Pd基氧还原反应纳米合金电催化剂研究进展

在电催化过程中,反应物、中间态和最终产物分子与电催化剂表面的相互作用至关重要,因此对电催化剂表面的活性位点进行调控与修饰是电催化研究中极其重要的一部分,直接决定了电催化过程的效率和成本.首先,简单介绍了电催化的相关基础知识,以燃料电池阴极氧还原反应(oxygen reduction reaction, ORR)为例,介绍了反应过程机理和高效电催化剂的设计原则.然后,综述了电催化剂活性位点调控的最新进展及面临的挑战,主要包括Pd基纳米合金催化剂的结构和组成;介绍了如何利用各种物理效应(例如晶格应变和电子耦合效应)提升催化活性和稳定性.最后,围绕Pd基纳米合金催化剂性能的进一步提升以及贵金属电催化剂成本控制这两个问题,对其未来的合成策略和发展进行了展望.     

氢燃料电池阴极氧还原反应电催化剂研究进展

氢燃料电池是一种将化学能直接转换为电能的能量转换装置,具有转换效率高、噪声低、无污染、原料多样且用途广泛等优点,但其阴极氧还原反应(oxygen reduction reaction,ORR)动力学缓慢,极大地限制了其大规模应用与发展．因此,研发高效、耐用兼具经济性的ORR电催化剂是当前研究热点之一．在众多科研工作者的努力下,关于ORR电催化剂的研究工作已取得了许多重要突破性进展．本综述系统介绍了ORR反应机制和目前3种主流类别的ORR电催化剂(贵金属、非贵金属、碳基)的研究进展,着重分析了不同催化剂体系的性能与优缺点,并探讨了高性能ORR电催化剂的合成策略及其未来的发展方向．      

SnO2对氧还原催化剂(Ag,Pd,Pt)催化活性的增效研究

为进一步提高催化剂(Ag,Pd和Pt)对氧还原反应(ORR)的催化活性,通过原位还原法将催化剂选择性沉积在碳纳米管(CNTs)负载的SnO_2表面,制得相应复合催化剂,同时制备了将SnO_2溶解处理的催化剂以作比较.电化学测试结果显示,SnO_2可显著改善贵金属催化剂ORR催化活性,表明利用SnO_2提高表面负载金属催化剂ORR活性有普适意义.     

过渡金属修饰的杂原子掺杂多孔碳基氧还原和析氧催化剂的研究进展

高效且清洁的能源储存和转换装置对未来的社会发展至关重要.然而,金属空气电池、燃料电池、电解水制氢等设备中涉及的氧还原反应(ORR)迟缓的动力学和析氧反应(OER)较大的过电势限制了这些设备的能源效率和运行寿命.廉价、高效、稳定且环保的ORR和OER催化剂的制备是推动能源转换装置商用的关键环节.本文总结了过渡金属修饰的杂原子掺杂多孔碳基ORR和OER催化剂的最新研究进展,并重点评述了其结构与性能之间的关系.最后,从理论计算的角度讨论了活性位点的电子结构特性对碳基材料电化学性能的影响,并展望了该领域所面临的挑战和机遇.     

钴基氧还原电催化材料研究进展

氧还原反应(oxygen reduction reaction,ORR)是能量转换和储存系统的关键电极反应。目前,贵金属基材料,如铂和钯,是ORR最有效的催化剂,但其地球储量稀少、价格昂贵,且抗甲醇和CO性能差。因此,开发新型、低成本、高性能的氧还原电催化剂对能源转化和储存具有重要意义。综述了近年来非贵金属钴(Co)基氧还原电催化材料的研究进展及其性能调控策略,分为Co合金、Co-N-C、Co纳米粒子、Co基氧化物、Co基磷化物和Co基硫化物等多种形式,并对未来开发低成本、高性能的氧还原催化剂进行了展望。     

Pd掺杂方式对Pt/KL分子筛正己烷芳构化及抗硫性能的影响

以浸渍法和水热合成法向Pt/KL催化剂中掺杂金属Pd,对催化剂进行改性和表征,并在固定床微型反应装置上考察Pd掺杂方式对Pt/KL催化剂正己烷芳构化性能及抗硫性能的影响.结果表明:不同方式掺杂Pd对分子筛的晶体结构和孔径分布等影响较小,对催化剂表面酸碱性质的影响较大;浸渍法掺杂金属Pd较水热法更能提高Pt/KL催化剂的正己烷芳构化反应活性、芳烃选择性及抗硫性能.这是由于通过浸渍法制备催化剂Pt-Pd/KL中的Pd与Pt相互作用增强了催化剂的金属催化功能,使得其芳构化活性和抗硫性增强;通过水热法制备催化剂Pt/PdKL中的Pd增强了催化剂酸性,从而降低了催化剂芳构化活性和抗硫能力所致.     

NP共掺杂的多孔碳材料在氧还原方面的应用

可持续清洁能源的发展对缓解能源和环境危机有着不可或缺的作用,燃料电池具有可循环性、产物清洁等优点,其中氢氧燃料电池有很大的发展前景,而寻找非贵重催化剂替代Pt基催化剂成为研究氢氧燃料电池阴极(ORR)氧还原反应的研究重点之一.本课题选择廉价易得的工业废料-木屑作为框架材料,通过N和P双掺杂的方法,对其表面进行后修饰.利用其协同效应,得到具有良好ORR活性的多孔碳材料,并利用电化学工作站对其进行ORR性能测试,结果表明calZIF-wood-24h具有较高ORR活性和较好的稳定性,而且其较低的成本为广泛的实际应用提供了可能.     

微结构对纳米碳纤维氧阴极还原性能影响

在制备微结构可控纳米碳纤维基础上,研究纳米碳纤维微结构对氧气电催化还原反应(oxygen reduction reaction,ORR)性能的影响.利用化学还原法合成了Pt电催化剂,研究了纳米碳纤维微结构对Pt/CNFs电催化剂电催化性能的影响.研究发现,相对于基于活性炭的电催化剂,载于纳米碳纤维的电催化剂具有较高的ORR活性;同时,基于板式纳米碳纤维的电催化剂表现出最高的ORR活性.     

Pd/SBA-15催化剂的制备及交叉偶联反应研究

通过两步法制备了一种钯负载的介孔SBA-15催化剂(Pd/SBA-15),并将其应用于Suzuki反应,研究其催化交叉偶联反应性能.结果发现Pd/SBA-15催化剂对该反应具有良好的催化效果,催化循环实验表明其结构稳定、易于回收,有较好的应用前景.     

Pd对Cu/ZnO催化甘油氢解制取1,2-丙二醇性能的影响

通过共沉淀法和浸渍法制备负载微量Pd的Pd/Cu/ZnO (n(Cu)/n(Zn)=1/1.4)催化剂,采用H2程序升温还原 (H2TPR)、N2O吸附和H2吸附等方法对催化剂进行表征,在连续流动固定床反应器中考察Pd/Cu/ZnO催化甘油氢解的反应性能.结果表明:引入微量Pd降低了催化剂的还原温度,增强了催化剂氢吸附性能,但对催化剂活性Cu表面积的影响较小,有效地提高了催化剂上甘油氢解反应的稳定性.从Pd表面溢流到Cu表面的活化氢原子降低了H2O对催化剂活性Cu的氧化.     

Surface-confined Pt-based catalysts for strengthening oxygen reduction performance

Developing highly efficient catalysts for the oxygen reduction reaction (ORR) is a key to the fabrication of commercially viable fuel cell devices for future energy applications. Considerable progress has been made to reduce Pt usage and improve performance of the Pt catalysts by modulating exposed facets of Pt nanocrystals and combining Pt with other metals to generate bimetallic nanocrystals with structures in the form of alloys, core-shells, branches or anisotropies. Apart from the above methods, confining Pt-based nanoparticles (NPs) surfaces with elaborately selected layers such as polymers, silicon or carbons can also lead to an optimized Pt electronic structure, which is beneficial to ORR process. In this minireview, we summarize the recent advancements in the area of surface-confined Pt-based electrocatalysts for ORR with emphasis on introducing the design strategies and synthesis methodologies. The integration of these catalysts into ORR operations and the resulting performance as well as the strengthening mechanisms is also discussed. Meanwhile, the insights into the research directions are proposed in order to shed light on the future development of surface-confined Pt-based ORR catalysts.     

金属基氧电极材料催化机理研究进展

燃料电池作为一种高效、无污染的能源转换器件,受到广泛关注.其阴极氧还原反应是决定电池性能最重要、最关键的因素之一,也是制约其商业化的关键瓶颈因素之一.因此,研究和开发高效氧还原催化剂及其催化机理,对于燃料电池的发展和商业化进程具有十分重要的意义.在简要介绍燃料电池的基础上,综述了近年来金属基氧还原电极材料催化氧还原反应的机理,金属基氧还原电极材料包括Pt催化剂、Pt-M催化剂、杂原子掺杂碳载金属类催化剂等,总结了提高催化活性和稳定性、降低催化剂制备成本和催化剂制备工艺等方面所取得的研究结果,并指出了各类催化剂目前尚待解决的问题和发展方向.     

基于3d过渡金属的氧电极材料研究进展

氧还原催化剂及缓慢的阴极氧还原动力学是制约低温燃料电池商业化的关键瓶颈因素之一.非贵金属氧还原催化剂是近年来低温燃料电池最受关注的研究热点之一.在简要介绍燃料电池及氧还原反应机理的基础上,详细地综述了近年来低温燃料电池用3d过渡金属基氧还原催化剂的主要研究进展,包括过渡金属大环化合物、过渡金属-氮/碳类化合物、过渡金属硫族化合物和过渡金属氧化物,总结了提高催化活性和稳定性、降低催化剂制备成本以及催化剂制备工艺等方面所取得的研究结果,并指出了各类催化剂目前尚待解决的问题和发展方向.     

Low-dimensional catalysts for oxygen reduction reaction

Developing highly efficient electrocatalysts to facilitate the sluggish cathodic oxygen reduction reaction (ORR) is a key challenge for high-performance fuel cells. Low-dimensional materials have attracted great attention recently because of their unique structure and properties. In this review, the application of zero-dimensional (0D), one‐dimensional (1D), and two‐dimensional (2D) materials in ORR are discussed and particular attention is given to the relationship between their structure and the ORR activity. Graphene-based materials, transition metal dichalcogenides, transition metal oxide, nanotubes, nanoribbons, nanowires, and single-atom ORR catalysts are introduced and classified by their geometric dimension.     

电催化析氧反应过渡金属硫化物催化剂研究进展

析氧反应（oxygen evolution reaction, OER）、析氢反应（hydrogen evolution reaction, HER）和氧还原反应（oxygen reduction reaction, ORR）为电解水、金属-空气电池等能源器件的半反应。其中,OER由于涉及4e^-转移和O-O键的形成而导致反应动力学迟缓和过电势高,因此,开发优异的OER电催化剂能够有效提高能量转换效率。到目前为止,过渡金属硫化物催化剂（transition metal sulfide catalysts, TMSs）被研究人员大量研究和报道,并且取得飞跃发展。介绍在不同电解质中的OER机制,并通过对近几年相关文献的综合归纳,探究TMSs催化剂的组成、导电性、质子传输、缺陷程度、界面化学等多种因素对OER的影响。综述目前过渡金属硫化物电催化剂在OER领域所面临的挑战和研究进展,希望为TMSs的研究者提供借鉴。     

Central electron-enriched NO-FeN4 sites as superior acidic oxygen reduction reaction electrocatalysts for proton exchange membrane fuel cells

Developing nobel-metal-free catalysts, especially for iron-nitrogen on carbon (FeNC) materials, has been an urgent demand for wide applications of proton exchange membrane fuel cells (PEMFCs). However, the inferior oxygen reduction reaction (ORR) activity of traditional iron-nitrogen sites in acidic conditions seriously impedes the further improvement of their performance. Herein, we synthesized FeN₄ with NO (nitric oxide) group axial modification (denoted as NO-FeN₄) on a large scale through a confined small molecule synthesis strategy. Benefitting from the strong electron-withdrawing effect of the NO group, the central electron-rich FeN₄ site exhibits ultrahigh ORR activity with a three times higher mass activity (1.1 A·g?1 at 0.85 V) compared to the traditional FeN₄ sample, as well as full four-electron reaction selectivity. Moreover, the PEMFC assembled with the as-prepared electrocatalyst also exhibits a greatly enhanced peak power density (>725 mW·cm?2). This work provides a new approach to rationally design advanced M-N_x nonnoble electrocatalysts for the ORR.     

Effect of supporting materials on the electrocatalytic activity,stability and selectivity of noble metal-based catalysts for oxygen reduction and hydrogen evolution reactions

Carbonaceous and alternative supporting materials for platinum(Pt) and palladium(Pd) have been explored for the cathodic electrocatalysis in low-temperature fuel cells. Pd and Pt are widely used for catalysis owing to their remarkable electrocatalytic activity toward water splitting and fuel cell reactions. Supporting materials play a paramount role in defining electrocatalytic properties such as durability, selectivity, and activity. The conventional supporting material such as carbon black is unable to fit all the requirements under the severe operating conditions of fuel cells due to its poor corrosion resistance and limited mass transport of fuels to active catalyst sites. Nowadays the scientific research is being concentrated on devising different altered carbonic and carbonfree supporting materials for catalysts to improve the catalytic activity, stability, and selectivity of noble metal electrocatalysts. Lately, Pt, Pd and their alloy catalysts supported on modified carbonaceous and carbon-free materials have attracted solid interest owing to their prominent characteristics contributing to the remarkable fuel cell efficacy. Therefore, it is reasonable to explore this theme, regarding a variety of supporting materials,their advantages, drawbacks and future perspectives. In this mini-review, we selectively summarize recent advancements on several types of key supporting materials: carbon(graphene, carbon nanotubes, mesoporous carbon, and doped carbon nanostructures), non-carbon(transition metals oxides, borides, nitrides, and carbides)and hybrid nanocomposites.