过渡金属磷化物的制备与光/电催化的应用研究进展

过渡金属磷化物(TMPs)价廉易得,因其独特的结构特征具有丰富的活性位点、良好的导电性和结构稳定性,逐渐在催化领域引起了人们的广泛关注,被应用于有机物硫化、脱氢、电催化、光催化等方面.本文主要综述了过渡金属磷化物的结构特征、常用的制备方法以及在电催化和光催化方向应用的最新进展.     

基于铁、钴、镍金属磷化物纳米催化剂的碱性条件下电解水制氢的研究进展

过渡金属磷化物(TMPs)因其导电性好、稳定性高而被广泛认为是电解水析氢反应(HER)的优异电催化材料。 本文主要围绕基于过渡金属Ni、Co、Fe磷化物纳米材料的合成、表征、以及在碱性介质中的电催化HER性能等方面展开。 从中得出结论,在一定范围内,TMPs体系中富磷相越多,其在碱性电解液中的HER活性越高。 为以后的研究提供了方向。     

富磷型贵金属磷化物的绿色制备及电催化

正过渡金属磷化物(TMPs),由于具有独特的物理化学性质,在电解水、燃料电池、金属空气电池等能源电催化领域展现出极大的应用潜力。理论研究表明,由于磷(P)原子半径较大,P的引入使金属原子间距相对增加,原子间相互作用减弱,导致金属d带收缩,费米能级附近态密度增加~(1,2)。因此,     

过渡金属磷化物的制备和催化性能研究*

原油的重质化和日益严格的环境法规使燃料油加氢精制技术面临新的挑战,过渡金属磷化物由于具有优异的加氢脱硫、加氢脱氮活性和稳定性成为催化材料领域研究的焦点,本文综述了过渡金属磷化物的制备方法、催化性能和活性相,在加氢脱硫过程中过渡金属磷化物表层可能被硫化形成磷硫相,其可能与磷化物的催化活性和稳定性有关,过渡金属磷化物催化剂有望成为MoS₂催化剂之后的又一代深度加氢脱硫催化剂。     

有机硒参与的硒环化反应研究进展

有机硒化物是一类重要的分子,在药物、农用化学品、有机材料以及催化等领域有着广泛的应用,在有机分子中引入硒原子在合成化学中具有重要意义.杂环化合物是构成多种生物活性分子的重要骨架,因此,合成含硒杂环衍生物的研究备受关注.分别描述了近年来快速发展的金属催化、电化学驱动、可见光驱动、有机分子催化以及其它类型的硒环化反应,并对...     

钯催化惰性碳-氢键胺化反应研究进展

胺化反应是有机化学中最重要的反应之一,近年来,过渡金属催化的碳-氢键胺化反应已经成为合成有机胺化物的重要方法.本文综述了钯催化碳-氢键胺化反应的研究进展,按照底物类型和所活化碳-氢键的类型进行分类,并对该领域目前存在的局限性和未来发展进行了总结和展望.     

过渡金属磷化物析氢催化剂的掺杂调控

过渡金属磷化物因其优异的催化性能成为最有可能取代贵金属的廉价电催化分解水制氢催化材料, 对其进行元素掺杂将有望大幅提升其活性和稳定性. 本文综合评述了近年来通过掺杂改性手段调节过渡金属磷化物性能的相关研究. 讨论了元素种类(金属掺杂、 非金属掺杂、 共掺杂)、 元素数量(单元素掺杂、 多元素掺杂、 高熵化)和掺杂位置等因素对过渡金属磷化物电子结构的影响; 并从实验和理论相结合的角度, 分析了掺杂元素对氢吸附强度、 水吸附解离及电荷转移传输等方面的作用规律, 获得了掺杂结构-电子结构-析氢反应催化性能间的构效关系. 最后, 讨论并提出了相关研究存在的挑战和未来的研究方向.     

Pd催化P-C偶联合成膦配体的进展

本文综述了Pd催化的P-C偶联反应在多种膦化物合成中的应用,以及近年来利用Pd催化的P-C偶联和C-C偶联相结合在合成复杂的手性膦化物和对有机膦功能化研究中的成就。     

共轭微孔聚合物的制备与应用

共轭微孔聚合物(CMPs)是一类有机多孔聚合物,与常规共轭聚合物或多孔材料相比,其最大的特点是既有π共轭骨架又具有大量微孔.这类材料在解决能源和环境问题方面显示出巨大的潜力,已在气体吸附、非均相催化、发光材料、化学传感器、电能存储和生物杂化物等领域显示出巨大的应用前景.目前已开发出多种用于CMPs结构单元设计与合成的新...     

磷化钴@铁-锌双金属磷化物多级纳米复合物的制备及其电催化水分解性能

氢能源因其储量丰富、高效、零污染等特性而受到广泛关注.电解水产氢作为一种有效的获取氢能源的方式成为当前研究的重点.但由于电极表面反应过电势的存在极大增加了电解水的能耗,因此需要开发高效的电催化材料以提高电解水反应动力学.考虑到实际应用,设计和构筑在同一电解液中同时具有高效催化产氢和释氧能力的双功能催化材料更为重要且更具挑战.目前,越来越多的非贵金属基双功能催化材料被开发和报道,比如过渡金属硫化物、氧化物、层状双金属氢氧化物、碳化物、氮化物和磷化物等,其中又以磷化物的研究更为广泛.金属有机骨架化合物(MOFs)因其具有独特的性能(孔隙率高、超高比表面积、可调控的化学组分和孔道结构等)在能源转化等领域得到广泛应用.但是,基于MOFs材料转化的多组分过渡金属磷化物应用于全分解水体系的报道还比较少.先前的研究表明,优化催化材料的微纳结构和化学组成是提高材料催化性能的关键.我们利用三步法(晶体生长、自组装和磷化)设计并制备了一种基于MOFs转化的新型分级纳米复合材料CoP@ZnFeP.透射电子显微镜(TEM)结果显示,自组装形成的花状Co3O4@Fe-MOF-5中空结构在磷化后形貌能够很好地保持.X射线衍射(XRD)表明, CoP@ZnFeP纳米复合物是由大量的混合纳米晶体组成,主要包括Co2P, ZnP2和Fe2P.在碱性(1.0mol/L KOH)条件下, CoP@ZnFeP纳米复合物表现出优异的催化产氢(HER)和释氧(OER)性能,其释氢和产氧的启动电位分别为–50和148m V(vs.RHE),相应的Tafel斜率分别为76和53.9m V/decade.优异的电催化性能主要归功于复合材料的多级纳米结构组元(纳米粒子、纳米笼和纳米管),其有序的多孔结构和大的比表面积有利于电解液的渗透、气体的扩散和电子的转移.作为对比,我们利用相似方法制备了CoP和ZnFeP纳米粒子的机械混合物(CoP/ZnFeP).测试数据表明, CoP@ZnFeP分级复合材料的催化性能优于CoP/ZnFeP机械混合物.鉴于CoP@ZnFeP复合材料优异的催化性能,我们将其应用于全分解水体系.在两电极体系中,达到10m A/cm~2电流密度仅需1.6V电压,表明材料具有优异的全分解水性能.同时该复合物也显示出较好的稳定性,经过24h连续水解后,电解电位仅升高70m V.但同时我们也注意到电极表面剧烈产生的气泡会对电极材料的稳定性有严重影响.此项研究可为设计高效的非贵金属催化材料应用于能源转化和储存等领域提供较好的思路和借鉴.     

Nanobundles of Iron Phosphide Fabricated by Direct Phosphorization of Metal–Organic Frameworks as an Efficient Hydrogen-Evolving Electrocatalyst

Transition-metal-based phosphides (TMPs) have been considered as attractive electrocatalysts for water splitting due to their earth-abundance and remarkable catalytic activity. As a representative type of precursors, metal-organic frameworks (MOFs) provide ideal plateaus for the design of nanostructured TMPs. In this work, the hierarchically structured iron phosphide nanobundles (FeP-500) were fabricated by one-step phosphorization of an iron-based MOF (MET(Fe)) precursor. The derived FeP-500 nanobundles were constructed by quasi-paralleled one-dimensional nanorods with uneven surface, which provided channels for electrolyte penetration, mass transport, and effective exposure of active sites during the water-splitting process. With the addition of conductive Super P, the obtained FeP-500-S exhibited a good electrocatalytic performance towards the hydrogen evolution reaction in alkaline electrolyte (1 mol L⁻¹ KOH). Furthermore, to investigate the influence of secondary metal doping, a series of isoreticular MOF precursors and bimetallic TMPs were fabricated. The results indicated that the catalytic performance is structure dominated.     

Recent research progress of bimetallic phosphides-based nanomaterials as cocatalyst for photocatalytic hydrogen evolution

Hydrogen energy（H2） has been considered as the most possible consummate candidates for replacing the traditional fossil fuels because of its higher combustion heat value and lower environmental pollution.Photocatalytic hydrogen evolution（PHE） from water splitting based on semiconductors is a promising technology towards converting solar energy into sustainable H2fuel evolution. Developing high-activity and abundant source semiconductor materials is particularly important to realize highly effici...     

Cobalt phosphide nanocages encapsulated with graphene as ultralong cycle life anodes for reversible lithium storage

Research on Chemical Intermediates - Transition-metal phosphides (TMPs) have emerged as anode materials for lithium-ion batteries owing to their high theoretical capacity and stable cyclability....     

Transition metal phosphides: A wonder catalyst for electrocatalytic hydrogen production

Hydrogen evolution from water electrolysis has become an important reaction for the green energy revolution. Traditional precious metals and their compounds are excellent catalysts for producing hydrogen; however, their high cost limits their large-scale practical application. Therefore, the development of affordable electrocatalysts to replace these precious metals is important. Transition metal phosphides(TMPs) have shown remarkable performance for hydrogen evolution and garnered considerable ...     

金属卟啉类超分子催化剂*

金属卟啉类超分子催化剂是超分子催化研究领域的重要内容之一,其关键环节是以金属卟啉为基础构建超分子微反应器,使反应活性中心处在一个特定的微环境中,从而实现高的催化效率和选择性。本文分别从超分子催化剂母体结构构筑（借助环糊精、模板等）和催化应用（模拟细胞色素P-450系列酶、光电催化等）的角度详细评述了近年来金属卟啉类超分子催化剂的设计、结构及催化作用的研究进展,并对该研究领域的前景进行了展望。     

Facile one-step synthesis of Ru doped NiCoP nanoparticles as highly efficient electrocatalysts for oxygen evolution reaction

Transition metal phosphides (TMPs) as ever-evolving electrocatalytic materials have attracted increasing attention in water splitting reactions owing to their cost-effective, highly active and stable catalytic properties. This work presents a facile synthetic route to NiCoP nanoparticles with Ru dopants which function as highly efficient electrocatalysts for oxygen evolution reaction (OER) in alkaline media. The Ru dopants induced a high content of Ni and Co vacancies in NiCoP nanoparticles, and the more defective Ru doped NiCoP phase than undoped NiCoP ones led to a greater number of catalytically active sites and improved electrical conductivity after undergoing electrochemical activation. The Ru doped NiCoP catalyst exhibited high OER catalytic performance in alkaline media with a low overpotential of 281 mV at 10 mA cm⁻² and a Tafel slope of 42.7 mV dec⁻¹.     

Incorporating Transition-Metal Phosphides Into Metal-Organic Frameworks for Enhanced Photocatalysis

Metal-organic frameworks (MOFs) have been shown to be an excellent platform in photocatalysis. However, to suppress electron–hole recombination, a Pt cocatalyst is usually inevitable, especially in photocatalytic H₂ production, which greatly limits practical application. Herein, for the first time, monodisperse, small-size, and noble-metal-free transitional-metal phosphides (TMPs; for example, Ni₂P, Ni₁₂P₅), are incorporated into a representative MOF, UiO-66-NH₂, for photocatalytic H₂ production. Compared with the parent MOF and their physical mixture, both TMPs@MOF composites display significantly improved H₂ production rates. Thermodynamic and kinetic studies reveal that TMPs, behaving similar ability to Pt, greatly accelerate the linker-to-cluster charge transfer, promote charge separation, and reduce the activation energy of H₂ production. Significantly, the results indicate that Pt is thermodynamically favorable, yet Ni₂P is kinetically preferred for H₂ production, accounting for the higher activity of Ni₂P@UiO-66-NH₂ than Pt@UiO-66-NH₂.     

Recent advances in nonmetallic atom-doped metal nanocrystals: Synthesis and catalytic applications

Metal nanocrystals have been recognized as the main catalytic materials in many fields, but insufficient activity and stability, as well as high prices, have limited their large-scale potential applications. As one of the extremely promising alternatives toward metal in boosting their catalytic performance, nonmetallic atoms-doped metal nanocrystals have recently received extensive attention because of their high efficiency, chemical and structural durability, abundant reserve, and low cost. In this review, we highlight the most recent progress in this field and provide insights into their catalytic applications. The metal-nonmetal nanocrystals prepared by doping metal nanocrystals with nonmetallic atoms are introduced and classified based on the types of nonmetallic atoms, including metal hydrides, borides, carbides, nitrides, oxides, phosphides, and chalcogenides. Besides, their applications in catalysis, especially in electrocatalysis and organic catalysis, have been summarized and discussed. Finally, the conclusions and perspectives are given for the catalysis-driven rational design of metal-nonmetal nanocrystals in this minireview.     

Nanosized Metal Phosphides Embedded in Nitrogen‐Doped Porous Carbon Nanofibers for Enhanced Hydrogen Evolution at All pH Values

Transition‐metal phosphides (TMPs) have emerged as promising catalyst candidates for the hydrogen evolution reaction (HER). Although numerous methods have been investigated to obtain TMPs, most rely on traditional synthetic methods that produce materials that are inherently deficient with respect to electrical conductivity. An electrospinning‐based reduction approach is presented, which generates nickel phosphide nanoparticles in N‐doped porous carbon nanofibers (Ni₂P@NPCNFs) in situ. Ni₂P nanoparticles are protected from irreversible fusion and aggregation in subsequent high‐temperature pyrolysis. The resistivity of Ni₂P@NPCNFs (5.34 Ω cm) is greatly decreased by 10⁴ times compared to Ni₂P (>10⁴ Ω cm) because N‐doped carbon NFs are incorporated. As an electrocatalyst for HER, Ni₂P@NPCNFs reveal remarkable performance compared to other previously reported catalysts in acidic media. Additionally, it offers excellent catalytic ability and durability in both neutral and basic media. Encouraged by the excellent electrocatalytic performance of Ni₂P@NPCNFs, a series of pea‐like M_xP@NPCNFs, including Fe₂P@NPCNFs, Co₂P@NPCNFs, and Cu₃P@NPCNFs, were synthesized by the same method. Detailed characterization suggests that the newly developed method could render combinations of ultrafine metal phosphides with porous carbon accessible; thereby, extending opportunities in electrocatalytic applications.