用于氧还原反应的碳基负载金属单原子催化剂研究进展

燃料电池能够将化学能转化为电能,是一种绿色高效的能量转换装置,但是受到阴极氧还原反应(ORR)动力学迟缓的限制,燃料电池需要使用Pt等贵金属作为催化剂,这就导致其成本显著增加.碳基负载单原子催化剂(C-SACs)展现出高原子利用率和高选择性等优异性能.另外,C-SACs在不同pH环境下都显示出优异的ORR催化活性,被视...     

铁氮共掺杂介孔碳材料的简易制备及其氧还原反应催化性能

氧还原反应(ORR)是燃料电池阴极重要的电化学反应过程,其自发反应进程缓慢,对氧还原反应起高效催化作用的催化剂面临价格昂贵、合成流程复杂、污染环境等问题,因此探索合成简单、环境友好的氧还原催化剂制备方法具有重要意义。铁氮共掺杂介孔碳材料(Fe-N/MC)是一种有巨大应用价值的非贵金属氧还原反应催化剂。本工作通过在马弗炉中的半封闭体系内高温碳化小分子前驱体得到介孔碳材料(MC_M),再把获得的MC_M与铁盐混合在管式炉中高温处理制备得到铁氮共掺杂介孔碳材料(Fe-N/MC_MT)。该方法热解条件简单,无需模板剂和NH₃、HF等有毒物质。由于MC_M含有较高的氮和氧元素,有利于提升介孔碳材料表面的亲水性和配位能力,通过MC_M和铁盐制备出的Fe-N/MC_MT含有丰富的、催化ORR的Fe-N_x活性位点,其起始电位和半波电位分别为0.941和0.831 V(vs RHE),比商业化Pt/C催化剂的起始电位和半波电位分别正34和16...     

质子交换膜燃料电池氮掺杂碳基催化剂研究进展

简要介绍了近年来氮掺杂碳基催化剂在质子交换膜燃料电池阴极氧还原方面的应用发展状况,详细总结了最近几年有关氮掺杂碳基催化剂制备及机理方面的研究结果,包括氮源前驱体种类、金属前驱体种类、金属的含量、碳源前驱体种类、热处理工艺等影响催化剂氧还原活性的主要因素,并指出了目前研究中的难点以及未来的发展方向。     

N掺杂碳基单原子催化剂在电化学生物传感领域的研究与应用

基于单原子催化剂(SACs)最大的原子利用率、可调控的电子结构、高活性位点、特殊的催化反应性能以及高度稳定性等特性,研究者以N掺杂碳基材料为载体,配体单元材料为模型,将单原子催化的研究拓展到电化学生物传感材料改性领域,研究了载体、金属配位单元对SACs催化活性的影响,总结了N掺杂碳基SACs在电化学生物传感领域中的最新研究进展,提出并探讨了该多相催化剂在电化学生物传感领域的应用前景以及面临的挑战。     

掺氮石墨烯的制备及其ORR催化性能的研究

由于掺氮石墨烯具有优异的电化学性能,受到研究者的关注,然而在石墨烯掺氮的方法中大部分（热解法、烧结法）需要过高的温度（500-900℃）和较长的反应时间（2-3 h）[1-3]。采用微波等离子体对氧化石墨进行还原改性制备掺氮石墨烯,在低功率条件下反应时间只需20 min就得到了催化活性良好的掺氮石墨烯。掺氮石墨烯的表征技术主要包括Raman和TEM,并使用电化学工作站对掺氮石墨烯进行ORR催化性能评估。     

氢氧化钾活化制备可再生多孔碳及其电催化氧还原性能研究

氧还原反应缓慢的动力学过程严重限制了燃料电池的能量转换效率, 而商用Pt/C催化剂成本太高、资源稀缺、稳定性差, 需要寻找合适的材料来取代商用的Pt/C催化剂。近年来, 氮掺杂多孔碳材料因其独特的物理和化学特性吸引了大量的关注。本文使用富含氮元素的可再生土豆作为生物质前驱体, 通过简单的一步热解过程和KOH活化方法相结合制备出了一系列氮掺杂多孔碳电催化剂; 并系统研究了KOH用量和活化温度对碳基体孔结构和电催化性能的影响。结果表明, 当活化温度为750 ℃、KOH与碳的质量比为3/1时, 所制备的催化剂(NPC-750)的氧还原活性最高, 起始电位和半波电位分别达到0.89和0.79 V (vs. RHE), 极限电流密度达到5.53 mA?cm ^-2。NPC-750优异的氧还原催化活性主要归因于其发达的孔结构、高的比表面积(1134.2 m ²?g ^-1)和合适的氮含量(1.57at%)。同时, 优异的循环稳定性和抗甲醇中毒性能进一步说明这些生物多孔碳材料是潜在的低成本氧还原电催化剂。此外, 这些高比表面积多孔碳在超级电容、吸附/分离、催化以及电池等领域也具有潜在的应用前景。     

镍基MOF衍生Ni@PC用于氧还原催化性能研究

开发高效、低成本的非贵金属氧还原催化剂是提高燃料电池效率的关键。以六水合硝酸镍和二甲基咪唑作为金属源和氮源,制备Ni-MOF前驱体,并采用低温热解法合成了纳米棒状镍掺杂多孔碳(Ni@PC)复合材料。通过扫描电子显微镜、X射线衍射仪、拉曼光谱和物理吸附仪等多种表征手段,对催化剂进行形貌和结构表征。利用旋转圆盘电极技术测试了其氧还原催化性能。结果表明：Ni@PC呈现三维交错的纳米棒状,其比表面积为178.7m²/g,具有介孔结构。在0.1mol/L KOH电解液中,Ni@PC的氧还原起始电位为0.89V(vs RHE),其极限电流密度可达4.91mA/cm²,在动力学电位区,Ni@PC的Tafel斜率为64mV/dec,氧气分子在Ni@PC催化剂上以四电子机理反应还原成水,该催化剂具有优异的耐久性和抗甲醇稳定性。因此,Ni@PC有望替代商业Pt/C催化剂,在能源领域具有广阔的应用前景。     

三维石墨烯基B-N-Fe/Co-G材料的制备及其氧还原催化性能研究

采用脲、硼酸、硝酸铁、硝酸钴分别作为N、B、Fe、Co源,与GO(氧化石墨烯)通过快速冷冻干燥与热解法,制得了三维石墨烯基B-N-Fe/Co-G催化材料,并对其结构和性能进行了测试和表征,研究其氧还原的活性物质与活性点。透射电子显微镜(TEM)、扫描电子显微镜(SEM)、拉曼光谱(Raman)、X射线衍射(XRD)及X射线光电子能谱(XPS)结果显示,所制得掺杂石墨烯表面褶皱呈三维孔洞结构,掺杂原子N、B、Fe、Co均匀掺杂于石墨烯中。通过循环伏安法(CV)、线性扫描伏安法(LSV)等手段对三维石墨烯基B-N-Fe/Co-G催化材料进行电化学性能测试,结果表明:B-N-Fe/Co-G在0.1 mol/L的 KOH碱性电解质中有较高的氧还原(ORR)催化活性,起始电位在1.0 V左右,为4电子转移,相比质量分数20%的商用Pt/C催化剂有更好的电化学稳定性。     

Biomass Derived N‐Doped Porous Carbon Supported Single Fe Atoms as Superior Electrocatalysts for Oxygen Reduction

Exploring sustainable and high‐performance electrocatalysts for the oxygen reduction reaction (ORR) is the crucial issue for the large‐scale application of fuel cell technology. A new strategy is demonstrated to utilize the biomass resource for the synthesis of N‐doped hierarchically porous carbon supported single‐atomic Fe (SA‐Fe/NHPC) electrocatalyst toward the ORR. Based on the confinement effect of porous carbon and high‐coordination natural iron source, SA‐Fe/NHPC, derived from the hemin‐adsorbed bio‐porphyra‐carbon by rapid heat‐treatment up to 800 °C, presents the atomic dispersion of Fe atoms in the N‐doped porous carbon. Compared with the molecular hemin and nanoparticle Fe samples, the as‐prepared SA‐Fe/NHPC exhibits a superior catalytic activity (E _1/2 = 0.87 V and J _k = 4.1 mA cm^?2, at 0.88 V), remarkable catalytic stability (≈1 mV negative shift of E _1/2, after 3000 potential cycles), and outstanding methanol‐tolerance, even much better than the state‐of‐the‐art Pt/C catalyst. The sustainable and effective strategy for utilizing biomass to achieve high‐performance single‐atom catalysts can also provide an opportunity for other catalytic applications in the atomic scale.     

High Density Single Fe Atoms on Mesoporous N-Doped Carbons: Noble Metal-Free Electrocatalysts for Oxygen Reduction Reaction in Acidic and Alkaline Media

It remains a challenge to develop efficient noble metal-free electrocatalysts for the oxygen reduction reaction (ORR) in various renewable energy systems. Single atom catalysts have recently drawn great attention as promising candidates both due to their high activity and their utmost atom utilization for electrocatalytic ORR. Herein, the synthesis of an efficient ORR electrocatalyst that is composed of N-doped mesoporous carbon and a high density (4.05 wt%) of single Fe atoms via pyrolysis Fe-conjugated polymer is reported. Benefiting from the abundant atomic Fe–N₄ sites on its conductive, mesoporous carbon structures, this material exhibits an excellent electrocatalytic activity for ORR, with positive onset potentials of 0.93 and 0.98 V in acidic and alkaline media, respectively. Its electrocatalytic performance for ORR is also comparable to that of Pt/C (20 wt%) in both media. Furthermore, it electrocatalyzes the reaction almost fully to H₂O (or barely to H₂O₂). Additionally, it is durable and tolerates the methanol crossover reaction well. Furthermore, a proton exchange membrane fuel cell and a zinc–air battery assembled using it on their cathode deliver high maximum power densities (320 and 91 mW cm⁻², respectively). Density functional theory calculation reveals that the material's decent electrocatalytic performance for ORR is due to its atomically dispersed Fe–N₄ sites.     

氮掺杂石墨烯@碳纳米纤维的原位制备及其电催化氧还原性能

结合静电纺丝和热处理技术, 在含钴碳纳米纤维上原位生长了氮掺杂石墨烯, 制备了三维互通纤维网结构。研究了钴含量对产物氧还原活性的影响。结果表明: 氮掺杂石墨烯的生成和钴的引入均显著提高了电催化活性。纺丝液中六水合硝酸钴与聚丙烯腈的质量比为1: 10时, 获得的催化剂活性最优, 起始电势为0.84 V(vs RHE), 反应为近四电子路径, 具有比铂碳更好的稳定性和耐甲醇毒化能力。三维互通结构促进了电子和质子传输, 并能提供更多的活性位点, 提高电催化活性。这种方法也可用于设计其它三维互通的纤维复合物, 在能源与环境领域具有更广泛的应用前景。     

Nano‐Intermetallic AuCu3 Catalyst for Oxygen Reduction Reaction: Performance and Mechanism

This paper introduces a new approach for catalyst design using the non‐precious metal Cu as one of the catalytic active centers. This differs from previous studies that considered precious metals to be responsible for the catalytic reaction in precious alloys. Intermetallic AuCu₃/C nanoparticles with a diameter of 3 nm were developed for the first time, with uniform dispersion and a narrow size distribution. The ca. 3 nm as‐synthesised AuCu₃/C showed superior catalytic performance for oxygen reduction reactions (ORR) in alkaline solutions, with comparable half‐wave potential and 1.5 times mass current density of commercial Pt/C at 0.80 V (vs. reversible hydrogen electrode (RHE)). The advanced catalytic activities are mainly attributed to the synergetic effects of electro‐active atomic Au and Cu on the particle surface, in which Cu helps to activate the O₂ molecule and Au benefits OH^? desorption. The excellent durability and methanol tolerance exhibited in alkaline solutions provide another advantage for AuCu₃/C to be considered as a potential alternative cathode catalyst in alkaline fuel cells.     

二维过渡金属硫属化合物氧还原反应催化剂的研究进展

氧还原(ORR)反应是燃料电池等清洁能源阴极的关键反应, 其反应动力学复杂, 阴极需使用Pt等贵金属催化剂。然而Pt价格昂贵, 且载体炭黑在高电位环境下稳定性欠佳, 导致电池部件成本高且寿命短。二维过渡金属硫属化合物(2D TMDs)具有高比表面积与可调节的电学性能, 且稳定性强, 有望在维持活性的同时提高燃料电池阴极的耐久性。本文梳理了近年来2D TMDs在ORR催化剂领域的最新研究进展: 首先概述了2D TMDs的结构、性质及ORR反应机理; 其次分析了调控2D TMDs的ORR性能策略, 包括异质元素掺杂、相转变、缺陷工程与应力工程等, 介绍了2D TMDs基异质结构对ORR性能的提升作用; 最后, 针对该领域目前存在的挑战进行展望与总结。     

Atomic Engineering Modulates Oxygen Reduction of Hollow Carbon Matrix Confined Single Metal-Nitrogen Sites for Zinc-Air Batteries

The systematical understanding of metal-dependent activity in electrocatalyzing oxygen reduction reaction (ORR), a vital reaction with sluggish kinetics for zinc-air batteries, remains quite unclear. An atomic and spatial engineering modulating ORR activity over hollow carbon quasi-sphere (HCS) confined in a series of single M-N (M = Cu, Mn, Ni) sites is reported here. Based on the theoretical prediction and experimental validation, Cu-N₄ site with the lowest overpotential shows a better ORR kinetics than Mn-N₄ and Ni-N₄. The ORR activity of single-atom Cu center can be further improved by decreasing the coordination number of N to two, namely Cu-N₂, due to the enhancement of electrons with lower coordination structure. Benefitting from the unique spatial confinement effect of the HCS structure in modulating electronic feature of active sites, the Cu-N₂ site confined in HCS also delivers highly improved ORR kinetics and activity relative to that on planner graphene. Additionally, the best catalyst holds excellent promise in the application of zinc-air batteries. The findings will pave a new way to atomically and electronically tune active sites with high efficiency for other single-atom catalysts.     

ZIF‐8 with Ferrocene Encapsulated: A Promising Precursor to Single‐Atom Fe Embedded Nitrogen‐Doped Carbon as Highly Efficient Catalyst for Oxygen Electroreduction

The oxygen reduction reaction (ORR) plays an important role in the fields of energy storage and conversion technologies, including metal–air batteries and fuel cells. The development of nonprecious metal electrocatalysts with both high ORR activity and durability to replace the currently used costly Pt‐based catalyst is critical and still a major challenge. Herein, a facile and scalable method is reported to prepare ZIF‐8 with single ferrocene molecules trapped within its cavities (Fc@ZIF‐8), which is utilized as precursor to porous single‐atom Fe embedded nitrogen‐doped carbon (Fe–N–C) during high temperature pyrolysis. The catalyst shows a half‐wave potential (E_1/2) of 0.904 V, 67 mV higher than commercial Pt/C catalyst (0.837 V), which is among the best compared with reported results for ORR. Significant electrochemical properties are attributed to the special configuration of Fc@ZIF‐8 transforming into a highly dispersed iron–nitrogen coordination moieties embedded carbon matrix.     

金属掺杂聚吡咯碳化物PPY-M的制备及其氧还原反应电催化活性

在Fe³⁺或Co²⁺存在下进行吡咯的聚合反应, 得到金属离子掺杂的聚吡咯, 并在N₂气氛下700℃碳化, 再将该碳化产物在900℃焙烧得到含有不同金属的复合催化剂PPY-M(M为不同的金属)。采用SEM、XRD等对催化剂的结构进行了表征。通过循环伏安和线性电位扫描等电化学手段, 研究了催化剂对氧还原(ORR)的电催化活性及其稳定性。结果表明, 掺杂金属钴的催化剂的活性最好, 在酸性溶液中ORR的起始电位达到0.54 V(vs SCE),电流密度为7.5 mA/mg@-0.3 V(vs SCE); 在碱性溶液中ORR的起始电位为-0.11 V(vs SCE),电流密度为5.7 mA/mg@-0.8 V。Fe或Co掺杂的聚吡咯碳化物对ORR具有较强的电催化活性, 而且制备过程简单、成本低, 有较重要的研究意义。