Metal Insertion Research Articles

Porous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.

Porphyrin‐based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co‐crystallisation of tetraphenylporphyrin (TPP) with octa(2’,6’‐di‐isopropylphenoxy) phthalocyanine or some of its metal complexes [(dipPhO)8PcM; M = H2, Al‐OH, Ti=O, Mn‐Cl, Fe‐Cl, Co, Ni, Cu, Zn, Ga‐Cl, Ag, In‐Cl or Au‐Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)8PcM, which is driven by the complementary shape and symmetry of the two macrocycles. The (dipPhO)8PcM component directs the crystal structure of the heterodimers to form Phthalocyanine Nanoporous Crystals (PNCs) of similar structure to those formed by (dipPhO)8PcM alone. The incorporation of TPP appears to partially stabilise the PNCs towards the removal of included solvent and for cocrystals containing (dipPhO)8PcCo stability can be enhanced further by the in‐situ addition of 4,4‐bipyridyl to act as a “molecular wall tie”. These stabilised PNC/TPP cocrystals have a Brunauer‐Emmett‐Teller surface area (SABET) of 454 m2 g‐1 and a micropore volume (Vmp) of 0.22 ml g‐1. The reactivity of both macrocycles within the PNC/TPP co‐crystals are demonstrated by in‐situ metal insertion.

Porous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.

Porphyrin-based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co-crystallisation of tetraphenylporphyrin (TPP) with octa(2',6'-di-isopropylphenoxy) phthalocyanine or some of its metal complexes [(dipPhO)8PcM; M = H2, Al-OH, Ti=O, Mn-Cl, Fe-Cl, Co, Ni, Cu, Zn, Ga-Cl, Ag, In-Cl or Au-Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)8PcM, which is driven by the complementary shape and symmetry of the two macrocycles. The (dipPhO)8PcM component directs the crystal structure of the heterodimers to form Phthalocyanine Nanoporous Crystals (PNCs) of similar structure to those formed by (dipPhO)8PcM alone. The incorporation of TPP appears to partially stabilise the PNCs towards the removal of included solvent and for cocrystals containing (dipPhO)8PcCo stability can be enhanced further by the in-situ addition of 4,4-bipyridyl to act as a "molecular wall tie". These stabilised PNC/TPP cocrystals have a Brunauer-Emmett-Teller surface area (SABET) of 454 m2 g-1 and a micropore volume (Vmp) of 0.22 ml g-1. The reactivity of both macrocycles within the PNC/TPP co-crystals are demonstrated by in-situ metal insertion.

Eliminating metal artifacts in dental computed tomography using an elaborate sinogram normalization interpolation method with CNR-based metal segmentation

Metal artifact reduction (MAR) in dental cone-beam computed tomography (CBCT) is critical for improving its clinical usefulness and remains a challenging problem. This study presents an elaborate sinogram normalization interpolation (SNI) method with contrast-to-noise ratio (CNR)-based metal segmentation to eliminate metal artifacts in dental CBCT. The proposed MAR method involves three main steps: (1) CNR-based segmentation of a metal trace in the sinogram domain; (2) generation of a residual artifact-reduced prior sinogram; and (3) sinogram completion using the prior sinogram, followed by filtered-backprojection (FBP)-based CBCT reconstruction and metal insertion processes. To verify the efficacy of the proposed method, simulations and experiments were performed using numerical and physical dental phantoms with several metal inserts. The quality of the resulting CBCT images was quantitatively evaluated using the structural similarity (SSIM) metric and compared to those obtained with other interpolation-based MAR methods. A tabletop setup for the micro-CT system was used in the experiment, which comprised an X-ray tube operated under tube conditions of 70 kV p and 5 mA and a flat-panel detector with a pixel size of 198 μm. Our results indicate that the CNR-based metal segmentation method precisely identified traces of metallic objects on the sinogram, and thereby, the proposed SNI-based MAR method considerably reduced metal artifacts in dental CBCT images without introducing any contrast anomalies. The SSIM values of the CBCT images obtained with the proposed MAR method were 0.99 and 0.95 for the simulation and experiment, respectively, which are approximately 11% and 9% greater than those with a simple threshold-based linear interpolation method, respectively, improving the image quality. The proposed MAR method can be applied to reduce metal artifacts in real-world dental CBCT systems.

Microstructure regulation of WxV1-xO2(B) nanorods with improved electrochemical properties

VO2(B) is regarded as a highly promising cathode material for secondary batteries due to its outstanding theoretical specific capacity and unique expansion tunnel structure, which facilitates reversible insertion and extraction of metal ions. Nonetheless, inherent structural instability, suboptimal ion/electron transport, and constrained capacity resulting from low redox potentials pose challenges to its wider adoption. Hence, in this paper, we proposed a strategy for synthesizing gradient concentration-doped WxV1-xO2(B) nanorods via a one-step hydrothermal method to solve the above problems. The experimental results demonstrated that as the W ion content increased, all fabricated WxV1-xO2(B) nanorods exhibited a monoclinic crystal phase along with noticeable lattice distortion. The positron annihilation lifetime spectra indicated that vacancy clusters were the predominant defect types in WxV1-xO2(B) nanorods. The synergistic effects of grain sizes and vacancy defects contributed to the superior electrochemical performance observed in the W0.01V0.99O2(B) sample. The capacitor retention reached 88.76 % at 0.10 A/g after 1000 charge/discharge cycles. These results had provided experimental foundation for improving electrochemical properties of WxV1-xO2(B) in metal ion secondary batteries.

Silver and Copper Nanoparticles Hosted by Carboxymethyl Cellulose Reduce the Infective Effects of Enterotoxigenic Escherichia coli:F4 on Porcine Intestinal Enterocyte IPEC-J2.

Zero-valent copper and silver metals (Ms) nanoparticles (NPs) supported on carboxymethylcellulose (CMC) were synthesized for treating Enterotoxigenic Escherichia coli fimbriae 4 (ETEC:F4), a major cause of diarrhea in post-weaned pigs. The antibacterial properties of Cu0/CMC and Ag0/CMC were assessed on infected porcine intestinal enterocyte IPEC-J2, an in vitro model mimicking the small intestine. The lower average particle size (218 nm) and polydispersity index [PDI]: 0.25) for Ag0/CMC, when compared with those of Cu0/CMC (367 nm and PDI 0.96), were explained by stronger Ag0/CMC interactions. The minimal inhibitory concentration (MIC) and half inhibitory concentration (IC50) of Ag0/CMC were lower in both bacteria and IPEC-J2 cells than those of Cu0/CMC, confirming that silver nanoparticles are more bactericidal than copper counterparts. IPEC-J2, less sensitive in MNP/CMC treatment, was used to further investigate the infective process by ETEC:F4. The IC50 of MNP/CMC increased significantly when infected IPEC-J2 cells and ETEC were co-treated, showing an inhibition of the cytotoxicity effect of ETEC:F4 infection and protection of treated IPEC-J2. Thus, it appears that metal insertion in CMC induces an inhibiting effect on ETEC:F4 growth and that MNP/CMC dispersion governs the enhancement of this effect. These results open promising prospects for metal-loaded biopolymers for preventing and treating swine diarrhea.

Porphyrin photosensitizer molecules as effective medicine candidates for photodynamic therapy: electronic structure information aided design.

Traditional photosensitizers (PS) in photodynamic therapy (PDT) have restricted tissue penetrability of light and a lack of selectivity for tumor cells, which diminishes the efficiency of PDT. Our aim is to effectively screen porphyrin-based PS medication through computational simulations of large-scale design and screening of PDT candidates via a precise description of the state of the light-stimulated PS molecule. Perylene-diimide (PDI) shows an absorption band in the near-infrared region (NIR) and a great photostability. Meanwhile, the insertion of metal can enhance tumor targeting. Therefore, on the basis of the original porphyrin PS segments, a series of metalloporphyrin combined with PDI and additional allosteric Zn-porphyrin-PDI systems were designed and investigated. Geometrical structures, frontier molecular orbitals, ultraviolet-visible (UV-vis) absorption spectra, adiabatic electron affinities (AEA), especially the triplet excited states and spin-orbit coupling matrix elements (SOCME) of these expanded D-A porphyrin were studied in detail using the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. PS candidates, conforming type I or II mechanism for PDT, have been researched carefully by molecular docking which targeted Factor-related apoptosis (Fas)/Fas ligand (Fasl) mediated signaling pathway. It was found that porphyrin-PDI, Fe2-porphyrin-PDI, Zn-porphyrin-PDI, Mg-porphyrin-PDI, Zn-porphyrin combined with PDI through single bond (compound 1), and two acetylenic bonds (compound 2) in this work would be proposed as potential PS candidates for PDT process. This study was expected to provide PS candidates for the development of novel medicines in PDT.

Engineering of Co/MgO interface with combination of ultrathin heavy metal insertion and post-oxidation for voltage-controlled magnetic anisotropy effect

The voltage-controlled magnetic anisotropy (VCMA) effect in ferromagnet/insulator junctions provides an effective way to manipulate electron spins, which can form the basis of future magnetic memory technologies. Recent studies have revealed that the VCMA effect can be strongly tuned by a process of “interface engineering” exploiting ultrathin heavy metal layers and an electron depletion effect. To further decrease the numbers of electrons, chemical reactions, such as surface oxidation of ferromagnets, may also be an effective way to achieve this depletion. However, the knowledge of combined effect of heavy metal layers and oxidation is still lacking. Here, we demonstrate that dual interfacial engineering using an insertion of heavy metals (Pt or Re) and a post-oxidation process can have a remarkable effect on the perpendicular magnetic anisotropy and the VCMA effect. Interestingly, a strong enhancement of the perpendicular magnetic anisotropy is observed by dual interfacial engineering with Pt insertion, although it does not occur with Pt insertion or surface oxidation alone. Furthermore, even a sign reversal of the additional VCMA effect due to the ultrathin heavy metal layers is observed by utilizing dual interfacial engineering. These findings provide another degree of freedom for designing voltage-controlled spintronic devices and pave the way to interfacial spin–orbit engineering for the VCMA effect.

Enhancing Rapid Li+/Na+ Storage Performance via Interface Engineering of Reduced Graphene Oxide-Wrapped Bimetallic Sulfide Nanocages.

Transition-metal sulfide is considered to be an admirable transformational electrode material due to low cost, large specific capacity, and good reversibility in lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). Herein, the reduced graphene oxide-wrapped open bimetallic sulfide (NiS2-Co3S4@rGO) nanocage, derived from nickel-cobalt Prussian blue, was obtained by two-step calcination. There are luxuriant pore structures in the nanocage composite with a specific surface area of 85.28 m2 g-1, which provides plentiful paths for rapid transmission of Li+/Na+ and alleviates the volume stress caused by insertion and extraction of alkali metal ions. The excellent interface combination of bimetallic sulfide wrapped in reduced graphene oxide improves the conductivity and overall performance of the battery. Thanks to the special interface engineering, the open NiS2-Co3S4@rGO nanocage composite displays rapid lithium storage properties with an average diffusion coefficient of 8.5 × 10-13 cm2 s-1. Moreover, after 300 cycles, the reversible capacity of the composite is 1113.2 mAh g-1 at 1 A g-1. In SIBs, the capacity of the open NiS2-Co3S4@rGO composite is 487.9 mAh g-1 when the current density is 5 A g-1. These preeminent performances demonstrate the enormous development prospects of bimetallic sulfide nanocage as anode material in LIBs and SIBs.

Thermal Studies of 3-D Stacked InGaAs HEMTs and Mitigation Strategy of Self-Heating Effect Using Buried Metal Insertion

Thermal Studies of 3-D Stacked InGaAs HEMTs and Mitigation Strategy of Self-Heating Effect Using Buried Metal Insertion

2D Rhenium- and Niobium-Doped WSe2 Photoactive Cathodes in Photo-Enhanced Hybrid Zn-Ion Capacitors.

Designing a multifunctional device that combines solar energy conversion and energy storage is an appealing and promising approach for the next generation of green power and sustainable society. In this work, we fabricated a single-piece device incorporating undoped WSe2, Re- or Nb-doped WSe2 photocathode, and zinc foil anode system enabling a light-assisted rechargeable aqueous zinc metal cell. Comparison of structural, optical, and photoelectric characteristics of undoped and doped WSe2 has further confirmed that ionic insertion of donor metal (rhenium and niobium) plays an important role in enhancing photoelectrochemical energy storage properties. The electrochemical energy storage cell consisting of Re-doped WSe2 (as the photoactive cathode and zinc metal as anode) showed the best photodriven enhancement in the specific capacitance of around 45% due to efficient harvesting of visible light irradiation. The assembled device exhibited a loss of 20% of its initial specific capacitance after 1500 galvanostatic charge-discharge cycles at 50 mA g-1. The cell also provided a specific energy density of 574.21 mWh kg1- and a power density of 5906 mW kg1- at 15 mA g-1. Under otherwise similar conditions, the pristine WSe2 and Nb-doped WSe2 showed photoenhanced induced capacitance of 43% and 27% at 15 mA g-1 and supplied an energy density of 436.4 mWh kg1- and 202 mWh kg1-, respectively. As a result, a reasonable capacitance improvement obtained by the Re-WSe2 photoenhanced zinc-ion capacitor could provide a facile and constructive way to achieve a highly efficient and low-cost solar-electrochemical capacitor system.

Synthesis of Green Brucite [NixMg1−x(OH)2] by Incorporation of Nickel Ions in the Periclase Phase (MgO) Applied as Pigments

Magnesium oxide is typically white and can be colorized with transition metal insertion by doping. We present the preparation of a green-colored hydroxide by the exchange of Mg2+ on the crystalline lattice with Ni2+ in MgO, using three nickel salts. MgOst was prepared by the colloidal starch suspension method, using cassava starch. The oxides and hydroxides, before and after, were characterized by X-ray diffraction (XRD), and show that a phase change occurs: a transition from periclase (MgO) to brucite (Mg(OH)2) due to the incorporation of nickel ions from different salts (acetate, chloride, and nitrate), resulting in the solid solution [NixMg1−x(OH)2]. The FTIR spectrum corroborates the crystallographic structure identified through XRD patterns, confirming the formation of a crystal structure resembling brucite. The new samples present a green color, indicative of the incorporation of the Ni2+ ions. The antimicrobial activity of products resulting from the doping of magnesium oxide with nickel and the precursor MgOst was assessed through the minimum inhibitory concentration (MIC) test. The evaluation included three bacterial strains: Staphylococcus aureus (ATCC 25923), Escherichia coli (ATCC 25922), Salmonella gallinarum (ATCC 9184), and a yeast strain, Candida albicans (ATCC 10231). The obtained results were promising; the tested samples exhibited antimicrobial activity, with a MIC ranging from 0.312 to 0.625 μg.μL−1. The nickel compound, derived from the precursor chloride salt, demonstrated superior MIC activity. Notably, all tested samples displayed bactericidal activity against the S. aureus strain and exhibited a broad spectrum of inhibition, encompassing both Gram-positive and Gram-negative strains. Only the nickel compounds derived from precursors with acetate and nitrate anions demonstrated antimicrobial activity against C. albicans, exhibiting a fungistatic behavior. Based on the conducted studies, [NixMg1−x(OH)2] has emerged as a promising antimicrobial agent, suitable for applications requiring the delay or inhibition of bacterial growth.

Hydrated Calcium Vanadate Nanoribbons with a Stable Structure and Fast Ion Diffusion as a Cathode for Quasi-Solid-State Zinc-Ion Batteries.

We demonstrated the use of hydrated calcium vanadate (CaV6O16·3H2O, denoted as CaVO-2) as a cathode for aqueous zinc-ion batteries (AZIBs). Nanoribbons of hydrated calcium vanadate facilitated shortening of the Zn2+ transport distance and accelerated zinc-ion insertion. The introduction of interlayer structure water increased the interlayer spacing of calcium vanadate and as a "lubricant". Ca2+ insertion also expanded the interlayer spacing and further stabilized the interlayer structure of vanadium-based oxide. The density functional theory results showed that the introduction of Ca2+ and structured water could effectively improve the diffusion kinetics, resulting in the rapid transport of zinc ions. As a result, AZIBs based on the CaVO-2 cathode offered high specific capacity (329.6 mAh g-1 at 200 mA g-1) and fast charge/discharge capability (147 mAh g-1 at 10 A g-1). Impressively, quasi-solid-state zinc-ion batteries based on the CaVO-2 cathode and polyacrylamide-cellulose nanofiber hydrogel electrolytes maintained an outstanding specific capacity and long cycle life (162 mAh g-1 over 10 000 cycles at 5 A g-1). This study provided a reliable strategy for metal-ion insertion and the structural water introduction of oxides to produce a high-quality cathode for ZIBs. Meanwhile, it provides ideas for the combination of vanadium-based materials and gel electrolytes to construct solid-state zinc-ion batteries.

Continuous Flow Electrochemical Synthesis of Olivine-Structured NaFePO4 Cathode Material for Sodium-Ion Batteries from Recycle LiFePO4.

To mitigate the environmental impact of the improper disposal of spent LiFePO4 batteries and reduce resource waste, the development of LiFePO4 recycling technologies is of paramount importance. Meanwhile, olivine-structured NaFePO4 in sodium-ion batteries has received great attention, due to its high theoretical specific capacity of 154 mAh g-1 and excellent stability. However, olivine NaFePO4 only can be synthesized from olivine LiFePO4. Accordingly, in this proposal, developing the continuous flow electrochemical solid-liquid reactor-based metal ion insertion technology is to utilize the olivine FePO4, recycled from LiFePO4, and to synthesize NaFePO4. Additionally, by employing I- as the reducing agent, NaFePO4 is successfully synthesized with a discharge-specific capacity of 134 mAh g-1 at 0.1C and a remarkable capacity retention rate of 86.5% after 100 cycles at 0.2C. And the reasons for sodium deficiency in the synthesized NFP are elucidated through first-principles calculations. Furthermore, the kinetics of the solid-solution reaction 2 (Na2/3+βPO4→ Na1-αFePO4) mechanism improve with cycling and are sensitive to temperature. Utilizing a minimal amount of reducing agent in the electrochemical reactor, NaFePO4 synthesis is successfully achieved. This innovative approach offers a new, cost-effective, and environmentally friendly strategy for preparing NaFePO4 from recycling LiFePO4.

Multivalent-Ion versus Proton Insertion into Nanostructured Electrochromic WO3 from Mild Aqueous Electrolytes.

Mild aqueous electrolytes containing multivalent metal salts are currently scrutinized for the development of ecosustainable energy-related devices. However, the role of soluble multivalent metal ions in the electrochemical reactivity of transition metal oxides is a matter of debate, especially when they are performed in protic aqueous electrolytes. Here, we have compared, by means of (spectro)electrochemistry, the reversible electrochromic reduction of transparent nanostructured γ-WO3 thin films in mild aqueous electrolytes of various chemical composition and pH. This study reveals that reversible proton insertion is the only charge storage mechanism over a large pH range and that it is effective for aqueous electrolytes prepared from either organic (such as acetic acid) or inorganic (such as solvated multivalent cations) Bro̷nsted acids. By refuting charge storage mechanisms relying on the reversible insertion of multivalent metal ions, notably in aqueous electrolytes based on Al3+ ions or a mixture of Al3+ and Zn2+ ions, these fundamental results pave the way for the rational development of electrolytes and active materials for a range of aqueous-based devices, such as the emerging concept of an energy-saving smart window, which we also address in this study.

Effect of metal insertion on the magnetic properties and anomalous Hall effect in MgO/CoFeB/Ta/MgO films

CoFeB-based nano-magnetic multilayers can be applied in magnetic sensors, magnetic random access memory and other logic devices, which have attracted wide attention. The magnetic properties and interface structure of the magnetic multilayers still need further research for future applications. The effects of Pt insertion on the perpendicular magnetic anisotropy (PMA) and the anomalous Hall effect (AHE) of MgO/CoFeB/Pt/Ta/MgO multilayers were studied. It is found that the sample with 0.2 nm Pt insertion at the CoFeB/Ta interface and annealed at 250 °C can transform the films from in-plane magnetic anisotropy to PMA. The effective magnetic anisotropy K eff can reach 1.82 × 106 erg cm−3. The Pt insertion and annealing heat treatment can promote the migration of oxygen from MgO at the top layer to CoFeB/Ta interface and combine with Fe to generate iron oxide, and improve the orbital hybridization of Fe 3d and O 2p, thus successfully inducing the PMA of the film samples. In addition, Pt insertion and annealing treatment can improve the side-jump mechanism and the skew scattering mechanism which contribute to the AHE. This work provides guidance for the application of PMA materials in magnetic sensor and memory devices.

Electrophoretic assisted fabrication of additive-free WS2 nanosheet anodes for high energy density lithium-ion batteries.

2D WS2 nanosheets (NSs) are gaining popularity in the domain of Li-ion batteries (LIBs) due to their unique structures, which can enable reversible insertion and extraction of alkali metal ions. While synthesis methods have mostly relied on the exfoliation of bulk materials or direct growth on substrates, here we report an alternative approach involving colloidal hot-injection synthesis of 2D WS2 in 2H and 1T' crystal phases followed by their electrophoretic deposition (EPD) on the current collector. The produced 2D WS2 NSs' films do not require any additional additives during deposition, which boosts the energy density of the additive-free LIBs produced. The 1T' and 2H NSs exhibit long-term stable cyclic performance at C/5 for 600 cycles. At a high cycling rate (1C), the 2H NSs outperform the 1T' NSs, delivering a 1st cycle reversible capacity of 513 mA h g-1 with capacity retention of 73% after 100 cycles (compared to 205 mA h g-1, and 84 mA h g-1 respectively for NS-1T'). Post-cycling investigation confirms that there is no leaching or cracking of the active material on the surface of anodes after 100 cycles at C/5, which enables mechanical stability, and impressive battery performance of the WS2 NS electrodes.

New frontiers in alkali metal insertion into carbon electrodes for energy storage.

With rising interest in new electrodes for next-generation batteries, carbon materials remain as top competitors with their reliable performance, low-cost, low voltage reactions, and diverse tunability. Depending on carbon's structure, it can attain high cyclability as with Li+ at crystalline graphite or exceptional capacities with Na+ at amorphous, porous hard carbons. In this review, we discuss key results and research directions using carbon electrodes for alkali ion storage. We start the first section with hard carbon (HC), a leading material of interest for next-generation Na-ion batteries. Methods for tuning the HC structure towards a high capacity pore-filling mechanism are examined. The rate performance of hard carbon electrodes is further discussed. We finish this section with soft carbons that mostly remain as low performing materials compared to other carbons. In the second section, we discuss alkali ion insertion into graphite and graphite-like materials. Though graphite has a long history with Li-ion batteries, it also shows promising characteristics for K-ion batteries. We discuss the significant progress made on improving the electrolyte for high cyclability of graphite with K+. Thereafter, we evaluate B/C/N materials that have a similar structure to graphite but can attain higher capacities for both Li+ and Na+. Finally, we touch on the recent developments using alternative solvents for Na+ cointercalation at graphite and deeper knowledge on the intercalant structure. Despite steady progress, carbon electrodes continue to improve as a key group of materials for alkali energy storage.

Redox-active electrolytes as a viable approach for the one-step assembly of metal-ion capacitors

The assembly of metal-ion capacitors is a very challenging task; the use of traditional metallic electrodes or sacrificial materials induces technical problems during cell assembly or affects its normal operation. Here, we report an efficient, one-step method for assembling metal-ion capacitors using redox-active electrolytes with thiocyanate-based salts. The addition of a redox-active salt compensates for the charge on the positive electrode while enabling the insertion of metal ions into the structure of the negative electrode. The proposed approach reduces assembly time and cost and results in increased specific energy compared to that from the traditional two-step assembled hybrid systems. Furthermore, we demonstrate that the proposed approach can be successfully implemented for sodium-ion and potassium-ion hybrid capacitors. Our results are supported by operando techniques and can potentially facilitate further research on metal-ion capacitors and applications of these devices.

Enhancement of the Rates for Insertion of Zinc(II) Ions into a Cationic Porphyrin Catalyzed by Poly(glutamate).

The self-assembly of porphyrins onto polyelectrolytes could lead to interesting changes in their reactivity with respect to the bulk solution. Here, we investigated the kinetics of Zn2+ incorporation into tetra-cationic water-soluble 5,10,15,20-tetrakis-(N-methylpyridinium-4-yl)porphyrin (TMpyP(4)) in the presence of poly(L-glutamic acid) (PGA) in a pH range from 4 to 6.5. Under these conditions, the porphyrin electrostatically interacted with the polymer, which gradually switched from an α-helical to a random coil structure. The profile of the logarithm of the observed rate constant (kobs) versus the pH was sigmoidal with an inflection point close to the pH of the conformation transition for PGA. At a pH of 5.4, when PGA was in its highly charged random coil conformation, an almost 1000-fold increase in the reaction rates was observed. An increase in the ionic strength of the bulk solution led to a decrease in the metal insertion rates. The role of the charged matrix was explained in terms of its ability to assemble both reagents in proximity, in agreement with the theory of counter-ion condensation around polyelectrolytes in an aqueous solution.

Synthesis of PbxCu1−xBi2O4 composites with enhanced visible-light-responsive photocatalytic degradation performance

The unintentional release of highly toxic dyes from various industrial sectors into aquatic environments caused an imminent threat to the aquatic ecosystem and human health. Therefore, it is highly imperative to develop efficient and sustainable treatment technologies. In this work, we have constructed a novel PbxCu1−xBi2O4 nanostructured composite through a facile hydrothermal method. The atomic ratio of Pb to Cu was systematically investigated. The optimized sample of Pb0.10Cu0.90Bi2O4 has a higher visible light responsiveness for the degradation of Congo red (CR) dye than that of CuBi2O4. The results show that CuBi2O4 has the least degradation potential for CR under optimal conditions (catalyst = 0.4 g/L, [CR] = 30 mg/L, pH = 5.0, T = 25 ± 2 °C), and 83.39% degradation was achieved in 80 min under visible light irradiation. Meanwhile, Pb0.10Cu0.90Bi2O4 photocatalyst has shown 99.23% degradation of CR dye. This enhancement in the degradation of CR was considered due to the increase in the surface area of Pb0.10Cu0.90Bi2O4 (67.32 m2/g) and exposed active sites compared with that of pure CuBi2O4 (49.73 m2/g). The insertion of Pb metal ions into basic framework of the CuBi2O4 leads to increase in the specific surface area of the material, resulting in enhanced degradation. Furthermore, the insertion of Pb metal ions also lowered the optical bandgap energy of the catalytic material, which enhanced the degrading potential of Pb0.10Cu0.90Bi2O4. The effect factors were further examined, including catalyst dosage, initial dye concentration, pH, temperature, and agitation rate. In addition, the effect of humic acid and interfering anions on CR degradation was also investigated. The results of these experiments show that these factors also influence the photocatalytic degradation of CR dye. Therefore, appropriate treatment of these factors would increase the wastewater treatment efficiency by the as-prepared Pb0.10Cu0.90Bi2O4 photocatalyst.