Two-step pyrolysis of ZIF-8 functionalized with ammonium ferric citrate for efficient oxygen reduction reaction

Zeolitic imidazolate frameworks(ZIFs) are widely employed in catalyst synthesis as parental materials for electrochemical energy storage and conversion. Herein, we have demonstrated a facile synthesis of highly efficient catalyst for oxygen reduction reaction in both alkaline and acidic medium, which is derived from ZIF-8 functionalized with ammonium ferric citrate via two-step pyrolysis in Ar and NH_3 atmosphere.The results reveal that the catalytic activity improvement after NH3 pyrolysis benefits from mesoporedominated morphology and high utilization of Fe-containing active sites. The optimum catalyst shows excellent performance in zinc-air battery and polymer electrolyte membrane fuel cell tests.     

Oxygen reduction on an iron–carbonized aerogel nanocomposite electrocatalyst

Iron–carbonized aerogel nanocomposite was prepared from highly porous polyacrylonitrile microcellular foams containing a salt of iron, followed by carbonization. The electrochemical reduction of oxygen at this material was studied by using the rotating disk electrode method. In common with Pt/C, iron–carbonized aerogel nanocomposite presented excellent electrocatalytic activity for the oxygen reduction under experimental conditions close to those of a fuel cell cathode, that is, at the catalyst/Nafion interface in acidic solutions.     

High performance platinized titanium nitride catalyst for methanol oxidation

Platinized TiN is shown to be a very good catalyst for the electrochemical oxidation of methanol; it does not contain Ru and the CO poisoning effect is alleviated by the presence of TiN.     

A Li-air fuel cell with recycle aqueous electrolyte for improved stability

A lithium-air fuel cell with a new designed cell structure for improved stability is proposed. The cell consists of two subunits: an energy conversion unit that employs a cation exchange membrane and a reaction-product recycling unit that collects/removes LiOH and thus protects the LISICON plate from corrosion under strong alkaline conditions. The aqueous electrolyte recycling system allows the newly structured Li-air fuel cell to attain higher theoretical energy density, and hence potential application as an alternative energy source for transportation.     

非水系锂空气电池的正极材料和电解液研究进展

锂空气电池的能量密度是传统锂离子电池的5~10倍,可与汽油相媲美。近几年来,锂空气电池因此受到了人们的广泛关注。本文概述了锂空气电池正极材料和电解液的最新研究进展。从商业碳、具有特定形态的碳材料、催化剂、导电聚合物等几个方面阐述了正极材料;从物质结构的角度,简要介绍了锂空气电池中常用的酯类、醚类、砜类、胺类和离子液体等电解液。最后指出了目前锂空气电池存在的问题,并对其进行了展望。     

非水系锂空气电池的正极材料和电解液研究进展

锂空气电池的能量密度是传统锂离子电池的5~10倍, 可与汽油相媲美。近几年来, 锂空气电池因此受到了人们的广泛关注。本文概述了锂空气电池正极材料和电解液的最新研究进展。从商业碳、具有特定形态的碳材料、催化剂、导电聚合物几个方面阐述了正极材料;从物质结构的角度, 简要介绍了锂空气电池中常用的酯类、醚类、砜类、胺类和离子液体等电解液。最后指出了目前锂空气电池存在的问题, 并对其进行了展望。     

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.     

Ho3＋对吸附CO电化学氧化的促进作用

研究了吸附在Pt/C催化剂上的Ho3＋对吸附CO的电氧化的影响.结果表明,无论在中性和酸性溶液中,在较大的温度范围内,Ho3＋对CO在Pt/C催化剂上的电氧化都有促进作用,其原因是吸附Ho3＋的存在减弱了CO在Pt/C催化剂上的吸附强度.其次,在中性溶液中,Ho3＋对吸附CO的电氧化的促进作用比在酸性溶液中大.第三,无论在酸性还是中性溶液中,温度的升高有利于发挥Ho3＋对吸附CO的电氧化的促进作用.     

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).     

High‐Activity PtRuPd/C Catalyst for Direct Dimethyl Ether Fuel Cells

Dimethyl ether (DME) has been considered as a promising alternative fuel for direct‐feed fuel cells but lack of an efficient DME oxidation electrocatalyst has remained the challenge for the commercialization of the direct DME fuel cell. The commonly studied binary PtRu catalyst shows much lower activity in DME than methanol oxidation. In this work, guided by density functional theory (DFT) calculation, a ternary carbon‐supported PtRuPd catalyst was designed and synthesized for DME electrooxidation. DFT calculations indicated that Pd in the ternary PtRuPd catalyst is capable of significantly decreasing the activation energy of the C? O and C? H bond scission during the oxidation process. As evidenced by both electrochemical measurements in an aqueous electrolyte and polymer‐electrolyte fuel cell testing, the ternary catalyst shows much higher activity (two‐fold enhancement at 0.5 V in fuel cells) than the state‐of‐the‐art binary Pt₅₀Ru₅₀/C catalyst (HiSPEC 12100).     

Passivity and electrocatalysis of nanostructured nickel encapsulated in carbon

Metallic nickel is a powerful electrocatalyst in alkaline solution and is able to be used in the alkaline fuel cell. However, in acidic solution, electrocatalysis is impossible because the metal is subject to rapid corrosion at low pH for all potentials at which an acidic fuel cell would operate. Here we report the synthesis and passive nature of a nickel-carbon nanostructured material which shows electrocatalytic activity. A thin film composed of nickel and carbon prepared by co-sputtering a graphite target partially covered with a nickel foil shows remarkable passivity against corrosion when polarized in hot sulphuric acid. The film, which contains 21 atom-% nickel, also shows significant electrocatalysis of the hydrogen oxidation reaction, and therefore forms the basis of a new type of fuel cell anode catalyst. High-resolution transmission electron microscopy (HRTEM) reveals a nanostructure of carbon-encapsulated nickel nanocrystals of ≤ca. 4 nm diameter. The passive nature of the material against corrosion is due to protection generated by the presence of a very thin carbon-rich layer encapsulating the nanoparticulate catalyst: this is a new form of passivation.     

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.     

Highly Rechargeable Lithium-CO2 Batteries with a Boron- and Nitrogen-Codoped Holey-Graphene Cathode

Metal-air batteries, especially Li-air batteries, have attracted significant research attention in the past decade. However, the electrochemical reactions between CO₂ (0.04 % in ambient air) with Li anode may lead to the irreversible formation of insulating Li₂CO₃, making the battery less rechargeable. To make the Li-CO₂ batteries usable under ambient conditions, it is critical to develop highly efficient catalysts for the CO₂ reduction and evolution reactions and investigate the electrochemical behavior of Li-CO₂ batteries. Here, we demonstrate a rechargeable Li-CO₂ battery with a high reversibility by using B,N-codoped holey graphene as a highly efficient catalyst for CO₂ reduction and evolution reactions. Benefiting from the unique porous holey nanostructure and high catalytic activity of the cathode, the as-prepared Li-CO₂ batteries exhibit high reversibility, low polarization, excellent rate performance, and superior long-term cycling stability over 200 cycles at a high current density of 1.0 A g⁻¹. Our results open up new possibilities for the development of long-term Li-air batteries reusable under ambient conditions, and the utilization and storage of CO₂.     

在氢气氧化反应中具有高催化活性的Pt修饰的Ni/C纳米催化剂

随着能源需求的进一步增多和化石能源的大幅度减少,新型环境友好型能源成为近十年许多科研工作者的着力点.其中,燃料电池作为一种高效率、高能量密度、环境友好型能源引起了人们的关注.氢氧燃料电池研究最早、应用最早,具有得天独厚的优势.此外,由于近些年CO2的大量排放,造成了严重的温室效应,其处理也是一个严峻的课题.谢和平课题组提出的CO2矿化发电,不仅可以处理CO2,也可以作为新型能源应用,前景广阔.而不论是氢氧燃料电池还是CO2矿化电池,其阳极反应均为氢气氧化反应(HOR).Pt作为目前仍无法取代的HOR反应催化剂,不仅全球储量有限且价格昂贵,所以,寻找一种价格低廉催化性能好的催化剂成为这些新能源进一步应用的重要课题之一.对此人们进行了大量探索,主要包括尝试不同的载体、改变金属颗粒尺寸形貌等.其中,伽伐尼置换法对于制备纳米核壳结构催化剂以及降低金属颗粒尺寸、增加比表面积均有很大帮助.基于此,本文采用浸渍法和伽伐尼置换法制备了用Pt修饰Ni/C的纳米催化剂,使得纳米级活性金属均匀分散在载体上,加之双金属效应,相对于纯Pt/C催化剂,催化能力提高.浸渍法制得Ni/C前驱体,再将其置于纯乙醇中,用H2PtCl6作为Pt源置换部分Ni,得到Pt修饰的Ni/C催化剂.XRD射线衍射测试结果表明,一般的PtNi合金由于晶格相互影响,只会出现Pt的偏移衍射峰,而该催化剂均出现明显的PtNi两种元素的衍射峰,PtNi晶格互相没有影响.循环伏安法测试结果表明,在Pt-Ni/C系列催化剂中,Pt和Ni含量不同,其电化学活性面积(ECSA)各不相同.在金属总含量一致的前提下,随着Pt含量的增加,催化剂ECSA先增加后减小,最大值为66.90 m2/g,是市售Pt/C(54.12 m2/g)的1.24倍.Tafel测试HOR/HER反应交换电流密度的结果与ECSA结果一致,而Pt-Ni/C催化剂的交换电流密度最高可达485.45 A/g,是市售Pt/C(301.91 A/g)的1.6倍.对性能较好的Pt-Ni/C催化剂进行了表征,X射线光电子能谱结果发现,该催化剂载体上只有少部分Ni的氧化物裸露在表面,大部分为Pt.而透射电镜结果表明,该催化剂纳米级活性金属颗粒尺寸一致,且均匀地分散在载体表面.综合催化剂表征和电化学性能测试结果可知,使用伽伐尼置换法得到的Pt修饰的Ni/C催化剂分散均匀、颗粒尺寸小,且由于Pt作为主要催化活性金属分散于催化剂表面,而Ni作为辅助金属并不直接参与HOR反应,使得该催化剂具有较高的电化学活性.在Pt含量较少时,由于有很多Ni在催化剂表面,且催化层厚度较大,故催化活性一般.随着Pt含量的增加和Ni含量的减少,当催化剂表面只有很少Ni及相关化合物时,由于Pt比表面积大,故活性最高.当Pt含量继续增加时,Pt在Ni表面厚度增加,很多Pt被包裹,故催化活性再次降低.     

Carbon-Based Electrocatalysts for Acidic Oxygen Reduction Reaction

Oxygen reduction reaction (ORR) is vital for clean and renewable energy technologies, which require no fossil fuel but catalysts. Platinum (Pt) is the best-known catalyst for ORR. However, its high cost and scarcity have severely hindered renewable energy devices (e.g., fuel cells) for large-scale applications. Recent breakthroughs in carbon-based metal-free electrochemical catalysts (C-MFECs) show great potential for earth-abundant carbon materials as low-cost metal-free electrocatalysts towards ORR in acidic media. This article provides a focused, but critical review on C-MFECs for ORR in acidic media with an emphasis on advances in the structure design and synthesis, fundamental understanding of the structure-property relationship and electrocatalytic mechanisms, and their applications in proton exchange membrane fuel cells. Current challenges and future perspectives in this emerging field are also discussed.     

质子交换膜燃料电池Pt纳米线电催化剂研究现状

质子交换膜燃料电池(PEMFC)能直接将化学能转换为电能,具有能量转换效率高、环境友好、启动快等优点.其中电催化剂是决定PEMFC性能、寿命及成本的关键材料之一.目前所采用的Pt催化剂成本较高,是阻碍其商业化的主要因素.而Pt纳米线电催化剂的Pt利用率和催化剂活性高,抗CO毒性以及耐久性好.本文综述了Pt纳米线电催化剂的制备及其电化学催化性能的研究现状.     

An Integrated CO2 Electrolyzer and Formate Fuel Cell Enabled by a Reversibly Restructuring Pb–Pd Bimetallic Catalyst

A single device combining the functions of a CO₂ electrolyzer and a formate fuel cell is a new option for carbon‐neutral energy storage but entails rapid, reversible and stable interconversion between CO₂ and formate over a single catalyst electrode. We report a new catalyst with such functionalities based on a Pb–Pd alloy system that reversibly restructures its phase, composition, and morphology and thus alters its catalytic properties under controlled electrochemical conditions. Under cathodic conditions, the catalyst is relatively Pb‐rich and is active for CO₂‐to‐formate conversion over a wide potential range; under anodic conditions, it becomes relatively Pd‐rich and gains stable catalytic activity for formate‐to‐CO₂ conversion. The bifunctional activity and superior durability of our Pb–Pd catalyst leads to the first proof‐of‐concept demonstration of an electrochemical cell that can switch between the CO₂ electrolyzer/formate fuel cell modes and can stably operate for 12 days.     

Non-noble metal catalyst for a future Pt free PEMFC

We have investigated the possibility of developing high-performance, cost-effective and durable non-noble Co metal electrocatalyst for PEMFC. In this work we applied electrodeposition process for PEMFC electrode preparation that is very efficient and far simpler than any other investigated method. The fuel cell with electrodeposited Co as anode catalyst has shown satisfying performance level. In determining FC’s operating conditions, subsequent electrochemical impedance and output power measurements were done, which enable the insight into the Co catalyst based anode behavior. Structure analysis of the electrodeposited anode layer was done by means of SEM and EDS technique. Although the Pt catalyst has higher efficiency, its cost performance ratio is significantly lower than for the Co catalyst, thus this investigation gives interesting possibilities in area of stationary fuel cell application.     

静电纺丝制备质子交换膜燃料电池催化剂层综述

质子交换膜燃料电池催化剂层在成本、耐久性以及性能上的局限是制约燃料电池汽车商业化的瓶颈. 已有文献证明静电纺丝技术制备的纳米纤维催化剂层能提高催化剂利用率、增加三相界面和三相通道以及提高耐久性. 作者结合所在课题组的工作综述了静电纺丝技术制备质子交换膜燃料电池催化剂层的研究进展. 首先,介绍了质子交换膜燃料电池催化剂层的发展历程,并从制备方式和结构两个方面对其进行分类和总结;接下来,从静电纺丝纳米纤维催化剂层的制备、物理特性表征、电化学性能分析及耐久性表征等方面进行了总结;最后,从三相界面、三相通道以及量产适用性的视点比较了三种结构的催化剂层,介绍了质子交换膜燃料电池催化剂层的发展趋势,并梳理了静电纺丝法制备质子交换膜燃料电池催化剂层领域待研的问题.     

基于微观格点模型模拟PEMFC定向结构催化层

用微观格点模型对质子交换膜燃料电池(PEMFC)定向结构阴极性能进行了模拟,并与随机结构电极进行了对比,研究了催化剂利用率及电池性能的变化.计算了催化层内的传递和电化学反应,研究了质子、氧气及电化学反应速率在电极厚度方向上的分布,并且通过对比氧气浓度、离子电势和电化学反应速率的分布,证明了Pt/C颗粒在电极厚度方向上定向排布有利于提高电池性能.另外,研究了电极厚度对定向结构电极性能的影响,发现与随机结构电极不同,定向结构电极厚度越小,高电流密度下电极性能越好.