Metal-organic framework derived Co3O4/PPy bifunctional electrocatalysts for efficient overall water splitting

In this work, we report Co₃O₄@PPy hybrid structured electrode materials for overall water splitting. The as-synthesized Co₃O₄/PPy-120 samples present excellent electrocatalytic performances for OER and HER and long durability. It only requires an operating potential of 1.67 V to deliver a current density of 10 mA/cm² with a remarkable durability for 28 h. The superior electrocatalytic performances mainly can be attributed to the unique heterostructures and the synergistic effects between PPy and Co₃O₄ electrode materials.     

Li Ion Exchanged α-MnO2 Nanowires as Efficient Catalysts for Li-O2 Batteries

Due to the limited energy densities, which could be achieved by lithium-ion cells, Li-O₂ batteries, which could provide a promising super energy storage medium, attract much attention nowadays. For its high activity, high storage and low cost, Mn-based oxides have shown versatile application in various batteries. To enhance the cyclability of Li-O₂ batteries, here, we synthesized a kind of α-MnO₂ nanowires as a bifunctional catalyst for Li-O₂ batteries. The particular structure of α-MnO₂ reduces the mass transfer resistance of the battery, and the MnO₂ nanowires were ion exchanged by saturated lithium sulfate solution so as to further improve the performance of the catalyst. The exchanged α-MnO₂ catalyst showed a high discharge specific capacity(6243 mA·h/g at a current density of 200 mA/g) and significantly improved the cyclability up to the 55th cycle(200 mA/g with capacity of 1000 mA·h/g). The results show that the Li ion exchange method is a promising strategy for improving the performance of MnO₂ catalyst for Li-O₂ batteries.     

无电沉积硼化镍材料对水氧化的电催化性能

通过无电沉积/化学镀的方法分别制得石墨烯(Graphene)、 镍网(Ni foam, NF)、 钛网(Ti mesh, TM)、 碳布(Carbon cloth, CC)负载的硼化镍材料. 其中在石墨烯基底上生长的硼化镍层由规则的纳米颗粒构成, 且均匀致密. 对几种材料在碱性条件下(1.0 mol/L KOH电解质中)的水氧化电催化性能进行了研究, 结果表明, 石墨烯基底上生长的硼化镍材料(NiB_x/graphene)具有最佳的水氧化电催化性能. 电流密度达到10 mA/cm²时的过电位仅为277 mV, 相应的Tafel斜率为57 mV/dec. 对石墨烯负载的硼化镍材料进行烧结, 测得过电位为330 mV, 与未烧结的样品相比电催化活性下降. 该方法所制的石墨烯负载的硼化镍材料兼具高电催化活性和稳定性, 为低成本、 高效率的水氧化非贵金属电催化剂的制备提供了新思路.     

铜-锑双金属合金高效电催化还原二氧化碳制乙烯

随着全球工业化进程的快速发展,日益增多的人类活动不仅加速化石燃料的消耗,还会导致温室气体二氧化碳(CO2)的大量排放.同时,CO2也是廉价、无毒无害、储量丰富的C1资源,将其转化为有价值的化学品具有碳资源合理利用和环境保护的双重意义.近年来,采用电化学方法温和条件下还原CO2为重要化学品和燃料引起广泛关注.其中,探索廉价电催化剂,高效催化还原CO2为C2产物仍是一个具有挑战性的课题.铜基催化剂由于自身低成本和可还原CO2为多种碳氢产物的优点而备受关注.然而,铜基电催化材料具有选择性差、失活严重和效率低等缺点,并且在电催化还原CO2过程中需要较高的过电位,反应过程中会受到氢气析出副反应的影响.为了得到一种化学性质稳定、高电流密度和高选择性等优点的材料在电催化CO2还原中得到了广泛的研究.然而,单纯的铜催化剂对CO2分子的活化以及反应中间体的吸附能力较低,导致了铜基材料催化剂电催化CO2还原活性及选择性较低.因此,开发出可实际应用的高效率和高选择性的电极材料是当前该技术研究中亟待解决的关键科学问题.近年来,铜基二元合金在电催化CO2还原反应中受到广泛关注.由于二元金属的电子结构和各元素的电子结合能发生变化,其催化活性明显优于单金属催化剂.因此,铜基双金属合金在提高CO2还原产物选择性方面具有广阔的前景.本文采用低温还原的方法制备了一系列不同组成的Cu-Sb双金属合金,系统研究了一系列不同配比的Cu-Sb双金属合金对电催化还原CO2为乙烯的影响.研究发现,当Cu/Sb比例为10/1(Cu10-Sb1)时,可有效提高乙烯的法拉第效率及电流密度.当以0.1 M KCl水溶液作为电解液,电位为-1.19 V vs.RHE时,乙烯的法拉第效率和电流密度分别为49.73%和28.5 mA cm-2.实验结果表明,Cu-Sb双金属合金催化剂优异的催化性能主要源于适宜的电子态、良好的CO2吸附性能、较大的电化学比表面积和较高的电子传输速率.迄今,用Cu-Sb作为催化剂进行电催化还原CO2制乙烯尚未见报道.     

双原子催化剂:制备、表征和应用

发展可持续和清洁的电化学能源转化技术是应对能源短缺和环境污染挑战的关键一步,燃料电池、电解电池和金属空气电池作为清洁能源储存和转换装置目前得到广泛应用推广,这些装置依靠电催化反应以及电极材料上发生的电荷转移过程来转换电能和化学能.而电催化剂是该类装置电极材料的核心部件,电催化反应的热力学和动力学过程与电催化剂的物理性质和化学状态密切相关.因此探索和开发性能优良、成本低廉的新型电催化剂,将进一步促进这些能源转化技术的商业化应用.单原子催化剂(SACs)以其暴露的活性位点、高选择性和最大限度地原子利用率而受到人们的广泛关注.然而,随着单原子表面自由能的增加,粒子在制备和催化过程中的聚集,催化活性位点的降低和催化剂负荷的相对较低,严重制约了SACs的发展和应用.考虑到SACs的缺点,为了进一步增加单原子活性位点的数量和负载,双原子催化剂(DACs)作为SACs家族成员的扩展近年来逐渐兴起,且两种金属原子(同核/异核)在DACs中的协同作用显著提高了催化剂的催化活性.本文基于当前最新的研究工作对比了同核/异核DACs的不同优势,列举了一系列包括原子层沉积法、湿化学吸附法以及高温热处理法等方法用于制备性能优异的DACs,其中高温热处理法因应用广泛被重点强调.同时,本文也对DACs的表征和识别手段进行了重点概括,包含XANES, EXAFS, IR, DFT等;详细概括和对比了当前DACs在电化学方面的主要应用,如氧还原反应(ORR)和二氧化碳还原反应.目前, DACs作为一个新兴的研究领域,由于其金属原子负载量高、活性位点比SACs更为灵活,已经在电催化领域取得了快速的发展.相对于同核DACs,原则上不同的两个金属原子会组成更多的异核DACs,因此,对于性能优异的异核DACs还有更多的可能性值得深入探索.可以预见, DACs的发展将弥补SACs的不足,在电化学能源的转换和储存方面发挥全面的优势;借助于异核DACs中不同的两个金属原子的多样性,探索以过渡金属为主的DACs,将会为节约贵金属资源及环境保护带来巨大贡献,进一步设计和优化DACs,有利于燃料电池和金属-空气电池创造出更大的经济效益和社会效益.因此,我们相信DACs的发展将成为材料研究的一个新前沿,并为合成更多的高效应用催化剂开辟一条新的途径.     

Electroanalytical Study of Methanol Oxidation and Oxygen Reduction at Carbon Nanohorns‐Pt Nanostructured Electrodes

This work reports a comprehensive electroanalytical study of carbon nanohorns (CNHs) in electrochemical applications. Compared to other types of carbons, the bare CNHs electrode exhibited higher peak current densities and lowest anodic peak‐to‐cathodic peak separation of less than 50 mV for the [Fe(CN)^4?]₆/[Fe(CN)^3?]₆ redox couple. Furthermore, CNHs exhibited excellent electrocatalyst supporting properties for porous Pt film towards methanol oxidation reaction reaching a peak current density of 127 mA cm^?2 or peak current mass activity 184 mA mg_Pt^?1. Regarding oxygen reduction reaction, an onset potential as positive as 0. 77 V vs. Ag/AgCl was achieved with CNHs/porous Pt film.     

Ruthenium-based electrocatalysts for oxygen reduction reaction—a review

A major impediment to the commercialization of fuel cells is the low activity of electrocatalysts for the oxygen reduction reaction that involves multiple electron transfer steps. Platinum is considered the best cathode catalyst toward oxygen reduction to water; however, Pt remains an expensive metal of low abundance, and it is of great importance to find Pt-free metal alternatives. Among various Pt-free catalysts under development, ruthenium-based compounds show significant catalytic activity and selectivity for four-electron reduction of oxygen to water in acidic environments. This article provides a short review on the different classes of Ru-based catalysts focusing on the catalytically active reaction sites and the oxygen reduction mechanism in acidic media. After a brief discussion of the oxygen reduction kinetics on a pure Ru metal, the paper reviews the catalytic properties of the selected Ru compounds, including crystalline Chevrel-phase chalcogenides, nanostructured Ru and Ru–Se clusters, and Ru–N chelate compounds. This paper is dedicated to Professor Su-Il Pyun, who has pioneered advances in interfacial electrochemistry in the field of corrosion and materials science in South Korea, on the occasion of his 65th birthday.     

Investigation of electrochemical performance of sol-gel derived MgFe2O4 nanospheres as aqueous supercapacitor electrode and bi-functional water splitting electrocatalyst in alkaline medium

Herein this work, we have used the sol-gel chemical synthesis method to prepare spherical shaped MgFe₂O₄ nanoparticles having size 45–50 nm. Using 1 mol L⁻¹ Sodium Perchlorate (NaClO₄) electrolyte, a capacitance of 61 F/g, a capacitance retention of 82.91% (after undergoing 1000 cycles), and an energy density of 41 Wh/kg have been achieved. Using 1 mol L⁻¹ Magnesium Perchlorate (Mg(ClO₄)₂) as electrolyte, a capacitance of 43 F/g, a capacitance retention of 82.15%, and an energy density of 29 Wh/kg have been realized. Furthermore, MgFe₂O₄ nanospheres exhibited an overpotential (η) = 1.09 V, a Tafel slope (b) = 317 mV/dec in regard to alkaline Oxygen Evolution Reaction (OER) electrocatalyst. It also achieved η = 402 mV and b = 241 mV/dec in regard towards alkaline Hydrogen Evolution Reaction (HER) electrocatalyst. These results signify the suitability of MgFe₂O₄ nanoparticles for high energy density aqueous supercapacitor and water splitting electrocatalyst applications.     

Cobalt Doped Titanium Dioxide Nanoparticles: Synthesis,Characterization and Electrocatalytic Study

In this work, green synthesis of cobalt doped titanium dioxide (Co‐TiO₂) has been carried out in aqueous medium using gelatin. The Co‐TiO₂ particles have been characterized using transmission electron microscopy (TEM), X‐ray diffraction (XRD), energy dispersive X‐ray (EDAX), FT‐IR spectroscopy and voltammetry techniques. XRD results show pure Co‐TiO₂ and TiO₂ powders with average crystallite size about 12 nm and 15 nm, respectively. Co loaded in TiO₂ hasn't influence crystalline structure. Moreover, efficient Co‐TiO₂‐based anode was fabricated by casting of the Co‐TiO₂ solution on glassy carbon electrode (Co‐TiO₂/GCE). The electrocatalysis of oxygen evolution reaction (OER) at Co‐TiO₂/GCE has been examined using linear scanning voltammetry (LSV) in alkaline media. The OER is significantly enhanced at Co‐TiO₂/GCE, as demonstrated by a negative shift in the LSV curve at the Co‐TiO₂/GCE compared to that obtained at the unmodified one. The value of energy saving of oxygen gas at a current density of 5 mA cm^?2 is 12.6 kW h kg^?1. The low cost as well as the marked stability of the modified electrode make it promising candidate in industrial water electrolysis process.     

Perovskite thin films deposited by pulsed laser ablation as model systems for electrochemical applications

Thin films of a bifunctional electrocatalyst with the compositions La_0.6Ca_0.4CoO_3−δ and La_0.7Ca_0.3CoO_3−δ have been deposited by a variation of pulsed laser deposition, i.e. pulsed reactive crossed-beam laser ablation. These perovskite phases have been used as catalysts for oxygen reduction and evolution in re-chargeable Zn/air batteries. The utilization of a synchronized reactive gas pulse with N₂O or O₂ allows the preparation of perovskite films with almost ideal oxygen content without additional annealing steps and to control the oxygen content of the films. The films with higher oxygen content reveal a lower resistivity. These compositions have been selected to study the influence of the texture on the electrocatalytical activity for oxygen reduction and evolution of the films. Amorphous films, or films with mixed or single orientation can be obtained by varying the target–substrate distance and substrate temperature without changing the composition of the films. A clear influence of the crystallinity on the catalytic activity, i.e. smaller overpotential for the two oxygen reactions, is observed. The amorphous films reveal the largest overpotential, followed by the polycrystalline films with one or more orientations, and the single crystalline films with (100) orientation.