镍前驱体的添加对于催化剂的沉积过程起到重要作用.电化学表征结果表明,在所选用的DMF有机体系中,镍的还原电位与铂的十分接近,但还原动力学更慢,趋向于先形成吸附原子后快速还原.由此可以推测,在二者合金的形成过程中,镍在碳载体表面的缓慢还原而形成的吸附原子能够成为铂还原的活性位点,从而降低了铂还原成核所需的能量,使得载体上的成核位点大大增加,这与DFT模拟结果一致.DFT建立了碳上镍的位点和铂的位点,分别在上面进行铂的还原,发现镍位点上比铂位点上更容易实现铂沉积.本文提出了铂镍共沉积的机理:在过电位(即还原能量)下,铂的还原动力学较镍稍快,于是铂先还原形成晶核,但难以达到生长的临界半径,于是单独铂体系中的沉积负载量很少.载体上还原的镍为铂还原提供了大量的活性位点,促进了铂还原,并与镍共沉积.Pt-Ni表面则进一步促进了铂的沉积和颗粒的生长.综上,本文提出了一种用于制备铂合金催化剂的有机电沉积体系,实现了单分散的碳载铂镍合金催化剂的一步制备.随后,本文将材料表征、电化学表征与DFT计算相结合,建立起了有机体系中铂镍合金成核-生长过程的机理模型.     

CoNi nanoparticles anchored inside carbon nanotube networks by transient heating:Low loading and high activity for oxygen reduction and evolution

Transitional metal alloy and compounds have been developed as the low cost and efficient bifunctional electrocatalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).However,a high mass loading of these catalysts is commonly needed to achieve acceptable catalytic performance,which could cause such problems as battery weight gain,mass transport blocking,and catalyst loss.We report herein the preparation of fine CoNi nanoparticles(5-6 nm)anchored inside a nitrogendoped defective carbon nanotube network(CoNi@N-DCNT)by a transient Joule heating method.When utilized as an electrocatalyst for oxygen reduction and evolution in alkaline media,the CoNi@N-DCNT film catalyst with a very low mass loading of 0.06 mg cm^-2 showed excellent bifunctional catalytic performance.For ORR,the onset potential(Eonset)and the half-wave potential(E_1/2)were 0.92 V versus reversible hydrogen electrode(vs.RHE)and 0.83 V(vs.RHE),respectively.For OER,the potential at the current density(J)of 10 mA cm^-2(E₁₀)was 1.53 V,resulting in an overpotential of 300 mV much lower than that of the commercial RuO₂ catalyst(320 mV).The potential gap between E_1/2 and E₁₀ was as small as 0.7 V.Considering the low mass loading,the mass activity at E₁₀ reached at 123.2 A g^-1,much larger than that of the RuO₂ catalyst and literature results of transitional metal-based bifunctional catalysts.Moreover,the CoNi@N-DCNT film catalyst showed very good long-term stability during the ORR and OER test.The excellent bifunctional catalytic performance could be attributed to the synergistic effect of the bimetal alloy.     

Effect of oxidation of activated carbon on its enrichment efficiency of metal ions: comparison with oxidized and non-oxidized multi-walled carbon nanotubes

The effect of oxidation of activated carbon (AC) with various oxidizing agents (nitric acid, hydrogen peroxide, ammonium persulfate) on preconcentration of metal ions (Cr3+, Mn2+, Pb2+, Cu2+, Cd2+ and Zn2+) from environmental waters prior to their flame atomic absorption spectroscopic analysis was investigated. The highest recoveries and adsorption capacities towards metal ions were achieved when using nitric acid-oxidized AC (sorbent AC-NA) as preconcentrating sorbent at pH 9. A preconcentration procedure was optimized using AC-NA as sorbent, which was then compared with non-oxidized AC in terms of analytical performance of the preconcentration method. Higher sensitivity, lower detection limits and wider linear ranges were achieved when AC-NA was used. The analytical performance of the method using AC-NA as preconcentrating sorbent was also compared with nitric acid-oxidized multi-walled carbon nanotubes (sorbent MWCNT-NA) and non-oxidized multi-walled carbon nanotubes (sorbent MWCNT). The analytical performance of the preconcentration method using AC-NA was close to MWCNT-NA, but AC-NA was better than non-oxidized MWCNT. Application of the optimized preconcentration method (using AC-NA sorbent) to environmental waters (tap water, reservoir water, stream water) gave spike recoveries of the metals in the range 63-104%.