Elevating Oxygen Evolution using Iron Phthalocyanine Infused Vanillic acid Electrocatalyst.

Oxygen evolution reaction (OER) is the bottle neck step in water splitting reaction towards the realization of hydrogen based clean energy production and storage. Metal air batteries and polymer electrolyte membrane fuel cells (PEMFC) are the alternative green energy systems that utilise O2 and H2 in the production of continuous and high energy output without the utilization of carbon based fuels which are the major sources of pollution. Transition metal based N4 organics are explored extensively as oxygen electrocatalysts i. e., OER and oxygen reduction reaction (ORR) catalysts because of their ease of synthesis, tuneable properties, low cost and high performance with long term stability. Here, vanillic acid functionalized iron phthalocyanine (FeVAPc) was synthesised and characterised by various spectroscopic techniques. The novel FeVAPc exhibited good thermal stability and was coated on Ni foam for OER studies. The scanning electron microscopy images showed net-work like surface morphology and the X-ray photoelectron spectroscopy indicated the presence of Fe in +3 oxidation state. The Ni/FeVAPc demonstrated excellent electrocatalytic activity for OER with overpotential of 312 mV at 10 mA.cm-2 current density in 1.0 M KOH electrolyte. The designed organic based catalyst exhibited lesser Tafel slope value which is nearer to the benchmark catalyst, IrO2. The proposed catalyst exhibited good stability as phthalocyanines are highly stable and do not undergo decomposition even in strong acidic and basic corrosive media. Integration of FeVAPc onto the Ni foam resulted in higher mass activity, lower charge transfer resistance, high active surface area leading to enhanced conductivity and activity. The fabricated Ni/FeVAPc is an appropriate cost-effective, efficient and stable catalyst for OER towards industrial applications.

Ab Initio Electronic, Magnetic, and Optical Properties of Fe Phthalocyanine on Cr2O3(0001).

The organic molecules adsorbed on antiferromagnetic surfaces can produce interesting interface states, characterized by charge transfer mechanisms, hybridization of molecular-substrate orbitals, as well as magnetic couplings. Here, we apply an ab initio approach to study the adsorption of Fe phthalocyanine on stoichiometric Cr2O3(0001). The molecule binds via a bidentate configuration forming bonds between two opposite imide N atoms and two protruding Cr ones, making this preferred over the various possible adsorption structures. In addition to the local modifications at these sites, the electronic structure of the molecule is weakly influenced. The magnetic structure of the surface Cr atoms shows a moderate influence of molecule adsorption, not limited to the atoms in the close proximity of the molecule. Upon optical excitation at the onset, electron density moves toward the molecule, enhancing the ground state charge transfer. We investigate this movement of charge as a mechanism at the base of light-induced modifications of the magnetic structure at the interface.

Synergistic Effects of Amine Functional Groups and Enriched-Atomic-Iron Sites in Carbon Dots for Industrial-Current-Density CO2 Electroreduction.

Metal phthalocyanine molecules with Me-N4 centers have shown promise in electrocatalytic CO2 reduction (eCO2R) for CO generation. However, iron phthalocyanine (FePc) is an exception, exhibiting negligible eCO2R activity due to a higher CO2 to *COOH conversion barrier and stronger *CO binding energy. Here, amine functional groups onto atomic-Fe-rich carbon dots (Af-Fe-CDs) are introduced via a one-step solvothermal molecule fusion approach. Af-Fe-CDs feature well-defined Fe-N4 active sites and an impressive Fe loading (up to 8.5 wt%). The synergistic effect between Fe-N4 active centers and electron-donating amine functional groups in Af-Fe-CDs yielded outstanding CO2-to-CO conversion performance. At industrial-relevant current densities exceeding 400 mA cm-2 in a flow cell, Af-Fe-CDs achieved >92% selectivity, surpassing state-of-the-art CO2-to-CO electrocatalysts. The in situ electrochemical FTIR characterization combined with theoretical calculations elucidated that Fe-N4 integration with amine functional groups in Af-Fe-CDs significantly reduced energy barriers for *COOH intermediate formation and *CO desorption, enhancing eCO2R efficiency. The proposed synergistic effect offers a promising avenue for high-efficiency catalysts with elevated atomic-metal loadings.

Electron Spin-Dependent Electrocatalysis for the Oxygen Reduction Reaction in a Chiro-Self-Assembled Iron Phthalocyanine Device.

The chiral-induced spin selectivity effect (CISS) is a breakthrough phenomenon that has revolutionized the field of electrocatalysis. We report the first study on the electron spin-dependent electrocatalysis for the oxygen reduction reaction, ORR, using iron phthalocyanine, FePc, a well-known molecular catalyst for this reaction. The FePc complex belongs to the non-precious catalysts group, whose active site, FeN4, emulates catalytic centers of biocatalysts such as Cytochrome c. This study presents an experimental platform involving FePc self-assembled to a gold electrode surface using chiral peptides (L and D enantiomers), i.e., chiro-self-assembled FePc systems (CSAFePc). The chiral peptides behave as spin filters axial ligands of the FePc. One of the main findings is that the peptides' handedness and length in CSAFePc can optimize the kinetics and thermodynamic factors governing ORR. Moreover, the D-enantiomer promotes the highest electrocatalytic activity of FePc for ORR, shifting the onset potential up to 1.01 V vs. RHE in an alkaline medium, a potential close to the reversible potential of the O2 /H2 O couple. Therefore, this work has exciting implications for developing highly efficient and bioinspired catalysts, considering that, in biological organisms, biocatalysts that promote O2 reduction to water comprise L-enantiomers.

Molecular catalysts with electronic axial stretching for high-performance lean-oxygen seawater batteries.

A dissolved-oxygen seawater battery (SWB) can generate electricity by reducing dissolved oxygen and sacrificing the metal anode at different depths and temperatures in the ocean, acting as the basic unit of spatially underwater energy networks for future maritime exploration. However, most traditional oxygen reduction reaction (ORR) catalysts are out of work at such ultralow dissolved oxygen concentration. Here, we proposed that the electronic axial stretching of the catalyst is essentially responsible for enhancing the catalyst's sensitivity to dissolved oxygen. By modulating the lattice of iron phthalocyanine (FePc) as a model catalyst, the unique electronic axial stretching in the z-direction of planar FePc molecules was realized to achieve a boosted adsorption and electron transfer and result in a much improved ORR activity in lean-oxygen seawater environment. The peak power density of a homemade SWB using a practical carbon brush electrode decorated by the FePc is estimated to be as high as 3 W L-1. These results provide inspiring insights into the interaction between the catalyst and complicated seawater environment, and propose the electronic axial stretching as an effective indicator for the rational design of catalysts to be used in extremely lean-oxygen environment.

Development of Electrochemical Sensor Using Iron (III) Phthalocyanine/Gold Nanoparticle/Graphene Hybrid Film for Highly Selective Determination of Nicotine in Human Salivary Samples.

Nicotine is the one of the major addictive substances; the overdose of nicotine (NIC) consumption causes increasing heart rate, blood pressure, stroke, lung cancer, and respiratory illnesses. In this study, we have developed a precise and sensitive electrochemical sensor for nicotine detection in saliva samples. It was built on a glassy carbon electrode (GCE) modified with graphene (Gr), iron (III) phthalocyanine-4,4',4″,4'''-tetrasulfonic acid (Fe(III)Pc), and gold nanoparticles (AuNPs/Fe(III)Pc/Gr/GCE). The AuNPs/Fe(III)Pc/Gr nanocomposite was prepared and characterized by using FE-SEM, EDX, and E-mapping techniques to confirm the composite formation as well as the even distribution of elements. Furthermore, the newly prepared AuNPs/Fe(III)Pc/Gr/GCE-nanocomposite-based sensor was used to detect the nicotine in phosphate-buffered solution (0.1 M PBS, pH 7.4). The AuNPs/Fe(III)Pc/Gr/GCE-based sensor offered a linear response against NIC from 0.5 to 27 µM with a limit of detection (LOD) of 17 nM using the amperometry (i-t curve) technique. This electrochemical sensor demonstrated astounding selectivity and sensitivity during NIC detection in the presence of common interfering molecules in 0.1 M PBS. Moreover, the effect of pH on NIC electro-oxidation was studied, which indicated that PBS with pH 7.4 was the best medium for NIC determination. Finally, the AuNPs/Fe(III)Pc/Gr/GCE sensor was used to accurately determine NIC concentration in human saliva samples, and the recovery percentages were also calculated.

Iron-Catalyzed Biomimetic Dimerization of Tryptophan-Containing Peptides.

Biomimetic oxidative dimerization of tryptophan derivatives in aqueous media with oxygen as a bulk oxidant catalyzed by an iron octacarboxy phthalocyanine complex was established. The discovery of the extremely active iron catalyst enables aerobic enzyme-mimetic oxidation to be performed in a flask. This method was applicable to the oxidative dimerization of a wide range of tryptophan derivatives, including various dipeptides and oligopeptides, with remarkable functional-group tolerance without the protection of the amino acid residues. Furthermore, oxidative dimerization of tryptophan derivatives bearing dioxopiperazine units enabled the convergent total synthesis of five natural pyrroloindole compounds and unnatural congeners. The established chemical method provides facile access to a broad range of dimerized peptides with a unique scaffold to link two turn structures, which will serve as a powerful tool to create new small- and medium-sized-molecules as drug candidates.

Highly sensitive and selective serotonin (5-HT) electrochemical sensor based on ultrafine Fe3O4 nanoparticles anchored on carbon spheres.

Neurotransmitter serotonin (5-HT) is involved in various physiological and pathological processes. Therefore, its highly sensitive and selective detection in human serum is of great significance for early diagnosis of disease. In this work, employing iron phthalocyanine as Fe source, ultrafine Fe3O4 nanoparticles anchored on carbon spheres (Fe3O4/CSs) have been prepared, which exhibits an excellent electrochemical sensing performance toward 5-HT. With carbonecous spheres turned into conductive carbon spheres under the heat treatment in N2 atmosphere, iron phthalocyanine absorbed on their surfaces are simultaneously pyrolysised and oxidized, and finally transformed into ultrafine Fe3O4 nanoparticles. Electrochemical results demonstrate a high sensitivity (5.503 µA µM-1) and a low detection limit (4 nM) toward 5-HT for as-prepared Fe3O4/CSs. In combination with the morphology and physicochemical property of Fe3O4/CSs, the enhanced sensing mechanism toward 5-HT is disscussed. In addition, the developed electrochemical sensor also displays a good sensing stability and an anti-interferent ability. Further applied in real human serum samples, a satisfactory recovery rate is achieved. Promisingly, the developed electrochemical sensor can be employed for the determination of 5-HT in actual samples.

Electrochemical Sensor Based on Iron(II) Phthalocyanine and Gold Nanoparticles for Nitrite Detection in Meat Products.

Nitrites are widely used in the food industry, particularly for the preservation of meat products. Controlling the nitrate content in food is an important task to ensure people's health is not at risk; therefore, the search for, and research of, new materials that will modify the electrodes in the electrochemical sensors that detect and control the nitrate content in food products is an urgent task. In this paper, we describe the electrochemical behavior of a glass carbon electrode (GCE), modified with a Fe(II) tetra-tert-butyl phthalocyanine film (FePc(tBu)4/GCE), and decorated with gold nanoparticles (Au/FePc(tBu)4/GCE); this electrode was deposited using gas-phase methods. The composition and morphology of such electrodes were examined using spectroscopy and electron microscopy methods, whereas the main electrochemical characteristics were determined using cyclic voltammetry (CV) and amperometry (CA) methods in the linear ranges of CV 0.25-2.5 mM, CA 2-120 µM in 0.1 M phosphate buffer (pH = 6.8). The results showed that the modification of bare GCEs, with a Au/FePc(tBu)4 heterostructure, provided a high surface-to-volume ratio, thus ensuring its high sensitivity to nitrite ions of 0.46 µAµM-1. The sensor based on the Au/FePc(tBu)4/GCE has a low limit of nitrite detection at 0.35 µM, good repeatability, and stability. The interference study showed that the proposed Au/FePc(tBu)4/GCE exhibited a selective response in the presence of interfering anions, and the analytical capability of the sensor was demonstrated by determining nitrite ions in real samples of meat products.

Electronic Structure Regulation of Iron Phthalocyanine Induced by Anchoring on Heteroatom-Doping Carbon Sphere for Efficient Oxygen Reduction Reaction and Al-Air Battery.

Aluminum-air batteries (AABs) are deemed as a potential clean energy storage device. However, exploiting high-efficiency and stable oxygen reduction reaction (ORR) electrocatalysts in AABs is still a challenge. Iron phthalocyanine (FePc) shows a great prospect in ORR but still far from Pt-based catalysts. Here, the hybrid electrocatalysts of monolayer FePc and hollow N,S-doped carbon spheres (HNSCs) are innovatively constructed through π-π stacking to achieve high dispersion. The resulting FePc@HNSC catalyst exhibits an outstanding ORR activity, outperforming that of pristine FePc and even most Fe-based catalysts reported to date. Moreover, the AAB using FePc@HNSC catalyst not only demonstrates a superior power density than the battery with Pt/C, but also displays stable discharge voltages and excellent durability. Furthermore, the theoretical calculations confirm that the charge distribution and d-band center of the Fe atom in FePc are efficiently optimized by hybrid configuration via the introduction of N,S-doped carbon substrate. The design leads to an enriched electron density around Fe active sites and significant reduction of energy barrier for OH* formation, which are favorable for the improvement of electrocatalytic ORR performance. This work provides a chance to expand the application of metallic macrocyclic compound electrocatalysts in various energy technologies.

Boosting Electrochemical Oxygen Reduction Performance of Iron Phthalocyanine through Axial Coordination Sphere Interaction.

Precise regulation of the electronic states of catalytic sites through molecular engineering is highly desired to boost catalytic performance. Herein, a facile strategy was developed to synthesize efficient oxygen reduction reaction (ORR) catalysts, based on mononuclear iron phthalocyanine supported on commercially available multi-walled carbon nanotubes that contain electron-donating functional groups (FePc/CNT-R, with "R" being -NH2 , -OH, or -COOH). These functional groups acted as axial ligands that coordinated to the Fe site, confirmed by X-ray photoelectron spectroscopy and synchrotron-radiation-based X-ray absorption fine structure. Experimental results showed that FePc/CNT-NH2 , with the most electron-donating -NH2 axial ligand, exhibited the highest ORR activity with a positive onset potential (Eonset =1.0 V vs. reversible hydrogen electrode) and half-wave potential (E1/2 =0.92 V). This was better than the state-of-the-art Pt/C catalyst (Eonset =1.00 V and E1/2 =0.85 V) under the same conditions. Overall, the functionalized FePc/CNT-R assemblies showed enhanced ORR performance in comparison to the non-functionalized FePc/CNT assembly. The origin of this behavior was investigated using density functional theory calculations, which demonstrated that the coordination of electron-donating groups to FePc facilitated the adsorption and activation of oxygen. This study not only demonstrates a series of advanced ORR electrocatalysts, but also introduces a feasible strategy for the rational design of highly active electrocatalysts for other proton-coupled electron transfer reactions.

Coherent Spin Control of Single Molecules on a Surface.

Control of single electron spins constitutes one of the most promising platforms for spintronics, quantum sensing, and quantum information processing. Utilizing single molecular magnets as their hosts establishes an interesting framework since their molecular structure is highly flexible and chemistry-based large-scale synthesis directly provides a way toward scalability. Here, we demonstrate coherent spin manipulation of single molecules on a surface, which we control individually using a scanning tunneling microscope in combination with electron spin resonance. We previously found that iron phthalocyanine (FePc) molecules form a spin-1/2 system when placed on an insulating thin film of magnesium oxide (MgO). Performing Rabi oscillation and Hahn echo measurements, we show that the FePc spin can be coherently manipulated with a phase coherence time T2Echo of several hundreds of nanoseconds. Tunneling current-dependent measurements demonstrate that interaction with the tunneling electrons is the dominating source of decoherence. In addition, we perform Hahn echo measurements on small self-assembled arrays of FePc molecules. We show that, despite additional intermolecular magnetic coupling, spin resonance and T2Echo are much less perturbed by T1 spin flip events of neighboring spins than by the tunneling current. This will potentially allow for individual addressable molecular spins in self-assemblies and with application for quantum information processing.

Study of the Interaction of an Iron Phthalocyanine Complex over Surface Modified Carbon Nanotubes.

Carbon nanotubes (CNT) were prepared by a modified chemical vapor deposition (CVD) method. The synthesized carbon materials were treated with acidic and basic solutions in order to introduce certain surface functional groups, mainly containing oxygen (OCNT) or amine (ACNT) species. These modified CNTs (OCNT and ACNT) as well as the originally prepared CNT were reacted with a non-ionic Fe complex, Iron (II) Phthalocyanine, and three composites were obtained. The amount of metal complex introduced in each case and the interaction between the complex and the CNT materials were studied with the aid of various characterization techniques such as TGA, XRD, and XPS. The results obtained in these experiments all indicated that the interaction between the complex and the CNT was greatly affected by the functionalization of the latter.

Application of µ-Nitrido- and µ-Carbido-Bridged Iron Phthalocyanine Dimers as Cathode-Active Materials for Rechargeable Batteries.

µ-Nitrido- and µ-carbido-bridged iron phthalocyanine dimers, when used as cathode-active materials for rechargeable lithium batteries, showed four stable redox waves in cyclic voltammetry studies in solution and a stable discharge capacity of approximately 60 mAh g-1 after 200 cycles. These results indicate that µ-heteroatom-bridged iron phthalocyanine dimers are good platforms for designing novel phthalocyanine-based electrode-active materials.

Tailoring spatial structure of electroactive biofilm for enhanced activity and direct electron transfer on iron phthalocyanine modified anode in microbial fuel cells.

Electroactive biofilm (EAB) has been considered as the core determining electricity generation in microbial fuel cells (MFCs), and its spatial structure regulation for enhanced activity and selectivity is of great concern. In this study, iron phthalocyanine (FePc) was introduced into a carbon cloth (CC) electrode, aiming at improving the affinity between the anode and outer membrane c-type cytochromes (OM c-Cyts) and achieving a highly active EAB. The FePc modified CC anode (FePc-CC) effectively improved the viability of EAB and enriched the Geobacter species up to 44.83% (FePc-CC) from 6.97% (CC). The FePc-CC anode achieved a much higher power density of 2419 mW m-2 than the CC (560 mW m-2) and a remarkable higher biomass loading of 2477.2 ± 84.5 µg cm-2 than the CC (749.3 ± 31.3 µg cm-2). As the charge transfer resistance was decreased by 58.6 times from 395.2 Ω (CC) to 6.74 Ω (FePc-CC), the interfacial reaction rate was accelerated and the direct electron transfer via OM c-Cyts was promoted. This work provides an effective method to improve the EAB activity by regulating its spatial structure, and opens the door toward the development of highly active EAB using metal phthalocyanines in MFCs.

Extended iron phthalocyanine islands self-assembled on a Ge(001):H surface.

Self-assembly of iron(II) phthalocyanine (FePc) molecules on a Ge(001):H surface results in monolayer islands extending over hundreds of nanometers and comprising upright-oriented entities. Scanning tunneling spectroscopy reveals a transport gap of 2.70 eV in agreement with other reports regarding isolated FePc molecules. Detailed analysis of single FePc molecules trapped at surface defects indicates that the molecules stay intact upon adsorption and can be manipulated away from surface defects onto a perfectly hydrogenated surface. This allows for their isolation from the germanium surface.

A Photoresponsive Nanozyme for Synergistic Catalytic Therapy and Dual Phototherapy.

Dual phototherapy, including photodynamic therapy (PDT) and photothermal therapy (PTT), has shown a great prospect in cancer treatment. However, its therapeutic effect is restricted by the depth of light penetration in tissue and tumor hypoxia environment. Herein, inspired by the specific response of nanozymes to the tumor microenvironment (TME), a simple and versatile nanozyme-mediated synergistic dual phototherapy nanoplatform (denoted as FePc/HNCSs) is constructed using hollow nitrogen-doped carbon nanospheres (HNCSs) and iron phthalocyanine (FePc). FePc/HNCSs simultaneously exhibit peroxidase (POD)- and catalase (CAT)-like activities, which not only can convert endogenous hydrogen peroxide (H2 O2 ) into highly toxic hydroxyl radicals (•OH) for catalytic therapy, but also decompose H2 O2 to oxygen (O2 ) to enhance O2 -dependent PDT. In addition, their enzyme-like activities are significantly enhanced under light irradiation. Combining with the excellent photothermal effect, FePc/HNCSs realize a high tumor inhibition rate of 96.3%. This strategy opens a new horizon for exploring a more powerful tumor treatment nanoplatform.

Dual-Regulation Strategy to Improve Anchoring and Conversion of Polysulfides in Lithium-Sulfur Batteries.

The sluggish reaction kinetics at the cathode/electrolyte interface of lithium-sulfur (Li-S) batteries limits their commercialization. Herein, we show that a dual-regulation system of iron phthalocyanine (FePc) and octafluoronaphthalene (OFN) decorated on graphene (Gh), denoted as Gh/FePc+OFN, accelerates the interfacial reaction kinetics of lithium polysulfides (LiPSs). Multiple in situ spectroscopy techniques and ex situ X-ray photoelectron spectroscopy combined with density functional theory calculations demonstrate that FePc acts as an efficient anchor and scissor for the LiPSs through Fe···S coordination, mainly facilitating their liquid-liquid transformation, whereas OFN enables Li-bond interaction with the LiPSs, accelerating the kinetics of the liquid-solid nucleation and growth of Li2S. This dual-regulation system promotes the smooth conversion reaction of sulfur, thereby improving the battery performance. A Gh/FePc+OFN-based Li-S cathode delivered an ultrahigh initial capacity of 1604 mAh g-1 at 0.2 C, with an ultralow capacity decay rate of 0.055% per cycle at 1 C over 1000 cycles.

FePc and FePcF16 on Rutile TiO2(110) and (100): Influence of the Substrate Preparation on the Interaction Strength.

Interface properties of iron phthalocyanine (FePc) and perfluorinated iron phthalocyanine (FePcF16) on rutile TiO2(100) and TiO2(110) surfaces were studied using X-ray photoemission spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and low-energy electron diffraction (LEED). It is demonstrated that the interaction strength at the interfaces is considerably affected by the detailed preparation procedure. Weak interactions were observed for all studied interfaces between FePc or FePcF16 and rutile, as long as the substrate was exposed to oxygen during the annealing steps of the preparation procedure. The absence of oxygen in the last annealing step only had almost no influence on interface properties. In contrast, repeated substrate cleaning cycles performed in the absence of oxygen resulted in a more reactive, defect-rich substrate surface. On such reactive surfaces, stronger interactions were observed, including the cleavage of some C-F bonds of FePcF16.

A simple and facile bioinspired catalytic strategy to decolorize dye wastewater by using metal octacarboxyphthalocyanine particles.

To explore the simple, facile, environmental friendly and low cost catalytic technique to decolorize harmful dye contaminants in solution and understand the mechanism is an interesting and practical research. In this paper, we provide a highly efficient and convenient method for fast decolorization of dyes (methylene blue and rhodamine B) in aqueous solution catalyzed by iron octacarboxyphthalocyanine (FeOCPc) or cobalt octacarboxyphthalocyanine (CoOCPc). Compared to the traditional methods, our method is very simple. The 30 mg/L methylene blue could be decolorized almost absolutely less than 30 min just by dispersing FeOCPc powders into the dye solution. The decolorization of rhodamine B at high concentration (30 mg/L) could be achieved to 100% decolorization degree less than 20 min in the presence of FeOCPc and tert-butyl hydroperoxide (BuOOH). Moreover, the ESR and HPLC-MS measurement were performed to determine the active radicals and various intermediates in decolorization processes and the possible catalytic mechanism was proposed. It is noted that both FeOCPc and CoOCPc catalysts show the different catalytic oxidation behaviors depending on the oxidant (O2 or BuOOH). Our investigation provides a novel, low cost and convenient strategy to purify the environmental pollutions.