Metal Ion Doping Research Articles

Highly Crystalline Copper Aluminum-Layered Double Hydroxides with Intrinsic Fenton-Like Catalytic Activity for Robust Oral Health Management.

As the main challenge of dental healthcare, oral infectious diseases are highly associated with the colonization of pathogenic microbes. However, current antibacterial treatments in the field of stomatology still lack a facile, safe, and universal approach. Herein, we report the controllable synthesis of copper aluminum-layered double hydroxides (CuAl-LDHs) with high Fenton-like catalytic activity, which can be utilized in the treatment of oral infectious diseases with negligible side effects. Our strategy can efficiently avoid the unwanted doping of other divalent metal ions in the synthesis of Cu-contained LDHs and result in the formation of binary CuAl-LDHs with high crystallinity and purity. Evidenced by experimental and theoretical results, CuAl-LDHs exhibit excellent catalytic ability toward the ·OH generation in the presence of H2O2 and hold strong affinity toward bacteria, endowing them with great catalytic sterilization against both Gram-positive and Gram-negative bacteria. As expected, these CuAl-LDHs provide outstanding treatments for mucosal infection and periodontitis by promoting wound healing and remodeling of the periodontal microenvironment. Moreover, toxicity investigation demonstrates the overall safety. Accordingly, the current study not only provides a convenient and economic strategy for treating oral infectious diseases but also extends the development of novel LDH-based Fenton or Fenton-like antibacterial reagents for further biomedical applications.

Electrochemiluminescence quenching effect of Cu2O towards flower-like ferric ion-doped g-C3N4 and its application for Cyfra21-1 immunosensing

In this article, ferric ion-doped floral graphite carbon nitride (Fe–CN-3, energy donor) was used to construct the substrate of the immunosensor and copper oxide nanocubes (Cu2O, energy acceptor) were taken as an efficient ECL quenching probe. A sandwich quench electrochemiluminescence (ECL) immunosensor for soluble cytokeratin 19 fragment (Cyfra21-1) detection was preliminarily developed based on a novel resonant energy transfer donor-acceptor pair. Fe–CN-3, a carbon nitride that combines the advantages of metal ion doping as well as morphology modulation, is used in ECL luminophores to provide more excellent ECL performance, which makes a significant contribution to the application and development of carbon nitride in the field of ECL biosensors. The regular shape, high specific surface area and excellent biocompatibility of the quencher Cu2O nanocubes facilitate the labeling of secondary antibodies and the construction of sensors. Meanwhile, as an energy acceptor, the UV absorption spectrum of Cu2O can overlap efficiently with the energy donor's ECL emission spectrum, making it prone to the occurrence of ECL-RET and thus obtaining an excellent quenching effect. These merits of the donor-acceptor pair enable the sensor to have a wide detection range of 0.00005–100 ng/mL and a low detection limit of 17.4 fg/mL (S/N = 3), which provides a new approach and theoretical basis for the clinical detection of lung cancer.

Boosting the Zn2+ storage capacity of MoO3 nanoribbons by modulating the electrons spin states of Mo via Ni doping

Aqueous zinc-ion batteries (AZIBs) have received considerable potential for their affordability and high reliability. Among potential cathodes, α-MoO3 stands out due to its layered structure aligned with the (010) plane, offering extensive ionic insertion channels for enhanced charge storage. However, its limited electrochemical activity and poor Zn2+ transport kinetics present significant challenges for its deployment in energy storage devices. To overcome these limitations, we introduce a new strategy by doping α-MoO3 with Ni (Ni-MoO3), tuning the electron spin states of Mo. Thus modification can activate the reactivity of Ni-MoO3 towards Zn2+ storage and weaken the interaction between Ni-MoO3 and intercalated Zn2+, thereby accelerating the Zn2+ transport and storage. Consequently, the electrochemical properties of Ni-MoO3 significantly surpass those of pure MoO3, demonstrating a specific capacity of 258 mAh g−1 at 1 A g−1 and outstanding rate performance (120 mAh g−1 at 10 A g−1). After 1000 cycles at 8 A g−1, it retains 76 % of the initial capacity, with an energy density of 154.4 Wh kg−1 and a power density of 11.2 kW kg−1. This work proves that the modulation of electron spin states in cathode materials via metal ion doping can effectively boost their capacity and cycling durability.

Yellow rare earth sulfide powders with near‐infrared reflectance and spectral modulation for energy‐saving applications

AbstractRadiative cooling pigments offer new opportunities for sustainable carbon neutrality as zero‐energy and zero‐pollution functional materials. However, it is a challenge to prepare inorganic yellow pigments simultaneously with environmentally friendly, high color value, and weather resistance. In this study, a series of alkali metal‐doped γ‐Sm2S3 yellow pigments with near‐infrared reflectance were synthesized. The doping of alkali metal ions reduced synthesis temperature of Sm2S3 from 1300°C to 1000°C. The change in energy band structure induced by alkali metal doping allows the products to exhibit modifiable colors. Typical γ‐[Na]‐Sm2S3 pigment powders have a high near‐infrared reflectance and impressive colors (b* = 78.6, C* = 77.6). Furthermore, colored films made by prepared yellow powders with polyvinylidene fluoride in certain ratios had high near‐infrared reflectance and excellent environmental weathering, resulting in an effective cooling of 4–8°C in outdoor experiments. This work expands the range of options for energy‐efficient building and yellow colorant.

Spin-Phonon Coupling in Iron-Doped Ultrathin Bismuth Halide Perovskite Derivatives.

Spin in semiconductors facilitates magnetically controlled optoelectronic and spintronic devices. In metal halide perovskites (MHPs), doping magnetic ions is proven to be a simple and efficient approach to introducing a spin magnetic momentum. In this work, we present a facile metal ion doping protocol through the vapor-phase metal halide insertion reaction to the chemical vapor deposition (CVD)-grown ultrathin Cs3BiBr6 perovskites. The Fe-doped bismuth halide (Fe:CBBr) perovskites demonstrate that the iron spins are successfully incorporated into the lattice, as revealed by the spin-phonon coupling below the critical temperature Tc around 50 K observed through temperature-dependent Raman spectroscopy. Furthermore, the phonons exhibit significant softening under an applied magnetic field, possibly originating from magnetostriction and spin exchange interaction. The spin-phonon coupling in Fe:CBBr potentially provides an efficient way to tune the spin and lattice parameters for halide perovskite-based spintronics.

Evidence and Practical Applications of Site Occupancy Theory (SOT) of Eu3+ in Scheelite Compounds.

The determination of the site occupancy of activators in phosphors is essential for precise synthesis, understanding the relationship between their luminescence properties and crystal structure, and tailoring their properties by modifying the host composition. Herein, one simple method was proposed to help determine the sites at which the doping of rare earth ions or transition metal ions occupies in the host lattice through site occupancy theory (SOT) for ions doped into the matrix lattice. SOT was established based on the fact that doping ions preferentially occupy the sites with the lowest bonding energy deviations. In order to provide detailed experimental evidence to prove the feasibility of SOT, several scheelite-type compounds were successfully synthesized using a high-temperature solid-phase method. When Eu3+ ions occupy a similar surrounding environment site, the photoluminescence spectra of the activators Eu3+ are similar. Therefore, by comparing the intensity ratio of photoluminescence spectra and the mechanism of all transitions of KEu(WO4)2, KY(WO4)2:Eu3+, Na5Eu(WO4)4, and Na5Y(WO4)4:Eu3+, it was proved that SOT can successfully confirm the site occupation when doped ions enter the matrix lattice. SOT was further applied to the sites occupied by Eu3+ ion-doped LiAl(MoO4)2 and LiLu(MoO4)2.

Ultraviolet-B and Near-Infrared Dual-Band Luminescence in Bi3+/Bi2+ Codoped Persistent Phosphor for Optical Storage Application.

Discovering multifunctional luminescent materials to meet the demands of modern spectroscopy is of great significance. However, it is a standing challenge to enable multiple luminescence properties in a single material system via single metal ion doping. Here, we report the inherently Bi3+/Bi2+ codoped Ca3Ga2Ge3O12 persistent phosphor where Bi3+ is in situ reduced to Bi2+. This phosphor can act as an efficient multimodal luminescence material, which simultaneously exhibits long-lasting (>12 h) ultraviolet-B (UVB) and near-infrared (NIR) dual-band persistent luminescence after irradiation by 254 nm ultraviolet (UV) light. UVB and NIR afterglow are ascribed to the distinct Bi3+ and Bi2+ emitters, respectively, proven by comprehensive spectroscopic investigations including X-ray absorption near-edge structure spectra and X-ray photoelectron spectroscopy. Besides, this phosphor also exhibits exceptional photochromic features, accompanied by a rapid body color transformation from white to brown in response to 254 nm UV light within 60 s and excellent recovery capacity upon thermal or blue/white light stimulation. The combination of UVB persistent luminescence of Bi3+ and NIR afterglow of Bi2+ coupled with reversible white-to-brown photochromism phenomenon offers one type of promising multifunctional luminescence material, showing potential to be used for optical storage and anti-counterfeiting applications.

Zn-doped CdSSe composite quantum dots synthesized by a two-step hydrothermal ion exchange in sensitized solar cells

Metal ion doping is an effective strategy for enhancing the photoelectric properties of quantum dots (QDs). In this study, Zn-doped CdSSe composite QDs (ZnCdSSe) were synthesized using a two-step hydrothermal ion exchange method. The synthesis process involved the exchange reaction of Cd2+ with Zn2+, followed by the exchange reaction of Se2− with S2−, based on ZnS templates. The morphology, composition and crystalline phase of synthesized QDs were characterized using X-ray and electron-based techniques such as XRD, SEM, TEM, and XPS. The results indicate ZnCdSSe QDs were synthesized while preserving a similar morphology to that of ZnCdS. Performance tests demonstrated that quantum dot sensitized solar cells (QDSSCs) equipped with ZnCdSSe/TiO2 photoanodes achieved a power conversion efficiency (PCE) of 3.61% by optimizing the hydrothermal reaction temperature and time. This efficiency was 33.2% higher than that of CdSSe (2.17%) QDSSCs synthesized via a one-step hydrothermal exchange reaction using CdS templates. The significant enhancement in PCE can be attributed to improvements in light absorption and charge carrier transport. Notably, Zn doping reduced interface charge recombination and prolong electronic lifetime (τn), facilitating more effective charge collection in QDSSCs.

Research Progress on Preparation of SnO2 Gas-Sensing Materials and Modification by Metal Ions Doping

This paper delineates the developmental trajectory of SnO2-based gas sensing sensors and conducts an in-depth analysis of the prevalent preparation methodologies employed for nano-powder and thin film SnO2 materials. Recent investigations underscore that the doping of metal ions primarily operates through atomic substitution and solid solution mechanisms, where partial distortions in the crystal structure and the creation of oxygen vacancies emerge as pivotal factors augmenting the gas sensing capabilities of doped SnO2. Future research endeavors aimed at refining the modification of SnO2 through doping are anticipated to pivot towards mitigating its susceptibility to cross-sensitivity when confronted with mixed gas environments, while concurrently exploring physicochemical and biologically inspired preparation methodologies to imbue the process with greater eco-friendliness.

Cobalt doped K-birnessite as ultrastable cathode for aqueous calcium-ion batteries

Aqueous Ca ion batteries (ACIBs) are one of the emerging energy-storage technologies due to their low costs and low polarization strength. Birnessite-MnO2 is one kind of promising cathode because of its large interlayer distance for facile Ca2+ ion intercalation and high theoretical specific capacity (241 mAh g−1), but the inferior cycling performance significantly limits its application in ACIBs. Herein, 2% Co-doped K-birnessite K0.11Co0.02Mn0.98O2·1.4H2O (CB-2) with superior structural stability is reported for the first time. The Co-doped K-birnessite exhibits enhanced conductivity and capacitance ability. Moreover, after Co doping, the Mn–O ionic bond is shortened and the banding energy is reduced, which effectively inhibits the Jahn-Taller effect and improves the thermodynamic stability. More interestingly, we find that Ca2+ can restrain the irreversible transition of birnessite from layered to spinel. CB-2 cathode delivers an excellent rate performance of 181.2 mAh g−1 at 200 mA g−1 and structural stability of 1000 cycles at 2 A g−1 with 90.4% capacity retention. Finally, a stable ACIB is constructed by using the CB-2 cathode and polyimide anode, which shows a decent specific capacity of 51.9 mAh g−1 at 200 mA g−1 and superior cycling stability. This demonstrates effective foreign metal ion doping for K-birnessite to achieve superior Ca2+ storage in aqueous batteries.

A Co-doped Ag3PO4 photocatalyst: Efficient degradation of organic pollutants and enhancement mechanism

In this study, an efficient Co-doped Ag3PO4 photocatalyst was prepared by the deposition method. Compared with Ag3PO4, the degradation efficiency of the optimal sample CAP-2 (the mole ratio of Co/Ag was 0.057 %) for MO (20 mgL−1) increased from 53.4 % to 95.0 % within 20 min, and the degradation efficiency for phenol (20 mgL−1) increased from 57.9 % to 91.8 % within 80 min. Moreover, the CAP-2 sample performed excellent mineralization ability and stable recycling capacity. Free radical capture experiments and electron spin resonance (ESR) measurements indicated that holes (h+) and superoxide radicals (⋅O2−) were the main active radicals. Doping Co ions broadened the optical absorption, introduced impurity level to promote the separation of carriers, and generated additional ⋅O2− owing to the mutual conversion of Co3+ and Co2+, thus considerably improving Ag3PO4 photocatalytic performance. This work provides a new reference for doping metal ions modified semiconductor photocatalysts to efficiently degrade organic pollutants.

Highly Selective and Reversible Detection of Simulated Breath Hydrogen Sulfide Using Fe-Doped CuO Hollow Spheres: Enhanced Surface Redox Reaction by Multi-Valent Catalysts.

The precise and reversible detection of hydrogen sulfide (H2S) at high humidity condition, a malodorous and harmful volatile sulfur compound, is essential for the self-assessment of oral diseases, halitosis, and asthma. However, the selective and reversible detection of trace concentrations of H2S (≈0.1ppm) in high humidity conditions (exhaled breath) is challenging because of irreversible H2S adsorption/desorption at the surface of chemiresistors. The study reports the synthesis of Fe-doped CuO hollow spheres as H2S gas-sensing materials via spray pyrolysis. 4 at.% of Fe-doped CuO hollow spheres exhibit high selectivity (response ratio ≥ 34.4) over interference gas (ethanol, 1ppm) and reversible sensing characteristics (100% recovery) to 0.1ppm of H2S under high humidity (relative humidity 80%) at 175 °C. The effect of multi-valent transition metal ion doping into CuO on sensor reversibility is confirmed through the enhancement of recovery kinetics by doping 4 at.% of Ti- or Nb ions into CuO sensors. Mechanistic detailsof these excellent H2S sensing characteristics are also investigated by analyzing the redox reactions and the catalytic activity change of the Fe-doped CuO sensing materials. The selective and reversible detection of H2S using the Fe-doped CuO sensor suggested in this work opens a new possibility for halitosis self-monitoring.

Adsorption of high-temperature CO2 by Ca2+/Na+-doped lithium orthosilicate: characterization, kinetics, and recycle.

High-temperature solid adsorbent Li4SiO4 has received broad attention due to its high theoretical adsorption capacity, high regeneration capacity, and wide range of raw materials for preparation. In this paper, a Li4SiO4 adsorbent was prepared by MCM-48 as the silica precursor and modified by doping with metal ions (Ca2+ and Na+) for high-temperature capture of low-concentration CO2. The results showed that the surface of the Ca-doped (or Na-doped) Li4SiO4 adsorbent developed some particles that are primarily composed by Li2CaSiO4 (or Li3NaSiO4). Furthermore, the grains of the adsorbents became finer, effectively increasing the specific surface area and enhancing adsorption performance. Under 15 vol% CO2, the maximum CO2 adsorption was 25.63 wt% and 32.86 wt% when the Ca2+ doping amount was 0.06 and the Na+ doping amount was 0.12, respectively. These values were both higher than the adsorption capacity before the metal ion doping. After 10 adsorption/desorption cycles, the adsorption capacity of Na-doped Li4SiO4 increased by 9.68 wt%, while that of Ca-doped Li4SiO4 decreased by 7.98 wt%. This difference could be attributed to the easy sintering of the Ca-containing adsorbent. Furthermore, a biexponential model was used to fit the CO2 adsorption curve of the adsorbent in order to study the adsorption kinetics. Compared to the conventional Li4SiO4, the Ca/Na-doped adsorbent offers several advantages, such as a high CO2 adsorption capacity and stable cycling ability.

Advancements in incorporating metal ions onto the surface of biomedical titanium and its alloys via micro-arc oxidation: a research review.

The incorporation of biologically active metallic elements into nano/micron-scale coatings through micro-arc oxidation (MAO) shows significant potential in enhancing the biological characteristics and functionality of titanium-based materials. By introducing diverse metal ions onto titanium implant surfaces, not only can their antibacterial, anti-inflammatory and corrosion resistance properties be heightened, but it also promotes vascular growth and facilitates the formation of new bone tissue. This review provides a thorough examination of recent advancements in this field, covering the characteristics of commonly used metal ions and their associated preparation parameters. It also highlights the diverse applications of specific metal ions in enhancing osteogenesis, angiogenesis, antibacterial efficacy, anti-inflammatory and corrosion resistance properties of titanium implants. Furthermore, the review discusses challenges faced and future prospects in this promising area of research. In conclusion, the synergistic approach of micro-arc oxidation and metal ion doping demonstrates substantial promise in advancing the effectiveness of biomedical titanium and its alloys, promising improved outcomes in medical implant applications.

Electrochemical activity of 3d transition metal ions in polyanionic compounds for sodium‐ion batteries

AbstractSodium‐ion batteries are expected to replace lithium‐ion batteries in large‐scale energy storage systems due to their low cost, wide availability, and high abundance. Polyanionic materials are considered to be the most promising cathode materials for sodium‐ion batteries because of their cycling stability and structural stability. However, limited by its poor electronic conductivity, the electrochemical performance needs to be further improved. This paper reviews the characterization and development of 3d transition metal ions polyanionic compounds, along with the summarized effect of structure and particle size on the performance and improvement of electrochemical properties. Meanwhile, crystal structure modulation, transition metal ion choice, and transition metal ion doping can improve the electrochemical performance and energy density of polyanionic compounds. Finally, this review points out the challenges of polyanionic compounds and puts forward some particular standpoints, contributing to the promising development of polyanionic compounds in the large‐scale energy storage market.

Fracture Resistant CrSi2-Doped Silicon Nanoparticle Anodes for Fast-Charge Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) has been developed over the last three decades. Increased amount of silicon (Si) is added into graphite anode to increase the energy density of LIBs. However, the amount of Si is limited, due to its structural instability and poor electronic conductivity so a novel approach is needed to overcome these issues. In this work, the synthesized chromium silicide (CrSi2) doped Si nanoparticle anode material achieves an initial capacity of 1729.3mAhg-1 at 0.2C and retains 1085mAhg-1 after 500cycles. The new anode also shows fast charge capability due to the enhanced electronic conductivity provided by CrSi2 dopant, delivering a capacity of 815.9mAhg-1 at 1C after 1000cycles with a capacity degradation rate of <0.05% per cycle. An in situ transmission electron microscopy is used to study the structural stability of the CrSi2-doped Si, indicating that the high control of CrSi2 dopant prevents the fracture of Si during lithiation and results in long cycle life. Molecular dynamics simulation shows that CrSi2 doping optimizes the crack propagation path and dissipates the fracture energy. In this work a comprehensive information is provided to study the function of metal ion doping in electrode materials.

Bimetallic zeolitic imidazolate frameworks Co/ZIF-8 crystals as carbonic anhydrase-mimicking nanozyme

Zeolitic imidazolate frameworks (ZIFs) materials are known for their excellent stability and their ability to provide an adjustable, controllable structure. The precise assembly of metal nodes and ligands in ZIFs enables them to possess active centers that closely resemble those found in natural enzymes. Building upon this, the objective of this study was to mimic the catalytic active center of natural carbonic anhydrase (CA) by employing defect coordination on the outer surface of bimetallic Co/ZIF-8 crystals. The synthesis process was meticulously controlled through the introduction of cobalt ions, resulting in the creation of a biomimetic CA with remarkable stability and catalytic prowess. The bimetallic Co/ZIF-8 nanozyme exhibited catalytic properties similar to those of natural enzymes. It efficiently facilitated the CO2 hydration reaction and demonstrated the ability to catalyze the reverse reaction. The esterase activity of all Co/ZIF-8 nanozymes was higher than that of the original ZIF-8 at room temperature. Notably, these nanozymes exhibited an impressive maximum esterase activity of 3.77 U/mg at 80 ℃, which surpassed the levels observed in natural CA. This enhancement can be attributed to the boosted catalytic activity of Co/ZIF-8, stemming from the introduction of metal ion doping, which increased the potential difference between bimetallic active centers and facilitated efficient charge transfer. Furthermore, thanks to the unique activation mechanism inherent in the structure of Co/ZIF-8, the esterase activity not only remained unaffected after 24 h of hydrothermal treatment, but also experienced a significant enhancement. This article represents a valuable breakthrough in the regulation and modification of ZIF-8, resulting in the fabrication of an efficient bimetallic Co/ZIF-8 nanozyme for CA-mimicking. These findings hold immense significance for further research and development in the realm of industrial CO2 capture catalysts.

Ag-Fe2O3 nanocomposites for synergistically enhanced antibacterial activity

Doping of metal or metal ions in the host lattice with good dopant distribution or forming a local contact boosts materials properties for specific applications. This work used the solution combustion approach (SCA) to synthesize Ag-Fe2O3 nanocomposites (SICs) following the single-source precursor doping strategy with good final material stoichiometry. The elemental distribution and composition, crystallinity, and morphology of SCA-based synthesized materials were analyzed using common techniques such as TEM, FESEM-EDS, and XRD. Even though the Lewis hard and soft acids and bases (HSAB) idea was precise for inclusion of Ag dopant in the Fe2O3 lattice, the formation of Schottky junctions between Ag and Fe2O3 is dominance as a result of dopant-host radii size differences. The independent peak for both Ag and Fe2O3 crystals on the XRD pattern analysis without peak shift confirms the dominance of Schottky junction formation. The presence of local contact between Ag and Fe2O3 was also confirmed by the HRTEM analysis, with d-spacing values of 0.22 and 0.36 nm, respectively. Compared to the bare Fe2O3, the antibacterial potential of the SIC is much greater, with a 23-mm zone of inhibition on Pseudomonas aeruginosa gram-negative bacteria, which confirms the presence of a synergistic effect.

Modulating the nonlinear optical properties of MAPbBr3 by metal ion doping

The nonlinear optical properties of MAPbBr3 are modulated by metal ion doping. After Zn and Bi ion doping, the nonlinear optical and optical limiting properties of MAPbBr3 are enhanced, owing to the adjustment of defects after doping.

Dopant effect on the optical and thermal properties of the 2D organic-inorganic hybrid perovskite (HDA)2PbBr4.

Lead-based two-dimensional organic-inorganic hybrid perovskites (2D HOIPs) are popular materials with various optical properties, which can be tuned through metal ion doping. Due to the size and valence misfit, metal ion dopants in 2D lead-based HOIPs are still limited. In this work, Mn2+, Sb3+ and Bi3+ are doped into 2D (HDA)2PbBr4 (HDA = protonated dopamine) successfully. As a result, the dopants in 2D (HDA)2PbBr4 can induce their characteristic optical spectra, which is studied at different temperatures and excitation powers. The temperature-dependent energy transfer in the Mn-doped sample has been clarified, in which abnormal phenomena including negative thermal quenching have been observed. In addition, the dopant ions can impact the phase transition temperatures of the samples, especially lowering their crystallization temperatures greatly. The mussel-inspired organic cation, feasible metal ion regulation, and superior stability provide (HDA)2PbBr4 potential for further applications.