Monodispersed Molecular Phthalocyanine with Sulfur-Driven Electron Delocalization for Enhanced Electrochemical Biosensing.

Heterogenizing the molecular catalysts on conductive scaffolds to achieve the isolated molecular dispersion and expected coordination structures is significant yet still challenging. Herein, a sulfur-driving strategy to anchor monodispersed cobalt phthalocyanine on nitrogen and sulfur co-doped graphene (NSG-CoPc) is demonstrated. Experimental and theoretical analysis prove that the incorporation of S dramatically improves the adsorption capability of NSG and evokes the monodispersion of the CoPc molecule, promoting the axial Co─N coordination and the electron delocalization of the Co catalytic center. Benefiting from the reduced activation energy barrier and boosted electron transfer, as well as the maximized active site utilization, NSG-CoPc exhibits outstanding H2O2 oxidization and sensing performance (used as a representative reaction). Moreover, the usage of NSG as a substrate can be readily extended to other metal (Ni, Cu, and Fe) phthalocyanine molecules with molecular-level dispersion. This work clarifies the mechanism of heteroatoms decoration and provides a new paradigm in devising monodispersed molecular catalysts with modulated chemical surroundings for broad applications.

Catalytic Degradation of Lignin over Sulfonyl-Chloride-Modified Lignin-Based Porous Carbon-Supported Metal Phthalocyanine: Effect of Catalyst Concentrations.

A sulfonyl-chloride-modified lignin-based porous carbon-supported metal phthalocyanine catalyst was prepared and used to replace the traditional Fenton's reagent for lignin degradation. The catalyst underwent a detailed characterization analysis in terms of functional group distributions, surface area, morphological structure, via FT-IR, XPS, BET, and SEM. The catalyst possessed a specific surface area of 638.98 m2/g and a pore volume of 0.291 cm3/g. The prepared catalyst was studied for its ability of oxidative degradation of lignin under different reaction conditions. By optimizing the reaction conditions, a maximum liquid product yield of 38.94% was obtained at 135 °C with 3.5 wt% of catalyst and 15 × 10-2 mol/L H2O2; at the same time, a maximum phenols selectivity of 32.58% was achieved. The compositions and properties of liquid products obtained from lignin degradation using different catalyst concentrations were studied comparatively via GC-MS, FT-IR, 1H-NMR, and EA. Furthermore, the structure changes of solid residues are also discussed.

Effects of Central Metal Ion on Binuclear Metal Phthalocyanine-Based Redox Mediator for Lithium Carbonate Decomposition.

Li2CO3 is the most tenacious parasitic solid-state product in lithium-air batteries (LABs). Developing suitable redox mediators (RMs) is an efficient way to address the Li2CO3 issue, but only a few RMs have been investigated to date, and their mechanism of action also remains elusive. Herein, we investigate the effects of the central metal ion in binuclear metal phthalocyanines on the catalysis of Li2CO3 decomposition, namely binuclear cobalt phthalocyanine (bi-CoPc) and binuclear cobalt manganese phthalocyanine (bi-CoMnPc). Density functional theory (DFT) calculations indicate that the key intermediate peroxydicarbonate (*C2O62-) is stabilized by bi-CoPc2+ and bi-CoMnPc3+, which is accountable for their excellent catalytic effects. With one central metal ion substituted by manganese for cobalt, the bi-CoMnPc's second active redox couple shifts from the second Co(II)/Co(III) couple in the central metal ion to the Pc(-2)/Pc(-1) couple in the phthalocyanine ring. In artificial dry air (N2-O2, 78:22, v/v), the LAB cell with bi-CoMnPc in electrolyte exhibited 261 cycles under a fixed capacity of 500 mAh g-1carbon and current density of 100 mA g-1carbon, significantly better than the RM-free cell (62 cycles) and the cell with bi-CoPc (193 cycles).

The Adsorption Mechanisms of SF6-Decomposed Species on Tc- and Ru-Embedded Phthalocyanine Surfaces: A Density Functional Theory Study.

Designing high-performance materials for the detection or removal of toxic decomposition gases of sulfur hexafluoride is crucial for both environmental monitoring and human health preservation. Based on first-principles calculations, the adsorption performance and gas-sensing properties of unsubstituted phthalocyanine (H2Pc) and H2Pc doped with 4d transition metal atoms (TM = Tc and Ru) towards five characteristic decomposition components (HF, H2S, SO2, SOF2, and SO2F2) were simulated. The findings indicate that both the TcPc and RuPc monolayers are thermodynamically and dynamically stable. The analysis of the adsorption energy indicates that H2S, SO2, SOF2, and SO2F2 underwent chemisorption on the TcPc monolayer. Conversely, the HF molecules were physisorbed through interactions with H atoms. The chemical adsorption of H2S, SO2, and SOF2 occurred on the RuPc monolayer, while the physical adsorption of HF and SO2F2 molecules was observed. Moreover, the microcosmic mechanism of the gas-adsorbent interaction was elucidated by analyzing the charge density differences, electron density distributions, Hirshfeld charges, and density of states. The TcPc and RuPc monolayers exhibited excellent sensitivity towards H2S, SO2, and SOF2, as evidenced by the substantial alterations in the band gaps and work functions of the TcPc and RuPc nanosheets. Our calculations hold significant value for exploring the potential chemical sensing applications of TcPc and RuPc monolayers in gas sensing, with a specific focus on detecting sulfur hexafluoride.

Electrocatalytic CO2 Upgrading to Triethanolamine by Bromine-Assisted C2 H4 Oxidation.

The electrocatalytic carbon dioxide (CO2 ) reduction is a promising approach for converting this greenhouse gas into value-added chemicals, while the capability of producing products with longer carbon chains (Cn >3) is limited. Herein, we demonstrate the Br-assisted electrocatalytic oxidation of ethylene (C2 H4 ), a major CO2 electroreduction product, into 2-bromoethanol by electro-generated bromine on metal phthalocyanine catalysts. Due to the preferential formation of Br2 over *O or Cl2 to activate the C=C bond, a high partial current density of producing 2-bromoethanol (46.6 mA⋅cm-2 ) was obtained with 87.2 % Faradaic efficiency. Further coupling with the electrocatalytic nitrite reduction to ammonia at the cathode allowed the production of triethanolamine with six carbon atoms. Moreover, by coupling a CO2 electrolysis cell for in situ C2 H4 generation and a C2 H4 oxidation/nitrite reduction cell, the capability of upgrading of CO2 and nitrite into triethanolamine was demonstrated.

Nanostructured transition-metal phthalocyanine complexes for catalytic oxygen reduction reaction.

Oxygen reduction reaction (ORR) plays a key role in the field of fuel cells. Efficient electrocatalysts for the ORR are important for fuel cells commercialization. Pt and its alloys are main active materials for ORR. However, their high cost and susceptibility to time-dependent drift hinders their applicability. Satisfactory catalytic activity of nanostructured transition metal phthalocyanine complexes (MPc) in ORR through the occurrence of molecular catalysis on the surface of MPc indicates their potential as a replacement material for precious-metal catalysts. Problems of MPc are analyzed on the basis of chemical structure and microstructure characteristics used in oxygen reduction catalysis, and the strategy for controlling the structure of MPc is proposed to improve the catalytic performance of ORR in this review.

Topological Band Engineering of Lieb Lattice in Phthalocyanine-Based Metal-Organic Frameworks.

Topological properties of the Lieb lattice, i.e., the edge-centered square lattice, have been extensively studied and are, however, mostly based on theoretical models without identifying real material systems. Here, based on tight-binding and first-principles calculations, we demonstrate the Lieb-lattice features of the experimentally synthesized phthalocyanine-based metal-organic framework (MPc-MOF), which holds various intriguing topological phase transitions through band engineering. First, we show that the MPc-MOFs indeed have a peculiar Lieb band structure with 1/3 filling, which has been overlooked because of its unconventional band structure deviating from the ideal Lieb band. The intrinsic MPc-MOF presents a trivial insulating state, with its gap size determined by the on-site energy difference (ΔE) between the corner and edge-center sites. Through either chemical substitution or physical strain engineering, one can tune ΔE to close the gap and achieve a topological phase transition. Specifically, upon closing the gap, topological semimetallic/insulating states emerge from nonmagnetic MPc-MOFs, while magnetic semimetal/Chern insulator states arise from magnetic MPc-MOFs, respectively. Our discovery greatly enriches our understanding of the Lieb lattice and provides a guideline for experimental observation of the Lieb-lattice-based topological states.

Metal Oxide/Nitrogen-Doped Carbon Nanosheet Heteronanostructures as Highly Efficient Electromagnetic Wave Absorbing Materials.

In this paper, we will discuss the excellent broadband microwave absorption behaviors of Cu/CuO/carbon nanosheet composites: traces of copper and oxide embedded in a carbon nano-sheet not only cut down the high permittivity of adsorbs but also induce more interfacial polarization centers. The results showed that at a cracking temperature of 900 °C, the fabricated material has a unique ripple-like structure, which promotes the hierarchical interfacial polarization. The prepared material has a maximum absorption bandwidth of 4.48 GHz at an exceedingly thin thickness of 1.7 mm and a maximum reflection loss of -25.3 dB at a thickness of 2 mm. It is a relatively ideal material for electromagnetic wave absorption.

Revealing the Impact of Aging on Perovskite Solar Cells Employing Nickel Phthalocyanine-Based Hole Transporting Material.

The enhancement of the photovoltaic performance upon the aging process at particular environment is often observed in perovskite solar cells (PSCs), particularly for the devices with 2,2',7,7'-tetrakis(N,N-di(4-methoxyphenyl)amino)-9,9'-spirobifluorene (spiro-OMeTAD) as hole transporting material (HTM). In this work, for the first time the effect of aging the typical n-i-p PSCs employing nickel phthalocyanine (coded as Bis-PF-Ni) solely as dopant-free HTM is investigated and as an additive in spiro-OMeTAD solution. This study reveals that the prolong aging of these devices at dry air condition (RH = 2%, 25 °C) is beneficial for the improvement of their performances. Various bulk and surface characterization techniques are utilized to understand the factors behind the spontaneous efficiency enhancement of the devices after storage. As a result, the changes in properties of the Bis-PF-Ni layer are observed and at perovskite/Bis-PF-Ni interface, which ultimately improves the charge transport and reduces non-radiative recombination. In addition, the devices with Bis-PF-Ni HTM reveal enhanced long-term ambient and thermal stability compared to the PSCs based on doped spiro-OMeTAD.

Homogeneous Adsorption of Multiple Potassiation Products of Red Phosphorus Anode toward Stable Potassium Storage.

Potassium ion batteries (PIBs) are a viable alternative to lithium-ion batteries for energy storage. Red phosphorus (RP) has attracted a great deal of interest as an anode for PIBs owing to its cheapness, ideal electrode potential, and high theoretical specific capacity. However, the direct preparation of phosphorus-carbon composites usually results in exposure of the RP to the exterior of the carbon layer, which can lead to the deactivation of the active material and the production of "dead phosphorus". Here, the advantage of the π-π bond conjugated structure and high catalytic activity of metal phthalocyanine (MPc) is used to prepare MPc@RP/C composites as a highly stable anode for PIBs. It is shown that the introduction of MPc greatly improves the uneven distribution of the carbon layer on RP, and thus improves the initial Coulombic efficiency (ICE) of PIBs (the ICE of FePc@RP/C is 75.5% relative to 62.9% of RP/C). The addition of MPc promotes the growth of solid electrolyte interphase with high mechanical strength, improving the cycle stability of PIBs (the discharge-specific capacity of FePc@RP/C is 411.9 mAh g-1 after 100 cycles at 0.05 A g-1). Besides, density functional theory theoretical calculations show that MPc exhibits homogeneous adsorption energies for multiple potassiation products, thereby improving the electrochemical reactivity of RP. The use of organic molecules with high electrocatalytic activity provides a universal approach for designing superior high-capacity, large-volume expansion anodes for PIBs.

Manganese(III) Phthalocyanine Complex Nanoparticle-Loaded Glucose Oxidase to Enhance Tumor Inhibition through Energy Metabolism and Macrophage Polarization.

Elevated levels of reactive oxygen species (ROS) have demonstrated efficacy in eliminating tumor cells by modifying the tumor microenvironment and inducing the polarization of tumor-associated macrophages (TAMs). Nevertheless, the transient nature and limited diffusion distance inherent in ROS present significant challenges in cancer treatment. In response to these limitations, we have developed a nanoparticle (MnClPc-HSA@GOx) that not only inhibits tumor energy metabolism but also facilitates the transition of TAMs from the M2 type (anti-inflammatory type) to the M1 type (proinflammatory type). MnClPc-HSA@GOx comprises a manganese phthalocyanine complex (MnClPc) enveloped in human serum albumin (HSA), with glucose oxidase (GOx) loaded onto MnClPc@HSA nanoparticles. GOx was employed to catalyze the decomposition of glucose to produce H2O2 and gluconic acid. Additionally, in the presence of MnClPc, it catalyzes the conversion of H2O2 into •O2- and 1O2. Results indicate that the nanoparticle effectively impedes the glucose supply to tumor cells and suppresses their energy metabolism. Simultaneously, the ROS-mediated polarization of TAMs induces a shift from M2 to M1 macrophages, resulting in a potent inhibitory effect on tumors. This dual-action strategy holds promising clinical inhibition applications in the treatment of cancer.

A Study on the Mechanism and Properties of a Self-Powered H2O2 Electrochemical Sensor Based on a Fuel Cell Configuration with FePc and Graphene Cathode Catalyst Materials.

Conventional electrochemical sensors use voltammetric and amperometric methods with external power supply and modulation systems, which hinder the flexibility and application of the sensors. To avoid the use of an external power system and to minimize the number of electrochemical cell components, a self-powered electrochemical sensor (SPES) for hydrogen peroxide was investigated here. Iron phthalocyanine, an enzyme mimetic material, and Ni were used as a cathode catalyst and an anode material, respectively. The properties of the iron phthalocyanine catalyst modified by graphene nanoplatelets (GNPs) were investigated. Open circuit potential tests demonstrated the feasibility of this system. The GNP-modulated interface helped to solve the problems of aggregation and poor conductivity of iron phthalocyanine and allowed for the achievement of the best analytical characteristics of the self-powered H2O2 sensor with a low detection limit of 0.6 µM and significantly higher sensitivity of 0.198 A/(M·cm2) due to the enhanced electrochemical properties. The SPES demonstrated the best performance at pH 3.0 compared to pH 7.4 and 12.0. The sensor characteristics under the control of external variable load resistances are discussed and the cell showed the highest power density of 65.9 µW/cm2 with a 20 kOhm resistor. The practical applicability of this method was verified by the determination of H2O2 in blood serum.

Floating metal phthalocyanine@polyacrylonitrile nanofibers for peroxymonosulfate activation: Synergistic photothermal effects and highly efficient flowing wastewater treatment.

Highly efficient floating photocatalysis has potential applications in organic pollutant treatment but remains limited by low degradation efficiency in practical applications. By introducing the photothermal effect into a peroxymonosulfate (PMS) coupled photocatalysis system, tetracycline hydrochloride (TCH) degradation could be significantly enhanced using floating metal phthalocyanine@polyacrylonitrile (MPc@PAN) nanofiber mats. MPc@PAN nanofibers with different metal centers showed similar photothermal conversion performance but different activation energies for PMS activation, resulting in metal-center-dependent synergistic photothermal effects, i.e., light-enhanced dominated, thermal-enhanced dominated, and conjointly light-thermal dominated mechanisms. The porous structures and floating ability of the FePc@PAN nanofibers provided a fast mass transfer process, with higher solar energy utilization and superior photothermal conversion performance than the FePc nanopowders. Meanwhile, the FePc@PAN nanofibers showed excellent TCH removal stability within 10 cycles (>92%) and extremely low Fe ion leaching (<0.055 mg/L) in a dual-channel flowing wastewater treatment system. This work provides new insight into PMS activation via photothermal effects for environmental remediation.

Promoting Oxygen Reduction Reaction by Inducing Out-of-Plane Polarization in a Metal Phthalocyanine Catalyst.

Metal phthalocyanine (MPc) material with a well-defined MN4 moiety offers a platform for catalyzing the oxygen reduction reaction (ORR), while the practical performance is often limited by the insufficient O2 adsorption due to the planar MN4 configuration. Here, a design (called Gr-MG -O-MP Pc) is proposed, where the metal of MPc (MP ) is axially coordinated to a single metal atom in graphene (Gr-MG ) through a bridge-bonded oxygen atom (O), introducing effective out-of-plane polarization to promote O2 adsorption on MPc. Manipulating the out-of-plane polarization charge by varying types of MP and MG (MP  = Fe/Co/Ni, MG  = Ti/V/Cr/Mn/Fe/Co/Ni) in the axial coordination zone of -MG -O-MP - are examined by density functional theory simulations. Among them, the catalyst of Gr-V-O-FePc stands out with the highest calculated O2 adsorption energy, which is synthesized successfully and verified by systemic X-ray absorption spectroscopy measurements. Importantly, it delivers a remarkable ORR performance with half-wave potential of 0.925 V (versus reversible hydrogen electrode) and kinetic current density of 26.7 mA cm-2 . This thus demonstrates a new and simple way to pursue high catalytic performance by inducing out-of-plane polarization in catalysts.

Iron, Cobalt, and Nickel Phthalocyanine Tri-Doped Electrospun Carbon Nanofibre-Based Catalyst for Rechargeable Zinc-Air Battery Air Electrode.

The goal of achieving the large-scale production of zero-emission vehicles by 2035 will create high expectations for electric vehicle (EV) development and availability. Currently, a major problem is the lack of suitable batteries and battery materials in large quantities. The rechargeable zinc-air battery (RZAB) is a promising energy-storage technology for EVs due to the environmental friendliness and low production cost. Herein, iron, cobalt, and nickel phthalocyanine tri-doped electrospun carbon nanofibre-based (FeCoNi-CNF) catalyst material is presented as an affordable and promising alternative to Pt-group metal (PGM)-based catalyst. The FeCoNi-CNF-coated glassy carbon electrode showed an oxygen reduction reaction/oxygen evolution reaction reversibility of 0.89 V in 0.1 M KOH solution. In RZAB, the maximum discharge power density (Pmax) of 120 mW cm-2 was obtained with FeCoNi-CNF, which is 86% of the Pmax measured with the PGM-based catalyst. Furthermore, during the RZAB charge-discharge cycling, the FeCoNi-CNF air electrode was found to be superior to the commercial PGM electrocatalyst in terms of operational durability and at least two times higher total life-time.

Preparation of graphene-supported-metal-phthalocyanine and mechanistic understanding of its catalytic nature at molecular level.

The fundamental mechanistic understanding of the working principle of metal phthalocyanine (MPc) + H2O2 system, at molecular level, is in its nascent stage. In this paper, a green strategy was employed for the immobilization of sulfonated cobalt phthalocyanine (CoPc) onto reduced graphene with assistance of bio-synthesized nanocellulose, and the resulting graphene-supported-CoPc (CoPc&G) was applied for the catalytic degradation of phenol solution with H2O2 as oxidant. More than 90% of phenol can be removed within 75 min, and the existence of graphene clearly has a positive effect on the catalytic activity. Theoretical calculations were conducted to unveil the catalytic nature of CoPc&G. H2O2 was favorably chemisorbed onto CoPc&G in the form of OOH-, hydroxyl radicals were favorably formed by homolytic cleavage of OO bonds, and ΔG value for the formation of reactive species was decreased with the existence of graphene. Density of states (DOS) analysis shows that graphene could effectively boost the electronic activity, reduce HOMO-LUMO gap, and strengthen the polarizability of the catalyst, thereby lower the free energy gap for the enhanced generation of reactive species. A detailed catalytic degradation route of phenol with CoPc&G + H2O2 system was established based on the combination of theoretical calculations and experimental results.

The excited state behavior of Group IA alkaline-metal phthalocyanines revealed by photoluminescence and singlet oxygen formation.

Group IA alkaline-metal phthalocyanine (Pc) complexes (Li2Pc, Na2Pc, K2Pc, Rb2Pc, Cs2Pc) have been synthesized and purified to study their excited state behavior. Their UV-Vis electronic absorption spectra, fluorescence emission and excitation spectra, fluorescence quantum yields and lifetimes, as well as singlet oxygen formation quantum yields have been measured in DMF. These photophysical properties are compared with that of H2Pc. The fluorescence and singlet oxygen formation properties reveal that alkaline metal Pcs show weak heavy atom effect. The results also reveal that alkaline-metal Pcs (Na2Pc, K2Pc, Rb2Pc, and Cs2Pc) show very different excited singlet state (S1) behavior from that of Li2PC and H2Pc. While S1 decay of Li2PC is mainly via intersystem crossing and fluorescence, the S1 decay of M2Pc (M = Na, K, Rb, Cs) is mainly metal ion dissociation: M2Pc(S1) â†’ 2 M+ + [Pc]2-(S1), in addition to the intersystem crossing.

Electrochemical Sensors for Determination of Bromate in Water and Food Samples-Review.

The application of potassium bromate in the baking industry is used in most parts of the world to avert the human health compromise that characterizes bromates carcinogenic effect. Herein, various methods of its analysis, especially the electrochemical methods of bromate detection, were extensively discussed. Amperometry (AP), cyclic voltammetry (CV), square wave voltammetry (SWV), electrochemiluminescence (ECL), differential pulse voltammetry and electrochemical impedance spectroscopy (EIS) are the techniques that have been deployed for bromate detection in the last two decades, with 50%, 23%, 7.7%, 7.7%, 7.7% and 3.9% application, respectively. Despite the unique electrocatalytic activity of metal phthalocyanine (MP) and carbon quantum dots (CQDs), only few sensors based on MP and CQDs are available compared to the conducting polymers, carbon nanotubes (CNTs), metal (oxide) and graphene-based sensors. This review emboldens the underutilization of CQDs and metal phthalocyanines as sensing materials and briefly discusses the future perspective on MP and CQDs application in bromate detection via EIS.

Ultrahigh Spin Filter Efficiency, Giant Magnetoresistance and Large Spin Seebeck Coefficient in Monolayer and Bilayer Co-/Fe-/Cu-Phthalocyanine Molecular Devices.

The spin related electrical and thermoelectric properties of monolayer and bilayer MPc (M = Co, Fe, Cu) molecular devices in a parallel spin configuration (PC) and an anti-parallel spin configuration (APC) between the V-shaped zigzag-edged graphene nanoribbon electrodes and the center bilayer MPc molecules are investigated by combining the density functional theory and non-equilibrium Green's function approaches. The results show that there is an ultrahigh spin filter efficiency exceeding 99.99995% and an ultra-large total conductance of 0.49996G0 for FePc-CoPc molecular devices in the PC and a nearly pure charge current at high temperature in the APC and a giant MR ratio exceeding 9.87 × 106% at a zero bias. In addition, there are pure spin currents for CuPc and FePc molecular devices in the PC, and an almost pure spin current for FePc molecular devices in the APC at some temperature. Meanwhile, there is a high SFE of about 99.99585% in the PC and a reserved SFE of about -19.533% in the APC and a maximum MR ratio of about 3.69 × 108% for the FePc molecular device. Our results predict that the monolayer and bilayer MPc (M = Co, Fe, Cu) molecular devices possess large advantages in designing high-performance electrical and spintronic molecular devices.

Theoretical investigation of the interaction between the metal phthalocyanine [MPc]a(M = Sc, Ti, and V; a = -1, 0, and +1) complexes and formaldehyde.

Formaldehyde (FA, CH2O) is one of the toxic volatile organic compounds that cause harmful effects on the human body. In this work, the interaction of FA gas with metal phthalocyanine (MPc) molecules was studied by employing density functional theory calculations. A variety of [MPc]a (M = Sc, Ti, and V; a = -1, 0, and +1) complexes were studied, and the electronic properties, interaction energies, and charge transfer properties of all of the studied molecules were systematically discussed. Among the studied complexes, the Sc and Ti phthalocyanines were more reactive toward the adsorption of FA gas. Moreover, it was revealed that the interaction of the [ScPc]+1 and [TiPc]0 complexes with the CH2O molecule was stronger, in which the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap of 46% and 36% decreased after FA adsorption. The results indicated that the MPc-based materials may be a promising candidate for the detection of FA gas.