An Efficient Bio-inspired Oxygen Reduction Reaction Catalyst:MnO_(x)Nanosheets Incorporated Iron Phthalocyanine Functionalized Graphene

Oxygen reduction reaction(ORR)catalysts play a critical role in energy storage and conversion devices and have been attracted enormous interests,and however,it remains challenging to develop highly active cheap catalysts in a simple and green route.Inspired by the heme-copper oxidases(HOCs),in which the ORR active center is originated from the incorporation of Fe-N_(4)with copper atom,we here developed a fine manganese oxide nanosheets(MnO_(x)NSs)integrated with iron phthalocyanine(FePc)anchored on highly conductive graphene(MnO_(x)/FePc-G)through a green route only involve ethanol as the reagent.The bio-inspired catalyst MnO_(x)/Fe Pc-G demonstrated high ORR activity with a half-wave potential(E_(1/2))of 0.887 V,about 57 mV more positive than that of Pt/C.And the current density(j)at 0.9 V is about 1.9 m A cm^(-2),which is three times of Pt/C and FePc-G.More importantly,the bio-inspired systems show superior stability in comparison to commercial Pt/C,showing a potential of 0.863 V to deliver a j of 3 mA cm^(-2)after 18000 s polarization,about 80 mV higher than that of 0.783 V for Pt/C.The high activity is contributed by the integration of the Fe Pc and MnO_(x)NSs that plays the role to assist the cleavage of the O_(2)bond.Our approach provides a new evidence to develop highly efficient ORR catalysts through imitate the naturally involved systems through a simple route.

Tuning the Electrochemical Property of the Ultrafine Metal-oxide Nanoclusters by Iron Phthalocyanine as Efficient Catalysts for Energy Storage and Conversion

Nanoclusters(NCs)have been demonstrated of outstanding performance in electrochemical energy storage and conversion technologies due to their strong quantum confinement effects and strong interaction with supports.Here,we developed a class of ultrafine metal-oxide(MOx,M=Fe,Co and Ni)NCs incorporated with iron phthalocyanine(FePc),MOx/FePc-G,supported on graphene as high-performance catalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and carbon dioxide reduction(CO2RR).The high activities for ORR and OER are attributed to the electron donation and accepting ability of the highly redox active of FePc-G that could tune the properties of MOx.The FeOx/FePc-G exhibits an extremely positive half-wave potential(E1/2)of 0.888 and 0.610 V for ORR in alkaline and neutral conditions,respectively,which is around 60 mV more positive than that of Pt/C.And NiOx/FePc-G shows similar OER activity with the state-of-the-art catalysts,Ir/C,and better performance than NiFeO NCs supported on graphene.Remarkably,the CoOx/FePc-G and NiOx/FePc-G show high activity and selectivity to reduce CO2 into CO with a low onset potential of-0.22 V(overpotential is 0.11 V).

Role of buffer layer in electronic structures of iron phthalocyanine molecules on Au(111)

We investigate the electronic structures of one and two monolayer iron phthalocyanine （FePc） molecules on Au（111） surfaces. The first monolayer FePc is lying flat on the Au（111） substrate, and the second monolayer FePc is tilted at -15° relative to the substrate plane along the nearest neighbour [101] direction with a lobe downward to the central hole of the unit cell in the first layer. The structural information obtained by first-principles calculations is in agreement with the experiment results. Furthermore, it is demonstrated that the electronic structures of FePc molecules in one-monolayer FePc/Au（111） system are perturbed significantly, while the electronic structures of FePc molecules in the second monolayer in two-monolayer FePc/Au（111） system remain almost unchanged due to the screening of the buffer layer on Au（111）.

Single-molecule imaging of dinitrogen molecule adsorption on individual iron phthalocyanine

Nitrogen fixation is a vital process for both nature and industry.Whereas the nitrogenase can reduce nitrogen in ambient environment in nature,the industrialized Haber-Bosch process is a high temperature and high-pressure process.Since the discovery of the first dinitrogen complex in 1965,many dinitrogen complexes are prepared in a homogeneous solution to mimic the nitrogenase enzyme in nature.However,studies of the heterogeneous process on surface are rarely addressed.Moreover,molecular scale characterization for such dinitrogen complex is lacking.Here,we present a simple model system to investigate,at the single-molecule level,the binding of dinitrogen on a surface confined iron phthalocyanine(FePc)monolayer through the combination of in-situ low-temperature scanning tunneling microscopy(LT-STM)and X-ray photoelectron spectroscopy(XPS)measurements.The iron center in FePc molecule deposited on Au(111)and highly oriented pyrolytic graphite(HOPG)surface can adsorb dinitrogen molecule at room temperature and low pressure.A comparative study reveals that the adsorption behaviors of FePc on these two different substrates are identical.Chemical bond is formed between the dinitrogen and the Fe atom in the FePc molecule,which greatly modifies the electronic structure of FePc.The bonding is reversible and can be manipulated by applying bias using a STM tip or by thermal annealing.

Theoretical Study of Electronic Structure, Formation Mechanism and Intramolecular Sulfoxide Imidation Reactivity of Iron Phthalocyanine Nitrene Complex

Density functional theory(DFT) calculations are performed to investigate recent experimentally studied ring-closing sulfoxide imidation catalyzed by Fe(Ⅱ)-phthalocyanine(FeⅡPc). Our results reveal that the ground state of iron phthalocyanine nitrene intermediate(PcFeNR, R =(CH_(2))_(3)(SO)Ph), which is believed to mediate the intramolecular imitation, is triplet state featuring a diradical structure. The formation of Pc Fe NR is the result of a denitrification process with a calculated high-barrier of 23.4 kcal/mol which is in good agreement with the experimentally observed high reaction temperature of 100 ℃. The generated Pc Fe NR undergoes a low-barrier intramolecular nucleophilic attack by proximal nitrogen atom on the sulfur accomplishing the cyclization of sulfoxide. This study provides theoretical insights into the mechanism-based design of useful catalysts for nitrene transfer reactions.

Enhancing Heterogeneous Catalytic Activity of Iron(II) Phthalocyanine by Ethanol and Its Application in 2,4-dichlorophenol Detection

A chemical system for facile and accurate detection of 2,4-dichlorophenol （DCP） via iron （Ⅱ） phthalocyanine （Fe（Ⅱ）Pc） catalyzed chromogenic reaction is reported for the first time. In this system, DCP could be oxidized by dioxygen with the catalysis of Fe（Ⅱ）Pc and then coupled with 4-aminoantipyrine （4-AAP） to generate pink antipyrilquinoneimine dye. Control experiments showed that the addition of ethanol could obviously enhance the catalytic activity of heterogeneous Fe（Ⅱ）Pc catalysts because of the partial dissolution of Fe（II）Pc nanocubes, which was confirmed by the SEM analysis. On the basis of the detection results of DCP in the range from 2×10^-5 to 9×10^-4 mol/L, we obtained a regression equation （A = 0.187 5 ＋ 0.01 209C （R2=-0.995 6）） with the detection limit （3σ） of 3.26×10^-6 mol/L, which could be successfully used in detecting the real samples.

A Fiber Optic Sensor for Determination of 2,4-dichlorophenol based on Iron(Ⅱ) Phthalocyanine Catalysis

A new fi ber optic sensor based on the oxidation of 2,4-dichlorophenol（DCP） catalyzed by iron（II） phthalocyanine（Fe（II）Pc） was developed for the determination of DCP. The optical oxygen sensing fi lm containing fl uorescence indicator Ru（bpy）3Cl2 was used to detect the consumption of oxygen in solution. Moreover, a lock-in amplifier was used to determine the lifetime of the sensor head by detecting its phase delay change. The results reveal that the sensor has a linear detection range of 1.0×10^-6- 9.0×10^-5 mol/L and a response time of 5 min. The sensor also has high selectivity, good repeatability and stability. It can be used effectively to determine DCP concentration in real samples.

P-functionalized carbon nanotubes promote highly stable electrocatalysts based on Fe-phthalocyanines for oxygen reduction: Experimental and computational studies

Iron(Ⅱ) phthalocyanines(FePc) supported on functionalized nanostructured carbon materials have been studied as electrocatalysts for the oxygen reduction reaction(ORR) in an alkaline medium. Herein, two types of carbon nanotubes(CNTs) have been explored as support, Single-Walled Carbon Nanotubes and Herringbone Carbon Nanotubes(SWCNTs and h CNTs, respectively), both electrochemically modified with ortho-aminophenylphosphonic acid(2APPA), which provides phosphate axial coordinating ligands for the immobilization of FePc molecules. All the catalysts were prepared via a facile incipient wetness impregnation method. Comprehensive experimental analysis together with density functional theory(DFT) calculations has demonstrated both the importance of the five-coordinated Fe macrocycles that favor the interaction between the FePc and the carbon support, as well as the effect of the CNT structure in the ORR. FePc axial coordination provides a better dispersion, leading to higher stability and a favorable electron redistribution that also tunes the ORR performance by lowering the stability of the reaction intermediates. Interestingly, such improvement occurs with a very low content of metal(~1 wt% Fe),which is especially remarkable when h CNT support is employed. This work provides a novel strategy for the development of Fe-containing complexes as precious metal-free catalysts towards the ORR.

A shortcut for determining growth mode

Thin and thick films of iron phthalocyanine （FePc） molecules are deposited on a Ag （110） surface. The nature of the FePc growth and the interaction with the substrate have been studied by X-ray photoelectron spectroscopy （XPS）. All of the core level spectra exhibit rigid shifts towards lower binding energies following the deposition of the organic films, each by a different magnitude. A greater change and a larger shift in the Fe2p level as compared to Cls core level reveals that the adsorbate interacts with the substrate mainly via the Fe atom, located at the center of the molecule. An increase/decrease in the intensity of C1 s/Ag3d level is found to be exponentially linked to the overlayer molecular coverage. Finally, the so- called growth/decay curve indicates that FePc thin films initially develop following the FM growth mode and then transform to SK mode, resulting in 3D island aggregation.

Differences in the adsorption of FePc on coinage metal surfaces

A study of the electronic and structural properties of iron phthalocyanine （FePc） molecules adsorbed on coinage metal surfaces Cu （100） and Cu （110） has been conducted by means of density functional theory calculations. The strength of the molecule-substrate interactions is interpreted in terms of the lateral adsorption geometry and the site specific electronic structure of the molecule. In the case of FePc on a （100）-oriented copper surface, the benzopyrrole leg is found to be oriented at an angle of 9°or 3°from the [01-1] substrate direction. Further, an upward bend in the molecular plane ranging from 7° to 10°is also observed; giving an almost buckled shape to the molecule. However, in the case of FePc on Cu （110）, neither a bend nor a sizable rotation is observed. From the knowledge of the principle structural and electronic properties, it is concluded that FePc-Cu （100） interaction is relatively stronger than FePc-Cu （110） interaction, which is further evidenced by the charge transfer, work function changes, changes in the shape of the adsorbed molecular orbitals, and the orbital shifts. Furthermore, density of states analysis shows that the valence band level shift is surface- and site-dependent.

Highly electroactive N–Fe hydrothermal carbons and carbon nanotubes for the oxygen reduction reaction

Glucose-derived carbons were prepared by hydrothermal carbonization of glucose followed by carbonization or activation to obtain carbon materials with different microporosities. These microporous carbons and carbon nanotubes(CNTs) were functionalized with melamine and/or iron(Ⅱ) phthalocyanine(FePc)following three different methodologies:(i) Functionalization with melamine via thermal treatment,(ii)incorporation of the lowest amount of FePc reported in the literature via incipient wetness impregnation followed by thermal treatment and(iii) functionalization with melamine followed by Fe Pc incorporation.The chemical and textural characterization of the prepared materials and their electrochemical assessment allowed to understand the role of microporosity in the incorporation of FePc and its effect on the oxygen reduction reaction(ORR). It was observed that FePc was preferentially incorporated inside the porous structure, especially in samples with more developed microporosity. However, functionalization with melamine modified the textural properties and the surface chemistry, favoring the incorporation of FePc on the surface. Regarding the electrochemical performance, the presence of FePc greatly enhanced the electroactivity of the microporous catalysts. An onset potential of 0.88 V and a four-electron pathway were obtained for glucose-derived carbons, whereas the limiting current densities and kinetic current densities rose by 126% and 222%, respectively, in comparison to the base sample. Notwithstanding, the highest electrochemical activity was observed for the sample prepared with CNTs, due to the synergy between the active metal centers and their highly graphitic carbon structure. The electrochemical parameters of CNTFeP csurpass the commercial Pt/C. The half-wave potential is 40 mV higher, the limiting current density increases by 17%, and a negligible production of by-products(< 1%) was observed.

石墨烯负载分子铁酞菁催化剂的形貌结构调控与氧还原催化应用

分散在纳米碳基底上的分子催化剂由于具有明确的活性位点和结构可调的特点,成为了一类独特的单原子催化剂,有望代替贵金属催化剂用于电催化氧还原反应.本文中,我们开发了一种高活性氧还原催化剂,该催化剂由均匀且密集分散在泡芙状石墨烯载体上的铁酞菁(FePc/PG)构成.泡芙状石墨烯载体由于具有独特的皱褶和球状形貌,具有较大的比表面积和多尺度的孔结构,有利于FePc的高密度负载、活性位点的暴露和催化过程中传质效率的提高.当用旋转圆盘电极评估性能时,FePc/PG表现出优异的半波电位,达0.909 V(相对于可逆氢电极).此外,当用作气体扩散电极时,FePc/PG在高电流密度下表现出优异的高倍率和高功率性能.这项工作为设计纳米碳材料的形貌以及高性能异相分子催化剂提供了有效的策略,有望在多种能源转换和存储技术中得到应用.

电子轴向拉伸提升贫氧环境海水电池性能

长寿命溶解氧海水电池是深远海观测能源网络的重要组成单元,但海水贫氧复杂环境对设计高性能氧还原催化剂提出了重要挑战.本文以酞菁铁为模型催化剂,通过理论计算与实验验证,提出了活性位点电子轴向拉伸可大幅提升催化剂在极端贫氧环境中的氧还原活性和稳定性.该研究为构建高性能海水电池提供了材料学解决方案,同时为极端环境下催化剂的变革性设计提供了新的思路.

Ligand centered electrocatalytic efficient CO_(2) reduction reaction at low overpotential on single-atom Ni regulated molecular catalyst

Electrochemical CO_(2) reduction reaction(CO_(2)RR)into value-added chemicals/fuels is crucial for realizing the sustainable carbon cycle while mitigating the energy crisis.However,it is impeded by the relatively high overpotential and low energy efficiency due to the lack of efficient electrocatalysts.Herein,we develop an isolated single-atom Ni catalyst regulated strategy to activate and stabilize the iron phthalocyanine molecule(Ni SA@FePc)toward a highly efficient CO_(2)RR process at low overpotential.The well-defined and homogenous catalytic centers with unique structures confer Ni SA@FePc with a significantly enhanced CO_(2)RR performance compared to single-atom Ni catalyst and FePc molecule and afford the atomic understanding on active sites and catalytic mechanism.As expected,Ni SA@FePc exhibits a high selectivity of more significant Faraday efficiency(≥95%)over a wide potential range,a high current density of~252 mA·cm^(−2) at low overpotential(390 mV),and excellent long-term stability for CO_(2)RR to CO.X-ray absorption spectroscopy measurement and theoretical calculation indicate the formation of NiN_(4)-O_(2)-FePc heterogeneous structure for Ni SA@FePc.And CO_(2)RR prefers to occur at the raised N centers of NiN4-O_(2)-FePc heterogeneous structure for Ni SA@FePc,which enables facilitated adsorption of*COOH and desorption of CO,and thus accelerated overall reaction kinetics.

Catalytic oxidation of cyclohexene to cyclohexanone by a triple system in acidic aqueous acetonitrile medium

The catalytic oxidation of cyclohexene to cyclohexanone using Pd(OAc)(2)/HQ/FePc was investigated in an acidic aqueous solution of acetonitrile. The role of each component of this system in the oxidation of cyclohexene was explored by means of UV-VIS, IR, XPS spectroscopy and. cyclic voltammetry, respectively. Based on the experimental results, the mechanism of the oxidation of cyclohexene catalyzed by Pd(OAc)(2)/HQ/FePc was elucidated.

Reversible switching of Kondo resonance in a single-molecule junction

The control of the Kondo effect is of great interest in single-molecule junction due to its potential applications in spin based electronics.Here,we demonstrate that the Kondo effect is reversibly switched on and off in an iron phthalocyanine(FePc)single-molecule junction by using a superconducting Nb tip.In a scanning tunneling microscope-based Nb-insulator-FePc-Au junction,we achieve a reversible switching between the Kondo dip and inelastic electronic tunneling spectra by simply adjusting the tip-sample distance to tune the tunnel coupling at low temperature.Further approaching the tip leads to the picking up of the molecule to the tip apex,which transfers the geometry of the single-molecule junction into a Nb-FePc-insulator-Au type.As the molecule forms an effective magnetic impurity embedded into the superconducting ground states of the Nb tip,the out-gap Kondo dip switched to an in-gap Yu-Shiba-Rusinov state.Our results open up a new route for manipulating the Kondo effect within a single-molecule junction.

酞菁铁纳米点用于化学催化-声动力肿瘤联合治疗

声动力疗法(SDT)是一种新型无创治疗方式,由于其较强的组织穿透深度和较高的安全性而受到广泛关注.然而,目前声敏剂仍存在声敏化效率低的局限性,从而限制了其治疗效果和生物应用.因此,开发安全高效的声敏剂至关重要.本文中,我们通过简便的高温有机相法合成了一种新型超小酞菁铁纳米点(FePc NDs)声敏剂用于化学催化与声动力联合肿瘤治疗.高温处理后酞菁铁结中的N-H键的增强导致其声敏化作用大幅度提高,在超声作用下产生大量单线态氧(^(1)O_(2)).此外,由于Fe的存在,FePc NDs还可以通过芬顿催化反应生成羟基自由基(·OH),进一步提高活性氧治疗水平.值得注意的是,经过聚乙二醇(PEG)修饰的FePc-PEG NDs通过尾静脉注射入小鼠体内后呈现出较好的肿瘤富集能力.在超声作用下,FePc-PEG NDs具有明显的细胞杀伤效果和肿瘤抑制作用.更重要的是,得益于超小纳米结构,FePc-PEG NDs更易于从体内代谢,未引起明显的生物毒性,证明其具有良好的生物安全性.在此研究中,FePc-PEG NDs做为一种高效低毒的新型声敏剂在肿瘤声动力治疗领域具有广阔的应用前景.