Search Results (53)

With increasing energy demands, fuel cells are a popular avenue for portability and low waste emissions. Hydrogen fuel cells are popular due to their potential output power and clean waste. However, due to storage and transport concerns, hydrogen peroxide fuel cells are a promising alternative. Although they have a lower output potential compared to hydrogen fuel cells, peroxide can act as both the oxidizing and reducing agent, simplifying the structure of the cell. In addition to reducing the complexity, hydrogen peroxide is stable in liquid form and can be stored in less demanding methods. This paper investigates chelated metals as electrode material for hydrogen peroxide fuel cells. Chelated metal complexes are ring-like structures that form from binding organic or inorganic compounds with metal ions. They are used in medical imaging, water treatment, and as catalysts for reactions. Copper(II) phthalocyanine, phthalocyanine green, poly(copper phthalocyanine), bis(ethylenediamine)copper(II) hydroxide, iron(III) ferrocyanine, graphene oxide decorated with Fe₃O₄, zinc phthalocyanine, magnesium phthalocyanine, manganese(II) phthalocyanine, cobalt(II) phthalocyanine are investigated as electrode materials for peroxide fuel cells. In this study, the performance of these materials is evaluated using cyclic voltammetry. The voltammograms are compared, as well as observations are made during the materials’ use to measure their effectiveness as electrode material. There has been limited research comparing the use of these chelated metals in the context of hydrogen peroxide fuel cells. Through this research, the goal is to further the viability of hydrogen peroxide fuel cells. Poly(copper phthalocyanine) and graphene oxide doped with iron oxides had strong redox catalytic activity for use in acidic peroxide single-compartment fuel cells, where the poly(copper phthalocyanine) electrode compound generated the highest peak power density of 7.92 mW/cm² and cell output potential of 0.634 V. Full article

Developing novel gas-sensing materials is critical for overcoming the limitations of current metal oxide semiconductor technologies, which, despite their widely commercial use, require high operating temperatures to achieve optimal performance. In this context, integrating graphene with molecular organic layers provides a promising platform for next-generation gas-sensing materials. In this work, we systematically explore the gas-sensing properties of metal phthalocyanine/graphene (MPc/Gr) interfaces using density functional theory calculations. Specifically, we examine the role of different MPcs (FePc, CoPc, NiPc, and CuPc) and Gr doping levels (p-doped, neutral, and n-doped) in the detection of NH₃ and NO₂ molecules, used as representative electron-donor and -acceptor testing gases, respectively. Our results reveal that a p-doped Gr is necessary for NH₃ detection, while the choice of metal cation plays a crucial role in determining sensitivity, following the trend FePc/Gr > CoPc/Gr > NiPc/Gr, with CuPc/Gr exhibiting no response. Remarkably, FePc/Gr demonstrates sensitivity down to the limit of a single NH₃ molecule per FePc. Conversely, NO₂ detection is possible under both neutral and n-doped Gr, with the strongest response observed for n-doped FePc/Gr and CoPc/Gr. Crucially, we identify the d_z2 orbital of the MPc as a key factor in mediating charge transfer between the gas molecule and Gr, governing the electronic interactions that drive the sensing response. These insights provide valuable guidelines for the rational design of high-sensitivity graphene-based gas sensors. Full article

Developing low-cost, efficient, and scalable non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) remains a critical challenge in the field of energy conversion. Among various candidates, Fe-N-doped carbon materials have garnered attention as promising alternatives to commercial Pt/C catalysts for ORR. In this study, we report an Fe-N catalyst synthesized by incorporating iron phthalocyanine with Cinnamomum longepaniculatum waste leaves as the carbon source. This catalyst exhibited an excellent four-electron ORR activity and the half-wave potential (E_1/2) reaches 0.875 V, which was superior to that of commercial Pt/C (E_1/2 = 0.864 V). Additionally, the catalyst exhibits superior methanol tolerance and stability compared to commercial Pt/C. This approach, which utilizes biomass waste for the synthesis of electrocatalysts, not only provides an effective solution for reducing environmental waste but also addresses the issue of sluggish cathodic ORR kinetics in fuel cells, making it suitable for low-cost, large-scale industrial production. Full article

Ascorbic acid (AA) and glutathione (GSH) play a pivotal role in health assessment, drug development, and quality control of nutritional supplements. The development of a new and efficient method for their detection is highly desired. In this work, we fabricated magnetic core–shell nanocomposites (Fe₃O₄@MnPc-NDs) by a one-pot hydrothermal method with citric acid and manganese tetraamino phthalocyanine (MnTAPc) as precursors. Fe₃O₄@MnPc-NDs exhibited enhanced peroxidase activity compared to bare Fe₃O₄ nanoparticles, enabling catalytic oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) to blue ox-TMB in the presence of H₂O₂. Leveraging the antioxidant properties of AA/GSH to reduce ox-TMB, a colorimetric assay achieved a low detection limit of 0.161 μM for AA and 0.188 μM for GSH with broad linear ranges. Moreover, this method displayed high specificity against 12 interfering substances and excellent recyclability (>90% activity after five cycles). Finally, the Fe₃O₄@MnPc-NDs could act as an efficient colorimetric sensor for accurately detecting AA in genuine VC tablets and GSH in whitening serums with high accuracy. Therefore, Fe₃O₄@MnPc-NDs exhibited great potential in bioassay applications, benefiting from their outstanding sensitivity and high recycling rate. Full article

In the quest for more sensitive gas sensors, researchers have studied how heating the sensors, using UV light, and thermally annealing sensors improve performance. During thermal annealing, the heating process can improve the crystallinity of the material while also increasing the electrode and sensing material interactions to create more available active sites and thus improve sensor performance. Hexadecafluorinated iron (II) phthalocyanine (FePcF₁₆) nanowires have high sensitivity towards NH₃ selectively, and thermally annealing the NWs after the deposition can further improve the sensing response and recovery. For this reason, the effect of annealing FePcF₁₆ NWs at different temperatures was studied to optimize these systems. In this work, FePcF₁₆ NWs were synthesized using physical vapor deposition (PVD) to deposit on interdigitated electrodes. The NWs were characterized by SEM, EDS, PXRD, FTIR, and Raman spectroscopy to confirm their purity. The sensors were annealed at different temperatures, inserted into a gas sensing chamber, and exposed to 1 ppm NH₃ in air, and the electrical current was measured. The results show that the optimized FePcF₁₆ NWs have excellent sensing properties, with a 58% increase in response towards NH₃ after a stepwise annealing at 300 °C confirming these systems are good prospective candidates for sensing NH₃ at room temperature. Full article

As a promising structure for fabricating inorganic—organic-based optoelectronic devices, metal—metallophthalocyanine (MPc) hybrid layers are highly important to be considered. The efficient charge injection and transport across the metal/MPc interface are strictly dependent on the precise molecular orientation of the MPcs. Therefore, the efficiency of MPc-based optoelectronic devices strictly depends on the adsorption and orientation of the organic MPc on the inorganic metal substrate. The current review aims to explore the effect of the terminated atoms or surface atoms as an internal stimulus on molecular adsorption and orientation. Here, we investigate the adsorption of five different phthalocyanine molecules—free-based phthalocyanine (H₂Pc), copper phthalocyanine (CuPc), iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), vanadyl phthalocyanine (VOPc)—on three metallic substrates: gold (Au), silver (Ag), and copper (Cu). This topic can guide new researchers to find out how molecular adsorbance and orientation determine the electronic structure by considering the surface–molecule interactions. Full article

Phthalocyanine-sensitized TiO₂ significantly enhances photocatalytic performance, but the method of phthalocyanine immobilization also plays a crucial role in its performance. In order to investigate the effect of the binding strategy of phthalocyanine and TiO₂ on photocatalytic performance, a dual-pathway study has been conducted. On the one hand, zinc-tetra (N-carbonylacrylic) aminephthalocyanine (Pc) was directly grafted onto the surface of Fe₃O₄@SiO₂@TiO₂ (FST). On the other hand, Pc was immobilized on a silane coupling agent ((3-aminopropyl) triethoxysilane) grafted onto the surface of the FST. Through photocatalytic experiments on the two types of composite materials synthesized, the results showed that the photocatalyst obtained by directly sensitizing Pc (FSTP) exhibited better performance on rhodamine B(RhB) removal than did the other photocatalyst using the silane coupling agent (FSTAP). Further mechanistic studies showed that directly sensitized FSTP exhibited more efficient photogenerated electron–hole pair separation, whereas FSTAP linked by a silane coupling agent created an additional transport distance that might greatly affect the photogenerated electron transport. Therefore, the dual-pathway research in this work provides new guidance for efficiently constructing phthalocyanine-sensitized TiO₂ photocatalysts. Full article

A series of composites was prepared starting from five types of LDHs, which were then exchanged with three types of metallo-phthalocyanines, and, in the end, magnetic nanoparticles were attached. In the case of LDHs containing Fe, characterization data showed that there was a partial oxidation from Fe²⁺ to Fe³⁺. Samples containing evident LDH structures performed better in general than the ones containing iron oxide mixtures, the composites being more active towards amoxicillin removal compared with ampicillin removal. The nature of the phthalocyanine did not have such a great influence, although some differences in the activity were observed. The removal was a combination between adsorption and photocatalytic degradation. The best composites for this application were those based on Mg_0.325Fe_0.325Al_0.25-LDH prepared by co-precipitation in the presence of NaOH and Na₂CO₃. They presented high adsorption capacity in 10 min and, at the same time, high photocatalytic activity for both amoxicillin and ampicillin. Full article

In this paper, iron phthalocyanine nanowires on a nickel foam (FePc@NF) composite catalyst were prepared by a facile solvothermal approach. The catalyst showed good electrochemical oxygen evolution performance. In 1.0 M KOH electrolyte, 289 mV low overpotential and 49.9 mV dec⁻¹ Tafel slope were seen at a current density of 10 mA cm⁻². The excellent electrochemical performance comes from the homogeneous dispersion of phthalocyanine nanostructures on the surface of the nickel foam, which avoids the common agglomeration problem of such catalysts and provides a large number of active sites for the OER reaction, thus improving the catalytic performance of the system. Full article

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. Full article

Microbial fuel cells (MFCs) are sustainable energy recovery systems because they use organic waste as biofuel. Using critical raw materials (CRMs), like platinum-group metals, at the cathode side threatens MFC technology’s sustainability and raises costs. By developing an efficient electrode design for MFC performance enhancement, CRM-based cathodic catalysts should be replaced with CRM-free materials. This work proposes developing and optimizing iron-based air cathodes for enhancing oxygen reduction in MFCs. By subjecting iron phthalocyanine and carbon black pearls to controlled thermal treatments, we obtained Fe-based electrocatalysts combining high surface area (628 m² g⁻¹) and catalytic activity for O₂ reduction at near-neutral pH. The electrocatalysts were integrated on carbon cloth and carbon paper to obtain gas diffusion electrodes whose architecture was optimized to maximize MFC performance. Excellent cell performance was achieved with the carbon-paper-based cathode modified with the Fe-based electrocatalysts (maximum power density-PD_max = 1028 mWm⁻²) compared to a traditional electrode design based on carbon cloth (619 mWm⁻²), indicating the optimized cathodes as promising electrodes for energy recovery in an MFC application. Full article

Currently, photocatalysis of the two-dimensional (2D) conjugated phthalocyanine framework with a single Fe atom (CPF-Fe) has shown efficient photocatalytic activities for the removal of harmful effluents and antibacterial activity. Their photocatalytic mechanisms are dependent on the redox reaction—which is led by the active species generated from the photocatalytic process. Nevertheless, the molecular mechanism of CPF-Fe antimicrobial activity has not been sufficiently explored. In this study, we successfully synthesized CPF-Fe with great broad-spectrum antibacterial properties under visible light and used it as an antibacterial agent. The molecular mechanism of CPF-Fe against Escherichia coli and Salmonella enteritidis was explored through multi-omics analyses (transcriptomics and metabolomics correlation analyses). The results showed that CPF-Fe not only led to the oxidative stress of bacteria by generating large amounts of h⁺ and ROS but also caused failure in the synthesis of bacterial cell wall components as well as an osmotic pressure imbalance by disrupting glycolysis, oxidative phosphorylation, and TCA cycle pathways. More surprisingly, CPF-Fe could disrupt the metabolism of amino acids and nucleic acids, as well as inhibit their energy metabolism, resulting in the death of bacterial cells. The research further revealed the antibacterial mechanism of CPF-Fe from a molecular perspective, providing a theoretical basis for the application of CPF-Fe photocatalytic antibacterial nanomaterials. Full article

Cyclic tetrapyrrole derivatives such as porphyrins, chlorins, corrins (compounds with a corrin core), and phthalocyanines are a family of molecules containing four pyrrole rings usually coordinating a metal ion (Mg, Cu, Fe, Zn, etc.). Here, we report the characterization of some representative cyclic tetrapyrrole derivatives by MALDI-ToF/ToF MS analyses, including heme b and c, phthalocyanines, and protoporphyrins after proper matrix selection. Both neutral and acidic matrices were evaluated to assess potential demetallation, adduct formation, and fragmentation. While chlorophylls exhibited magnesium demetallation in acidic matrices, cyclic tetrapyrroles with Fe, Zn, Co, Cu, or Ni remained steadfast against demetallation across all conditions. Phthalocyanines and protoporphyrins were also detectable without a matrix using laser desorption ionization (LDI); however, the incorporation of matrices achieved the highest ionization yield, enhanced sensitivity, and negligible fragmentation. Three standard proteins, i.e., myoglobin, hemoglobin, and cytochrome c, were analyzed either intact or enzymatically digested, yielding heme b and heme c ions along with accompanying peptides. Furthermore, we successfully detected and characterized heme b in real samples, including blood, bovine and cod liver, and mussel. As a result, MALDI MS/MS emerged as a powerful tool for straightforward cyclic tetrapyrrole identification, even in highly complex samples. Our work paves the way for a more comprehensive understanding of cyclic tetrapyrroles in biological and industrial settings, including the geochemical field, as these compounds are a source of significant geological and geochemical information in sediments and crude oils. Full article

A detailed inverse photoemission study unveils the unoccupied electronic structure induced by the adsorption of CuPc and CoPc phthalocyanines on Au(110) reconstructed channels. The different behavior in the two systems is related to the different intermixing of orbitals with the underlying gold states. Broadening of the density of states at the Fermi level is detected after CoPc adsorption, absent in the case CuPc. A detailed comparison with the element-selective X-ray absorption spectroscopy enlightens and complements the IPES results and confirms a surface-driven intermixing of the CoPc orbitals involved in the interaction, with the out-of-plane Co 3d_z² orbital strongly hybridized with the gold electronic states. Moreover, the contribution of the 3d empty states to the IPES data is reported for FePc, CoPc, and CuPc thin films. Full article